RSC Green Chemistry Series

Edited by Rainer Höfer

Sustainable Solutions for

Modern Economies

Foreword by Paul Anastas

Sustainable Solutions for Modern Economies
RSC Green Chemistry

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Sustainable Solutions for Modern
Economies

Edited by

Rainer Höfer
Cognis GmbH, Monheim, Germany
The front cover image has been taken from the website of EFPRA, the
European Fat Processors and Renderers Association, Rijswijk, Netherlands,
http://www.efpra.eu. The picture shows SARIA Bio-Industries’ SIFDDA SAS
site in Benet, France. Reproduction with kind permission of EFPRA and
SARIA Bio-Industries, Selm, Germany.

RSC Green Chemistry No. 4

ISBN: 978-1-84755-905-0
ISSN: 1757-7039

A catalogue record for this book is available from the British Library

r Royal Society of Chemistry 2009

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Foreword
There’s a funny thing about design. You can’t do design by accident. If you
wind up with a wonderful new product through serendipity, you can say all
kinds of things about it but you can never claim that it was designed. This is
important because what we face today is the greatest design challenge of all
time. How do we design the products and processes that are the basis of our
society and our economy so that they are benign to humans and the environ-
ment and are sustainable? It is a difficult challenge for many reasons.
First, we have designed things so wrong for so long, we have many old, bad
habits to break. As we look across the Twelve Principles of Green Chemistry,
one could view them as common sense. However, common sense is not com-
mon in chemical design. The amount of waste generated per kilogram of
product is often of higher magnitude than the production volume. Our feed-
stocks are usually depleting finite resources, our reagents are often toxic and
our products persistent and bioaccumulating. The good news is that many of
the best practitioners in the world have recognized the shortcomings of our
chemical design and their work is featured in this book.
Second, we don’t view hazard as a design flaw. We are very good at designing
for performance. The past 150 years of chemistry can be viewed as nothing
short of a technological miracle in the development of new medicines, dyes,
materials and catalysts. However, adverse consequence to humans or the
environment was never considered as a design criterion. In part, this was due to
the fact that we didn’t have the molecular basis of understanding hazard in a
way that would inform design. However, with the advancement of the science,
we have insights that allow us to design intrinsically less hazardous products
and processes as can be seen in this volume.
Third, we don’t think in terms of systems. Even when we approach some of
the big sustainability challenges, climate change, renewable energy, pure water,
food supply, toxics, etc., we approach these challenges in a fragmented manner.
We often forget that climate change is inextricably linked to energy, and energy
to water purification, and water to food, etc. We often wind up doing the ‘‘right
things, wrong’’. We purify water with acutely lethal substances. We make
energy-efficient bulbs with neurotoxins, and solar energy with scarce, depleting
and toxic metals. The Twelve Principles of Green Chemistry have supplied a
framework by which to recognize how to do the ‘‘right things, right’’. In other

v
vi Foreword
words, to know when your solutions to sustainability challenges are themselves
sustainable.
This book is a collection of work by thoughtful designers who have
approached their work with sustainability in mind; who recognize the errors
of our past and are designing new systems that reduce or eliminate intrinsic
hazard wherever possible. It is one of the great scientific challenges that we
face and we need to face it with creative, rigorous design. We cannot count on
accident or serendipity to get us off the unsustainable trajectory that we are on
currently.
The achievements of the field of Green Chemistry and sustainable design
in its short life are truly amazing. They span every molecular sub-discipline.
The achievements can be found across virtually every industry sector that
chemistry touches from electronics to aerospace, to chemicals, pesticides and
medicines, to paints, plastics and cosmetics. However, the most remarkable
thing about the accomplishments of the field of Green Chemistry thus far is
that collectively they are just a small fraction of the power and the potential
of the achievements yet to be realized. The achievements in this book are yet
another glimmer of how thoughtful design can lead us towards a sustainable
civilization.

Paul T. Anastas
Teresa and H. John Heinz III Professor
In the Practice of Chemistry for the Environment
Yale University
USA
Preface
Apocalypse now? Was the financial crisis which erupted in 2008 the ‘‘writing
on the wall’’, the Menetekel for the Industrial Age? Is mankind approaching
the impasse of Easter Island, Anasazi and Maya societies shortly before
collapse – ‘‘which followed swiftly upon the society’s reaching its peak of
population, monument construction and environmental impact’’? Or will
mankind be capable of a new global common sense? After 200 years
of industrial development largely based on easily available, abundant, and
hence cheap fossil raw materials, will there be a concept and an agreed-upon
action plan to preserve these more and more precious materials, because they
are finite, fossil resources and substitute them with renewable raw materials,
enforcing sustainable development on a global basis and bringing global
warming to a halt?
This introduction to Sustainable Solutions for Modern Economies has been
written in the first week of April 2009, after the G20, NATO and EU-USA
summits in London, Kehl-Strasbourg and Prague, which have created hope
that such a vision might become a reality. There is no doubt, however, that
concepts for energy savings on a global basis and a fair value for finite fossil
resources need to be part of such reality.
Sustainable Solutions for Modern Economies is not meant as a political
pamphlet. However, the very concept of sustainability and its social, eco-
nomical and ecological aspects have been established and accepted at the Earth
Summit in Rio de Janeiro as a political initiative obligating the signatory states
to implement Agenda 21, the wide-ranging blueprint for action to achieve
sustainable development worldwide. Sustainable Solutions for Modern Econo-
mies is meant as an essay to reflect the aspects of sustainability in the different
sectors of national and global economies, to draft a roadmap for public and
corporate sustainability strategies, and to outline the current status of markets,
applications, use and research and development for renewable resources.

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

vii
viii Preface
Besides history of the sustainability concept, Chapter 1 brings up philoso-
phical aspects of the relationship between man and nature and highlights
the key sustainability initiatives of the chemical industry, i.e. The Responsible
Cares Global Charter and the 24 Principles of Green Chemistry and Green
Engineering.
Chapter 2 depicts the position and the systemic role of the financial market in
the economic circuit on the one hand and, on the other, recently developed key
performance indicators for the sustainability rating of companies used
as criteria for socially responsible investments and asset management, and
to analyze and measure the non-financial enterprise value on a normative
basis. A normative basis necessary to comparatively measure sustainability
in industrial products, processes and applications is provided by the eco-
efficiency analysis. Chapter 3 describes the eco-efficiency analysis as a man-
agement tool incorporating economic and environmental aspects for the
comprehensive evaluation of products over their entire life-cycle from concept
development, design, implementation and marketing to end-of life issues like
recycling or disposal. For the first time, Chapter 4 describes a holistic approach
to define sustainability as a guiding principle for modern logistics, i.e.
throughout the process that plans, implements and controls the effective, effi-
cient, forward and reverse flow and storage of goods, services, finance and/or
information between the point of origin and the point of consumption in order
to meet customers’ requirements.
Consumer behaviour and expectations, indeed, are crucial aspects to be
considered when dealing with further development of the sustainability con-
cept. This is done in Chapter 5 for consumer goods, taking detergents as an
example with the life-cycle of the washing process acting as indicator, while
Chapter 6 specifies the achievement of food security at a global level as a key
element of sustainable development and details the importance of, and atten-
tion attributed to, the food and nutrition industries to consumer expectations
throughout the value chain starting with green agriculture, animal husbandry
and fishing followed by sustainable food production and processing, packa-
ging, retailing and service.
Key challenges for society at the beginning of the twenty-first century are
energy economy and alternative energies. Tens of millions of years ago, bio-
mass provided the basis for what we actually call fossil resources and biomass
again is by far the most important resource for renewable energies today. The
actual status and the potential of biomass as well as biomass conversion
technologies to provide green energy in the form of heat and/or power are
detailed in Chapter 7, while Chapter 8 summarizes the manufacturing and
usage of first-generation biofuels and gives an outlook to biomass-based
second- and third-generation transportation fuels.
Together with the increasingly efficient utilization of fossil resources for heat
and power generation and as fuel for transportation of people and goods, the
chemical industry has established the basis for more or less all modern indus-
tries. Machinery wouldn’t work and cars and trucks wouldn’t move without
synthetic lubricants. The chemical industry provides dyes and pigments which
Preface ix
make our world bright and colourful. Hunger has been a problem throughout
history until chemical fertilizers and pesticides made efficient agriculture and
plant protection possible. Lightweight and shock resistant plastics guarantee
the safe transport and storage of goods. Modern communication and infor-
mation storage systems depend on liquid crystals, printed circuit boards or
ultrapure silicon wafers. Human population growth, increased life expectancy
and reduced risk of physical infirmity (as well as voluntary birth control) only
became possible when the chemical industry emanated into the pharmaceutical
industry, and when synthetic detergents ensured hygiene in personal care,
laundry care and institutional cleaning. It needs to be noted, however, that
organic molecules are composed of small molecular building blocks pre-
dominantly derived from coal, natural gas and crude oil. The efficient
complementation and eventual substitution of these raw fossil materials by
biomass is the subject matter of green chemistry and is comprehensively
described in Chapter 9, which comprises lipid-based biomass (natural fats and
oils, Chapter 9.1), industrial applications of carbohydrate-based biomass
(starch, Chapter 9.2, and sucrose, Chapter 9.3), wood (Chapter 9.4), natural
rubbers (Chapter 9.5), natural fibres (Chapter 9.6) and plant-based biologically
active ingredients for cosmetics (Chapter 9.7).
The notion of sustainability in highly specialized markets where specifica-
tions and performance are key requirements is discussed in Chapter 10 (green
solvent alternatives for fine chemicals, for metal treatment, for coatings and for
crop protection formulations) and in Chapter 11 (sustainable solutions for
adhesives and sealants).
Last but not least, White Biotechnology (Chapter 12) is largely regarded as a
particularly promising gateway to a sustainable future. Reduction in green-
house gas emissions, energy and water usage are examples of the benefits
brought about by greener, cleaner and simpler biotechnology processes. White
biotechnology can contribute to the reduction in the dependency on fossil
resources through the utilization of renewable raw materials. An especially
notable feature of white biotechnology, though, is the ability to perform spe-
cific biochemical reactions without by-product formation or waste generation,
which synthetic chemistry is not able to provide.
As an employee of Henkel and Cognis I have had the chance to follow,
observe and contribute to the successful implementation of sustainability
as a guiding principle and business model for the company and for relations
with our customers. I would like to thank my colleagues Benoı̂t Abribat,
Carsten Baumann, Manfred Biermann, Joaquim Bigorra, Paul Birnbrich,
Christoph Breucker, Wolfgang H. Breuer, Stefan Busch, Dieter Feustel, Mat-
thias Fies, Roland Grützmacher, Bernhard Gutsche, Jochen Heidrich, Uwe
Held, Karlheinz Hill, Klaus Hinrichs, Ronald Klagge, Alfred Meffert, Harald
Rößler, Thorsten Roloff, Setsuo Sato, Harald Sauthoff, Jörg Schmitz, Ulrich
Schörken, Markus Scherer, Heinz-Günther Schulte, Alfred Westfechtel,
Andreas Willing and Guido Willems, who have accompanied this enterprise
and, in one way or another, have framed the concept and the content of
this book.
x Preface
I would like to thank all the authors for their commitment and for bringing
in their knowledge, their professional experience and their expertise.
I would also like to thank the Management Board of Cognis GmbH,
particularly Paul Allen, Helmut Heymann and Antonio Trius, for their support
of this project.

Rainer Höfer
Düsseldorf
Contents

Abbrevations xxi

Chapter 1 History of the Sustainability Concept – Renaissance of

Renewable Resources 1
Rainer Höfer

1.1 From Evolution to Apocalypses 2

1.2 Our Common Future 3
1.3 Sustainable Chemistry 6
1.4 Renaissance of Renewable Raw Materials 7
References 9

Chapter 2 Sustainability in Finance – Banking on the Planet 12

Philippe Spicher, Juliane Cramer von Clausbruch and
Pablo von Waldenfels
2.1 Introduction 12
2.2 Sustainability and Asset Value 13
2.3 Socially Responsible Investment, SRI 15
2.3.1 Exclusion 17
2.3.2 Best-in-class 18
2.3.3 Engagement 19
2.4 Responsible Investment: the Mainstreaming of SRI 19
2.5 Conclusion 22
References 23

Chapter 3 Metrics for Sustainability 25

Peter Saling

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

xi
xii Contents

3.1 Introduction 25
3.2 The Eco-Efficiency Analysis as an Approach for the
Checking of Sustainability in Industrial Products and
Applications 26
3.2.1 Conducting an Eco-Efficiency Analysis 27
3.3 Industrial Examples for Using Sustainability
Metrics 29
3.3.1 Eco-Efficiency Study of Curing Alternatives
for Wooden Substrates 29
3.3.2 Vitamin B2 Case Study 30
3.3.3 Eco-Efficiency Analysis Confirms: Ionic
Liquids Provide Benefits 33
3.4 Beneficial Uses of Eco-Efficiency Analysis and
Metrics for Sustainability 34
3.5 Outlook 35
References 35

Chapter 4 Sustainable Logistics as a Part of Modern Economies 37

Thierry Jouenne

4.1 Introduction 37
4.2 Definition and Role of Logistics 38
4.3 Current Situation 40
4.4 The Four Logistic Drivers 41
4.4.1 Logistic Reliability 42
4.4.2 Logistic Efficiency 43
4.4.3 Logistic Agility 45
4.4.4 Eco-logistics 46
4.5 Towards Sustainable Logistics in the Service of
Sustainable Development 48
4.6 Conclusion 50
References 51

Chapter 5 Sustainable Solutions for Consumer Products 53

Frank Roland Schroeder

5.1 Introduction 53
5.2 Demographic Dynamics and Global Megatrends 54
5.3 Life-cycle of the Washing Process – an Example for
Sustainability in Consumer Goods 57
5.3.1 Raw Materials 59
5.3.2 Logistics 61
5.3.3 Production 61
5.3.4 Use Phase 61
5.3.5 Disposal Phase 62
Contents xiii

5.4 Sustainability Profiles of Detergent Formulations 62

5.5 Conclusion 65
References 65

Chapter 6 Sustainable Solutions for Nutrition: A Consumer

Expectation 68
Sven Thormahlen

6.1 Introduction 68
6.2 Sustainability in Food and Nutrition 69
6.2.1 Sustainable Milk Procurement in Rural
Turkey 71
6.2.2 Sustainable Cow Feed in France 74
6.2.3 Sustainable Exploitation of the Evian Mineral
Water Source 80
6.3 Conclusion 84
References 85

Chapter 7 Biomass-based Green Energy Generation 86

Martin Kaltschmitt and Daniela Thrän

7.1 Introduction 86
7.2 Biomass Sources 90
7.2.1 Properties 90
7.2.2 Biomass Potential 93
7.3 Biomass Conversion 95
7.3.1 Thermo-chemical Conversion 95
7.3.2 Physico-chemical Conversion 107
7.3.3 Bio-chemical Conversion 109
7.4 Biomass Use 113
7.5 Final Considerations 115
7.5.1 Competition Areas 116
7.5.2 Effects on Competition 118
7.5.3 Configuration Approaches 119
7.5.4 Conclusions and Recommendations 122
References 123

Chapter 8 Green Fuels – Sustainable Solutions for Transportation 125

Eckhard Dinjus, Ulrich Arnold, Nicolaus Dahmen,
Rainer Höfer and Wolfgang Wach

8.1 Introduction 125

8.2 First-generation Biofuels 126
8.2.1 Bioethanol 127
8.3 Lipid-based Biofuels 137
8.3.1 Vegetable Oils as Transportation Fuels 137
xiv Contents

8.3.2 Vegetable Oils as Biodiesel Feedstock 138

8.3.3 Fats and Oils as BTL Raw Material 140
8.3.4 Lipid-based Jet Fuels 141
8.3.5 Conclusions for Lipid-based Biofuels 142
8.4 Methane via Anaerobic Digestion 142
8.5 Second-generation Biofuels 142
8.5.1 Hydrogen via Biomass Gasification 144
8.5.2 Synthetic Natural Gas via Biomass
Gasification 144
8.5.3 Biobutanol 144
8.5.4 HTU Diesel 145
8.5.5 Pyrolysis Oil 145
8.5.6 Syngas-based Biofuels 145
8.6 Third-generation Biofuels and Beyond 157
References 158

Chapter 9 Biomass for Green Chemistry 164

Karlheinz Hill and Rainer Höfer

References 166

Chapter 9.1 Natural Fats and Oils 167

Karlheinz Hill and Rainer Höfer

9.1.1 Introduction 167

9.1.2 Paradigm Changes in Global Fats and Oils
Production, Use and Trade 168
9.1.3 Production of Oils and Fats 174
9.1.3.1 Production of Vegetable Oils and Fats 174
9.1.3.2 Production of Animal Oils and Fats 178
9.1.4 Chemical Composition of Fats and Oils 179
9.1.4.1 Animal Fats and Oils 182
9.1.4.2 Vegetable Fats and Oils 182
9.1.5 The Value Chain of Fats and Oils – Industrial
Non-food Uses 213
9.1.5.1 Fats and Oils as Precursors for
Biopolymers 214
9.1.5.2 Fatty Acids – Keystones of
Oleochemistry 216
9.1.5.3 Fatty Acid Esters 218
9.1.5.4 Green Lubricants and Carrier Oils 218
9.1.5.5 Glycerine as C3-Building Block 222
9.1.5.6 Fatty Alcohols 222
9.1.5.7 Green Surfactants 224
9.1.6 Perspectives 228
References 228
Contents xv

Chapter 9.2 Starch: A Versatile Product from Renewable Resources for

Industrial Applications 238
Andrea Gozzo and Detlev Glittenberg

9.2.1 Markets 238

9.2.2 Starch and Derivatives 239
9.2.3 Food Applications 245
9.2.4 Pharmaceutical and Chemical Applications 247
9.2.5 Industrial Binder Applications 256
9.2.6 Paper and Board Applications 257
9.2.7 Outlook 259
References 262

Chapter 9.3 Industrial Sucrose 264

Stefan Frenzel, Siegfried Peters, Thomas Rose and
Markwart Kunz

9.3.1 Industrial Production of Sucrose 266

9.3.2 Chemistry of the Sucrose Molecule 270
9.3.2.1 Basic Organic Chemicals by Sucrose
Degradation 272
9.3.2.2 Sucrose-derived Products of Industrial
Relevance Maintaining the Sugar
Skeleton 276
9.3.2.3 Sugar Derivatives While Maintaining
Carbohydrate Structure 279
9.3.3 Outlook 290
References 291

Chapter 9.4 Wood 300

Elisabeth Windeisen and Gerd Wegener

9.4.1 Introduction 300

9.4.1.1 Perspectives of Sustainability 302
9.4.1.2 Forest as Ecosystem and Resource 303
9.4.1.3 From Wood Resources to Wood
Products 303
9.4.2 Chemistry of Wood 306
9.4.2.1 Survey 306
9.4.2.2 Cellulose 307
9.4.2.3 Polyoses (Hemicelluloses) 309
9.4.2.4 Lignin 311
9.4.2.5 Extractives 313
9.4.2.6 Inorganic Components (Ash) 318
9.4.3 Pulp and Paper 319
xvi Contents

9.4.3.1 Production and Environmental Aspects 319

9.4.3.2 Products 324
9.4.4 Wood-based Composites 325
9.4.4.1 Conventional Concepts and Products 325
9.4.4.2 New Concepts and Products 326
9.4.5 Modified Solid Wood Products 329
9.4.5.1 Chemical Modification 330
9.4.5.2 Thermal Modification 331
9.4.6 Outlook 334
References 335

Chapter 9.5 Natural Rubber 339

Laurent Vaysse, Fre´de´ric Bonfils, Philippe Thaler and
Je´rôme Sainte-Beuve

9.5.1 Introduction 339

9.5.2 Challenges Facing the Supply Chain 340
9.5.3 Water and Carbon Budget of the Rubber Tree 343
9.5.3.1 Carbon and Water in Plants 343
9.5.3.2 Photosynthesis and Water in the Rubber
Tree 343
9.5.3.3 Tapping, Latex Yield and Carbon Budget
of the Rubber Tree 344
9.5.3.4 Tapping and Water Budget of the Rubber
Tree 345
9.5.4 Biosynthesis of poly(cis-1,4-isoprene) 347
9.5.4.1 Polyisoprenoids 347
9.5.4.2 Biosynthetic Pathway 347
9.5.4.3 Localization of Rubber Biosynthesis 351
9.5.4.4 Conclusion 351
9.5.5 Natural Rubber Structure 351
9.5.5.1 Introduction 351
9.5.5.2 Microstructure 352
9.5.5.3 Mesostructure 352
9.5.6 Non-isoprene Components of Natural Rubber 355
9.5.6.1 Non-isoprene in the Different
Compartments of Hevea brasiliensis
Latex 355
9.5.6.2 Non-isoprene Families 356
9.5.6.3 Conclusion 359
9.5.7 Specific Properties versus Synthetic Counterparts 359
9.5.7.1 Elasticity 360
9.5.7.2 Strain-induced Crystallization 360
9.5.7.3 Heat Build-up 360
9.5.7.4 Tack and Green Strength 361
Contents xvii

9.5.7.5 Vulcanization 361

9.5.8 Conclusion 361
Acknowledgement 362
References 362

Chapter 9.6 Natural Fibres 368

Martin Möller and Crisan Popescu

9.6.1 Generalities 368

9.6.2 Demands and Restraints for Sustainable Fibres 369
9.6.3 Fibre Structure 371
9.6.3.1 Chemistry and Structure of the Cellulose
Fibres 372
9.6.3.2 Chemistry and Structure of the Protein
Fibres 374
9.6.4 Fibre Sourcing 380
9.6.4.1 Cotton 380
9.6.4.2 Bast Fibres (Flax, Hemp) 381
9.6.4.3 Animal Fibres 383
9.6.4.4 Silk 384
9.6.5 Summary of the Properties of Natural Fibres 385
9.6.6 Processing of Natural Fibres 385
9.6.6.1 Operations which Transform Fibres into
Fabric 388
9.6.6.2 The Cleaning Operations 388
9.6.6.3 Stabilizing the Dimensions 389
9.6.6.4 Coating and Infiltrating 389
9.6.6.5 Surface Treatments 391
9.6.7 Conclusions 391
References 391

Chapter 9.7 Plant-based Biologically Active Ingredients for Cosmetics 394

Charlotte d’Erceville, Florence Henry, Patrice Lago and
Andreas Rathjens

9.7.1 Introduction 394

9.7.2 Active Ingredients and their Functionality in
Cosmetic Applications 395
9.7.3 Plant-based Raw Materials 396
9.7.4 Sustainability Concept and Corporate Social
Responsibility (CSR) 397
9.7.5 From the Botanical Raw Material Towards
the Final Product 398
xviii Contents

9.7.6 Sustainable Development and CSR for the

Supply of Natural Products Derived from the
Argan Tree 399
9.7.6.1 Targanine Network 401
9.7.6.2 Partnership Between EIG Targanine
and Cognis 402
9.7.7 Conclusion 404
References 405

Chapter 10 Sustainable Solutions – Green Solvents for Chemistry 407

Carles Este´vez

10.1 Introduction 407

10.2 The Design of Safer Chemicals and Solvent
Innovation 408
10.3 SOLVSAFE: A Roadmap for the Design and
Application of Safer Functional Organic
Solvents 411
10.3.1 Background and Sustainability Goals 411
10.3.2 Design Strategy 412
10.4 Industrial Application of SOLVSAFE Solvents:
Results and Perspectives 416
10.4.1 Fine Chemicals 416
10.4.2 Metal Degreasing 418
10.4.3 Paints and Varnishes 419
10.4.4 Crop Protection Formulations 420
10.5 Conclusions 422
References 423

Chapter 11 Sustainable Solutions for Adhesives and Sealants 425

Jürgen O. Wegner

11.1 Introduction 425

11.2 Features and Requirements of Adhesives and
Sealants 426
11.3 Chemical Composition of Adhesives and
Sealants over Time 428
11.4 Ongoing Sustainability Evolution 429
11.5 Quality Features and Gaps with Natural-based
Adhesives and Sealants 432
11.6 Current Use of Renewable Raw Materials in
Adhesives and Sealants 432
Contents xix

11.7 Major Use Areas for Adhesives Based on

Natural Resources 433
11.8 Outlook and Conclusion 433
References 434

Chapter 12 White Biotechnology 436

Thomas Haas, Manfred Kircher, Tim Köhler,
Günter Wich, Ulrich Schörken and Rainer Hagen

12.1 The Status of White or Industrial Biotechnology 436

12.1.1 Introduction 436
12.1.2 Relevant Market Segments 437
12.1.3 The Drivers of White Biotechnology 447
12.2 Recent Examples 449
12.2.1 Sphingolipids 449
12.2.2 L-Cysteine 457
12.2.3 Lipid Biotechnology 462
12.2.4 PLA (Polylactic Acid) 466
12.3 Outlook of White Biotechnology 472
References 473

Subject Index 479

Abbreviations
AcTR acetyl-CoA:long chain base acetyltransferase
A.I.S.E. Association Internationale de la Savonnerie, de la
Détergence et des Produits d’Entretien
ALA a-linolenic acid
AMF atomic force microscopy
AMT accepted modern technology
API active pharma ingredients
APME Association of Plastics Manufacturers in Europe,
now PlasticsEurope
ARA arachidonic acid
BAT best available technology
BSE Bovine spongiforme Enzephalopathie, also known as
‘Mad Cow Disease’
CAP Common Agricultural Policy (of the European
Community)
CBOT Chicago Board of Trade
CDM Clean Development Mechanism, an arrangement
under the Kyoto Protocol allowing industrialised
countries with a greenhouse gas reduction commit-
ment to invest in projects that reduce emissions in
developing countries as an alternative to more
expensive emission reductions in their own countries
CEFIC Conseil Européen des Fédérations de l’Industrie
Chimique
CEN European Committee for Standardization
CEPEA Research Center of the University of São Paulo/BR,
focused on agribusiness issues, market analysis and
price discovery, international trade, entrepreneur-
ship and family farming
CIS Commonwealth of Independent States: Russia,
Ukrainia, Kazakhstan, Belarus, Moldova, Armenia,
Aserbaijan, Georgia, Kyrgystan, Tajikistan,
Turkmenistan, Uzbekistan
CLA conjugated linoleic acid
CMAI Chemical Market Associates
xxi
xxii Abbreviations
CMC carboxymethyl cellulose
CR Corporate Responsibility
DHA docosahaxaenoic acid
DJSI Dow Jones Sustainability Index
dl decilitre
DLS Dynamic Light Scattering
DMDHEU dimethylol dihydroxy ethylene urea
DOE Department of Energy (USA)
DP degree of polymerization
DPNR Deproteinized Natural Rubber
DP-s direct polycondensation in high boiling solvents
DVFA Deutsche Vereinigung für Finanzanalyse und Asset
Management
EBFM Ecosystem-based fisheries management
ECF elemental chlorine-free
EFA essential fatty acid[s]
EFFAS European Federation of Financial Analysts Societies
EDI Electronic Data Interchange
ERP Enterprise Resource Planning
EU-27 European Union: Austria, Belgium, Bulgaria,
Cyprus, Czech Republik, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary,
Ireland, Italy, Latvia, Lithuania, Luxemburg, Malta,
Netherlands, Poland, Portugal, Romania, Slovakia,
Slovenia, Spain, Sweden, United Kingdom
EPA eicosapentanoic acid
EPD Environmental Product Declaration
EPS expanded polystyrene
ESG Environmental sustainability, Social responsibility
and corporate Governance (often referred to as
‘‘extra-financial criteria’’)
FAME fatty acid methyl ester
FAO Food and Agriculture Organization of the United
Nations
GFSI Global Food Safety Initiative
GJ gigajoule, equal to 109 joules
GM genetically modified
GTA Glyphosate tolerant soybeans, also referred to as
Roundup Readys soybeans
Ha hectar
HDR Human Development Report
HDT heat distortion temperature
HEC hydroxyethyl cellulose
HERA human and environmental risk assessment
HRT Hevea Rubber Transferase
Abbreviations xxiii
ICE Intercontinental Exchange, https://www.theice.com/
homepage.jhtml
ICIS Chemical & Oil Industry business information
system, part of Reed Business Information (RBI), a
division of Reed Business and a member of Reed
Elsevier plc.
IL ionic liquid
INRA Institut Scientifique de Recherche Agronomique
IP intellectual property, biotech.: inositol phosphoryl
IPP Isopentenyl diphosphate
IR isoprene rubber (polyisoprene rubber)
IRSG International Rubber Study Group
LA linoleic acid
LCA Life-Cycle Assessment
LCI Life-Cycle Inventory
LCIA Life-Cycle Impact Assessment
LOHAS Lifestyle of Health and Sustainability
MC methyl cellulose
MDF medium-density fibreboard
Mercosur or Mercado Común del Sur, Portuguese: Mercado
Mercosul Spanish Comum do Sul, English: Southern Common Market is
a Regional Trade Agreement (RTA) among Brazil,
Argentina, Uruguay and Paraguay, founded in 1991
by the Treaty of Asunción, which was later amended
and updated by the 1994 Treaty of Ouro Preto. Its
purpose is to promote free trade and the fluid
movement of goods, people, and currency
Mio million
MPa megapascal ¼ 1 Million Pa ¼ 1 N/mṁ
Mto metric tons
MSC Marine Stewardship Council
MSCI Morgan Stanley Capital International
MMD Molar Mass Distribution
MWL milled-wood-lignin
NAS N-acetylserine
NMMO 4-methylmorpholine-4-oxide
NMR nuclear magnetic resonance
NOW new option wood
NR natural rubber
NREL National Renewable Energy Laboratory (USA)
NTFP non-timber-forest-products
OAS O-acetylserine
OHT oil-heat-treatment
OSB oriented strand board
PA polyamide
xxiv Abbreviations
PBT polybutylene terephthalate
PDO propanediol
PE polyethylene
PET polyethylene terephthalate
PETA People for the Ethical Treatment of Animals
PJ Peta joule ¼ 1015 mJ
PLA polylactic acid
PLATO provided lasting advanced timber option
PL/DLA poly-rac.-lactide
PLLA poly-L-lactide, the product resulting from
polymerization of L,L-lactide
PP polypropylene
PPO processed palm oil (‘‘processed’’ stands for neu-
tralized, bleached, deodorized and/or fractionated)
PS polystyrene
PSR Product Specific Requirements
PVC polyvinyl chloride
PUFA polyunsaturated fatty acid
PUR polyurethane
REACH Registration, Evaluation and Authorisation of
Chemicals
REF Rubber Elongation Factor
RFID Radio Frequency Identification
ROP ring opening polymerisation
RSS ribbed smoked sheets: rubber quality, prepared from
intentionally coagulated latex
SARS Severe Acute Respiratory Syndrome, a respiratory
illness caused by a virus. SARS was first reported in
Asia in 2003. It spread worldwide over several
months before the outbreak ended
SBR styrene- butadiene-rubber
SC stratum corneum
SCF Scientific Committee for Food
SEC Size Exclusion Chromatography
SME small & medium enterprises
SMR Standard Malaysian Rubber
SR synthetic rubber
SRI Socially Responsible Investment
TAPS tetraacetyl phytosphingosine
TCF totally chlorine-free
TFA trans-fatty acid[s]
Tg glass transition temperature
TLV-TWA Threshold Limit Value-Time Weighted Average
TMP thermo mechanical pulp
TMT thermally treated timber
TOE Tons of Oil Equivalent
Abbreviations xxv
TPS thermoplastic starch
TriASa triacetyl sphinganine
TriASo triacetyl sphingosine
TS technical specification
TSR Technically specified natural rubber
TÜV Technischer Überwachungsverein
UNEP United Nations Environment Program
VOC volatile organic compound[s]
WPC wood plastic composites
WUE Water use efficiency
CHAPTER 1

History of the Sustainability

Concept – Renaissance of
Renewable Resources
RAINER HÖFER

Cognis GmbH, Rheinpromenade 1, D-40789 Monheim, Germany

‘‘One World One Dream’’

Slogan of the Beijing 2008 Olympic Games

‘‘One World One Dream’’ fully reflects the essence and the universal values of
the Olympic spirit – Unity, Friendship, Progress, Harmony, Participation and
Dream. It expresses the common wishes of people all over the world, inspired
by the Olympic ideals, to strive for a bright future for Mankind. In spite of
the differences in colors, languages and races, we share the charm and joy
of the Olympic Games, and together we seek the ideal of Mankind for
peace. We belong to the same world and we share the same aspirations and
dreams.’’ (The Official Website of the Beijing 2008 Olympic Games.)
‘‘In the middle of the 20th century, we saw our planet from space for the
first time . . . . From space, we see a small and fragile ball dominated not by
human activity and edifice but by a pattern of clouds, oceans, greenery, and
soils. Humanity’s inability to fit its activities into that pattern is changing
planetary systems, fundamentally. Many such changes are accompanied by life-
threatening hazards. This new reality, from which there is no escape, must be
recognized – and managed.’’ (Brundtland-Report ‘‘Our Common Future’’ –
Introduction: From one Earth to one world.)1

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

1
2 Chapter 1
‘‘Warming of the climate system is unequivocal, as is now evident from
observations of increases in global average air and ocean temperatures,
widespread melting of snow and ice, and rising global average sea level.’’
(Summary for Policymakers of the Synthesis Report of the IPCC Fourth
Assessment Report.)2

1.1 From Evolution to Apocalypses

The twentieth century has seen a phenomenal growth of the global economy, a
continuous improvement of the standard of living in industrialized countries
and the transformation of ‘‘underdeveloped’’ or ‘‘Third World’’ nations into
emerging economies. Since the Iron Curtain disappeared at the beginning of the
1990s mankind has become aware that the Earth is not ‘‘endless’’, that there are
no longer insuperable borders setting limits to migration, that there is no
unknown territory left to be discovered, conquered, cultivated or exploited.3
The motto of the Beijing Olympic Games 2008 was aimed at expressing this
awareness and the common wishes of people all over the world to strive for a
bright future of mankind. Anticipating the development towards a global
community, Hans Küng developed programmatically the idea of a Global
Ethic, a fundamental consensus on binding values, irrevocable standards and
personal attitudes common to all religions emanating into the Global Ethic
project and the ‘‘Declaration towards a Global Ethic’’, which was endorsed by
the Parliament of the World’s Religions in Chicago in 1993.4
Globalization, global growth of economies and increases in living standards,
though, have had their price: exploitation of natural resources to their limits
and an ever-increasing contamination of the environment.5
History of mankind to a large extent means history of the relations between
human beings and nature.6 Evolution of the human species in prehistoric
times was driven by nature, by genetic selection and by geological
and climatic changes. In biblical times mankind received the divine message
to ‘‘replenish the earth and subdue it’’ (Genesis 1:28). This has been read
not only by Jews but also by Christians and Muslims and by the western
hemisphere, at least, as man’s charter, granting him the right to ‘‘have
dominion over the fish of the sea, and over the fowl of the air, and over the
cattle, and over all the earth, and over every creeping thing that creepeth upon
the earth’’ (Genesis 1:26). However, ‘‘heaven and earth, . . . and every thing that
creepeth upon the earth’’ has been made by God and ‘‘after his kind: and
God saw that it was good’’ (Genesis 1:1–1:25), a clear statement that the entire
Creation is divine, although creation care (Bewahrung der Schöpfung in
German) does not directly appear as a divine commandment. Nature
virtually exists as a resource. It is man’s relationship with God, however, that
really matters.7
Nature in early times was largely regarded as uncontrollable and threatening.
Early man feared the night and the wilderness.8 Natural phenomena, like
History of the Sustainability Concept – Renaissance of Renewable Resources 3
floods, thunderstorms, famine and plagues of locusts, were perceived as the
wrath of God. Outside the Abrahamic religions, Nature was regarded as
God or Gods, arguably because of such threats. The theorem of a direct link
between the biblical subordination of nature to man and devastation of
the environment by mankind.9,10 though, is doubtful.6 Indeed, the outcry
‘‘spectant victores ruinam naturae . . .’’ (English: triumphant they contemplate
their victory over Nature . . .) goes back to the Roman officer and encyclopedist
Plinius the Elder (AD 23–79).11 Collapses of ancient civilizations, such as
the Maya, Easter Island and Anasazi,12 generally happened outside the
Hebrew–Christian sphere and it was the Greek philosopher Plato, living
around 400 BC, who gave us the oldest description of a natural disaster, the
deforestation of Attika.13 Although the antique Greek culture and later the
Roman Empire before converging in Christianity apparently had a close rela-
tion to Nature, venerated river gods, Nereids and Naiads, they are claimed to
be at the origin of one of the first ecological disasters, the complete defor-
estation of all areas around the Mediterranean Sea and the resulting erosion,
loss of humus soil and formation of karsts landscape in the plains followed by
climatic changes which last until our modern times. Cedar trees, which once
flourished throughout the Levant, the Mountains of southern Lebanon and
Syria, much heralded in the times of antiquity for their beauty and fragrance,
were nearly extinct when the Phoenicians ruled the Mediterranean Sea between
1200 and 900 BC. Cedar trees simply were too good a raw material for ship-
building and construction.
The perception that Earth is a fragile body and easily thrown out of balance
by the hand of man may have surfaced for the first time after the Trinity nuclear
test on July 16, 1945, when Robert Oppenheimer quoted the Sanskrit Bhagavad
Gita (English: ‘‘Song of God’’) text I am become Death, the shatterer of
Worlds.14

1.2 Our Common Future

In 1972, the UN Stockholm Conference on the Human Environment marked
the first great international meeting on how human activities were harming the
environment and putting humans at risk. In the same year, the Club of Rome’s
report Limits to Growth15 was published, which, together with the first oil crisis
in 1973, had an enormous impact on public opinion worldwide and started a
political debate and thinking process. Based on a mathematical simulation
technique known as systems dynamics16 and with input factors such as popu-
lation growth, food production and fertilizer demand, energy consumption,
availability of non-renewable raw materials, the report predicted that, within a
time span of less than 100 years, with no major change in physical, economic
or social relationships, society will run out of the non-renewable resources
on which the industrial base depends. The economic system will consume
4 Chapter 1
successively larger amounts of depletable resources until they are completely
used up. The characteristic behaviour of the system is overrun and collapse.
In autumn 1983 the General Assembly of the United Nations asked the
Secretary General to appoint a World Commission on Environment and
Development. The idea was to forecast, on a global scale, how man-made
activities would affect the environment of the Earth encompassing the indus-
trial as well as the social and economic aspects. The Secretary General of the
UN entrusted the chair of this committee to Mrs Gro Harlem Brundtland, who
was then Prime Minister of Norway. Work on the report was completed in
March 1987 and it was published later that year under the title Our Common
Future.1 Working on that subject, the commission faced a double problem: on
the one hand it was obviously human activities that were behind the dete-
rioration of the environment, especially in developed nations. On the other
hand, it was inconceivable for the UN to create difficulties for developing
nations, for people who had no access to decent living conditions but who, by
catching up en masse, would significantly add to the deleterious effects of
pollution and degradation of the environment. One of the ways in which
the Brundtland commission sought to overcome this dilemma consisted in the
creation of the ‘‘sustainable development’’ concept. This concept was meant to
provide a long-term balance between the environment, the economy and the
social well-being of humanity – i.e: whereas in prehistoric times of evolution the
human race was driven by nature, since biblical times humans were filling and
subduing the Earth, now, at the doorstep of the third millennium, the concept
of balance was born – the conclusion was drawn that the nature and action of
humans between themselves and towards nature need to be in balance.3
In fact, the term and the concept of sustainability (Nachhaltigkeit in German)
dates back to the eighteenth century. Historically, depletion of natural
resources (Raubbau in German) is not new and hit renewable resources first.
Scarcity of wood was the concern of feudal Europe and led to the introduction
of sustainability principles in forest management. It was in order to preserve
wood supplies for the important silver mines in the Erzgebirge, the economic
backbone of the Kingdom of Saxony and its famous capital Dresden, when
Hannß Carl von Carlowitz (Oberberghauptmann and Chief Executive of the
Royal Saxon Mining Department) in 1713 for the first time clearly formulated
the concept that forestry had to be ‘‘sustainable’’, which meant that logging
and reforestation had to be in balance.17 Similar concepts arose in France
(La grande re´formation des foreˆts, Colbert18) and in Japan.12,19 The home of
von Carlowitz, a Renaissance-style townhouse built in 1542, can still be visited
at the Obermarkt, the market square of the Saxony mining burg of Freiberg
(Figure 1.1). The principles of sustainability since then have emanated into the
worlds of finance20 (see Chapter 3), education21 and administration.22
Our Common Future was the third in a series of important UN initiatives;23
the first being the Brandt Commission’s North-South: A Program for Survival
and Common Crisis – North-South Co-operation for World Recovery, which
spelt out the extent of the mutual interests between north and south and
appealed for a program to avert disaster for the poorest countries, the need for
History of the Sustainability Concept – Renaissance of Renewable Resources 5

Hannß Carl von Carlowitz

Obermarkt Freiberg Skyline Dresden

Figure 1.1 Hannß Carl von Carlowitz (copper engraving, Johann Martin Bernigeroth
(1711), with the permission of Stadt- und Bergbaumuseum, Freiberg),
Obermarkt Freiberg (Aquarell, Carl August Müller (1883), with the per-
mission of Stadt- und Bergbaumuseum, Freiberg) and Skyline Dresden
(with the permission of D. Berthold, B&V Verlag, Dresden).

a longer-term reorganization of the global economic system and methods to

deal with worsening economic conditions and the lack of global cooperation.24
The Brandt reports were followed by the Palme Commission’s work on security
and disarmament, Common Security.25 Appearing on the public scene at the
end of the cold war, Our Common Future cannot be separated from these
earlier UN initiatives. Coinciding with the upcoming public awareness of the
environment, the World Commission on Environment and Development
emphasized the fact that sustainable development should be employed to
safeguard the Earth’s resources thereby improving social well-being and
creating a better quality of life for future generations, in other words:

‘‘Development that meets the needs of the present without compromising the
ability of future generations to meet their own needs’’ (Brundtland, 1987).

This way, the report became the catalyst for global thinking processes
about the relationship between man and nature9,26 and about future prospects
of mankind in the potentially conflicting contexts of ethics, state policies and
social, ecological and economical interests.4,23,27 In 1992, the UN Conference
on Environment and Development (UNCED), more commonly known as the
6 Chapter 1
Rio Earth Summit, established a number of initiatives to promote the uptake of
sustainable development worldwide:

1. The Convention on Biological Diversity with three main goals:

 conservation of biodiversity;
 sustainable use of its components; and
 fair and equitable sharing of benefits arising from genetic resources.
The convention recognized for the first time in international law that the
conservation of biological diversity is ‘‘a common concern of humankind’’
and is an integral part of the development process. The agreement
covers all ecosystems, species and genetic resources. It links traditional
conservation efforts to the economic goal of using biological resources
sustainably. It sets principles for the fair and equitable sharing of the
benefits arising from the use of genetic resources, notably those destined
for commercial use.
2. The Rio Declaration on Environment and Development, reaffirming the
Declaration of the UN Conference adopted at Stockholm, 1972.
3. A Statement of Principles for the Sustainable Management of Forests.
4. The Agenda 21, a comprehensive and dynamic plan of action for the
twenty-first century addressing the UNCED goals and initiatives and
identifying means and resources for their implementation.

1.3 Sustainable Chemistry

Chemistry has laid the foundations for many essential materials that have
shaped our modern world. Earlier than many other sectors of the economy, the
chemical industry has faced an imbalance in the utilization of its products
(excessive use of fertilizers and pesticides in agriculture, Silent Spring, Rachel
Carson28), malpractice when applied as weapons (Napalm, Agent Orange) and
a series of critical safety issues during manufacturing (ICMESA, Seveso; UCC,
Bhopal; Sandoz, Basel). Consequently a set of guiding principles for pollution
prevention, employee health and safety, product stewardship, process
safety and distribution codes originally developed since 1977 by the Canadian
Chemical Producers’ Association (CCPA) merged into Responsible Care, ‘‘the
chemical industry’s own, unique initiative’’.29 Under Responsible Care, the
worldwide chemical industry is committed to continual improvement in all
aspects of health, safety and environmental performance and to open com-
munication about its activities and achievements. Broken down to the level
of individual companies, Responsible Care became a mission statement for
sustainable operations (Figure 1.2).
In February 2006, The International Council of Chemical Associations
(ICCA) launched the Responsible Care Global Charter and the Global Product
Strategy (GPS), marking a renewal of the chemical industry’s former
commitment.
History of the Sustainability Concept – Renaissance of Renewable Resources 7

We do not own the

world, we
borrowed it from
our children
Responsible
Care® Cognis’ guiding principle following a
saying by Antoine de Saint Exupéry

Figure 1.2 Responsible Cares.

The Responsible Cares initiative achieved a kind of normative enforcement,

when Paul Anastas, then of the Environmental Protection Agency (EPA), in
1991 coined the phrase Green Chemistry and together with John C. Warner30
and J. B. Zimmerman31 developed the 24 Principles Of Green Chemistry &
Green Engineering (Figure 1.3). Green chemistry, also termed sustainable
chemistry, is an umbrella concept that seeks to unite government, academic and
industrial communities by placing more focus on environmental impacts at the
earliest stage of innovation and invention. Paul Anastas and John Warner also
provided the first definition of green chemistry: ‘‘Applying fundamental
knowledge of chemical processes and products to achieve elegant solutions with
the ultimate goal of hazard-free, waste-free, energy efficient synthesis of non-
toxic products without sacrificing efficacy of function.’’30 This approach
represents a significant departure from the traditional principles. Instead of
trying to minimize exposure to chemicals, green chemistry emphasizes the
design and creation of chemicals that are not hazardous to people or the
environment, in other words a kind of molecular-level pollution prevention,
applying the principle that it is better to consider waste prevention options
during the design and development phase, rather than disposing or treating
waste after a process or material has been developed.

1.4 Renaissance of Renewable Raw Materials

Use of renewable rather than depletable feedstock is one of the Green Chem-
istry principles.
Renewable raw materials are already making an extensive contribution to
positioning the concept of sustainability even more firmly in the public mind
8 Chapter 1

Figure 1.3 24 Principles of Green Chemistry & Green Engineering.

7% 93 %
Petroleum chemistry energy

Agricultural 5% 95 %
products: others food + feed

Oleo-
chemicals 14 % 86 %
chemistry food + feed
(2004):

Oleo-
10 % 25 % 65 %
chemicals chemistry biodiesel food + feed
(2010):

Figure 1.4 Utilization of carbonic raw material sources.

worldwide. Renewable raw materials may in the future also be the only solution
when fossil resources are gradually exhausted.
Currently, 93% of crude petroleum is used for energy generation, while only
7% is used for chemistry. Similarly, 95% of agricultural products are used for
food and feed, with only 5% being used for the chemical industry (Figure 1.4).
45 Mio mto of annual worldwide biodiesel capacity (forecast for 2010 based on
published projects;32 a more conservative forecast envisages 32 Mio mto by
201233) would already represent 25% of total renewable fats and oils produc-
tion and would reduce the share of food and feed from 86% to 65% and the
History of the Sustainability Concept – Renaissance of Renewable Resources 9
percentage of chemical uses from 14% to 10%. Finally, 30% of the global
arable land (450 Mio ha of 1.4 billion ha) is needed for biomass cultivation to
meet 10% of the 2030 annual world oil demand34 (41 billion barrels forecast;
forecast 2009: 32 billion barrels35).
These figures demonstrate the rift that must be overcome before renewable
resources can completely substitute fossil supplies of raw materials.36 If both
the emerging energy gap and the fuel crisis are to be solved while at the same
time providing sufficient feedstock for the chemical industry and foodstuffs
for humans and animals by cultivation of renewable raw materials, then a
well-organized, anticipatory, cross-border cultivation policy including water
management is required. This entails concrete measures to increase yields per
area unit; that means concentrated advancement of green agricultural research
and green crop protection, including white biotechnology and green genetic
engineering.37 A great deal could be gained by giving worldwide priority to
sparing fossil resources to permit development of constructive and long-term
successful solutions based on renewable raw materials.

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32. R. Gubler, Biodiesel, SRI Consulting, ed., CEH Marketing Research
Report, Nov. 2006.
33. S. Hansen, Rabobank’s View on the Global Biofuel Market, 6th European
Motor BioFuels Forum, Rotterdam, 2008.
34. S. Marcinowski, Renewable Raw Materials – a Novel Approach in Polymers,
Bio & Polymers, Biannual Meeting of the GdCh-Division of ‘‘Macro-
molecular Chemistry’’, Aachen, 2008.
35. IEA, Oil Market Report, http://omrpublic.iea.org/ (retrieved 30.09.2008).
36. R. Höfer and J. Bigorra, Green Chemistry Letters and Reviews, June 2008,
1(2), 79.
37. R. Höfer in F. Brickwedde, R. Erb, M. Hempel and M. Schwake, Hrsg.,
Nachhaltigkeit in der Chemie-13. Internat. Sommerakademie St. Marienthal,
Initiativen zum Umweltschutz Bd. 70, Erich Schmidt Verlag, Berlin, 2008,
p. 150–166.
CHAPTER 2

Sustainability in Finance –
Banking on the Planet
PHILIPPE SPICHER,a JULIANE CRAMER VON
CLAUSBRUCHb AND PABLO VON WALDENFELSb
a
Centre Info SA, Sustainable Investment Consulting, Rue de Romont 2,
CH-1700 Fribourg, Switzerland; b PricewaterhouseCoopers AG
Wirtschaftsprüfungsgesellschaft, Germany

2.1 Introduction
Markets are a product of society and must reflect society’s concerns; society
simply could not exist without financial services (Figure 2.1: economic circuit,
Wirtschaftskreislauf in German). In the production industry material flow is
paralleled by ‘‘cash flow’’; from buying a house to insuring a car or saving for a
pension, financial services also touch every aspect of private households; central
banks are responsible for achieving price stability and maintaining the overall
financial stability of a country or a community of countries.
As an integral part of the economy, financial systems ex ante produce and
screen information about potential investments which enable the market par-
ticipants to make investment decisions; they mobilize investment capital and ex
post monitor the investment. Monitoring includes supervising investments
to ensure they are on-course and on-schedule in meeting the objectives and
performance targets in order to effect value enhancement and preclude value
destruction. With regard to Corporate Responsibility (CR) and the contribu-
tion of enterprises to sustainable development, screening operations of financial
systems fix capital expenditure and the marginal productivity of invested

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

12
Sustainability in Finance – Banking on the Planet 13

tax tax
transfer Government expenditures

public saving public

wage borrowing

Financial
Household saving investment Corporation
Market

consumption

Figure 2.1 Economic circuit (adapted from http://de.wikibooks.org/wiki/Betriebs-

wirtschaft/_Grundlagen/_Wirtschaftsteilnehmer).

capital (via allocation of capital to selected projects or assets) while monitoring

and risk management control the sustainability of investments.1

2.2 Sustainability and Asset Value

Whereas the book value of enterprises is calculated retrospectively based on
financial data, the market value contains a strategic prospect and depends on its
sustainability rating (in the sense of ‘‘fitness for the future’’ (Zukunftsfähigkeit
in German). The analysis comprises elements like:

 Climate change;
 Energy efficiency;
 Social aspects in the supply chain;
 Corruption handling and compliance with laws and regulations;
 Health and safety of products and services.

It values soft factors like reputation, customer satisfaction, intellectual

capital, R&D-expenses, innovation pipeline, talent attraction, staff turnover,
risk management and deployment of renewable energies. Since March 2008 the
Deutsche Vereinigung für Finanzanalyse & Asset Management (DVFA) has for
the first time published a terminology for ESG (Environmental, Social, Gov-
ernance) aspects, and defined performance requirements for ‘‘non-financial’’
CR-data, which are key performance indicators (KPIs) for analysis and rating
of companies (Figure 2.2). In May 2008 the DVFA framework received the
endorsement of the European Federation of Financial Analysts Societies
(EFFAS) and gained the status of an official EFFAS standard as a guideline for
corporates on how to report on ESG and as a benchmark for investment
professionals on how to integrate ESG into financial analysis.2
 14
Chapter 2
Figure 2.2 ESG grid and KPIs for the analysis of ‘‘non-financials’’.2
Sustainability in Finance – Banking on the Planet 15
2.3 Socially Responsible Investment, SRI
Nevertheless, should banks use financial instruments to allow sustainable
development in their own dealings, i.e. base their credit and investment policy
on sustainability ratios instead of exclusively financial ratios?3 The question has
turned out to be rhetorical. In the past, in many businesses, protection

Main Socially Responsible Indices

Domini 400 Social Index (DS400)
In 1990, Domini Social Investments and Kinder, Lyndenberg, Domini &
Co. (KLD) created the Domini 400 Social Index (DS400) – the first
socially responsible investment benchmark – to measure how social and
environmental screens affect investment performance.
Over the years, KLD has created a family of indexes to provide
investors with a variety of ways to integrate environmental, social and
governance factors into their investment decisions; among them KLD
Broad Market Social Index series, KLD Global Climate 100 Index, KLD
Global Sustainability Index.
For more information, visit www.kld.com.

Dow Jones Sustainability Indexes

Launched in 1999, the Dow Jones Sustainability Indexes are the first
global indexes tracking the financial performance of the leading sus-
tainability-driven companies worldwide. Based on the cooperation of
Dow Jones Indexes, STOXX Limited and SAM, they provide asset
managers with benchmarks to manage sustainability portfolios.
For more information, visit www.sustainability-index.com.

FTSE4Good Index Series

Launched in 2001, the FTSE4Good Index Series (acronym for Financial
Times & Stock Exchange for Good) is a series of benchmark and tradable
indices for responsible investors. The index series is derived from the
FTSE Global Equity Index Series.
The FTSE4Good criteria are applied to the FTSE Developed Index
Series, which covers 23 markets and over 2000 potential constituents.
In the UK, the universe of eligible constituents is drawn from the FTSE
All-Share Index. The series consists of five benchmark indices covering
the Global and European regions, the US, Japan and the UK.
For more information, visit www.ftse.com/Indices/FTSE4Good_
Index_Series/index.jsp.
16 Chapter 2
of the environment has been regarded as a burden, leading to an increase
in manufacturing and other business costs. However, since Sarokin and
Schulkin’s paper ‘‘Environmental Concerns and the Business of Banking’’ was
published in the Journal of Commercial Bank Lending4 there is mounting
recognition of the importance of environmental and social issues to industry
clients across sectors and markets, and to their financial sector partners, from
banks to asset managers to private equity investors. In the public sector as a
result of the Rio Conference UNEP FI a global partnership between the United
Nations Environment Program (UNEP) and the financial sector was initiated
in 1992. The partnership comprises over 160 institutions, including banks,
insurers and fund managers, working with UNEP to understand the impacts of
environmental and social considerations on financial performance. Sustain-
ability definitely entered the financial scene, when in 1999 the Dow Jones
Sustainability Indexes (DJSI) were launched.
This chapter aims to explore the role the financial sector can play in pursuing
sustainable development. This problematic area is generally referred to as
‘‘sustainability in finance’’ and has two different meanings:

1. financing sustainable development (clean technologies, renewable energies,

micro-credit, etc.)
2. financial activities generating sustainable development benefits.

There are several ways or channels through which financial activities (or
transactions) have the potential to impact – positively and negatively – upon
sustainable development (project finance, credit activities, retail banking, etc.).
We will focus in this chapter on asset management (in traditional asset classes,
e.g. stock quoted companies and corporate bonds).
Under the generic name of socially responsible investment, there are actually
a multitude of different philosophies: ethics, sustainable development, materi-
ality of extra-financial factors, etc. These various approaches differ as regards
both the criteria and analytical tools used to assess corporate behaviour and
performance, and the techniques used to build portfolios.
Even though the term ‘‘Socially Responsible Investment’’ covers many dif-
ferent approaches, it is useful to adopt a general definition:

Socially Responsible Investment (SRI) can be defined as the process by which

factors other than standard financial ones are affecting investment decision-
making and ownership practices.

Those factors are generally referred to as ‘‘extra-financial criteria’’ and

encompass ethical considerations, environmental sustainability, social respon-
sibility and corporate governance (ESG) issues. The abbreviation ESG in newer
terminology is often used synonymously with SRI.
With the first fund created in 1928 and documented practices of making
investment decisions based on moral grounds before that, the practice
of taking into account extra-financial criteria when making investment
Sustainability in Finance – Banking on the Planet 17
decisions is not new. This was initially the initiative of mostly faith-based
organizations. However, it is generally admitted that the modern area of
socially responsible investment started in 1971 when the Episcopal Church
presented at the General Motors annual meeting a shareholder resolution
calling for the company to withdraw from segregated South Africa.
Since then assets managed under the SRI label have increased dramatically,
particularly over the past decade. According to Eurosif (European Social
Investment Forum),5 ‘‘the growth of the broad SRI market between 2003 and
the amount identified in 2006 is estimated at 106%; adjusted to the progression
of the Morgan Stanley Capital International (MSCI) Europe Index, the real
growth of European Broad SRI is 36%’’.
A key differentiating factor of the different approaches hidden behind the
general and broad definition given above is how extra-financial criteria are
taken into account alongside financial ones for the construction of the port-
folio. As a matter of fact, the different approaches used in integrating ethical,
environmental, social and governance factors into investment processes fall
into the following three broad categories:

 Exclusion;
 Best-in-class;
 Engagement.

There is a continuum between these approaches and two of them, or even all
three, are quite commonly applied together. It is, however, true that many
investors focus only on one. It is worth noting that exclusion and best-in-class
techniques affect the selection of the stocks which are held in the portfolio (ex
ante screening), while the engagement technique does not (ex post monitoring).
In the following pages we will review each of these approaches by focusing on
the underlying research needed to implement them, the kind of results
this research delivers and to what extent and how investors are actually using
these results.

2.3.1 Exclusion
Exclusion involves the creation of an investable universe. In other words, it
means defining some companies as eligible for an investment and some others
as not. The companies that are not eligible – the excluded companies – are
those that do not meet certain criteria, called the exclusion criteria or screen.
These criteria can be of three types:

1. activity-based
2. policy-based
3. practice-based

Activity-based criteria focus on the products and services a company pro-

duces and brings to the market. Some common activity-based criteria
18 Chapter 2
include weapons and military contracting, tobacco, alcohol, nuclear power,
gambling, pornography and genetically modified organisms (GMO).
Policy-based criteria seek to identify companies that have not adopted formal
policies on one or several environmental, social or governance (ESG) related
issues. In that context, the adoption of a formal policy by a company is
considered as a necessary condition for investment. Although any kind of
issue can fit into this criteria, in practice the most commonly used issues
specifically relate to human rights and to the environment.
Practice-based criteria are intended to capture the actual corporate behaviour
and not just the corporate commitments. As for policy-based criteria, the
practice-based ones are generally aimed at capturing human rights violations
by companies. This specific type of exclusion is also sometimes called norm-
based screening.

According to Eurosif, 266,000 Mio h are invested in Europe based on simple

exclusion screens,6 with the arms trade (138,000 Mio h) and human rights
(61,000 Mio h) the most commonly used screens. In the United States, the
Social Investment Forum7 reports that in 2005 a total of 1,679,000 Mio US$
was invested using social screens, among these approximately 17% included a
human rights screen. It has to be noted that while the data reported by Eurosif
makes a clear distinction between exclusion screen and best-in-class strategy
(see also the next section), reflecting current practice in Europe, it is not the case
for the data reported by the US Social Investment Forum. This makes a direct
comparison difficult, as part of the 1,679,000 Mio US$ reported as using social
screens may also include some best-in-class strategies.

2.3.2 Best-in-class
A best-in-class approach involves the selection or the overweighting of stocks
of companies that perform particularly well compared to their peers. A best-in-
class approach thus involves the realization of an assessment of corporate
ESG performance and behaviour. Such a sustainability rating can be based on a
sector assessment (chemical industry, energy industry, etc.) and on the sustain-
ability assessment of individual companies and their peers in different industry
sectors.8
This kind of assessment is conducted by dedicated teams within asset man-
agement firms or banks and, more generally, by specialized research organi-
zations and rating agencies. More recently, brokerage houses, encouraged by
the Enhanced Analytics Initiative (EAI, see below) growing demand, have
started to deliver interesting pieces of research in this area.
According to Eurosif, a total of 29,000 Mio h is invested in Europe using
best-in-class strategies. This figure may be slightly underestimated as a part of
the 641,000 Mio h assets managed using an ‘‘integration’’ approach9 is most
probably using the best-in-class technique as defined above.
Sustainability in Finance – Banking on the Planet 19
2.3.3 Engagement
Engagement is used by investors to apply direct pressure to corporations to
improve their social and environmental performance. It encompasses various
means to gain dialogue with management and influence corporate behaviour,
including letter writing, meetings with top management and board of directors,
proxy voting and ultimately filling in shareholder resolutions. In 2005, invest-
ment through engagement strategies accounted for 703,000 Mio $ in the United
States7 and 730,000 Mio h in Europe.5
Shareholder advocacy is a particular form of engagement that is used by
stakeholders other than investors, mainly Non-Governmental Organizations
(NGOs, e.g. Amnesty International and Reporters Without Borders) and
unions. Shareholder advocacy is more popular in countries where shareholders’
rights require little capital to bring resolutions to an annual general meeting
such as in the United States.
Table 2.1 below gives an overview of the importance of engagement strate-
gies in the US market in 2005 as reported by the US Social Investment
Forum. Among a total of 348 resolutions, 98 were withdrawn, which is an
indication of the responsiveness of companies to pre-vote dialogues and
negotiations. On average, the shareholders’ resolutions that have been voted on
received 10% of the votes. This low figure does not necessarily mean, however,
that these resolutions were not successful since quite often companies take
these votes as a signal and undertake some of the requested changes.

2.4 Responsible Investment: the Mainstreaming of SRI

The evolution of assets under management in socially responsible investment
presented in the previous chapter is accompanied by and probably also – at
least to some extent – supported by an institutionalization and a mainstreaming
of such practices.
This institutionalization and mainstreaming phenomenon is characterized
by changes in the legal environment pushing pension funds into SRI (see box
on p. 20) as well as by several financial industry initiatives encouraging major
players to embrace the SRI concept.

Table 2.1 Shareholder advocacy: Resolutions to

Annual Meetings, USA 2005.7
Number of
resolutions Issue

42 Political contributions
35 Climate change
25 Global labour standards
11 Human rights
20 Chapter 2

Changing legal environment pushes pension funds

into SRI
United Kingdom
Since July 2000, the ‘‘Trustee Act’’ requires all pension fund trustees to
disclose their policies on socially responsible investment.

Germany
Since January 2002, the new pension law requires private and corporate
pension schemes to disclose their policies on socially responsible investment.

France
Since February 2001, the French law on Employee Saving Plans requires
mutual funds, which collect money from the Employee Saving Plans, the
Inter-companies Saving Plans and the Voluntary Partnership Employee
Saving Plans, to report on their policies on socially responsible investing.

Sweden
Since January 2001, the five biggest public pension funds have to consider
the environmental and social aspects in their environmental policy.

The UNEP-FI/Freshfields Bruckhaus Deringer study10

UNEP and lawyers at Freshfields Bruckhaus Deringer in 2005 released a
study entitled ‘‘A Legal Framework for the Integration of Environmental,
Social and Governance Issues into Institutional Investment’’, surveying the
law and legal trends in the jurisdictions of the world’s largest capital
markets, including Australia, Canada, France, Germany, Italy, Japan,
Spain, the United Kingdom and the United States. The study states that
ESG considerations must be integrated into an investment decision where
a consensus (express or in certain circumstances implied) amongst the
beneficiaries mandates a particular investment strategy and may be inte-
grated into an investment decision where a decision-maker is required to
decide between a number of value-neutral alternatives. Particularly insti-
tutional investors have a far greater opportunity – and in some cases a
legal obligation – to incorporate environmental, social and governance
issues into their investment decision-making than is traditionally believed.

Two important financial industry initiatives were launched in 2004:

The Who Cares Wins initiative was launched by mainstream investment
houses representing 6,000,000 Mio US$ in assets following an invitation by Kofi
Sustainability in Finance – Banking on the Planet 21
Annan to ‘‘develop guidelines and recommendations on how to better integrate
environmental, social and corporate governance issues in asset management,
securities brokerage services and associated research functions’’.11
The Enhanced Analytics Initiative (EAI) was launched by fund managers
representing 1,000,000 Mio US$ in assets to encourage ESG research by bro-
kers. This initiative is designed to give research providers a commercial
incentive to produce research that captures the value of ESG issues on cor-
porate performance. Twice a year, the EAI evaluates the research submitted by
research providers and the EAI members then allocate a minimum of 5% of
brokerage commissions to the producers of the selected extra-financial
research. The EAI has definitely been a key driver in the growing interest of
mainstream financial analysts for ESG issues; in turn this gives investors access
to more and more research into these areas.
Later, in April 2006, the Principles for Responsible Investment (see box
below) were launched by the United Nations and signed by asset owners and
investment managers representing more than 2,000,000 Mio US$.
One year later, more than 180 institutional investors managing assets worth
8,000,000 Mio US$ have signed up to these principles. In June 2008, signatories
of the Principles for Responsible Investment represented more than 13,000,000
Mio US$ of assets.

The Principles for Responsible Investment

As institutional investors, we have a duty to act in the best long-term
interests of our beneficiaries. In this fiduciary role, we believe that
environmental, social and corporate governance (ESG) issues can affect
the performance of investment portfolios (to varying degrees across
companies, sectors, regions and asset classes and through time). We also
recognize that applying these Principles may better align investors
with broader objectives of society. Therefore, where consistent with our
fiduciary responsibilities, we commit to the following:

1. We will incorporate ESG issues into investment analysis and deci-

sion-making processes.
2. We will be active owners and incorporate ESG issues into our
ownership policies and practices.
3. We will seek appropriate disclosure on ESG issues by the entities in
which we invest.
4. We will promote acceptance and implementation of the Principles
within the investment industry.
5. We will work together to enhance our effectiveness in implementing
the Principles.
6. We will each report on our activities and progress towards imple-
menting the Principles.
22 Chapter 2
12
As shown in the second annual report on PRI implementation, signatories –
asset owners and investment managers – have made considerable progress in
implementing the six principles.
From a niche market socially responsible investment as an integrative
approach (integration of ESG issues with industrial analysis and valuation on a
sector-by-sector basis to identify [mid- and long-term] investment opportu-
nities) has now definitely entered the mainstream arena,13 with a particular
focus on the link between ESG issues and financial performance.

2.5 Conclusion
As we have seen, the same words can have different meanings, depending
on who is using them and in what context. More particularly Sustainability in
Finance has two meanings which are overlapping but not identical: on one hand
we have a sustainable management of companies rated by financial and sector
specific strategic non-financial ESG aspects; on the other hand we have sus-
tainable investment strategies directing capital according to SRI/ESG princi-
ples. Whatever the meaning, and behind the differences in approaches and in
the objectives followed by the investors (investing according to own values,
seeking higher performance by capturing the materiality of ESG factors), in the
end, from a sustainable development perspective, the key question is:
Are these investment practices having a tangible impact on sustainable
development?
If SRI/ESG is able to push companies to rethink their activities and business
models, it certainly already makes a contribution to sustainable development.
The question that remains is: does SRI turn out to be the key driver for sus-
tainable development? To be able to answer this question, one would need to
have metrics actually measuring this impact. Research in this area is still in its
infancy and a lot remains to be done. In this regard, however, it is worth
mentioning two recent initiatives going in this direction.
In a paper14 published in May 2008, Christoph Butz and Olivier Pictet argue
that ‘‘Financial performance is not a sufficient condition for the success of an
SRI investment strategy. Social investors’ objectives are not one-dimensional
but multi-dimensional. Their utility function also explicitly includes a social
and an environmental performance dimension. Hence the need for a credible
and transparent extra-financial reporting.’’ They present in their paper how
such extra-financial reporting might look and ‘‘show that the companies in the
sustainable portfolio emit less CO2 and create more jobs than their peers and
thus provide the sustainable investor with a measurable social and environ-
mental added value’’.
In a similar attempt to inform investors, the Caisse d’Epargne – a French
banking group – introduced in June 2008 the sustainability label for savings
products. This labelling allows consumers to compare passbook savings
accounts, mutual funds and life insurance offerings on the basis of three
criteria: financial risk (Security Criterion), the use of social and environmental
Sustainability in Finance – Banking on the Planet 23
criteria in managing the product (Responsibility Criterion) and the impact on
the climate of the activities financed with the products (Climate Criterion).15
These two initiatives will most certainly be followed by others, which will
hopefully lead to a comprehensive system of reporting the extra-financial
performance – or sustainable added value – of investment.
In the same way as the chemical industry, following growing ecological
concerns over waste as well as catastrophic events like Seveso and Bhopal, had
to reconsider the way it was doing business, the current financial crisis will also
lead to a redefinition and reconsideration of the role and functioning of the
financial system. In order to make a sustainable contribution to the solution of
the current crisis the financial markets must return to their supportive function
(Figure 2.1). In the last years they have taken the goal setting position within
the economy which in turn has driven short termism within the real economy.
The concepts and current practices related to sustainability in finance presented
in this chapter are now more relevant than ever before.

References
1. R. Levine, Finance and Growth, Theory and Evidence, NBER Working
Paper 10766, NBER, Cambridge, 2004, http://www.econ.brown.edu/fac/
Ross_Levine/Publication/Forthcoming/Forth_-
Book_Durlauf_FinNGrowth.pdf (retrieved 17.03.2009); B. Scholtens,
J. Bus. Ethics, 2006, 68(1), 19–33.
2. H. Garz and F. Schnella, KPIs for ESG, DVFA Financial Papers, No. 8/
08_e, Version 1.1 – Draft, DVFA, Dreieich, 2008.
3. J. Bouma, M. H. A. Jeucken and L. Klinkers, Sustainable Banking – The
Greening of Finance, Greenleaf Publ., Sheffield, 2001.
4. D. Sarokin and J. Schulkin, Journal of Commercial Bank Lending, Feb.
1991, 73, 6–19.
5. European SRI Study, Eurosif, 2006, http://www.eurosif.org/publications/
sri_studies_2006_2003 (retrieved 14.10.2008).
6. In its ‘‘European SRI Study 2006’’, Eurosif defines simple screens as ‘‘an
approach that excludes a single given sector from a fund such as arms
manufacture, publication of pornography, tobacco, animal testing, etc.
Simple screens also include simple human rights screens (such as excluding
companies for activities in Sudan or Myanmar) and Norms-based screening’’.
7. Social Investment Forum, 2005 Report on Socially Responsible Investing
Trends in the United States, Washington, 2006, http://www.socialinvest.org/
pdf/research/Trends/2005%20Trends%20Report.pdf (retrieved 15.10.2008).
8. E. Plinke, in Nachhaltigkeit in der Chemie – 13. Internat. Sommerakademie
St. Marienthal, Initiativen zum Umweltschutz. ed. F. Brickwedde, R. Erb,
M. Hempel, M. Schwake, Bd. 70, Erich Schmidt Verlag, Berlin, 2008, p. 329.
9. Eurosif defines integration as ‘‘the explicit inclusion by asset managers of
[corporate governance]/[social, environmental, ethical] risk into traditional
financial analysis’’.
24 Chapter 2
10. UNEP FI/Freshfields Bruckhaus Deringer, A Legal Framework for the
Integration of Environmental, Social and Governance Issues into Institutional
Investment, Genève, October 2005.
11. The Global Compact, Who Cares Wins – Connecting Financial Markets to
a Changing World, Financial Sector Initiative, December 2004, http://
www.unglobalcompact.org/docs/news_events/8.1/WhoCaresWins.pdf
(retrieved 15.10.2008).
12. UNEP Finance Initiative, PRI Report on Progress 2008, New York, 2008,
http://www.unpri.org/files/2008PRI_Report_on_Progress.pdf (retrieved
15.10.2008).
13. W. Baue, Social Funds, Oct. 05, 2005, http://www.socialfunds.com/news/
article.cgi/1826.html (retrieved 14.03.2009); S. Forrest, Goldman Sachs ESG:
Integrating ESG into Investment Research, June 2006, www.ahcgroup.com/
powerpoint/GoldmanSachsPresentation.ppt (retrieved 14.03.2009).
14. C. Butz and O. Pictet, The SRI Performance Paradox – How to Gauge and
Measure the Extra-financial Performance of Socially Responsible Invest-
ment, Pictet & Cie, Geneva, May 2008, www.pictet.com.
15. Groupe Caisse d’Epargne & Utopies, Etiquetage De´veloppement Durable des
produits bancaires Premie`re approche méthodologique, M.-C. Korniloff, S.
Dupré (Coordination), Juin 2008, http://programme.beneficesfutur.fr/themes/
perso/pdf/Methodologie_Generale_Juin_2008.pdf (retrieved 15.10.2008).
CHAPTER 3

Metrics for Sustainability

PETER SALING

BASF SE, D-67056 Ludwigshafen, Germany

3.1 Introduction
Meeting society’s needs without damaging the environment requires new ways
of thinking. In spite of a strong record of innovation – in products that meet
customers’ needs, in manufacturing processes that protect the environment and
human health and in solutions that directly address environmental problems1 –
the greater public often has a critical relationship with industrial chemistry.
Society perceives a need that industry acts more responsibly and governments
all around the world introduce increasingly strict legislation to ensure it does
so.2 Quantifying the sustainability benefits of industrial chemistry is therefore
an important issue for the further development of this field of opportunities
in the future. A realistic and validated estimate of innovative potentials of
industrial chemistry by using quantitative methods is essential for the devel-
opment of new products and processes. Therefore, a link between industrial
chemistry and metrics for sustainability will be one of the key factors of
sustainable development within the chemicals industry. New approaches and
developments of ‘‘Green Chemistry’’, ‘‘Green Engineering’’, etc. in combina-
tion with the development of industrial processes should be evaluated with a
powerful and extensive methodology.3
The chemical industry has played a key role in the development of new tools
and techniques as well as in impact assessment research, consistently allocating
a large portion of its resources to research and development.4 To promote
communication and understanding between the academic community and the

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

25
26 Chapter 3
chemical industry is also important. The best way to bridge the gap between the
ideas that academia generate and the ideas that the product development
industry seeks should also be evaluated.5

3.2 The Eco-Efficiency Analysis as an Approach for

the Checking of Sustainability in Industrial
Products and Applications
A particularly important issue is the investigation and valuation of the envir-
onmental impacts of a given product or service caused or necessitated by its
existence. Different approaches have been made to analyze and standardize
such impacts throughout a product’s life-cycle:

 Life-Cycle Assessment (LCA, also known as life-cycle analysis, ecobalance

and cradle-to-grave analysis) is the method to evaluate the mass balance of
inputs and outputs of systems and to organize and convert those inputs
and outputs into environmental impacts relative to different ecological
areas. The procedures of LCA are part of the ISO 14000 environmental
management standards: in ISO 14040:2006 and 14044:2006. One of the
first steps before starting an LCA is to define the ‘‘functional unit’’, which
is related to the function that a product or service will deliver. LCA also
allows comparisons between equivalent stages of life-cycles (i.e. the con-
sumer stage of product A and the consumer stage of product B), provided
that the LCIs as basic data rely on the same databases and the same
assumptions. LCA normally follows the ‘‘cradle-to-grave’’ approach and
means the full Life-Cycle Assessment from manufacture (‘‘cradle’’) to use
phase and disposal phase (‘‘grave’’).
 Life-Cycle Inventory (LCI) pursues the compilation and quantification of
inputs and outputs for a given product system throughout its life-cycle on
a volume or mass basis (e.g. kg of CO2, kg of cadmium, cubic metre of
solid waste).
 Product-Specific Requirements (PSR) is the phase of life-cycle assessment
involving the compilation and quantification of inputs and outputs, for
a given product system throughout its life-cycle. Additionally, specific
technical data information will be a part of PSR or EPD (Environmental
Product Declaration).
 Life-Cycle Inventory analysis result (LCI result) provides information
about all inputs and outputs in the form of elementary flow to and from the
environment from all the unit processes involved in the study. An outcome
of a life-cycle inventory analysis result includes the flows crossing the system
boundary and provides the starting point for life-cycle impact assessment.
 Life-Cycle Impact Assessment (LCIA) is the phase of life-cycle assessment
aimed at understanding and evaluating the magnitude and significance of
the potential environmental impacts of a product system.
Metrics for Sustainability 27
 Life-Cycle Interpretation is the phase of life-cycle assessment in which the
findings of either the inventory analysis or the impact assessment, or both,
are combined in consistence with the defined goal and scope in order to
reach conclusions and recommendations.

Following these general methodology approaches, a new approach was

developed in the late 1990s by BASF in cooperation with Roland Berger
Consulting, Munich. This methodology, the Eco-Efficiency Analysis, among the
other tools mentioned above, is seen as a life-cycle management tool and can
be involved in assessments of the entire product life-cycle, from concept
development to design and implementation, further to marketing and, finally,
end-of-life issues. The analysis method may incorporate both economic and
environmental aspects and lead to a comprehensive evaluation of products and
processes over their entire life-cycle.
In the method of Eco-Efficiency Analysis, results are presented as aggregated
information on costs and environmental impact and show the strengths
and weaknesses of a particular product or process. The ecological calculations
of the single results in each category follow the ISO-rules 14040 and 14044.
The quantitative weighting steps to obtain the ecological fingerprint and the
portfolio are additional features.

3.2.1 Conducting an Eco-Efficiency Analysis

Every eco-efficiency analysis passes through several key stages. This ensures
consistent quality and the comparability of different studies. Environmental
impacts are determined by LCA and economic data is calculated using the
usual business or, in some instances, national economical models.
The basic preconditions in eco-efficiency analysis are:

 Products or processes studied have to meet the same defined customer

benefit;
 The entire life-cycle is considered;
 Both an environmental and an economic assessment are carried out.

The eco-efficiency analysis is worked out by following specific and defined

calculations:

 Calculation of total cost from the customer viewpoint;

 Preparation of a specific life-cycle analysis for all investigated products or
processes according to the rules of ISO 14040 ff;
 Determination of impacts on the health, safety and risk to people, asses-
sing use of area over the whole life-cycle;
 Calculation of relevance and calculation factors for specific weighting;
 Weighting of life-cycle analysis factors with societal factors;
 Determination of relative importance of ecology versus economy;
 Creation of an eco-efficiency portfolio;
28 Chapter 3
 Analyses of weaknesses, scenarios, sensitivities and business options;
 Optionally: inclusion of social aspects.

The methodology has been approved by the German TÜV (‘‘Technischer

Überwachungsverein’’, English: ‘‘Technical Inspection Association’’) and
was also used by the Öko-Institut (‘‘Institute for Applied Ecology’’) in
Freiburg, Germany, in different APME-studies (APME, now ‘‘Plastics
Europe’’, ‘‘Association of Plastics Manufacturers in Europe’’). TNO in the
Netherlands is using the BASF standard method with a different weighting
system (Figure 3.1).
For the calculation and comparison of the environmental position of
each alternative, data from the different production methods is assimilated
and analyzed to provide a value for energy consumption, raw-material
consumption, emissions and use of area, risk potential and toxicity potential.
All raw-materials required in the process and how these are derived are
factored into the study, as are the steps required to bring the product to the
end-user.
In the same manner economical data from the life-cycle chain of a product
application or process evaluation may also be calculated and summarized.
In the end, this analysis can lead to better decisions with regard to product
design, material utilization and capital investment. The rationale behind this
assessment tool has been described by Saling et al. and by Landsiedel and
Saling.6,7
Practical examples can show how the metrics for sustainability can support
decision-making processes answering different questions.

define determine costs of

calculate total life normalize
customer individual life cycle
cycle costs costs
benefit segments

determine ecological
impacts of individual life determine relevance
identify cycle segments and society factors
products / for aggregation of the
processes effects categories
aggregate impacts to form
effects categories
normalize
establish life environmental
cycle impact
combine the effects
categories for each life
DIN-ISO 14040; 14044 cycle segment create eco-
efficiency portfolio

Figure 3.1 Process steps of eco-efficiency analysis.

Metrics for Sustainability 29
3.3 Industrial Examples for Using Sustainability
Metrics
3.3.1 Eco-Efficiency Study of Curing Alternatives for Wooden
Substrates
In this example radiation curing is compared with several other coating
technologies, such as solvent-based two-component polyurethane, acid curing,
nitrocellulose and water-based coatings. In the application discussed here, a
specific customer use was defined as: performance application of 1,000 wooden
front doors.
The most important differences between the processes are the curing
mechanisms of each alternative. With radiation curing technology, UV-light is
used for curing. This allows the skipping of the energy-intensive thermal-oven
drying process steps, which are required for all other alternatives.
The objective is to express the properties of the UV-curable coating technol-
ogies with the method of eco-efficiency. The eco-efficiency fingerprint (Figure
3.2) shows that the UV-roller coating has the best results in all environmental
categories. The low film weight and the absence of a need for thermal drying
induce high productivity and the lowest production costs, as shown in Figure 3.3.
This overall result is shown in the eco-efficiency portfolio in Figure 3.4.
The alternative with the highest eco-efficiency is in this case the UV-curing
alternative. It might be different in other applications, so a ‘‘case-by-case’’
decision is necessary. A lot of scenarios are also evaluated in this study. One of
these shows the influence of the radiation energy of the UV-curing system
(Figure 3.5). Even if the energy is doubled, the UV system is still the most
eco-efficient alternative.8

Energy consumption Aqueous Coating

2 C-PU Coating
1
AC-Coating
0.8 NC-Coating
UV Coating
0.6
Raw materials 0.4
consumption Emissions into
0.2 air, water, ground
0

1,0 = worst position

better numbers <1

Risk potential Toxicity potential

Figure 3.2 Ecological fingerprint for alternative curing systems.

30 Chapter 3

0.1 Aqueous varnish

Environmental position [normalized]

UV-varnish
UV 2 C-PU varnish
AC-varnish
Customer NC-varnish
related
benefit:
Coating of
1,000 wooden 1.0
doors with a AC NC
semi gloss, The base case
transparent Aqua. shows the UV-
texture varnish as the most
2C-PU eco-efficient
alternative

1.9
1.9 1.0 0.1
Costs (normalised)

Figure 3.3 Life-cycle cost calculation of alternative curing systems.

Primer Coating Stain Machinery Personnel costs Energy

4000
Costs [ /user benefit]

3000

2000

1000

0
UV-system Aqueous 2 C-PU AC-system NC-system
system system

Figure 3.4 Eco-efficiency portfolio for alternative curing systems.

Manufacturers need to take the results of an eco-efficiency analysis into

consideration for future planning. It could support the process of switching
over to the more eco-efficient UV-technology. Eco-efficiency analysis provides
guidance for internal planning and decisions.

3.3.2 Vitamin B2 Case Study

Vitamin B2 is produced by BASF’s Agricultural Products & Nutrition segment
for use as a vitamin for human and animal nutrition. As a component of animal
Metrics for Sustainability 31

0.1
Aqueous varnish

Environmental position [normalized]

UV-varnish
UV 2 C-PU varnish
AC-varnish
Customer NC-varnish
related
benefit:
Coating of
1,000 wooden 1.0
doors with a AC NC
semi gloss, In this scenario
transparent Aqua. the UV-coating is
texture still the most
eco-efficient
alternative

1.9
1.9 1.0 0.1
Costs (normalised)

Figure 3.5 Scenario of the eco-efficiency analysis for alternative curing systems.
2 CPU ¼ two-component polyurethane, AC ¼ acid curing, NC ¼ nitro-
cellulose.
feed, it is vital to ensure the animals’ health and fitness; vitamin B2 deficiency
leads to slower growth and poor feed conversion.9
Eco-efficiency demonstrated which vitamin B2 production process is the most
eco-efficient. Three ‘‘bio-technological’’ processes and one ‘‘chemical’’ process
were evaluated for the production of 100 kg of vitamin B2 for use in animal feed
pre-mix. All of the processes include renewable resources such as plant oil or
glucose as a raw material (Figure 3.6). The bio-technological processes use
fermentation, while the chemical process starts with a bio-technological pre-
cursor like glucose or soybean oil and afterwards uses traditional chemistry to
produce the vitamin B2.
As Figure 3.7 shows, Biotech process 1 was the most eco-efficient. It had
the least overall environmental impact, and was one of the lowest cost alter-
natives. Biotech process 3 had noticeably higher environmental impact and
higher costs. In this case the chemical process alternative had the highest
cost and a greater environmental impact than Biotech process 1, resulting in the
lowest eco-efficiency. BASF produces vitamin B2 via one-step fermentation
from vegetable oil by using the fungus Ashbya gossypii. BASF pioneered the
shift from chemical to biotechnological vitamin B2 production on an industrial
scale and runs a production facility in Korea. It is an excellent example of
industrial-scale production using the most eco-efficient technology currently
available.
The eco-efficiency analysis in this case study was able to outline and to
describe new goals of research activities. It was able to highlight the most
important factors that influence the system.
The results can be used for decision-making processes in ‘‘white bio-
technology’’, which can be assessed and compared to the actually established
chemical processes. The eco-efficiency study is able to support strategic
decision-making processes with a different life-cycle-based view on the different
32 Chapter 3

Fermentation Chemical Process

Biomass Glucose

K arabonate

Ca arabonate

Production Ca ribonate
of vitamin B2

Ribonolactone

Ribose

Ribitylxylidine

Phenylazo-RX

Vitamin B2

Figure 3.6 Chemical and biotechnological production pathways for vitamin B2.

0.4
High eco-efficiency
Environmental burden (normalized)

Biotech
process 1
Chemical
Customer-related
process
benefit: 1.0
100 kg vitamin B2
Biotech
for production of process 2
Biotech
feed premix
process 3

Low eco-efficiency
1.6
1.6 1.0 0.4
Costs (normalized)

Figure 3.7 Portfolio of vitamin B2 production for the feed segment.

Metrics for Sustainability 33
technologies. Without any prejudices and preferences for a certain technology,
the most sustainable process can be selected and realized.9,10

3.3.3 Eco-Efficiency Analysis Confirms: Ionic Liquids Provide

Benefits
On account of their unique set of characteristics, ionic liquids are potentially
suited for numerous applications and are thus attracting increasing attention.
Today, they are viewed as promising alternatives in chemical reactions and
separation processes, as well as in processing metals and polymers – especially
biopolymers such as cellulose.11
Using the BASILt process (the acronym stands for Biphasic Acid Scaven-
ging utilizing Ionic Liquids), BASF was the first company to transfer ionic
liquids from laboratory to commercial dimensions, and the BASILt process
became the first large-scale industrial process worldwide that uses ionic liquids.
The use of BASF’s BASILt process for scavenging hydrochloric acids in the
chemical synthesis of phosphorus compounds like Ø2POR or ØP (OR)2 by
reaction of Ø2PCl (or ØPCl2) and ROH12 offers significant advantages over the
conventional system (Figure 3.8).
Compared to amines, which have traditionally been used as HCl-scavengers in
this type of reaction, the BASF process based on 1-methylimidazole circumvents
the problematic, time-consuming and expensive filtration of a solid ammonium
hydrochloride cake by yielding an ionic liquid, the 1-methylimidazolinium

Existing process

+ 2 R3 N P O + 2 R3N * HCl
O

DEPP

H
+ 2 O + NaOH
P Cl
Cl
1-methylimidazole as an acid scavenger
DCPP

P O
+ 2 MIA
O + 2 MIA * HCl

DEPP
New process

Figure 3.8 BASILTM: a process alternative for the synthesis of alkoxyphenylpho-

sphines. DCPP ¼ dichlorphenylphosphine; MIA ¼ 1-methylimidazome;
DEPP ¼ diethoxyphenylphospine.
34 Chapter 3

-0.5
High eco-efficiency
Amine
Customer EDPP

Environment (normalized)
benefit:

Providing
acid quench BASIL
chemicals for EDPP
neutralization 1.0
of acids in
the
production of
1,000 kg
Phenyl- In the Base case
phosphine the BASIL
Products process is the
Low eco-efficiency
most eco-efficient
2.5 alternative
2.5 1.0 -0.5
Costs (normalized)
Sector of significant
differences

Figure 3.9 Portfolio of the use of BASILt in EDPP (ethoxydiphenyl phosphine)-

production alternatives.

hydrochloride salt. The BASILt process is less cost-intensive and at the same
time better for the environment (Figure 3.9). The new process for synthesizing
phosphorus compounds, which are used as chemical building blocks to produce
photo initiators in UV-curable coatings, reliably avoids a number of problems
encountered to date. Stability and product yield improve, and the process is less
laborious. The ionic liquids can be easily separated from the desired products,
like oil from water, and can also be recycled.
The eco-efficiency analysis has demonstrated that BASILt is much more
eco-efficient than the conventional method.13
This tool can be used for further improvement, even for chemical synthesis in
the laboratory phase to realize more sustainable chemical processes.
The BASILt developers received the ‘‘Innovation Award’’ of the ‘‘European
Chemical News’’ trade journal and the BASF Innovation Award in October
2004.

3.4 Beneficial Uses of Eco-Efficiency Analysis and

Metrics for Sustainability
Since 1996 more than 350 analyses have been carried out in key fields at BASF
(paints and dyes, plastics, life science, oil and gas, chemicals) but also externally
with customers, retailers, associations and authorities by eco-efficiency experts.
In doing so, eco-efficiency analysis has been employed in four major fields of
Metrics for Sustainability 35
application; strategic decisions, research and product development, commu-
nication with policy makers and marketing.
In strategic decisions it is possible for the application investigated to identify
solutions with a promising future. Even in investment decisions eco-efficiency
analysis provides valuable perspectives.
The second field of application relates to research and product development.
Promising products are identified at an early stage, thus facilitating decision-
making about the prime thrust of the development.
The third field of application is the drawing up of position papers for
discussions with opinion and policy makers. Eco-efficiency analysis makes it
possible to present the complex, holistic interconnections in industrial pro-
duction and product use in a graphic and readily communicable form. By these
means, it is possible to conduct quantitative discussions, with politicians for
instance, about the effects of planned legislation.
Eco-efficiency analysis is even used in marketing, the fourth main application
area. Since the entire life-cycle of a product is considered, the effects for cus-
tomers are integrated into the analysis. As a result the total vision inherent in
products can be communicated to customers.
Determination of the sustainability of products and processes should be done
by employing an accepted scientific method such as the presented eco-efficiency
analysis.
Results of an evaluation with metrics of sustainability can be expressed by
a label that is designed for b-2-b or b-2-c purposes. BASF labelled about
15 products with such a label; examples can be found on the internet
(www.ecoefficiency.basf.com).
Sustainability will be an important key factor for the development of new
products, processes and services.

3.5 Outlook
In order to arrive at a comprehensive assessment of products or processes, it
is in general necessary to include all three dimensions of sustainability. The
objective was to develop a tool, comparable to the BASF eco-efficiency ana-
lysis, which is simple to use by LCA-experts and easy to understand for people
without any prior experience in the field. Moreover, the results of even the most
complex studies should be understandable at a glance.
This new method is named SEEBALANCE. SEEBALANCE targets the
adoption of life-cycle social data to the results of eco-efficiency analysis for a
complete sustainability assessment methodology. It is a helpful tool in different
fields for the evaluation of product or process alternatives.14

References
1. P. T. Anastas and J. B. Zimmerman, Environ. Sci. Technol., 2003, 37(5),
94A.
36 Chapter 3
2. J. Bigorra and R. Höfer, Comunicaciones, Jorn. Com. Esp. Deterg.,
Barcelona, 2008, 38, 179.
3. D. R. Shonnard, A. Kicherer and P. Saling, Environ. Sci. Technol., 2003,
37(23), 5340.
4. Cefic, the European Chemical Industry Council: One Vision, One Voice
http://www.cefic.be.
5. H. Gavaghan, Nature, 2000, 406(6797), 809.
6. P. Saling, A. Kicherer, B. Dittrich-Krämer, R. Wittlinger, W. Zombik,
I. Schmidt, W. Schrott and S. Schmidt, Int. J. LCA, 2002, 7(4), 203.
7. R. Landsiedel and P. Saling, Int. J. LCA, 2002, 7(5), 261.
8. P. Saling, Kunststoff-Trends, GIT Verlag, 2007, 4, 8.
9. BASF Group, ed., Press release, A big step forward in the extension of
BASF’s vitamins business, 10 November 2003, P-03-495.
10. P. Saling, Appl. Microbiol. Biotechnol., 2005, 68, 1.
11. R. P. Swatloski, R. D. Rogers and J. D. Holbrey, US 2003/0157351, 2002
(Univ. of Alabama); J. Holbrey, R. P. Swatloski, J. Chen, D. Daly and
R. D. Rogers, US 2005/0288484, 2005 (Univ. of Alabama); D. A. Fort,
R. C. Rensing, R. P. Swatloski, P. Moyna, G. Moyna and R. D. Rogers,
Green Chem., 2007, 9, 63.
12. M. Maase, C & E News, 2003, 81(13), 9.
13. P. Saling, M. Maase and O. Huttenloch, ACHEMA, Frankfurt, 2006; P.
Saling, Green Innovation in the Chemical Industry, E.N.G.’s 2 senior
executive summit, Amsterdam, 2007; http://corporate.basf.com/de/sus-
tainability/oekoeffizienz/label.htm.
14. I. Schmidt, M. Meurer, P. Saling, A. Kicherer, W. Reuter and C. Gensch,
in Greener Management International, ABI/INFORM Global, ed. S.
Seuring, Greenleaf Publishing Ltd., Sheffield, Spring 2004, 45, p. 79.
CHAPTER 4

Sustainable Logistics as a Part

of Modern Economies
THIERRY JOUENNE

Conservatoire National des Arts et Métiers (CNAM), 292, rue Saint Martin,
F-75003 Paris, France

4.1 Introduction
Given the close relationship with transportation, logistics clearly lies at the
heart of sustainable development issues because of the environmental pollution
generated in supplying factories, warehouses, sales outlets and consumers. But
logistics also makes a major contribution to social equity in terms of
employment, regional development and fair trade. At the same time, it con-
tributes to sustainable growth by the enormous saving potentials still to be
raised by quality improvement and efficient supply chain management.
Transport consumes 70% of the oil used in Europe and represents the primary
generator of greenhouse gas emissions (in 2004, inland transport accounted
for 21% of total greenhouse gas emissions in the EU-15). Other factors on the
downside are traffic congestion in urban areas, energy consumption, toxic
exhaust emissions, noise and the imprint left by logistic infrastructure on the
environment. The situation is all the more alarming if we consider that a 60%
increase in trade is expected between 2005 and 2015 within the European
Union. Conversely, under the Kyoto Protocol greenhouse gases are due to be
reduced by 5.2% with respect to the 1990 levels between 2008 and 2012. While
it is the subject of much criticism regarding the negative impact of transport on
the environment, the logistic function gives rise to a great deal of expectation in

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

37
38 Chapter 4
meeting the challenges of sustainable development, as in the broadest sense this
management discipline plays a role in controlling and optimizing production
and distribution systems. This feature makes it one of the key players capable
of contributing across the board to sustainable development, operating
not only on reducing greenhouse gas emissions but also on business competi-
tiveness and the economic vitality of society. This less well-known aspect
of logistics as a performance driver connects it de facto with the other two
pillars of sustainable development – the economic and social – once it is able
to influence economic growth, employment and purchasing power while
reducing the impact of its activities on the environment. While acknowledging
that there is still a lot of headway to be made, the purpose of this chapter is to
show how sustainable logistics can reconcile the three economic, social and
environmental aspects by developing eco-technological solutions and adopting
‘‘responsible practices’’ between suppliers, manufacturers, retailers and logistic
service providers. We shall see that this global project calls for the same vision
of the value chain to be shared and for collaboration in achieving common
objectives for the benefit of business, society and the environment.

4.2 Definition and Role of Logistics

Several definitions have been put forward over the last 40 years but what is
known as modern logistics is generally viewed as a business planning frame-
work for the management of material, service, information and capital flows.
It includes the increasingly complex information, communication and control
systems required in today’s business environment. It fits into the supply chain
as defined by Mentzer et al. ‘‘as a set of three or more entities (organizations
or individuals) directly involved in the upstream and downstream flows of
products, services, finances and/or information from a source to a customer’’
(see Figure 4.1).12
The logistics approach is global and applies to all the players in the logistic
chain from the design, manufacture and distribution phase until the products
are withdrawn from the market. The logistic strategy is in line with corporate
and marketing strategies.
The NF X 50-600 standard specifies that the purpose of the logistic function
is to ‘‘meet expressed or latent needs, internal or external, at the best economic
conditions for a given level of service’’.1 This definition calls up the many
dimensions of logistics, the boundaries of which extend beyond the particular
company to reach a global optimum and meet the expectations of all the
stakeholders in the supply chain. In order to fully appreciate developments
over the last few years, we shall recall that logistics, until the 1970s, focused on
the techniques tied to the physical processing of flows of goods (inventory
management, transportation optimization, job shop scheduling). For the last
20 years or so, the assignments have been considerably extended and the
associated information flows have linked up with physical flows. The logistic
function extends henceforth from the design of the industrial and logistic
Sustainable Logistics as a Part of Modern Economies 39

Figure 4.1 Types of channel relationships. Source: Mentzer et al.12

system – necessary for the manufacture, distribution and support of products

throughout their life-cycle – to the management of the logistic system dedicated
to controlling flows and inventories up to the point of consumption, including
the management of returns.
In the same way, we may note that performance indicators have moved from
a management philosophy focused on the achievement of local performance to
a philosophy of management of the supply chain as a driver of value creation
for all stakeholders.
Logistics is a cross-cutting, multi-disciplinary function covering, according
to the AFNOR reference model, no less than 25 trades and 600 activities spread
along the value chain. It plays a primary role from day-to-day business to
major corporate projects. Its field of operation has widened, its missions have
diversified – becoming more complex than before – and its competencies have
developed, just as the range of its methods has become more elaborate. This
transformation has occurred over the last 15 years and has not yet ended.
Under the impetus of Supply Chain Management (SCM), a concept that
appeared in the early 1990s and is defined as the integrated management of the
logistic process in a coordinated flow between companies linked in the same
value chain, logistics is increasing its scope of operation. It benefits nowadays
from all the headway brought by developments in the computing world and, in
particular, since it deals with a chain of interfaces, the progress made in
information and communication technology.
The logistic function runs the supply chain in terms of customer service
objectives under the best economic conditions. This is an exercise calling on
planning, coordination and management capabilities. It requires also educative
and mediation abilities so as to get all internal and external players singing
from the same hymn sheet despite conflicts of interest. This approach is global
40 Chapter 4
and targets the general interest of business in a spirit of intra- and inter-
company collaboration.

4.3 Current Situation

Industry is faced today with endemic problems that remain difficult to solve
despite the progress in technology. For instance, through lack of flow control
and proper synchronization, shelf out-of-stocks amount on average to 10% of
items, which translates into a loss of revenue for 1449 hypermarkets in France
alone estimated at 200 million euros per quarter.2 The capacity utilization of
the trucks – assessed at 60–70% on average – is also problematic. It is reckoned
that there are today some 20–25% empty miles, a rate which goes up to 35%
for private carriers.3 It should be recalled here that the Just-in-Time require-
ment when taken to the extreme is not irrelevant to deliveries being split up and
the increase in empty returns. Other individualistic practices generate situations
that are counterproductive in terms of sustainable development. For example,
the search for the lowest production costs in the so-called low-cost countries –
dictated by short-term profitability considerations – entails an explosion of
logistic costs and CO2 emissions and a loss of responsiveness, which is none-
theless essential to meet the fluctuations in demand.
Let us also mention the practices of some contractors in terms of customer
service rates with penalties – which may reach 80% of the order in the event of
delayed delivery – that deter any attempt at optimising the logistic chain
overall. E-commerce is also costly and polluting, particularly in the last mile.
These practices certainly have an impact on product price, company profit-
ability margins and of course on the environment, exacerbated by the fact that
not all companies have the same logistic maturity or the same capacity for
optimization. For example, small and medium enterprises (SMEs) do not have
the critical size, the organization or the facilities to optimize their flows. In such
cases, frequent deliveries of small batches (fragmented orders) to distant cus-
tomers weigh heavily on the transport bill and the carbon footprint.
At the same time, urban areas are saturated and do not permit effective
distribution of goods in the absence of logistic hubs set up in sufficient numbers.
Frequent imbalances between transport supply and demand are seen leading
to shortages of road transportation capacity on certain routes at certain times
of year, for which alternatives are difficult to find because of the lack of
availability and responsiveness of rail freight. Lastly let us mention the lack
of maritime and rail motorways and the lack of harmonization for legislation
in goods transport Europe-wide to appreciate the structural difficulties that
players on the supply chain have to contend with.
This alarming observation in terms of the survival of businesses and
respect for the environment calls for a breakthrough transformation in
doing business at all levels in the value chain in the direction of better
balance, transparency, responsibility and collaboration between stakeholders.
Vigorous step changes are needed to significantly reduce CO2 emissions, traffic
Sustainable Logistics as a Part of Modern Economies 41
congestion, infrastructure footprint and supply-chain costs, while at the same
time reducing out-of-stocks. The Grenelle Environment meeting in France in
October 2007 highlighted the economic, social and environmental impacts
of human activities in general, and transportation in particular. It already
advocates an assessment of greenhouse gas emissions from transport services.
The consequences for the organization of production, distribution networks,
warehousing and circulation of goods are considerable. To assist businesses in
meeting the challenges of sustainable development and translate their strategic
objectives into concrete realities, logistics offers four essential drivers in the
service of economic growth, social development and the protection of the
environment.

4.4 The Four Logistic Drivers

Logistics extends from end to end of the value chain where its role consists of
connecting the two poles of the economy in synchronizing effectively and on the
best economic terms the supply chain with real consumer demand, however
complex, uncertain and fluctuating it may be. In line with company strategy,
well orchestrated and integrated, it makes it possible, according to Christopher
Martin’s dictum to do ‘‘better, quicker, cheaper and nearer’’, to obtain com-
petitive advantage:4

 Better, by delivering perfect orders and achieving customer satisfaction;

 Quicker, by cutting down lead-times and cutting out unnecessary activities
that hamper process flow;
 Cheaper, by reducing stock, operating costs and structural costs that bear
down on the logistic chain;
 Nearer, through establishing customer loyalty by offering added-value
services like customized products, responsiveness to demand, flow trace-
ability, order tracking via the internet, etc.

This attractive vision is nonetheless difficult to achieve. It calls for a gradual,

long-haul approach and depends on the ability of companies to modernise their
working methods, integrate the logistic process, cut down costs and lead-times,
measure performance, automate information exchange (Electronic Data
Interchange, EDI and interfacing the Enterprise Resource Planning, ERP),
coordinate activities and share information, resources and facilities between
partners.
Incorporating sustainable development brings in two further dimensions –
social and environmental. These add to the economic challenge for the logis-
ticians who, let us note, have not yet – specifically in small and medium-sized
businesses – taken it on board that they have to incorporate the other two.
Fortunately, the three features to be reconciled are not mutually contradictory –
as the economic feature lies in the same direction as the environmental and
social ones – although this statement remains to be demonstrated.
42 Chapter 4
We introduce here the concept of logistic drivers making the link between the
company’s strategic objectives and their operational translation in the supply
chain. These drivers are in line with the aim of logistics as defined by James
Hesket (1977) in these terms: ‘‘Respond to demand at a given level of service at
the lowest cost’’ and also cross-check with Martin Christopher’s dictum. Four
in total, they incorporate in addition the new environmental component. We
quote:

 logistic reliability;
 logistic efficiency;
 logistic agility;
 eco-logistics.

Far from being limited in action, logistics consequently offers several drivers
in the service of sustainable development. In the following sections we shall
be attempting to show how logistics can reconcile the expectations of share-
holders, customers, the staff, society and the environment by being more reli-
able, efficient, agile and mindful of the preservation of social and environmental
balances.

4.4.1 Logistic Reliability

An organization is called reliable when the probability of it fulfilling its mission
within a given time corresponds to what is laid down in the contract or spe-
cifications. In the case of logistics, reliability of operations consists of the ability
to meet customer demand according to a service rate fixed on the best eco-
nomic, social and environmental terms. Portrayed as a lever in balance, logistic
reliability covers the concepts of respect for the commitment of input and
outcome in accordance with the specifications and pre-defined expectations (see
Figure 4.2). It requires reliable and appropriate resources, skills and knowledge
all the way along the supply chain with regard to the agreed-upon compe-
tencies. Information must be in phase with products. For example, the product
information must correspond to the products, and stocks on the computer
screen must reflect physical inventories.

Customer Customer
service requirements
Correspondence between:
Informations Products
Resources Needs
etc. etc.

Figure 4.2 ‘‘Logistic reliability’’ drives.

Sustainable Logistics as a Part of Modern Economies 43
The application of procedures and the use of equipment and packaging in
accordance with the regulations and/or best practices for secure handling and
transport of products contribute equally to respecting the quality and integrity
of merchandize and limiting its impact on the environment. The global lan-
guage used by players in the supply chain, i.e. the international coding and
marking standards for products and logistic units, just like EDI message
standards, is also a means of producing and exchanging reliable, precise and
complete information.
To counter risks of incidents or crises, input errors, errors in receiving,
labelling, picking, shipping and billing but also delivery delays, possible
wrongdoing, etc., programmes to make information and flows secure, tech-
nologies based on barcodes, radiofrequency (Radio Frequency IDentification,
RFID) and geo-location for tracking products and vehicles, Supply Chain
Event Management (SCEM) and risk pooling systems are already at work.
Logistic reliability measures at the various levels of the supply chain mainly
concern customer service, logistic service and supplier service ratios, as well as
the quality of product information, the record accuracy, the supply chain
inventory visibility, the sales forecast accuracy, the shrinkage rate, the scrap
rate, the incident rate, the procedure compliance rate, the absentee rate, staff
training, the certification of skills, the number of insurance contracts, etc. The
issues for the stakeholders are found in savings in terms of finance, time, nat-
ural resources and image quality. The proper application of procedures and
regulations reduces the risk of breakdowns that may be prejudicial particularly
in the case of storage, handling, transport and the use of perishable and/or
hazardous materials.
‘‘First time round, deliver the right product to the right place at the right time
under the specifications’’ also means reducing on-costs and pollution connected
to delays and the need for re-deliveries. Besides company-internal ratings, no
published study quantifying the cost of non-reliability in the supply chain is
available to date, but we can safely say that it is not negligible. Lastly, reliability
of operation is not just a driver to reduce costs and pollution; it also represents a
business driver tied to satisfaction and customer loyalty. This point is particu-
larly true in an economic context overshadowed by hyper-competition.

4.4.2 Logistic Efficiency

Efficiency is the ‘‘effectiveness/cost’’ ratio. It specifies the achievement of an
objective with minimum engagement of resources. It is not to be confused with
effectiveness, which measures only the achievement of an objective without
reference to the outlay involved. The principles of industrial efficiency call upon
economies of scale, the standardization of products and processes, automation,
improvement of visibility of demand, organization into process flows, demand-
driven systems, the optimization of resources, the sharing of logistic facilities
and IT applications, the pooling of company functions (order processing
management, planning, monitoring, optimization of process flows, etc.) and
44 Chapter 4

Economies of scale, improvement of visibility,

reduction of waste, optimization, collaboration

Figure 4.3 ‘‘Logistic efficiency’’ driver.

intercompany collaboration. They also involve Total Quality Management

techniques for the streamlining of products and processes, the reduction of
costs and the systematic elimination of waste under a continuous improvement
approach. Logistic efficiency is portrayed as a lever reducing the effort required
to achieve an optimum outcome. (Figure 4.3)
Being efficient is being effective in making proper use of resources (human,
informational, material, financial, etc.) with a positive impact upon company
profitability and cash-flow and on the environment, once consumption of
resources is minimized. Developing leverage for internal optimization is the
first stage. This involves, for example, defining inventory and service policy
per segment of products/market and determining key variables like the
order quantity, process batch, safety stock, delivery frequency and delivery
lead-time in terms of customer requirements and economic and environmental
trade-offs.
The repercussions on the fall of inventories and costs of transport with equal
service quality are generally spectacular. We recall here that logistic costs lie
between 5 and 30% of product cost depending on the sector of activity and
company supply-chain maturity. From a systemic viewpoint, ‘‘the whole being
greater than the sum of its parts’’, the participants in the supply chain tend to
go further in search of overall optimization greater than the sum of local
optimizations. This requires collaboration between economic partners. First
applied to product development in the automotive and aeronautical industries
(simultaneous engineering), the practise of intercompany collaboration made
its appearance in the middle of the 1990s with Vendor-Managed Inventory
(VMI) in the fast-moving consumer goods industry.
This revolutionary management model was a genuine intercompany colla-
borative process and made it possible for stocks to be cut down by 50% in retail
warehouses and significantly reduced transport costs by maximizing truck fill
rate while ensuring a service level close to 99%. It was supplemented in 1999
by CPFR (Collaborative Planning, Forecasting and Replenishment),5 a cus-
tomer–supplier collaboration based on plans, promotions and sales forecasts.
Henceforth pitched at extending throughout the industrial sector, collaborative
supply-chain management techniques bring in an increasing number of players
such as logistic service providers and small and medium-sized industries
Sustainable Logistics as a Part of Modern Economies 45
through joint implementation of collaborative warehousing and transportation
programmes.
These approaches are new to most companies which need time to catch up in
their operational modes and technology investments. However, they represent
global efficiency drivers capable of reducing stocks, handling costs, transport
costs, total truck kilometres travelled and CO2 emissions to an unheard-of
degree with no negative impact on customer service. We should recall that
stocks weigh heavily on cash-flow and the growth of business. According to
economists, it is a strategic issue. Thanks to a global vision and optimum
inventory management in the supply chain, companies are able to unlock
tied-up capital so that they increase their cash-flow and finance growth while
at the same time avoiding applying to the banks. The same is true of
warehousing and transport optimized by consolidating different delivery
streams (different products based on different orders from different ordering
facilities, all for the same customer). Efficiency measures rely on different
performance indicators, mainly based on costs. We find, for example, ordering
cost, carrying cost, storage cost, picking cost, transportation cost, price list,
hourly rate, etc., the variables connected with productivity like utilization, yield
factor, turnover ratio, vehicle fill rate, etc. and other variables like demand
visibility, order quantity, lead-time, delivery frequency, rate of standard
pallets, etc.

4.4.3 Logistic Agility

Agility is at the heart of reactive organizations. A reactive company enjoys
flexible facilities, which, if they are lightweight enough, enable it to be agile.
Reactivity is the ability to rapidly adapt production volumes and product
variety to fluctuations of demand and speed up getting a new product to
market. From an agility viewpoint, it is the flexibility and adaptability
of processes, resources, organizations and logistic chains that are sought after
to cope with unstable, turbulent, uncertain and risky environments, and to seize
market opportunities. One of the keys of agility is the systematic reduction of
lead-times in design, sourcing, manufacturing, arranging setup (SMED: Single-
Minute Exchange of Die) and adapting logistic services to fluctuations of
demand.
For hybrid products (half-generic, half-customized), postponement is
another technique that achieves mass customization by offering the customer
greater variety at a lower total cost. This strategy makes use of the advantages
of standardization in terms of reducing costs (low cost production of compo-
nents and generic modules, more flexible generic stocks, more reliable generic
forecasting), while maximizing the commercial offering by customizing pro-
ducts to the local market. By way of example, agility indicators refer typically
to time-to-market, time-to-volume, inventory turnover, flow velocity, cycle
time, run time, tact time, transit time, wait time, down time, lot size, order-to-
cash cycle, cash-to-cash cycle, etc.
46 Chapter 4

Agility, flexibility, reactivity

Figure 4.4 ‘‘Logistic agility’’ driver.

The various time-based strategies also offer prospects for sustainable devel-
opment by enabling local industries to be more reactive while holding less stock
to meet a demand that is more difficult to forecast. In responding to demand
better, quicker and more cheaply, turnover, profitability and working capital
are all up, while the impact on the environment is down, particularly as regards
excess inventory and obsolete products to recycle. To illustrate logistic agility,
we use a flexible lever consisting of quickly serving products and services in
terms of fluctuations in demand, as in Figure 4.4.

4.4.4 Eco-logistics
According to Martinet and Reynaud, ‘‘companies must internalise a part of the
environmental costs and the social costs they would [earlier] have rejected.
Managing sustainable development becomes an element of differentiation’’.6
Today, the application of several sustainable development programmes is
possible, such as ISO14001 certification concerning environmental manage-
ment, the use of renewable energies, reduction of water consumption, sorting
and recycling packaging (the Eco-packaging program) and regional develop-
ment, thanks in particular to the development of local products, the develop-
ment of fair trade, the integration of social workers, etc. But these projects have
to be balanced against the achievement of economic and financial performance
if they are to be sustained and develop.
In terms of logistics, sustainable programmes concern more specifically fuel-
efficient driving, the use of hybrid modes of propulsion or a shift towards
environmentally friendly transport modes. Freight initiatives concern multi-
modal transport combining road, rail, waterway, air freight and shipping to
reduce energy consumption, greenhouse gas emission and traffic congestion.
Limitations on packaging and the increased recyclability of products also
represent practical measures to reduce the ecological footprint of goods. In the
same way, reverse logistics provides the collection, sorting, dismantling and
recovery of value from used products.
Other avenues concern the certification of logistic platforms and buildings
according to the HEQs (High Environmental Quality) method promoted by
the AFILOG association in France. This standard exists in other forms in
Sustainable Logistics as a Part of Modern Economies 47

Economic Environmental

Social

Figure 4.5 ‘‘Eco-logistic’’ driver.

other countries in Europe and reviews various criteria such as flow impact on
the immediate environment, the use of combined transport, energy consump-
tion in offices and warehouses, water management (reduced waterproofing on
the grounds, landscaping of catchment area, saving water for fire extinguishing
purposes, etc.), the treatment of hazardous materials, health quality of air and
of working conditions.
Finally, the transport and logistic trades offer a considerable source of
employment with the development of trade and commerce. According to a
study by the Centre d’Analyse Stratégique,7 it should offer about 700,000 new
positions to be filled between 2005 and 2015, out of a total of 2 million jobs
dedicated to logistics in a country like France.
Because of its approach directed towards social and environmental objectives
allied to economic performance, the eco-logistic driver is represented as a vir-
tuous loop combining the three pillars of sustainable development applied to
logistics (see Figure 4.5).
The measurement of eco-logistic performance potentially uses several indi-
cators such as energy consumption, number of tonnes of CO2 emitted by
logistics platforms and transport (according to weight carried, mode used and
distance travelled), traffic congestion rate, infrastructure simplification rate,
hours of staff training, the number of social disparities, etc.
Combined with the three leverage drivers of reliability, efficiency and logistic
agility – sources of social, economic and environmental benefits – the eco-
logistic lever strengthens the contribution of the supply chain to the social and
environmental aspects of sustainable development.
Mastery of these four logistic drivers ensures optimum customer service
without out-of-stocks or overstocks under the best economic, social and
environmental terms. It requires a structure, an organization and a process to
be set up plus an integrated cross-cutting information system as demonstrated
in the Supply Chain Wheel8 (Figure 4.6).
This figure symbolizes all the logistic supply chain components drawn
from the Supply Chain Masters reference model. To improve their logistic
performance, companies have these drivers available dedicated to reliability,
48 Chapter 4

Figure 4.6 The Supply Chain Wheel.8

efficiency, agility and eco-logistics which clearly have a positive effect on eco-
nomic growth, social development and the protection of the environment.
The whole issue now hangs on the ability of the players in the supply chain, in
particular SMEs, to operate these drivers in accord with all the partners to get
significant leverage on sustainable development.

4.5 Towards Sustainable Logistics in the Service of

Sustainable Development
Following the revision of the European Sustainable Development Strategy in
2006, Member States reaffirmed their determination to promote sustainable
transport with a series of measures concerning:

 behaviour;
 policy on inter-modality development;
 infrastructure developments;
 pricing for the use and management of infrastructure;
 technological improvements.

The guide published in 2007 highlights the Marco Polo programme9 aimed at
encouraging the use of combined transport and developing more efficient and
sustainable transport chains. The idea is to combat congestion, environmental
Sustainable Logistics as a Part of Modern Economies 49
degradation, accidents and the danger of loss of competitiveness of European
industry, which needs to be able to rely on cost-effective and reliable transport
systems to manage its supply chains. However, forecasts on the increase of road
freight in 2013 exceed 60% in the European Union and it is expected to double
in the ten new states by 2020. In this context, greater use of inter-modality is
required. It contributes to better use of existing infrastructure and service
resources by integrating short journey shipping, rail and waterway transport in
the supply chain. The sea highways are an illustration of this with the launch
in 2009 of the sea link between the French Atlantic coast (Nantes) and the
north of Spain (Gijón – Asturias) short-cutting and relieving thousands of
kilometres of international state roads.
Other initiatives for logistics directed towards the requirements of sustain-
able development are under way. For example, in the fast-moving consumer
goods industry, the Global Commerce Initiative (GCI) defined the key changes
required for the future supply chain in 2016.10 Seven areas for improvement are
identified in:

 in-store logistics: includes in-store visibility, shelf-ready products, shopper

interaction;
 collaborative physical logistics: shared transport, shared warehouse,
shared infrastructure;
 reverse logistics: product recycling, packaging recycling, returnable assets;
 demand fluctuation management: joint planning, execution and
monitoring;
 identification and labelling;
 efficient assets: alternative forms of energy, efficient/aerodynamic vehicles,
switching modes, green buildings;
 joint scorecard and business plan.

Thus, the players in the supply chain are called on to play their part in
bringing about the changes that partially cover existing challenges but also
fresh challenges involving sustainable development. According to the GCI
estimates, ‘‘the total impact of this supply chain redesign could potentially reduce
transport costs per pallet to the order of more than 30%, cut handling costs per
pallet to the order of 20%, reduce lead time by 40% and lower CO2 emissions per
pallet to the order of 25%, while also improving on-shelf availability. This does
not include additional energy cost savings stemming from more efficient assets
such as green buildings and fuel-efficient/aerodynamic and jumbo trucks’’.
These improvements hinge on maximizing loads, cutting down empty jour-
neys, training drivers in eco-driving, the renewal of truck fleets and the transfer
from road to combined freight. Apart from eco-technological innovations,
collaboration between the players in the supply chain is the sine qua non for
the programme’s success. While customer–supplier collaboration has been
developing successfully for fifteen years driven jointly by ECR (Efficient
Consumer Response), VICS (Voluntary Inter-industry Commerce Solutions)
and GS1 organizations in different models (Vendor-Managed Inventory,
50 Chapter 4
Collaborative Planning, Forecasting and Replenishment, stream consolidation,
cross-docking, better traceability, etc.), it must be backed up and henceforth
take in the transporters, warehouse operators and the small and medium-sized
industries hitherto not generally incorporated in this approach.
To do this, real-time information sharing and particularly point-of-sales data
sharing in standardized formats must become general practice between retai-
lers, manufacturers, logistic service providers and suppliers. This development
is designed to enhance visibility of demand and events on the supply chain with
a view to limiting out-of-stocks and further optimizing the use of resources. To
reduce stocks, transport costs and CO2 emissions, the emergence of colla-
borative warehouses and hubs – where flows from different industries and
different retailers can be bulked and cross-docked before being distributed
optimally to consumers (to city stores, local stores and home delivery via shared
facilities) – will revolutionize the way the supply chain works today.
According to the Global Commerce Initiative, the challenges ahead will force
the players in the supply chain to change their operation to a future model
leading to sustainability and new business opportunities. It is actually under way.
Companies are by no means helpless. Several technologies and support tools are
available today such as global communications standards (product identifica-
tion, barcodes, RFID, EDI), Supply Chain Management software, tracing and
tracking tools, the optimization of shipping units and of secondary and tertiary
packaging, etc. The real challenge lies elsewhere: it involves adopting in unison
‘‘new ways of working together in the physical supply chain (including management
of required investments, capabilities, organisational resources and design, incentives
and measures, social regulations like working hours, etc.).11
To achieve this, the key success factor is to convince tens of thousands of small
and medium-sized businesses to join the future supply chain so as to reach the
critical mass necessary for the reduction by 20 to 40% of the impact of supply
chain activities on the environment. Of course, this objective has to be reconciled
with the needs of economic growth and the sharing of the gains between the
players while supporting purchasing power and regional development.

4.6 Conclusion
Representing an essential function to trade, logistics is a complex system made
up of a multitude of players and interrelationships between suppliers, manu-
facturers, logistic service providers and the retailers whose job it is to deliver to
the end user the product or service required under the best economic, social and
environmental conditions. Meanwhile, its impact on the environment is impor-
tant because of the many forms of pollution generated by road transport – the
major delivery mode used today. The transport sector consumes 70% of all
petrol consumed in the EU and produces 21% of all greenhouse gas emissions.
At the same time, it is well recognized that transport is the very life blood of a
modern economy and its effects go far beyond the direct economic effects of
employment and the added value of the transport sector in an economy.
Sustainable Logistics as a Part of Modern Economies 51
In this chapter, we have reported the principal initiatives launched in Europe
to ensure that transport systems meet society’s economic, social and environ-
mental needs while minimizing their undesirable impacts on the economy,
society and the environment. But the biggest challenge seems to come from the
difficulty of getting the supply chain players to work together on the three
aspects of sustainable development and to prepare all the people involved for
the new world of collaboration. To assist them in working together, we have
outlined the purpose of ‘‘modern’’ logistics and highlighted the existence of
the four logistic drivers of individual, joint and global performance. Taken
separately, these aim at improving reliability, efficiency, agility and relations
with the environment. Operating together, they prove to be powerful perfor-
mance activators in the service of economic growth, social development and
protection of the environment. This includes shared success measures across
financial, operational, environmental and consumer-based dimensions that
drive outcomes throughout the value chain and greater overall value for all
stakeholders.
Finally, we note that the economic, social and environmental aspects of
logistics are indissociable and all three participate in the emergence of this
strategic function in the service of sustainable development, alongside the
sustainable solutions of eco-design, eco-industrialization and eco-production
used in industry.

References
1. AFNOR, NF X 50-600, Logistique – Fonction et de´marche logistiques,
AFNOR 2005, 12, 4.
2. Cf. Barometre ECR France IRI based on the analysis of out-of-stocks
(OOS) of 61 categories of products in 1449 hypermarkets in France,
2008.
3. S. Pasi, Chargements moyens, distances et parcours à vide dans le transport
routier de marchandises, Eurostat, 2007, 8, 6.
4. M. Christopher, Supply Chain Management, Create networks with high
added value, Cre´er des re´seaux à forte valeur ajoute´e, Village Mondial, 2005,
318, 288.
5. Collaborative Planning, Forecasting and Replenishment Voluntary Guide-
lines; Roadmap to CPFR, VICS, 1999.
6. E. Reynaud, De´veloppement durable et entreprise: vers une relation sym-
biotique? CNRS, 2003, 15, 9.
7. Rapport du groupe, Prospectives des métiers et qualifications, Les me´tiers
en 2015, Centre d’Analyse Strategique, DARES, 2007, 179, 123.
8. T. Jouenne, How to contribute to the competitiveness and development of
SMEs by using APICS concepts, Revue Française de Gestion Industrielle,
2008, 27(3), 3, 7.
9. European Commission, A sustainable future in our hands, European Com-
munities, Brussels (2008), http://bookshop.europa.eu/eubookshop/download.
52 Chapter 4
action?fileName=KA7007020ENC_002.pdf&eubphfUid=602686&catalog
Nbr=KA-70-07-020-EN-C (retrieved 21.06.2009).
10. Future Supply Chain 2016, Serving consumers in a sustainable way, Global
Commerce Initiative, Cap Gemini, 2008, 52, 24.
11. Future Supply Chain 2016, Serving consumers in a sustainable way, Global
Commerce Initiative, Cap Gemini, 2008, 52, 46.
12. J. T. Mentzer et al., Defining Supply Chain Management, Journal of Busi-
ness Logistics, 52(2), 2001, 5, 41.
CHAPTER 5

Sustainable Solutions for

Consumer Products
FRANK ROLAND SCHROEDER

+
Henkel AG & Co. KGaA, Henkelstrasse 67, D-40589 Dusseldorf, Germany

5.1 Introduction
‘‘Everybody in the consumer industry, from fast-food services to big-box
retailers, have put out their green agenda to assure customers, regulators,
shareholders and Non Governmental Organiations (NGOs) that they are
walking toward the right, ethical direction. Most of the key initiatives made by
global consumer businesses last year deal with reducing their carbon footprint,
such as using or selling more environmentally responsible products, reducing
carbon dioxide emissions in stores or supply chains, phasing out ingredients
and raw materials that they deem hazardous, reducing waste and pushing their
supply chains to improve their own sustainability, among others.’’1 This
statement reflects the current worldwide concern about climate change and the
state of the environment and consequently consumers are asking for more
sustainable products. Consumer goods manufacturers have to take these con-
cerns seriously and develop new types of product concepts, which combine
superior performance with improved environmental profile and greater social
benefits. Since there is no clear cut definition on how a sustainable product
might look, this chapter describes those elements in a fast-moving consumer
goods life-cycle that might contribute to the overall sustainability profile.
Detergents are chosen as an example since a lot of relevant information is
available for this product category.

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

53
54 Chapter 5
5.2 Demographic Dynamics and Global Megatrends
The human population has been increasing constantly since the beginning of
mankind. Between the years 1800 and 2006 population has increased more than
six-fold (see Figure 5.1). In parallel to this demographic development per capita
consumption and consequently total production volume have been growing
proportionally (see Figure 5.2). This process has been accelerated even further
by globalization.
However, with respect to population development there are striking differ-
ences between the northern and the southern hemisphere. In the developed
countries located in the northern hemisphere, population growth is generally
slow or even stagnant in some countries, resulting in a fundamental change in
societal structure. The development in Spain between 1995 and 2005 may serve
as a typical example:3

 0.7% p.a. population growth but 20% more households in 10 years;

 56% more smaller households (1 and 2 persons) in 10 years;
 30% more senior households (465 years old) in 10 years;
 50% decrease in women’s unemployment rate in 10 years.

All these factors, in addition to an increase in consumers’ income, result in a

profound change in consumer purchasing behaviour. In parallel to the growing
purchasing power, consumers feel that they are ‘‘poor in time’’. Convenience is
becoming a driver of the market, with slogans like ‘‘open and serve’’ or ‘‘boil and
eat’’. In the detergent industry this results in an increase of single dose products.
Moreover there is an increasing concern about health and environmental
matters. Consumers that are seen as environmentally aware, socially attuned
and with a view of the world that takes into account personal, community and
planetary outcomes are often characterized as LOHAS (Lifestyle Of Health
And Sustainability). LOHAS has become a megatrend, a term made popular by
John Naisbitt,4 since the increased desire for healthier and more sustainable
lives is leveraging the sociological developments described above. The LOHAS
construct has been adopted and embraced around the world over the past

6 6,3
6.3
5,3
5.3
4,5
4.5
3,7
3.7
3

1800 1960 1970 1980 1990 2000 2006

Figure 5.1 World population in billions.

Sustainable Solutions for Consumer Products 55

(a) 29,3
29.3
[kg/capita]

20,6
20.6
18,8
18.8

13
11 17,3
17.3
9,8 15,2
15.2
7,94
7.94
12
2,2
2.2 8 2.7
2,7 3,5
3.5
1,9
1.9
1.1
1800 1960 1970 1980 1990 2000 2003 2006

(b) [in Mio mto] 180

130
100

60 105
43 81 50
30 59
14.8 18.9
6.7 31
3,3
3.3 8,4
8.4
1800 1960 1970 1980 1990 2000 2003 2006

plastics oils and fats synthesis and semi-synthesis fibres

Figure 5.2 Per capita consumption (a) and total production (b) for major chemical
raw materials.

decade. In western countries, such as the USA and Europe, LOHAS is an

industry term while in Japan and East Asia LOHAS is a widely recognized
consumer term. International research estimates the LOHAS marketplace has a
global value in excess of 500,000 Mio $.
According to an analysis of the consumer market in Australia5

 nearly 4 million adult Australians (26% of the adult population) are

LOHAS aligned;
 individuals with a LOHAS outlook are drawn from all parts of society;
their values and world view are not strongly tied to income, geography or
gender.

LOHAS-aligned consumers seek to integrate healthier, more sustainable

options into all aspects of their lives by making consumption decisions for
products and services in key market segments including:

 food and nutrition – e.g. organic and natural food, vitamin supplements;
 home life – e.g. natural cleaning products, efficient appliances, recycled
paper;
56 Chapter 5
 buildings and energy – e.g. water tanks, solar hot water, ‘‘green’’ energy;
 work and money – e.g. socially responsible investing, ‘‘green’’ loans.

Contrary to the demographic development in the developed world, many

regions in the southern hemisphere are experiencing strong population growth,
so that the population of the Earth as a whole is increasing (Figure 5.1). At the
same time, the growing prosperity of emerging countries such as Brazil, China
and India is matched by their greater consumption of resources and energy.
Crucial factors include greater mobility and changes in eating habits. Many
emerging countries are experiencing a growth in demand for ‘‘high-quality’’
foods with a high proportion of animal protein. Since the production of one
kilogram of animal-based food needs about nine kilograms of grain there is a
considerable increase in water, fertilizers and land needed to fulfil the demand.
This change is especially dramatic in countries where vegetable protein has
always played a key role. China may serve as an example where meat con-
sumption has doubled over the last twenty years.6 All these factors manifest
themselves in a mounting scarcity of raw materials and in higher prices.
The change in eating behaviour not only reinforces pressure on resources but
additionally there is a marked effect on the climate. Intensive livestock farming
of ruminants results in methane (CH4) as a waste product of digestion.
Methane, weight for weight, is 21 times more potent as a greenhouse gas than
CO2. Overall, the agricultural sector’s emissions account for 14% of all
greenhouse gases.7
The emission of greenhouse gases and the associated rise in temperature
have far-reaching consequences in several areas. Rising temperatures enable
pests and their vectors (i.e. host organisms transmitting pathogens) to spread
more easily, resulting in a greater risk of infectious diseases and even epidemics
occurring. This applies especially to densely populated tropical regions, where
the population in conurbations is expanding disproportionately rapidly. Hence,
appropriate measures have to be taken to counter the possible spread of
infectious diseases associated with the rise in temperature.
Rising temperatures also increase the pressure on freshwater resources. 96% of
the Earth’s freshwater is locked up in glaciers and geological strata. Of the
remaining 4%, equivalent to 110,000 Mio m3, humans use 4,000 Mio m3 for their
needs. There is a qualitative rather than a quantitative shortfall here, as 1 billion
people do not have access to clean drinking water. The development of agri-
culture is putting additional stress on freshwater resources since agriculture is
responsible for 70% of ‘‘blue water’’ consumption, i.e. liquid water in rivers, lakes
and groundwater aquifers. Food production to satisfy a person’s daily dietary
needs takes about 3000 litres of water – a little more than one litre per calorie.6
Although it is virtually impossible to carry out a quantitative analysis of
all these factors and their effects on future development, some of them can be
illustrated very well in qualitative terms (arrow model). Given the increasing
population of the southern hemisphere and the increase in living standards in
these regions, raw materials will steadily become scarcer. At the same time there
will be growing pressure on water resources. This, and a general rise in
Sustainable Solutions for Consumer Products 57
temperatures, will tend to promote the incidence of infectious diseases and
impair hygiene. Scarcer resources, growing pressure on water resources and
poorer hygiene are the three megatrends on which we will have to focus in
future (see Figure 5.3).

5.3 Life-Cycle of the Washing Process – an Example

for Sustainability in Consumer Goods
The washing process can be seen as an example of how an industrial sector can
provide technology and innovation to improve the sustainability profile of a
market segment that is relevant to virtually all consumers.
The global household detergent and cleanser market had a value in 2008 of
86,565 Mio h.
The washing process and the technology of laundry detergents it requires are
an integral part of human cultural history.8–10 Currently, washing is carried out
in all regions of the Earth under widely varying environmental and economical
conditions. Nonetheless, consumers have very clear expectations. A detergent
used in a household has to deliver excellent performance in soil removal and
general cleaning. The consumer wants to save energy and money through a low
washing temperature and short washing cycle. The textile fibres and the colour
must look like they did before washing, or even better. The consumer wants a
detergent that is simple and convenient to use and has an individual appeal
through a special product form or aesthetics such as perfume. Clustering the
demands from consumers in three different claim dimensions results in:

 performance;
 convenience;
 aesthetics.11

The functions of detergents, however, go beyond laundry care and aesthetic

considerations as they make an important contribution to hygiene and there-
fore to the maintenance of good health. Obviously those megatrends described
earlier, like scarcity of raw materials and freshwater as well as increasing
demand for better hygiene, clearly impact the washing process.
For an assessment of the sustainability profile, it is not enough to look at
laundry detergent surfactants in isolation; the whole life-cycle has to be taken
into account.12 In order to arrive at soundly based conclusions, the total
washing process must be analyzed. To enable the findings for different systems
to be compared, all results must be related to a functional unit e.g. the cleaning
of 1 kg of laundry. A systematic analysis of the total process is then carried out
in the context of a so-called life-cycle assessment (LCA), in which all the sys-
tem’s inputs and outputs are systematically recorded and assessed.13
Figure 5.4 gives a schematic overview of the different stages of the washing
process. The most relevant ones are discussed below from the point of view of
sustainability.
 58
Packaging

growing
population
Packaging waste
Fresh water

Raw materials
Food

Energy
plants

cattle
rice Drought

Mineral oil Biodiversity

CO2 CH4
Infectious diseases

Global warming (Green house effect)

Chapter 5
Rising sea level Flooding

Figure 5.3 Arrow model to illustrate development megatrends.

Sustainable Solutions for Consumer Products 59

Raw Materials:
Mineral Oil,
Naturals, Minerals
Transportation

Manufacturing
Disposal of Ingredients
Cradle to Gate
includes 4 stages

Cradle to Grave
includes 7 stages

Manufacturing of Detergents
Use phase + Packaging
Transportation + Trade

Figure 5.4 Key phases of the life-cycle of the washing process.

5.3.1 Raw Materials

Household detergents (whether liquid or powder products) are mixtures of
inorganic and organic chemicals. Detergents for household and institutional
use can be categorized into:

 surfactants (organic);
 builders (typically inorganic);
 bleaching agents (typically inorganic);
 auxiliaries.

Inorganic chemicals are obtained either chemically or by mining of natural

resources. In general, it is possible to recover inorganic chemicals from waste
streams (recycling), but this usually requires considerable technical effort and
the consumption of correspondingly large amounts of energy. Such processes
have therefore not yet been used on an industrial scale.
Most organic chemicals are derived from mineral oils, and in earlier times
they were also obtained to a large extent from coal. Since the increasing
pressure on the Earth’s resources is a megatrend, renewable raw materials have
also been increasingly used as a source of organic chemicals in recent years14
and especially in detergents.15 The most important feedstock for chemicals
based on renewable raw materials are oils derived from plants or materials
generated by means of biotechnical methods.
Palm kernel oil and coconut oil are the most common plant oils for the
production of surfactants. Through chemical reactions, the oils are
60 Chapter 5
transformed to yield glycerol, as well as surfactants with medium carbon chain
lengths (C12–14), which have a number of especially advantageous properties for
washing and cleaning processes. Fatty alcohol sulfates, fatty alcohol ether
sulfates and fatty alcohol ethoxylates are typical representatives (see Chapter
9.1). All these surfactants are usually made up of a combination of a chemical
moiety deriving from renewable raw materials and a part based on inorganic or
classical organic chemistry derived from mineral oils. Product concepts based
on the greatest possible use of renewable resources have led to the development
of sugar-based surfactants by reacting fatty alcohols with glucose yielding alkyl
polyglycosides (APGs-surfactants).16
Fermentation is the conversion of biological feedstock to functional chemical
substances on an industrial scale with the help of specialized micro-organisms.
Organic acids like citric acid and lactic acid as well as enzymes are typical
detergent ingredients manufactured by fermentation processes on an industrial
scale. The biological feedstock is typically relatively cheap and can be either
derived from agricultural crops (e.g. starch, which is obtained from corn or
wheat) or biological waste materials (e.g. molasses, which is a residue in the
production of sugar).
At first sight there are two striking advantages of chemicals based on
renewable raw materials. Since plants use atmospheric CO2 for the build-up of
biomass they are, in theory, climate neutral. Moreover, plants are a nearly
unlimited resource for renewable raw materials.14 On the other hand energy for
processing and transportation needs to be taken into account. Additionally,
many crops used as sources for vegetable raw materials require fertilizers,
which are one source of agricultural greenhouse gases. Therefore, the full effects
of renewable raw materials on the generation of greenhouse gases can only be
evaluated by LCA.
To explore the full picture with respect to sustainability, social factors have
to be taken into account as well. At present, the effect of the increased use of
renewable raw materials on the availability and price of food is a subject of
intense debate. It is not yet clear which factors are responsible for the recent
volatility in food prices. While the World Bank estimates the influence of
biofuels at 75%, the FAO also points to other factors that contribute to the rise
in prices. These include changed nutritional habits in many emerging countries,
poor harvests and increased fuel prices, which account for about 30% of
production costs.
In 2008, the total vegetable oil market amounted to 128.3 Mio mto (see
Chapter 9.2). Palm oil, with 38 Mio mto, accounted for the largest share. 80% of
palm oil comes from Southeast Asia (Malaysia and Indonesia). Palm kernel oil
and coconut oil both provide medium carbon chain oils (C12–14) often referred to
as laurics. Together they account for 7.4 Mio mto. While palm oil is mainly used
for nutritional purposes palm kernel oil, which can be seen as a side product of
palm oil production, is preferred for the production of surfactants. Against the
background of a growing demand for biofuels, there has been an increasing
demand for vegetable oils as well that has increased the pressure on primary
forests (rainforests). While only 12% of Malaysia’s primary forest is still intact,
Sustainable Solutions for Consumer Products 61
Indonesia has 25%. To further protect high conservation areas (e.g. primary
forests, peat lands) and the animals that live in them, the Roundtable on Sus-
tainable Palm Oil, an alliance of palm oil growers, down stream users, non-
governmental organizations and financing institutes, has developed a certifica-
tion system intended to ensure that vegetable oils – and above all palm oil and
palm kernel oil – are produced under sustainable conditions (see Chapter 9.4.2.2).

5.3.2 Logistics
From an energy perspective (this also includes the generation of greenhouse
gases) logistics plays a minor role in the life-cycle of a detergent. Nevertheless,
there are clear differences between the various modes of transport. One metric
ton of freight transported by ship generates about 6–11 kg CO2 eq km 1, while
its transport by rail and road generates respectively 39 and 117 kg CO2
eq km 1.17 An optimized transport mode mix can therefore be devised to take
account of the geographical circumstances.

5.3.3 Production
In general, there are basic differences between the production of liquid and
powder laundry detergents. In terms of energy, liquid detergents are more
favourable, as no drying steps are required.18 Other opportunities for opti-
mizing production with respect to the use of primary energy include the recy-
cling of process water, and combined heat and power generation.

5.3.4 Use Phase

Based on figures retrieved for Germany in 2006, laundry washing accounts for
only 3% of households’ total energy19 and for 12% of households’ water
consumption,20 respectively.
If the washing life-cycle is looked at in isolation, the use phase is the
most critical with regard to energy consumption with the heating of the
washing water playing the most important role. This is especially true for
countries with a high prevalence for washing at elevated temperatures. If energy
is generated from the combustion of lignite and coal, considerable amounts
of greenhouse gases (mainly CO2) and solid waste (slag and ash created
by burning solid lignite and coal) are generated. If the main source of energy
is hydroelectric or nuclear power plants, the contribution to the greenhouse
effect is low, although the use of nuclear energy may entail other problems.
Reducing the washing temperature is therefore a key means of saving energy
and reducing greenhouse gases as well as waste material. The main challenge
is to retain the same level of washing performance and hygiene at lower
temperatures.
62 Chapter 5
5.3.5 Disposal Phase
Relative to other anthropogenic activities, the disposal phase plays only a
minor role as regards energy consumption and the generation of greenhouse
gases. However, since the wash water is discharged to the sewer and, depending
on the country, this wastewater is treated or it is discharged directly into
the environment, the contribution of detergent ingredients to the loads
in surface waters is considerable.21 Surfactants in particular must be viewed
critically. Their surface activity makes them relatively toxic to water organisms,
and they show the potential to produce easily visible foam on surface waters.
Aquatic toxicity is an inherent property of these substances, so their biode-
gradability is especially important, as it reduces the amount of surfactants in
surface waters.
For this reason, the industry started to develop biodegradable surfactants in
the 1950s. In parallel, screening tests were devised, which allow biodegradation
potential to be verified in the laboratory. The OECD has officially recognized
six of these test methods (OECD 301 A–F) that measure biodegradability in the
presence of oxygen. They involve inoculating relatively high concentrations of
surfactants with relatively small amounts of micro-organisms from public
sewage treatment plants. The OECD test methods differ in how the biode-
gradation is monitored. If the limit values (60 or 70% biodegradation) are
reached within the specified time period, the test substance can be described as
‘‘readily biodegradable’’. There are also test methods that determine biode-
gradability in the absence of oxygen (anaerobic biodegradability). The data
obtained is relevant for, e.g., sediments or the digesters of sewage treatment
plants. Finally there is also the metabolites test. A positive result in the
metabolites test indicates that no poorly biodegradable molecular groups are
still present.
Subsequently, an efficient method of ecological risk assessment was devel-
oped. It is based on a comparison of the predicted environmental concentration
(PEC) and the predicted no-effect concentration (PNEC). If PEC r PNEC, the
substance under consideration is expected to pose no ecological risk in the
environment. A comprehensive review about the ecological profile was pro-
vided by J. Steber.21
In the HERA project,22 a European voluntary initiative commissioned by
A.I.S.E.23 (representing the formulators and manufacturers of household and
industrial and institutional cleaning products) and CEFIC24 (representing the
suppliers and manufacturers of the raw materials), the most important ingre-
dients of laundry detergents are subject to a systematic risk assessment. This
covers product safety from an ecological and human health perspective. The
underlying reports are available to the public via the HERA website.

5.4 Sustainability Profiles of Detergent Formulations

At the beginning of the industrial revolution, the societal focus was clearly on
increasing production and multiplying capital. Only in individual companies
Sustainable Solutions for Consumer Products 63
did additional considerations play a role. In the second half of the nineteenth
century, as the power of the workers increased, social issues also moved into
the foreground. Occupational health, working hours and pay now played an
increasingly important role. Nature and environmental protection were still
neglected, however, and it was not until the 1960s that environmental protec-
tion became a major social, political and industrial issue.
But how to improve sustainability in this context? Improving sustainability
implies that all three elements, the economic, ecological and social factors, need
to be developed in parallel to achieve an overall optimum for the whole system.
If a product or service is optimized with respect to their sustainability profile
the optimization process can be best illustrated by using a graphic model
(Sustainability Profile Circle – SPC, Sustainability Masters). The starting point
of the optimization is a group of three equal circles, representing the economic,
ecological and social dimensions, with a surface area that is chosen to be 100%
by default. The circle’s centres are connected, resulting in an equilateral triangle –
the ‘‘sustainability zone’’. Changing relevant parameters will impact the surface
area of the appropriate circle – and consequently the shape and area of the
resulting triangle (Figure 5.5).
One example makes this clear. A household cleaner based on a sugar ether as
a surfactant would certainly have an excellent ecological profile, given its ready
biodegradability and the renewable raw materials that serve as its basis. The
circle representing the ecological dimension would therefore grow. These
surfactants do not have such good performance characteristics, however, so
that the social dimension reflecting consumers’ benefit would tend to shrink.
In view of the higher price, the consumer would have to pay more (causing this
circle to shrink still further) or the producer’s profit margin would be reduced

Figure 5.5 SPC model, Sustainability Masters to describe the sustainability profile of
an ecological cleanser – reference scenario; all circles set to 100%.
64 Chapter 5

Figure 5.6 SPC model, Sustainability Masters to describe the sustainability profile of
an ecological cleanser – environmental, social and economic circles set to
120, 70 and 70% of original area, respectively.

Figure 5.7 SPC model, Sustainability Masters to describe the impact of compaction
on the sustainability profile – environmental, economic and social circles
set to 120, 120 and 100% of original area, respectively.

resulting in a decreased economic profile. By using the SPC approach it can

be clearly visualized that a growing ecological benefit alone will not increase the
area of sustainability if there is a decrease in the economic and social profile (see
Figure 5.6).
Sustainable Solutions for Consumer Products 65
25
Another example: modern laundry detergents are made more compact in
order to reduce the environmental burden of disposal to receiving surface
waters. Moreover, these compacted products show a positive environmental
profile since they require less material for packaging and less energy for
transportation. At the same time material and logistics costs decrease as well,
resulting in an increase of the economic dimension. Since there is no impact on
the performance, provided the detergents are added in the correct dosages, the
area of the ‘‘social circle’’ would therefore remain constant. Overall this
example would result in an increased sustainability zone (see Figure 5.7).

5.5 Conclusion
Against the background of a growing concern about the global climate and the
general state of the world’s environment, sustainability became a megatrend in
recent years. Consumer goods manufacturers have to take public concerns and
the demand of consumers into account and develop new product concepts. To
fulfil all requirements, a holistic approach is needed that takes all single phases
of a product’s life-cycle into account. In the case of laundry detergents this
encompasses the raw material extraction, the manufacture of the ingredients
and the formulation of the end product as well as transportation, consumer use
of the product, disposal and treatment in the wastewater treatment plant. To
collate all this information, ‘‘Life-Cycle Assessment’’ provides useful infor-
mation. To further consolidate this information and visualize the impact on the
area of sustainability, the Sustainability Profile Circle (SPC) model, Sustain-
ability Masters is introduced. Using the SPC approach the individual impact
of ecological, economical and social parameters can be assessed separately and
their contribution to a ‘‘sustainability zone’’, where these parameters converge,
can be displayed.

References
1. D. De Guzman, ICIS Chemical Business, 30 Jan. 2008, http://www.icis.
com/Articles/2008/02/11/9096925/consumer-industry-increases-sustainability-
initiatives.html (retrieved 16.10.2008).
2. R. Höfer and J. Bigorra, Green Chem. Lett. Rev., June 2008, 1(2), 79.
3. C. Miñarro Garcı́a, in Comunicaciones, 36 Jorn. CED, Barcelona, 2006,
p. 219.
4. J. Naisbitt, Megatrends, Warner Books, Clayton, 1982.
5. Research and Markets, Detailed Analysis of the Lifestyles of Health and
Sustainability Consumer Market in Australia, Mobium Group, Dublin,
Aug 2007, http://www.researchandmarkets.com/reports/c86981 (retrieved
27.10.2008).
6. Anonymous, Agricultural Ecosystems, Facts and Trends, World Business
Council for Sustainable Development/IUCN, Gland, Conches-Geneva,
2008.
66 Chapter 5
7. Stern review on the economics of climate change, Annex 7g: Emissions from
the agriculture sector, http://www.hm-treasury.gov.uk/stern_review_final_
report.htm (retrieved 22.11.2008).
8. F. Bertrich, Kulturgeschichte des Waschens, Econ-Verl., Düsseldorf, Wien,
1966.
9. E. Smulders, Laundry Detergents, Wiley-VCH, Weinheim, 2002.
10. E. Smulders, W. von Rybinski, E. Sung, W. Rähse, J. Steber, F.Wiebel and
A. Nordskog, in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-
VCH, Weinheim, online posting 2007.
11. U. Lehner, Surfactants Surfing Around the World, 6th World Surfactant
Congress, CESIO, Berlin, 2004.
12. M. Stalmans, H. Berenbold, J. L. Berna, L. Cavalli, A. Dillarstone,
M. Franke, F. Hirsinger, D. Janzen, K. Kosswig, D. Postlethwaite,
T. Rappert, C. Renta, D. Scharere, K. P. Schick, W. Schul, H. Thomas and
R. Van Sloten, Tenside Surf. Det., 1995, 32(2), 84–109.
13. C. Gutzschebauch, G. van Hoof, H. King, H. J. Klüppel, E. Saouter and
T. Taylor, 2001, Life Cycle Assessment of Washing Systems: Results from
the AISE-LCA Working Group, European Climate Change Program
(ECCP), Renewable Raw Materials Working Group 5, AISE presenta-
tion; E. Saouter, G. van Hoof and P. White, in Handbook of Detergents,
Part B: Environmental Impact, ed. U. Zoller, Surfactant Science Series,
121, Marcel Dekker, New York, 2004, p. 195.
14. W. Umbach, in Perspektiven nachwachsender Rohstoffe in der Chemie, ed.
H. Eierdanz, VCH, Weinheim, 1996.
15. F. R. Schroeder, in Nachhaltige Chemie, ed. M. Angrick, K. Kümmerer
and L. Meinzer, Metropolis Verl., Marburg, 2006.
16. K. Hill, W. von Rybinski and G. Stoll, ed., Alkyl Polyglycosides, VCH,
Weinheim, 1996.
17. Data Ecoinvent 2.1, www.ecoinvent.org.
18. M. Franke, H. J. Klüppel, K. Kichert and P. Olschewski, Tenside Surf.
Det., 1995, 32, 508.
19. K. Schmitt, Ökoinstut, Freiburg, personal communication.
20. BDEW Bundesverband der Energie und Wasserwirtschaft, Berlin, 2008, http://
www.bdew.de/bdew.nsf/id/DE_7DBKHD_Grafiken (retrieved 01.12.2008).
21. Miljøstyrelsen, Environmental and Health Assessment of Substances in
Household Detergents and Cosmetic Detergent Products, Miljømini-
steriet, Environmental Project 615, 2001, http://www2.mst.dk/common/
Udgivramme/Frame.asp?http://www2.mst.dk/udgiv/publications/2001/87-
7944-596-9/html/helepubl_eng.htm (retrieved 23.11.2008); E. Smulders, W.
Rähse, W. von Rybinski, J. Steber, E. Sung and F. Wiebel, Laundry
Detergents, Wiley-VCH, Weinheim, 2002.
22. http://www.heraproject.com.
23. http://www.aise.eu.
24. http://www.cefic.be.
Sustainable Solutions for Consumer Products 67
25. Concentrated Laundry Detergents Become Latest Trend in Green Retail
Packaging, http://www.sustainableisgood.com/blog/2007/09/concentrated-
la.html; Wal-Mart to Only Sell Concentrated Liquid Laundry Detergent
by 2008, http://www.sustainableisgood.com/blog/2007/09/wal-mart-to-onl.
html (retrieved 23.11.2008); Sustainability Report 2006, Henkel KGaA,
Düsseldorf, 2007, p. 20; M. McCoy, C&EN, January 29, 2007, 85(5),
13–19.
CHAPTER 6

Sustainable Solutions for

Nutrition: A Consumer
Expectation
SVEN THORMAHLEN

Danone Research, Centre Daniel Carasso, Direction Générale, Route

départementale 128, F-91767 PALAISEAU CEDEX, France

6.1 Introduction
Sustainable development has become a subject of animated public discussion in
recent years. The term covers economic, social and environmental dimensions.
The heightened interest in the subject can be explained by challenges and
threats from already observed or merely anticipated changes in climate and
environment. Innovative companies have identified the field of sustainable
development as a source of differentiation and opportunity. Consumers have
become very sensitive to the environmental impact of their consumption habits.
They have begun to modify their behaviour and have come to expect from
consumer brands the inclusion of sustainability aspects in their product design
and marketing. At Danone, sustainable development has always been a point
of great importance and attention. Over the years stable practices were devel-
oped inside the company: fundamental social principles; a business, environ-
mental and health and nutrition charter; as well as a biodiversity charter; form
the company’s approach to sustainable growth. It is of importance for the
company to build a trust relationship with consumers, to guarantee absolute
product safety, to respect the environment and to be concerned with the social

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

68
Sustainable Solutions for Nutrition: A Consumer Expectation 69
and societal impact to the various markets where the business is present.
Equally important is the solid foundation of mutually profitable relationships
with suppliers. This chapter reports on recent progress in sustainable devel-
opment efforts, which were undertaken by the company. In the area of agri-
culture Danone decided to become more involved with upstream processes in
order to assure more sustainable processes for the production of key agri-
cultural ingredients. For Danone’s water business a comprehensive water
source protection policy guides all businesses in all markets.

6.2 Sustainability in Food and Nutrition

Food and drink satisfy the elementary needs of humans. They provide liquids
and calories to feed the human metabolism. Eating and drinking also con-
tribute to social togetherness with family or friends. Achieving food security at
a global level for this and future generations is a key element of sustainable
development. The value chain of sustainability in the food industry1 as a pre-
requisite for high-quality food products and nutrition starts with green agri-
culture, animal husbandry and fishing followed by sustainable food production
and processing, packaging, retailing and service.
The world’s most pressing problem is poverty and associated hunger
(Figure 6.1). 600 million children live in absolute poverty (SCF, Beat Poverty
2003). Over 1 billion people live on less than $1 a day with nearly half the
world’s population (2.8 billion) living on less than $2 a day (UN HDR, 2003).
Eradication of hunger and extreme poverty is now the first millennium goal of
the United Nations.2,3
Agricultural intensification including growing of bioengineered crop vari-
eties, an agro-industrial model that stresses uniformity and standardized
technologies maximizing yields of commercial crops have fuelled a global food
system during the last decades. As a result in North and Latin America, for
example, agricultural production per agricultural worker has more than dou-
bled between 1980 and 2003 and also crop production per hectare has seen a
noticeable increase.4 On the other hand, hunger is predominantly a problem of
rural regions, where families who own smallholdings often possess too little
fertile land of their own, live in agriculturally disadvantaged regions or are
denied access to credits for equipment or seeds and have no alternative source
of employment or income. Ensuring the income and the long-term productivity
of the rural production in order to combat hunger5 and to achieve sustainable
agriculture and rural development is a challenge that has been entrusted to the
FAO by the Rio Conference. More particularly for the introduction of the
micro-credit instrument (giving loans to poor people without sufficient financial
security) Muhammad Yunus and Grameen Bank have been awarded the Nobel
Peace Price.6
Prerequisites for a pro-poor policy in a globalizing world are peace,
democracy and good governance. ‘‘Good governance’’ comprises stimulation
of the development process by national governments, banishing corruption,
70 Chapter 6

Figure 6.1 FAO hunger map. http://www.fao.org/es/ess/_faostat/foodsecurity/

FSMap/_map14.htm, published 2007.

ensuring civil order, providing access to credits, investing in human capital

(education, health, sanitary services), provision of physical infrastructure and
facilitating institutions (property rights, predictable dispute resolution, infor-
mation and communication).7
Since the BSE crisis, consumer protection is regarded as an essential element of
sustainability in food production.8 The need to enhance food safety, ensure
consumer protection, strengthen consumer confidence, by setting requirements
for food safety schemes and for improved cost efficiency throughout the food
supply chain, has led to the launch of the Global Food Safety Initiative (GFSI)
in May 2000. The purpose of the GFSI is to monitor issues around food safety
standards (The Global Standards Project). It has developed a Guidance Docu-
ment, against which food safety standards for manufacturing can be bench-
marked. The benchmark requirements in the Guidance Document are made up
of three key elements: Food Safety Management Systems, Good Practices for
Agriculture, Manufacturing or Distribution and HACCP (Hazard Analysis and
Critical Control Point) and those for the delivery of food safety systems.
The science of nutrition is the knowledge repository for the understanding
of essential nutrients, their quantitative requirements at different life stages,
the mechanisms behind their essentiality and the pathological phenotypes
Sustainable Solutions for Nutrition: A Consumer Expectation 71
experienced by populations who fail to consume sufficient quantities of them.9
But the contribution of diet to health is more than the sum of its chemical
components and goes beyond molecular science; it is more than the intake of
calories/kilojoules and nutrients recognized as essential. In 1995 FAO and
WHO sponsored an expert consultation on the preparation and use of popu-
lation-specific Food-Based Dietary Guidelines (FBDGs) advocating food cul-
tural differences, population genetic differences, the broad non-nutritional role
of food as well as physico-chemical properties and phytochemicals which
confer human biological advantage.10,11 Furthermore, food diversity, including
food processing variety, besides food adequacy and quality confers advantages
regarding health and survival. The traditional Mediterranean diet (notably
Spanish, Italian and French cuisine), for example, has a protective myocardial
effect and reduces the rate of recurrence after a first myocardial infarction as
has been demonstrated by the Lyon Diet Heart Study.12
The following three concrete examples are chosen to give the reader an
impression of the variety of activities a food company undertakes in the area of
sustainable development. The first example shows efforts in the improvement of
milk procurement in Turkey, the second example explains improvements in
cow feed quality in France and the third example demonstrates efforts and
progress in the responsible and sustainable exploitation of the mineral water
source in Evian, France.

6.2.1 Sustainable Milk Procurement in Rural Turkey

Milk is a staple food but it is also a key agricultural raw material. Danone
transforms milk into dairy products such as yoghurts, fresh cheeses and des-
serts and also manufactures probiotic milk-based products such as Actimel and
Activia. For these products fermentation is done using specially selected pro-
biotic cultures. These are living bacteria that, when consumed in sufficient
quantity, convey concrete health benefits to the consumer. Approximately
4.5 billion litres of milk are transformed per year in Danone factories world-
wide. Fresh dairy products require refrigeration, which is why most of them are
manufactured in the country where they are being marketed. One fast-growing
and dynamic market for dairy products is Turkey. After a successful launch of
some of Danone’s major brands in Turkey in 2002, the local team was soon
confronted with problems in milk procurement. Between 2002 and 2008 milk
quantities in Danone Turkey had already doubled and future volume growth
had to be secured. At the same time, the local team had to ensure that Turkish
milk complies with EU guidelines for milk quality, cow registration, recording
of illnesses and other items. The major threat to future growth came from
the large proportion of isolated small family farms in Turkey’s milk supply.
These farms are largely characterized by small numbers of cows, often just one
single cow, and low productivity with less than 2,000 litres per cow per year –
one of the lowest rates in Europe. For comparison, a German cow produces
72 Chapter 6
more than 6,000 litres of milk per year, a French cow produces 5,700 litres per
year. Bacteriological quality in milk from small Turkish family dairies was
also poor compared to other European countries. In order to improve this
situation Danone Turkey had to get involved upstream in the national milk
supply. The objectives of the milk development program were ambitious.
Four projects were run from 2002 to 2007 under a program called ‘‘Project
Village Farm’’, which tried to consolidate individual family farmers into small
milk producing co-operatives, to improve professionalism in milk farming
and to elevate quality. This program was composed of four projects. Between
2002 and 2004, during the first phase of the program, basic steps were under-
taken by Danone Turkey in collaboration with Turkish milk farmers in
order to improve milk quality. This was achieved by implementing a quality
premium system which was designed to give incentives for good quality and to
penalize poor quality. No such quality management system existed among
Turkish milk farmers prior to this period. The microbiological burden of raw
milk in Danone Turkey’s milk collection was diminished seven-fold during this
period. Regular antibiotic controls on milk trucks helped manage antibiotic use
in milk farms. Cold chain improvement allowed extension of shelf life of fin-
ished products. Training programmes for dairy farming professionals, in
combination with quality improvement in cow feed, helped to increase the
milk’s protein content. The second phase of this project, which started in 2004
and is still under way, has a double objective. On one side it aims to further
improve milk quality in Turkey (reaching EU standards), and to secure volume
growth and best cost. On the other side, this project creates better income for
Turkish dairy farmers, increases their professionalism and improves social life
among Turkish farmers and their families. In collaboration with Cargill,
DeLaval and Ecolab, Danone Turkey implemented a program designed to
provide farmers with cheaper meals. A credit support program was launched
with the Turkish Deniz Bank in order to give farmers access to affordable credit
and to improve livestock. Another project was designed to develop new agri-
cultural land in Turkey. Finally, in collaboration with the Turkish Ministry of
Education, Danone Turkey helped farmers to build schools in dairy farming
villages.
Four years into the projects the number of small-scale dairy co-operatives,
federated by Danone Turkey, has increased from 111 in 2005 to 172 in 2007 and
will be greater than 200 by the end of 2009. Total milk from these co-operatives
has risen from 36,912 mto in 2005 to 62,414 mto in 2007. The number of cows
per farm has risen to 31 on average in 2007, and productivity has gone up to
6,850 l per cow per year with improved protein content of 3.31 g l1 and greatly
improved bacteriological quality.
The following pictures illustrate this project. The example taken is from the
village of Yenikoy. The photos were taken on May 8, 2008. The Yenikoy
project represents an investment of 110,000 h plus a 50% incentive for milking
equipment from the Turkish government. A long-term loan for 75,000 h was
given from Deniz Bank over 4 years. Payback of this loan is planned to come
from Danone quality and productivity premiums, Figures 6.2–6.4.
Sustainable Solutions for Nutrition: A Consumer Expectation 73

Figure 6.2 Central milking parlour.

Figure 6.3 Central feed producing unit.

74 Chapter 6

Figure 6.4 The Yenikoy milk co-operative in 2008.

6.2.2 Sustainable Cow Feed in France

Danone France, one of Danone’s largest business units, decided to get involved
with upstream dairy farming practices for different reasons from those
described above. Danone France has strong traditional links with the French
dairy farming community where the company has developed exclusive milk
collectives, which work exclusively for Danone. France is Europe’s leading milk
producing country with a longstanding history of dairy farming. Traditional
agriculture has in large parts given way to large-scale farming practices at
very high productivity levels. In some parts of the country agricultural practices
can be described as intense. Intensive farming practices can badly influence
cows’ health and welfare. Furthermore, significant changes in feeding practices
today have largely modified the lipid composition of milk fat. This modified
lipid composition is no longer in accordance with generally recommended
dietary intakes. In cooperation with the French foundation Bleu-Blanc-Coeur,
Danone France has started an initiative to introduce extruded flax into the
cattle feed in order to improve the health of the animals and at the same time
improve the lipid composition pattern. This project was undertaken with a
double objective in mind: improvement of animal health and welfare, and
improvement of milk fat composition.
Dairy farmers in France, like anywhere else, are concerned about pro-
ductivity and profitability of their enterprises. Good breeding practices and
Sustainable Solutions for Nutrition: A Consumer Expectation 75
good farm management practices must be accompanied by good feeding
programs. Feeding for high milk production is highly efficient.13 Nutrient
requirement for maintenance comprises a smaller portion of the total
requirement of high-producing cows. Feeding dairy cows for efficient produc-
tion involves supplying energy, protein, minerals, vitamins and water in suffi-
cient amounts. The forage program is selected by the farmer. Danone France
provides best practices to their milk collective farmers in order to improve
yields and quality in the framework of responsible farming practices (agri-
culture raisonne´e in French). There is no single best forage program; all have
advantages and disadvantages. Pasture, the traditional cow feed, has low
harvesting costs and provides a convenient way of spreading manure. But
pasture is not well adapted to large herds in confinement systems. Furthermore,
quality varies through the season, which can influence the quality of finished
dairy products. Hay is somewhat close to pasture. It can be high in protein
content. It requires low equipment levels and also low facility costs. Some hay is
desirable to maintain good rumen function. High labour requirement, waste
problems and greater risk from weather at harvest make hay only the second
choice behind crop silage. Crop silage offers the advantage of high tonnage; it is
well adapted to automation and provides reduction of waste. There is, however,
the requirement of high upfront investment. Crop silage can be low in protein
and there is a considerable risk of nutrient loss due to spoilage. Grains com-
monly used in dairy feed include corn, barley, oats and wheat. By-product feeds
include protein supplements, brewers’ dried grains, corn gluten, whole cot-
tonseed, soy hulls, wheat bran and others. A problem associated with intensive
dairy farming is the control of acidity in the cow’s rumen. Digestion upsets
may occur if the cow feed is not sufficiently buffered. Sodium bicarbonate is
often added at 1.5% to cow feed.
Flax (also known as lin) was a traditional ingredient in cow feed frequently
used in earlier times. Flax is native to the region extending from the eastern
Mediterranean to India. It was extensively cultivated for the first time in
ancient Egypt. It is grown both for its seeds and for its fibres. Various parts of
the plant have been used to make fabric, dye, paper, medicines, fishing nets and
soap. For a long time flax was used as an important component in animal feed,
but today it has almost entirely vanished from cattle feeding. Only a handful of
horse or steer breeders, all fervent advocates of this century-old tradition,
continue to feed linseed to their animals. They do so because they know about
the particular nutritional value of flax, its natural richness in omega-3 fatty
acids (see chapter 9.1.4.2.18), for which they are willing to put in the extra
effort. Linseed cannot be used in its crude state. Horse breeders need to boil the
flax seeds before feeding them. Linseed meal is used in steer feeding. Raw
untreated linseeds are never used because of the difficulty animals have in
digesting them. But farm-side boiling and milling are time and labour intensive,
and so linseed has been replaced in general farming over time by soy and corn.
Soy and corn are easier to cultivate and to harvest and their grains do not
require boiling or milling. They are economically more favourable. At the
beginning of the twenty-first century linseed has almost completely vanished
76 Chapter 6
from animal feeding. As a consequence of changed feeding practices the lipid
composition of milk and animal fat has changed over time and today has
become poor in omega-3 and overly rich in omega-6 fatty acids. The following
paragraphs explain the importance of the ratio of o-6 : o-3 for human health
and animal welfare.
Fats and lipids are multi-functional nutrients. They supply energy to the
body. They are also structural building blocks for the formation of cellular
membranes. In addition, their metabolites affect numerous important physio-
logical systems such as the cardiovascular, the immune and the nervous sys-
tems. Official nutritional recommendations invariably stress the importance
of lipid control as a very important factor in prevention of poor nutrition. Such
recommendations primarily include quantitative aspects of lipid consumption
in relation to total energy need (no more than one-third of the total energy
contribution should come from lipids). Increasingly they also reflect on the
qualitative aspects of nutritional lipids, in particular with regard to essential
fatty acids (EFAs) and poly-unsaturated fatty acids (PUFAs). Insufficient
PUFA supply can deregulate the metabolism.
Sources of lipids in the food of Europeans are mainly of animal origin.
Approximately two-thirds of lipids come from livestock products. Dairy lipids
and lipids from pork are the dominating animal sources in Europe, followed by
lipids from eggs, beef, poultry and fish. The remaining third is from plant oils
with great differences occurring between the individual European countries.
Rapeseed (Colza, in French and Spanish) and sunflower oils, very different in
composition from one another, are the most used oils in Europe. Olive oil is
increasingly present in table oils, but it is quasi-absent from industrially pre-
pared foods (margarines, sauces, biscuits and prepared dishes). Various Eur-
opean consumption surveys have shown that lipid consumption in Europe has
exceeded recommendations for the past decades. According to these studies,
total energy contributions from lipids today reach between 35% and 45%.
These surveys also reveal considerable changes, both qualitative and quanti-
tative, that have occurred in lipid consumption over the past 40 years. Table 6.1
presents data from lipid consumption in France. These data are approximate as
they have been reconstituted from different published surveys.
The data presented here are representative of Western European consump-
tion patterns. There is an important gap between nutritional recommendations
and actual consumption. In addition to overall excessive lipid consumption
in Europe there is over-consumption of saturated fatty acids, as well as an
excessive ratio of o-6 : o-3 fatty acids. Based on many convergent data from
different epidemiological studies, this imbalanced consumption pattern is likely
to be at the origin of the steady increase of ‘‘lifestyle’’ related illnesses observed
in Europe. The extent of the gap between consumption and recommendations
is notable and calls for corrective measures such as nutritional education, a
better choice of plant oils and a better control of animal lipids. Since animal
lipids represent two thirds of all consumed lipids, it is of particular importance
to improve their composition. For several decades different research teams have
studied the link between animal feed and lipid composition of their products.
 Sustainable Solutions for Nutrition: A Consumer Expectation
Table 6.1 Recommended and reported daily consumption of Essential Fatty Acids.
Daily consumption of major Essential Fatty Acids (EFA) and EFA ratios (g day1)
P4 FA
EFA g day1 C16:0 C18:1 C18:2 n-6 C18:3 n-3 n-3 LA/ALA C16:0/ALA

TOTAL 104 24.6 30.6 17.6 1.0 0.74 17.6 24.6

Recommended daily 81 / / 10 2 / o5 /
ration (ANC)
Reported daily ration +28% / / +76% –50% / +252% /
over recommended
dose (in percentage)
LA ¼ linoleic acid; ALA ¼ a-linolenic acid

77
78 Chapter 6
Their studies have shown that animal fat composition depends almost exclu-
sively on the animal feed, regardless of the particular species involved. Changes
in cattle feeding practices directly influence the animal fat composition. For
example, conventional beef contains a 4 : 1 o-6 : o-3 ratio while grass-only diets
produce a 2 : 1 o-6 : o-3 ratio. As another example, progressive introduction of
cereals into dairy cattle feed has increased the level of palmitic acid, from 20%
in grass-fed dairy cows to 40% in cereal-fed cows.
In collaboration with the French foundation Bleu-Blanc-Coeur, and together
with the company Valorex, Danone France succeeded in introducing 5% of a
special linseed preparation into the daily ration for cows delivering milk for
Danone’s fresh cheese ‘‘Jockey’’. This product, popular in France, is manu-
factured in the Danone Ferrières-en-Bray factory in the north of France.
Valorex has been chosen as a supplier for their particular variety of linseed,
named Tradi-Lins, which is extremely rich in Omega-3 fatty acid content.
Approximately 60% of total fatty acids in this feed supplement are ALA
Omega-3. A patented high-pressure cooking and extrusion method transforms
raw linseed into extruded linseed pellets which are void of any toxic compo-
nents while being at the same time easily digestible for cows (Figures 6.5–6.8).14

Figure 6.5 Milling of linseeds.

Figure 6.6 Vapour treatment and maturation.

Sustainable Solutions for Nutrition: A Consumer Expectation 79

Figure 6.7 Compressing extrusion.

Figure 6.8 Extruded linseed pellets.

As already mentioned above, French dairy farmers are concerned about

productivity and profitability of their enterprises. They needed to be convinced
of the economic advantages of linseed fortification of cow feed. The initial
increase in feed cost is off-set over time by higher productivity, better health of
the cows and higher price obtained for omega-3 rich milk. The role of the
foundation Bleu-Blanc-Coeur was to share experiences and best practices
regarding Tradi-Lins fortification with French farming communities. Com-
parative analysis between Danone’s Jockey and similar products competing in
the marketplace clearly demonstrate the improved lipid profile of milk from
linseed-fed cows, Table 6.2.
Of all analyzed products, only Jockey does in fact correspond to the
recommended lipid profile.
In addition to the improved lipid profiles indicated above, linseed supple-
mentation of dairy feed offers another advantage. Farmers who participated in
the program soon realized improvements in health and welfare in their animals.
80 Chapter 6
Table 6.2 Saturated and unsaturated fatty acids in four fresh cheeses.
Target Jockey Competitor 1 Competitor 2 Competitor 3

Saturated Fatty Acids o68 65.6 72.4 70.3 70.9

Unsaturated Fatty Acids 430 33.8 27.3 28.8 28.4
Omega 3 40.6 0.7 0.3 0.3 0.5
Omega 6 40.8 2 1.7 1.8 1.7
Omega 6 : Omega 3 o5 2.9 5.7 6 3.4

in % of total fatty acids

These improvements are due to the better digestibility of linseed enriched feed.
Dairy cows ferment their food and produce fermentation gases, notably carbon
dioxide and methane. One cow produces up to 900 litres of CO2 per day along
with 600 litres of CH4. Both are greenhouse gases. Methane’s contribution to
atmospheric warming is 21 times that of CO2 per molecule. Patrick Herpin and
his group at the French National Institute of Agriculture (INRA) have shown
that linseed feeding in cows reduces methane emission by 37%. In view of the
actual debate about greenhouse gas emissions, this reduction appears to be
highly significant. Danone Research collaborates with the INRA group to
study possible gas reductions in the Danone milk collective. Extension of the
linseed project to Danone’s entire milk collective is under current investigation.

6.2.3 Sustainable Exploitation of the Evian Mineral Water

Source
Evian is a mineral water from Danone coming from several sources near
Evian-les-Bains, on the south shore of Lake Geneva. The virtues of Evian
mineral water were discovered in 1789 by the Marquis de Lessert. Bottling from
the spring started in 1826 and the first mineral water company was founded
three years later. The French Ministry of Health reauthorized the bottling of
Evian water on the recommendation of the Medicine academy in 1878. Evian
water began to be sold in glass bottles in 1908. In 1969 the first PVC bottle was
launched. Danone, at the time called BSN Group, took control of Evian in
1970. Evian switched to collapsible PET bottles in 1995 and to 50% recycled
PET in 2007. Over the years Evian established its name as a natural and healthy
beverage throughout the world. During the time of Evian’s commercial
development, Danone paid attention to sustainable growth and the relationship
with all stakeholders.
Danone is historically a pioneer in plastic recycling with collection programs
that were started in 1970 under the title ‘‘Vacances Propres’’. Today Danone is
involved with more than 20 national and international partners in the domain
of packaging recycling. At the same time continued efforts were made to reduce
the weight of packaging. Today, one empty bottle of Evian weighs 30 grams
compared to 43 grams in the early days. Evian has undertaken a series of other
Sustainable Solutions for Nutrition: A Consumer Expectation 81
environmental initiatives that include: the creation of the Evian Water Pro-
tection Institute, the incorporation of recycled PET plastic into the bottle
sizes that receive the most sales, and collaboration with the RecycleBank, an
award-based company that gives participating households redeemable points
according to the amount of materials they recycle.
But despite these continued efforts and improvements, consumers of bottled
mineral water these days are accused of committing an environmentally irre-
sponsible act. Recent newspaper headlines sent warning messages to its readers:
‘‘Give up bottled water to save the planet’’, ‘‘No to bottled H2O’’, ‘‘Just turn on
the tap and join the drive to stop drinking bottled water’’. At Danone we
remain convinced that Evian, being a pure mineral water, unadulterated and
free from chemicals such as nitrate, chlorine or heavy metals, presents a
valuable choice to consumers who are concerned about their health and well-
being. At the same time, now more than ever, Danone needs to explain actions
and initiatives undertaken by the company to protect the source and the water
quality of Evian and to make sure that the natural underground reservoirs are
not depleted. Consumers have begun to take interest in the nature and origin of
Evian mineral water. It is important to explain that the groundwaters that
generate Evian natural mineral water are not fossil waters; they take part in the
global water cycle. They find their origin in the infiltration of water coming
from rainfall and snowmelt in a specific zone called their catchment area. Their
main difference to surface waters is their residence time. While the surface
run-off needs only a few days to a few months to reach the sea through rivers,
the groundwaters usually stay several months to several decades underground
before reaching the surface. This long transit allows them to self-purify through
several processes (filtration, adsorption, buffering, bioremediation, etc.) and to
catch minerals from their aquifer (hydrolysis because of their CO2 content).
Therefore these waters can naturally reach the drinking water standards (spring
waters) or even get a specific constant mineral content (natural mineral waters)
that can favour human health, as is the case for Evian. Nevertheless, as with all
other natural resources, this one needs to be properly managed and protected
to ensure sustainability. A company policy was put in place in 2004, followed
by a comprehensive groundwater protection plan. These elements were created
to ensure sustainable management of the natural and patrimonial resources.
This policy is based on the following objectives: guarantee the purity and
quality of the water in order to ensure the quality of its products and the safety
of its consumers, guarantee the sustainability of its water resources, exercise
social responsibility at the local level and protect and promote the natural
heritage of the sites where we operate. To this end, the divisions, subsidiaries
and production facilities of Danone apply the policy by implementing the
following measures: understand the hydrogeology of water resources and the
natural and human environment of the sites, respect the natural recovery
capacity of the water resources, develop lasting relationships with local com-
munities and contribute to local development, train designated managers
and monitor and evaluate results regularly. The policy has been translated into
five related action fields: knowledge of the resource and its environment,
82 Chapter 6
management of the resource, actions of protection, local development and
organization. The target is to acquire a good knowledge of the groundwater
system and its surface environment in order to carry out the next actions in a
relevant way.
First, the focus is on the spring for which all characteristics must be estab-
lished (technical, geological, hydraulic), plus a local mapping of the neigh-
bouring activities abstracting groundwater; next, a geological report from a
local hydrogeologist must have defined all possible vulnerable areas around the
spring. In this area the land use and the human activities must be inventoried.
Finally hydrogeological studies must provide comprehensive and congruent
information of the groundwater system (catchment area, transit time, con-
ceptual model, vulnerability mapping, etc.) and a socio-environmental assess-
ment of the whole concerned area bringing understanding of the potential
hazards, risks of conflicts and socio-economic levers.
The Evian company understood early the need of management and protec-
tion of its mineral water resource. Thanks also to its local economic weight it
has been able to introduce, in 1992, a model of local cooperation which is still in
operation.

6.2.3.1 Knowledge of the Resource

Good geological and hydrogeological knowledge are important. Where does
water come from and how? Several studies including various methods

Impervious
Recharge area layer (clays)

Aquifer
(sands)

Flow path
Discharge area

Figure 6.9 Knowledge of resource and environment: cornerstones for sustainable

management.
Sustainable Solutions for Nutrition: A Consumer Expectation 83
(geohydrochemistry, isotopy) have been done in order to answer these ques-
tions. Geological maps of the aquifer were drawn up (Figure 6.9). A definition
of the catchment area, a description of all water flows and a full description of
the discharge area were established. The residence time of water in the Evian
water system was calculated to be 50 years on average. All vulnerable areas
were identified and drawn on a map. A complete environmental diagnosis,
current land use and an inventory of risk activities allow constant monitoring
of the water system.

6.2.3.2 Resource Management: Sustainable Exploitation

Based on flow rates, water levels and other parameters, a continuous hydro-
dynamical and hydrochemical assessment is made. Annual archives allow
proper forecasting for future exploitation. Maximum flow rates, minimum
water level and chemical and microbiological standard give the frame for
sustainable use of the Evian source. Figure 6.10 shows the water balance in a
simplified form.

6.2.3.3 Protection of the Resource

The natural geological protection, that is the integrity of the impermeable
layers of the reservoirs with a thickness of tens of metres and an average transit

• Water Balance: on long term, outlets = inlets

Qe
Qp

Qs

Qr

Qs=Qp–Qe–Qr

Figure 6.10 Illustration for the Water Balance at the Source, Qs ¼ amount of surface
water, Qe ¼ evaporation, Qp ¼ precipitation, Qr ¼ run-off.
84 Chapter 6
time of 20 years, is constantly monitored. Particular attention is drawn to the
installations at the catchment sites. This is an area of specific technical know-
how. Quality management includes sanitation protocols and detailed hazard
analysis of critical control points. A sanitary defence perimeter is described
around the discharge area. This is a physically enclosed zone prohibiting
all activity and entry of unauthorized persons. It corresponds to the size of the
zone owned by the company. The recharge area, the zone where water infil-
trates the reservoir, is protected in close collaboration with the local commu-
nity. A special association in Evian works with local partners to implement and
finance the protection of this sensitive zone. A specific convention has been
signed with local farmers to stop the use of phyto-sanitary products. Buildings
for livestock were constructed with the help of this association in order to
protect the source from animal waste. A risk management system was estab-
lished together with 12 villages in the vicinity of the Evian source. Risks related
to human activity such as drainage works, waste treatment, fuel storage, wet-
land management, road maintenance and others are identified and controlled in
this local network. Water exploitation limits have been established in conven-
tions signed by four villages in order to promote sustainable management of
the communal drinking water supply. Specific efforts were made to measure
and influence local economic and social impacts. Evian contributes largely to
the industrial employment of the region. Tourism is developed to introduce the
Evian area to Evian consumers. Transportation methods are constantly
optimized.

6.2.3.4 The ‘‘Observatory’’

This institution was created to verify the effectiveness of the protection actions
since there is, at Evian, an average delay of 20 years from the recharge area
(where the protection actions are implemented) and the discharge area (where
there are the sources and drillings). The Observatory is based on the measure
of certain physical, economic and social parameters, which can highlight the
evolution of risks. These parameters include chemical parameters of streams and
sources of the area, agricultural parameters such as the quantities of fertilizers,
phyto-sanitary products, de-icing salts and number of signed local conventions
and agreements. This Observatory allows the continuation or re-adjustment of
engaged actions in order to ensure proper water resource protection at all times.

6.3 Conclusion
Three different examples of projects for sustainable development inside a food
company were illustrated. They have two important elements in common:
first, they are strictly business oriented and firmly embedded with the overall
commercial strategy. Second, they are mid-term to long-term projects,
which require continued motivation, resources and energy from the entire
organization. It is fair to say that in today’s world sustainability aspects in
Sustainable Solutions for Nutrition: A Consumer Expectation 85
business projects are no longer ‘‘nice-to-haves’’, but they have become central
elements for successful business project management.

References
1. C. J. Baldwin, ed., Sustainability in the Food Industry, Institute of Food
Technologists Series, Wiley-Blackwell, Oxford, 2009.
2. United Nations Development Programme, Millennium Development Goals,
Millennium Declaration, UN Millennium Summit (Sept. 2000), http://
www.undp.org/mdg/basics.shtml (retrieved 19.09.2008).
3. M. L. Wahlquist, Publ. Health Nutr., Sept. 2005, 8(6A), 766.
4. FAO, ed., Summary of World Food and Agricultural Statistics, Rome
(2005), http://www.fao.org/ES/ESS/sumfas/sumfas_en_web.pdf (retrieved
22.09.2008).
5. SUSTAINET, Sustainable Agriculture Information Network, Combating
World Hunger through Sustainable Agriculture, gtz, ed., http://
www2.gtz.de/dokumente/bib/04-5888.pdf (retrieved 19.09.2008); M. A.
Altieri, P. Rosset and L. A. Thrupp, The Potential of Agroecology to
Combat Hunger in the Developing World, http://www.cnr.berkeley.edu/
Bagroeco3/the_potential_of_agroecology.html (retrieved 19.09.2008).
6. O. D. Mjøs, The Nobel Peace Price 2006: Presentation Speech, Oslo (2006),
http://nobelprize.org/nobel_prizes/peace/laureates/2006/presentation-
speech.html (retrieved 21.09.2008).
7. IFPRI (International Food Policy Research Institute), Putting globaliza-
tion to work for the poor, Summary Note, R. S. Johnson, Panelist, in 2020
Vision: Sustainable food security for all by 2020, Bonn (2001), http://
www.ifpri.org/2020conference/PDF/summary_johnsonrobbin.pdf; http://
www.ifpri.org/pubs/books/2020conpro/ch11.pdf (retrieved 23.09.2008).
8. K. Bergmann, in K.-M. Brunner and G. U. Schönberger, Hrsg., Nach-
haltigkeit und Ernährung: Produktion – Handel – Konsum, Campus Verl.,
Frankfurt, New York, 2005.
9. D. G. Lemay, C. J. Dillard and J. B. German, Food Structure for Nutrition,
Special publication – Royal Society of Chemistry, 2006, 308, 1.
10. World Health Organization/FAO, Preparation and use of food-based diet-
ary guidelines, WHO Technical Report Series No. 880, Geneva (1998).
11. M. L. Wahlqvist, Requirements for healthy nutrition: Integrating food sus-
tainability, food variety, and health, World Congress of Food Science and
Technology No. 12, Chicago, J. Food Sci., 2004, 69(1), CRH16, http://
www.iuns.org/features/requirement_for_healthy_nutrition.pdf.
12. M. de Lorgeril, P. Salen, J.-L. Martin, I. Monjaud, J. Delaye and
N. Mamelle, Mediterranean diet, traditional risk factors, and the rate of
cardiovascular complications after myocardial infarction: final report of the
Lyon Diet Heart Study, Circulation 99, 779–785.
13. M. J. VandeHaar, J. Dairy Sci., 1998, 81(1), 272; M. J. VandeHaar and
N. St-Pierre, J. Dairy Sci., 2006, 89(4), 1280.
14. P. Weill, EP1155626, 2001 (Valorex).
CHAPTER 7

Biomass-based Green Energy

Generation
MARTIN KALTSCHMITTa,b AND DANIELA THRÄNa
a
German Biomass Research Centre, Torgauer Str. 116, D-04347 Leipzig,
Germany; b Hamburg University of Technology, Institute for Environmetal
Technology and Energy Economics, Eissendorfer Str. 40, D-21073 Hamburg,
Germany

7.1 Introduction
Energy from biomass currently contributes on a world-wide basis 10 to 12% to
the gross primary energy demand.
Due to geographical, economic and climatic differences, the share of biomass
energy in relation to total energy consumption differs widely between different
countries, ranging from less than 1% in some industrialized countries like
the United Kingdom to significantly more than 50% in some developing
countries in Africa and Asia. Biomass is by far the most important renewable
energy source, being significantly larger in energetic terms than the second
largest, hydropower. This becomes obvious in Figure 7.1, which shows the
energy consumption exemplarily for Germany subdivided into the different
energy carriers contributing to cover the given energy demand. Overall on a
global scale the energy from the oldest fuels (i.e. biofuels) utilized by human
beings is much larger in absolute terms than the energy from the newest,
nuclear fuels. In terms of numbers of people, biofuels dominate the world
picture, for it is probably true to say that most people in the world still
rely on biomass fuels for most of their energy, a situation that has not changed

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

86
Biomass-based Green Energy Generation 87

Lignite
Hard Coal 12 %
14 %
Nuclear
11 % Hydro 0.5 %

Renew-
ables Biomass 4.9 %
6,7 %

Wind 1.0 %
Natural Gas
Others 0.3 %
22 %
Crude Oil
34 %
Total: 13.8 EJ (2007)

Figure 7.1 Primary energy consumption Germany (2007).1

since the mastery of fire a hundred thousand years ago. This is due to the
available conversion technology, the relatively low costs and the easy access of
biofuels, such as wood, dung and crop residues, in the poor rural areas of
developing countries where about half of the world population still lives.
However, soot from the burning of biomasses, largely wood and animal dung
used for cooking by Asia’s poor, has recently been identified by radiocarbon
analysis as causing the brown cloud that hovers over the Indian Ocean and
South Asia every winter. As well as being linked to global warming, the brown
cloud is believed to lengthen droughts, exacerbate monsoons and further melt
the Himalayan glaciers, which currently provide fresh water to billions of
people.2 In addition, however, more and more processed biofuels such as wood
chips, wood pellets, biogas, biodiesel and bio-ethanol play an important role in
many regions where they perform favourably compared to the given alter-
natives. The potential size of total biofuel resources is considerable throughout
the world. Depending on how they are utilized, biofuels also have the advan-
tage of being relatively environmentally sound compared to many other sources
of energy, a characteristic that has led to a resurgence in interest throughout the
world.
Cooking with biofuel is extremely rare today in rich countries, although there
is significant use of biofuel for space heating in regions with easy access to
forests. Specific space heat demand is generally decreasing because of improved
insulation of old and new buildings due to regulations and other incentives in
most industrialized countries. Average living area per citizen in most countries
of the western world is still increasing, however, while population itself is not
growing significantly or even decreasing. The net result is that space heat
demand is likely to remain more or less stable in industrialized countries for the
next decade. The household market in developing countries is still increasing
due to increasing population and economic growth. The rapid urbanization
88 Chapter 7
common in many developing countries acts as a countervailing trend, however,
because urban households tend to rely less on biofuels than do rural house-
holds. The net result is probably similar to that in developed countries, i.e.
overall consumption of household biofuels is relatively stable, although in this
case with large regional variations. China may well be an important exception
because there seems to be an on-going trend to substitute coal for biomass in
rural household applications.
The demand for electric energy is increasing in industrialized as well as in
developing countries. Therefore, electricity production from biomass is often
seen as one of the most important future markets for biomass worldwide. The
same is also true, in principle, for the production of transportation fuels from
biomass (see Chapter 8).
More broadly, expanded use of biomass in clean applications offers a way
toward more sustainable energy systems in all countries, an issue of growing
international concern. Because many renewable energy sources offer the
potential to provide useful energy with reduced emissions of e.g. greenhouse
gases and be additionally environmental advantageous compared to fossil fuel
energy, their attractiveness has been increasing during the last decade. In
particular, biomass is considered as environmentally and climatically sound
because:

 if operated with high combustion efficiency and produced in a sustainable

way, biomass fuel cycles are neutral to the climate, i.e. the carbon is
completely recycled and there is – if no other greenhouse gases (like CH4,
N2O) are released – no net increase of greenhouse gases in the atmosphere.;
 biomass combustion normally has low sulphur and nitrogen emissions
with consequently small contributions to secondary particle formation and
acid precipitation downwind;
 biomass has only a few other intrinsic contaminants that can pollute the
environment such as the toxic elements mercury, lead, arsenic, fluorine,
etc. found in some fossil fuels;
 in many circumstances, the residues produced during the processing and
combustion of biomass (i.e. fermentation residues, ash) can be usefully
recycled back onto the production area from which the biomass has been
grown.

Among the various possibilities for exploiting solar energy, biomass shares
with a hydropower reservoir the characteristic of being a form of ‘‘stored’’ solar
energy. This offers significant advantages over wind or direct solar energy (like
photovoltaic3), which need to be linked with expensive storage systems to be
available reliably throughout the day, month and year. In addition, being a
chemically based fuel, the energy density of biomass is fairly high, although not
as high as that of most fossil fuels.
Biofuel is rarely directly affected by energy crises, being an indigenous
energy carrier (i.e. biomass is, in most cases, produced close to the place where
it is used) characterized in most cases by short supply chains with low
Biomass-based Green Energy Generation 89

energy crops residues by-products waste

harvesting, collecting etc.

treatment transportation storage

physical-chemical
thermochemical conversion conversion biochemical conversion
pressing/extraction
gasifi- fermen- compo-
coaling pyrolysis digestion
cation esterification tation sting

gaseous
solid fuel liquid fuel
fuel

combustion

power heat

Figure 7.2 Possibilities to provide heat and/or power as well as fuels from biomass.4

risks of failure. This security of supply is increased by growing international

markets for some types of biofuels with relatively high energy density (pellets,
bio-ethanol, etc.). Also the production and utilization of biomass is widely
accepted by the greater public (unlike nuclear and coal power in some coun-
tries) and offers benefits for rural areas related to employment, rural infra-
structure, the conservation of cultivated areas and hence the attractiveness of
rural regions.
Most biomass used for energetic purposes is directly combusted to produce
heat and/or power, but a huge variety of additional possibilities are available to
provide environmentally sound heat and/or electricity as well as transportation
fuels from organic material. The most important conversion routes available
now or in the near future will be discussed according to the framework shown
in Figure 7.2.
It is useful to consider two major forms of biomass fuel: mechanically pro-
cessed and chemically processed. For mechanically processed biofuel in which
the material is used essentially in its natural form (as harvested) direct com-
bustion usually supplies heat for cooking, space heating or electricity produc-
tion, although there are also small- and large-scale industrial applications for
steam raising and other processes requiring low-to-medium temperature pro-
cess heat.
Chemically processed biofuels with clearly defined fuel characteristics allow
for a technically easy and environmentally sound conversion into the desired
useful energy. Such biofuels can then be traded easily and used with fewer
problems to meet a supply task efficiently and comfortably. To ensure this, the
following conversion routes are available (Figure 7.2).

 Thermo-chemical conversion summarizes all conversion processes of bio-

mass into a solid, liquid or gaseous fuel based on heat. Therefore
90 Chapter 7
gasification, pyrolysis and charcoal production count as these processes.
Of these possibilities only charcoal production is state of technology and
widely used so far. But gasification in connection with electricity produc-
tion seems to be a quite promising option which might become technically
available in the near future.
 A physical-chemical conversion process provides a liquid fuel based on
physical (such as pressing) and chemical (such as esterification) processes.
The most important process used by the industry so far is vegetable oil
production from oil seed and the transesterification of this vegetable oil to
Fatty Acid Methyl Ester (FAME) as a substitute for petroleum-based
diesel fuel.
 Bio-chemical conversion summarizes conversion processes based on bio-
logical processes. The most important possibilities are alcohol production
from biomass containing sugar, starch and/or celluloses and biogas pro-
duction from organic waste material. Both technologies are state of the art
and widely used for energy provision.

These upgraded biomass fuels can be used in engines, turbines, boilers or

ovens to provide thermal and/or mechanical energy (i.e. heat and power),
which in turn can be converted into electrical energy. Additionally, liquid
and gaseous fuels can be used directly or after treatment as transportation fuels.
Heat production is so far the most important use worldwide for biomass fuel.
Direct combustion devices are widely distributed with thermal capacities
ranging from a few kW in household stoves up to heating plants with several tens
of MW. The conversion efficiencies vary from 8 to 18% for simple three-stone
stoves up to approximately 95% and above for modern heating units with
high-end condensing boiler technology. Electricity production – which is of
minor importance on a world-wide scale – has been based mainly on the con-
ventional steam cycle with efficiencies around 30% and capacities of a few MW
and above.

7.2 Biomass Sources

7.2.1 Properties
Biomass consists primarily of the elements carbon (C), hydrogen (H) and
oxygen (O) (Table 7.1). Additionally, trace elements can be found in some
types of biomass. For example, straw can contain fairly high amounts of
chlorine (Cl) and/or silicon (Si) and rape seed shows a relatively high amount of
nitrogen (N). These trace elements can sometimes cause problems. For exam-
ple, during combustion chlorine is responsible for high temperature corrosion
in boilers, silica can lead to boiler slagging and nitrogen can cause high NOx
emissions.
In most practical applications the energy content of biomass is best described
by the lower heating value. The lower heating value (LHV; also known as net
 Biomass-based Green Energy Generation
Table 7.1 Energy content and concentrations of some elements in untreated biomass compared with coal.4
Volatile
Type of biomass Heating value1 Ash content compounds C H O N K Ca Mg P S Cl

in MJ/kg in % in % in % of dry substance

Spruce wood (with bark) 18.8 0.6 82.9 49.8 6.3 43.2 0.13 0.13 0.70 0.08 0.03 0.015 0.005
Beech wood (with bark) 18.4 0.5 84.0 47.9 6.2 45.2 0.22 0.15 0.29 0.04 0.04 0.015 0.006
Poplar wood (short rotation) 18.5 1.8 81.2 47.5 6.2 44.1 0.42 0.35 0.51 0.05 0.10 0.031 0.004
Willow wood (short rotation) 18.4 2.0 80.3 47.1 6.1 44.3 0.54 0.26 0.68 0.05 0.09 0.045 0.004
Bark (softwood) 19.2 3.8 77.2 51.4 5.7 38.7 0.48 0.24 1.27 0.14 0.05 0.085 0.019
Rye straw 17.4 4.8 76.4 46.6 6.0 42.1 0.55 1.68 0.36 0.06 0.15 0.085 0.40
Wheat straw 17.2 5.7 77.0 45.6 5.8 42.4 0.48 1.01 0.31 0.10 0.10 0.082 0.19
Triticale straw 17.1 5.9 75.2 43.9 5.9 43.8 0.42 1.05 0.31 0.05 0.08 0.056 0.27
Barley straw 17.5 4.8 77.3 47.5 5.8 41.4 0.46 1.38 0.49 0.07 0.21 0.089 0.40
Rape straw 17.1 6.2 75.8 47.1 5.9 40.0 0.84 0.79 1.70 0.22 0.13 0.27 0.47
Corn straw 17.7 6.7 76.8 45.7 5.3 41.7 0.65 0.12 0.35
Sunflower straw 15.8 12.2 72.7 42.5 5.1 39.1 1.11 5.00 1.90 0.21 0.20 0.15 0.81
Hemp straw 17.0 4.8 81.4 46.1 5.9 42.5 0.74 1.54 1.34 0.20 0.25 0.10 0.20
Rice straw 12.0 4.4
Husk 14.0 19.0
Rye whole crop 17.7 4.2 79.1 48.0 5.8 40.9 1.14 1.11 0.07 0.28 0.11 0.34
Wheat whole crop 17.1 4.1 77.6 45.2 6.4 42.9 1.41 0.71 0.21 0.12 0.24 0.12 0.09
Triticale whole crop 17.0 4.4 78.2 44.0 6.0 44.6 1.08 0.90 0.19 0.09 0.22 0.18 0.14
Rye grain 17.1 2.0 80.9 45.7 6.4 44.0 1.91 0.66 0.17 0.49 0.11 0.16
Wheat grain 17.0 2.7 80.0 43.6 6.5 44.9 2.28 0.46 0.05 0.13 0.39 0.12 0.04
Triticale grain 16.9 2.1 81.0 43.5 6.4 46.4 1.68 0.62 0.06 0.10 0.35 0.11 0.07
Rape grain 26.5 4.6 85.2 60.5 7.2 23.8 3.94 0.10
Miscanthus 17.6 3.9 77.6 47.5 6.2 41.7 0.73 0.72 0.16 0.06 0.07 0.15 0.22
Switch grass
Sugar cane stalk (bagasse) 8.0 4.0 80 45 6.0 35 0.0 0.0
Hay from various sources 17.4 5.7 75.4 45.5 6.1 41.5 1.14 1.49 0.50 0.16 0.19 0.16 0.31
Roadside green 14.1 23.1 61.7 37.1 5.1 33.2 1.49 1.30 2.38 0.63 0.19 0.19 0.88
Hard coal 29.7 8.3 34.7 72.5 5.6 11.1 1.3 0.94 o0.13
Lignite 20.6 5.1 52.1 65.9 4.9 23.0 0.7 0.39 o0.1
1
LHV.

91
92 Chapter 7
calorific value, net CV) of a fuel is defined as the amount of heat released by
combusting a specified quantity at a reference state and returning the tem-
perature of the combustion products to 150 1C. The LHV assumes that the
latent heat of vaporization of water in the fuel and the reaction products is not
recovered. It is useful in comparing fuels where condensation of the combustion
products is impractical, or heat at a temperature below 150 1C cannot be put to
use. By contrast, the higher heating value (HHV) (also known as gross calorific
value or gross CV) includes the heat of condensation of water in the com-
bustion products.
The LHV is greatly influenced by the water content. Figure 7.3 shows that
the LHV of wood decreases from approximately 18.5 MJ kg1 with increasing
water content. Normally the water content of air-dried wood is between 12
and 20% yielding a heating value of 13 to 16 MJ kg1. Freshly harvested wood
is characterized by a water content of about 50% or more. A low LHV is the
result.
Besides the LHV a lot of additional quality aspects are relevant concern-
ing biomass provision, storage, transportation and efficient conversion pro-
cesses. Density and heat capacity, for example, are important parameters for
unconditioned and for conditioned biomass. Particle density and particle-size
distribution are of importance for chips and pellets, viscosity for liquid
biomass.
For this reason during the last couple of years on a European level such
parameters characterizing solid fuels have been standardized to allow for
growing biomass-based fuel markets. Recently these activities have been also
moved to the international level and an ISO-Standardization Committee has
been founded to develop standards for biomass based fuels.

20

MJ/kg

15
Lower heating value LHV

10

0 20 40 60 80 % 100
Moisture content (wet basis)

Figure 7.3 LHV of wood depending on the water content.4

Biomass-based Green Energy Generation 93
7.2.2 Biomass Potential
For the energetic use of biomass a wide range of different resources is available
in principle (e.g. forest wood, straw, cereal, liquid manure). They derive from
the agricultural and silvicultural primary production respectively from the
industries that follow the primary production as well as from waste manage-
ment (i.e. when organic materials leave the production process).5
The amount of biomass available in total which is usable considering given
technical restrictions is characterized by the technical potential. Besides tech-
nical restrictions for its estimation, structural and environmental restrictions
(e.g. nature protection areas, biotope network areas) as well as the legal fra-
mework (e.g. legitimacy of hygienic precarious organic waste for use in biogas
plants) are also taken into consideration because such restrictions may reduce
the available biomass potential calculated under an exclusively technical point
of view significantly.
Table 7.2 shows the present technical biomass potential based on the criteria
mentioned above. Considering residues, by-products and waste they are differ-
entiated in herbaceous biomass (e.g. straw, landscape conservation material),
wood (e.g. forest residual wood, industrial residual wood) and other biomass
(e.g. excrements, organic industrial waste). The forest potentials include the
wood not used as a raw material (i.e. firewood, forest residual wood) and that
share of the annual incremental growth which is not used at the moment.
Furthermore there are energy crops, which can be cultivated as annual or
perennial cultures on agricultural land for exclusive energetic use.
Considering the current demand on food and fodder an available land area
of about 2 Mio ha can be assumed for biomass production exemplarily within
the Federal Republic of Germany as one country in Central Western Europe.
On this area different types of plants are cultivated for different purposes.

 Thermo-chemical conversion: mixed cultivation of different lignocellulosic

plants for the provision of solid biofuels;
 Physical-chemical conversion: rape-seed cultivation;
 Bio-chemical conversion: two-culture-system for the production of sub-
strates for biogas production, cultivation of input products for the ethanol
production.

Such a procedure leads to an estimation of an upper border, since in practice

the selection of suitable cultivation cultures is significantly reduced due to the
given local conditions.
However, the biomass declared (e.g. herbaceous biomass, energy crops) can
be used only once (either thermo-chemical or bio-chemical or physical-chemi-
cal). Thus the entire fuel potential amounts for the German example to
approximately 1,000 to 1,300 PJ a1 (approximately 8% of the present German
primary energy consumption).
Additional changes are to be expected with the potentials outlined here
in the years to come. These variations might be relatively small for residues,
 94
Table 7.2 Technical biomass potential exemplarily in the Federal Republic of Germany.6
Energetically usable Potential with thermo- Potential with bio- Potential with physical-
amount chemical conversion chemical conversion chemical conversion
Mio mtoraw material a1 PJ a1 PJ a1 PJ a1

Herbaceous residues, by-products and

waste
Straw 9.3 130 38–63 –
Grass from pastures etc. 2.6–4.0 37–56 15–23 –
Rural conservation material 0.9–1.8 11–22 8–16 –
Total 12.8–15.1 178–208 61–102 –
Wood residues, by-products and wastes
Forest residual wood 13.7 169 – –
Thinning 10 123 – –
Additionally available wood 10.7 132 – –
Demolition wood 6 78 – –
Industrial residual wood 4 58 – –
Landscape conservation wood 0.46 4 – –
Total 45 563 – –
Miscellaneous residues, by-products and
waste
Excrements and litter 162 – 96.5 –
Harvesting residues 7–14 – 9.1–18.3 –
Wastes from industries 3.1–4.7 – 6.4–12.2 –
Organic urban waste 7.6 – 12.5 –
Total 180–188 – 124–139 –
Gas from purification plants – 19.5 –
Landfill gas – 15–21 –
Total residues, by-products and wastes 741–770 219–282 –
Energy crops on 2 Mio ha 365 236a–252b 103c
Total amount 1,106–1,135 455–533 103
a
Biogas substrates.

Chapter 7
b
Ethanol from sugar beets (additionally biogas substrates (95 PJ a1) would be usable energetically).
c
Vegetable oil respectively FAME from rape seed (additionally straw (125 PJ a1) and whole grain (65 PJ a1) would be useable energetically).
Biomass-based Green Energy Generation 95
by-products and waste, whereas a clear increase is expected for energy crops – due
to presumably declining land area requirements for the production of food and
fodder caused by slightly fading population and ongoing yield increases. Thus an
increasing biomass potential – and hence an increasing importance of cultivating
energy crops – is likely in the future. According to forecasts the entire biomass
potential might sum up to approximately 1500 PJ a1 in Germany in the year
2010 and increase to approximately 2000 PJ a1 in the year 2020. Improvements
in the seeds for the energy crops can lead to even higher yields and thus higher
potentials. Improved environmental and nature protection requirements (e.g.
expansion of organic farming) might lead to a decrease of the agricultural area
available and thus downsize possible potential increases. But even then an
increase of the potential is expected. And this situation can be expected in most
European countries.

7.3 Biomass Conversion

7.3.1 Thermo-chemical Conversion
7.3.1.1 Basics
The most widely spread use of solid biomass is the provision of heat released
during combustion. During combustion, solid biofuels are oxidized primarily
to carbon dioxide and water by releasing heat. Equation 7.1 shows the
approximate process for wood, which can be described as CnHmOp.
 m p m
Cn Hm Op þ n þ  O2 ! nCO2 þ H2 O þ heat ð7:1Þ
4 2 2
The biomass combustion consists of the following steps: heating and drying,
pyrolytic decomposition, gasification and oxidation (Figure 7.4). These differ-
ent steps are explained below.

 Heating and drying. Before any chemical reaction of the organic material
can take place, water is evaporated at temperatures up to 200 1C. The
water may leave the area where the chemical reaction takes place with the
flue gas. Alternatively it may be converted to H2. This process requires
energy (i.e. it is endothermic).
 Pyrolytic decomposition. Within this step the biomass macromolecules are
decomposed by heat in the absence of oxygen and the volatile compounds
are driven out of the biomass material due to thermal effects. The process
of the pyrolytic decomposition starts at about 200 1C with the decom-
position of hemicellulose, which is a part of solid biomass like wood.
Decomposition of cellulose, which is another component of wood biomass
takes place at temperatures of 300 1C and higher. Lignin is decomposed at
even higher temperatures. During this process the volatile components of
the biofuel are vaporized at temperatures below 600 1C by a set of complex
96 Chapter 7

oxidation (λ > 1)
fully oxidation of the gaseous products produced during pyrolytic and
gasification processes

gasification (0 < λ < 1)

increasing oxidation

gasification of the remaining carbon

(i.e. charcoal)

pyrolytic decomposition (λ = 0)
start of more intensive maximum decomposition is
decomposition; decomposition; rate formation of fading away;
formation of small of decomposition hydrocarbons formation of
amounts of tar, is increasing and due to viscous tar
CO, CO2 and approaches the decomposition
condensables are maximum
produced

heating and drying decomposition areas of:

unbound physically bound
water is water is lignine
evaporated evaporated
cellulose

hemicellulose

0 100 200 300 400 500 °C 800

temperature

Figure 7.4 Example of thermo-chemical conversion for wood.4

decomposition reactions. As a result of such decomposition processes

the following components are formed:
 volatile compounds, such as hydrogen (H2), carbon monoxide (CO),
methane (CH4), carbon dioxide (CO2), nitrogen (N2) and steam (H2O);
 carbon rich solid fraction (char);
 low molecular weight organic compounds and high molecular
weight (condensable) compounds (i.e. liquid products).
Fixed carbon (char) and ash are the by-products that are not vaporized.
 Gasification. It is obvious that solid carbon necessarily remains as a
product of the pyrolytic decomposition. In order to convert this solid
carbon into a gas, an oxygen-containing agent such as air or pure oxygen
is required. At a temperature range between 700 and 1,500 1C the solid
carbon as well as gaseous products (CO, H2, CH4) are oxidized as follows:

Partial oxidation of solid carbon : C þ 1=2O2 ! CO DH ¼ 111 kJ=mol

ð7:2Þ

Complete oxidation of solid carbon : C þ O2 ! CO2 DH ¼ 197 kJ=mol

ð7:3Þ

Oxidation of carbon monoxide : CO þ 1=2O2 ! CO2 DH ¼ 283 kJ=mol

ð7:4Þ
Oxidation of hydrogen : H2 þ 1=2O2 ! H2 O DH ¼ 242 kJ=mol ð7:5Þ
Biomass-based Green Energy Generation 97
Oxidation of methane : CH4 þ 2O2 ! CO2 þ 2H2 O DH ¼ 802 kJ=mol
ð7:6Þ
Additionally, balance reactions take place. The most important are
the reduction of CO2 to CO (Boudouard reaction) and of H2O to H2
(heterogeneous water gas reaction). Simultaneously, carbon can be
transformed to CH4.

Boudouard reaction : C þ CO2 $ 2CO DH ¼ 173 kJ=mol ð7:7Þ

Heterogeneous water gas reaction : C þ H2 O ! CO þ H2

DH ¼ 131 kJ=mol ð7:8Þ

Heterogeneous methane production : C þ 2H2 ! CH4 DH ¼ 87 kJ=mol

ð7:9Þ

During the complicated mix of these and other reactions making up

gasification, sometimes energy is needed and sometimes energy is
released, depending on the given conditions. Additionally these reac-
tions can also take place during the pyrolytic decomposition at higher
temperatures because the biomass itself contains oxygen. Therefore the
border line between these two conversion steps is not always clearly
defined.
 Oxidation. Within this last step of the thermo-chemical conversion, the
gaseous products produced during the steps already performed are fully
oxidized to carbon dioxide and water releasing energy (i.e. they are
exothermic).

If equation (7.1) occurs in one step, we speak of full oxidation. Under these
conditions the excess air ratio is 1.0 or above (the excess air ratio is defined as
the ratio between the amount of oxidizing agent fed to the conversion process
and the amount of oxidizing agent needed to fully oxidize all reaction products;
per definition the excess ratio is 1.0 if the conversion process is realized exactly
as shown in equation (7.1)).
Oxidation can also be realized in two steps in which the excess air ratio of the
first step is below 1.0. Under these conditions the reaction products can be
further oxidized in a second step releasing the rest of the available energy.
Carbon monoxide and/or hydrocarbons are typically produced at the first step
and transported to another device for full oxidation. Within such processes the
procedure described above is paused; for example after the gasification step
(e.g. within a gasifier) is performed, the oxidizing step is realized at another time
and at another place (e.g. within the engine).

 If in such a two-stage process the intermediate product is a liquid we

call the process pyrolysis (the procedure described above is then suspended
98 Chapter 7
Table 7.3 Excess air ratio and reaction product composition for thermo-
chemical conversion processes.4
Excess air Temperature Pressure Products
ratio in 1C in bar Gas Liquid Solid

Oxidation lZ1 800–1300 1–30 Hu ¼ 0 LHV ¼ 0

Gasification 0olo1a 700–900 1–30 Hu40 LHV Z 0
Pyrolysis, l¼0 350–550 1–30 Hu Z 0 Hu40 LHV40
coalification
a
In most cases 0.2olo0.5.

after the pyrolytic decomposition). Under these conditions the excess air
ratio of the pyrolysis process is zero. Solid, liquid and gaseous products are
formed in varying amounts depending on the process conditions (e.g.
temperature, heating rate, pressure, water content).
 If a gas is to be produced at the first step, the excess air ratio is between
zero and one (Table 7.3). The gas, which often mainly contains carbon
monoxide, is called producer gas.

7.3.1.2 Direct Combustion

The thermo-chemical conversion of solid biofuels produced from biomass into
heat is called combustion. This heat released during the oxidation of organic
material mainly into carbon dioxide and water can be used directly at the
conversion plant (e.g. for cooking or space heating) or can be transported by
means of a heat carrier (i.e. hot water, steam) to the place of consumption (e.g.
district heating systems). The thermal energy can also be converted via a steam
turbine or by co-generation (also known as combined heat and power [CHP]
process) into electricity and low temperature heat. Because of economic limits,
only relatively low conversion rates of biomass fuel energy into electrical energy
(maximum of 30 to 35%) are possible at present. Therefore biomass co-firing in
modern large-scale coal power plants with efficiencies up to 45% is regarded as
a cost-effective option for the use of solid biofuels for power generation via
direct combustion.6
The technology required to optimize combustion depends on the capacity, fuel
consistency, water content, ash melting behaviour, trace element contaminants
and other factors. Where these conditions vary, for example with changeable
mixtures of biomass species in the feed, performance will inevitably suffer.
Due to the relatively high volatiles content and other characteristics of bio-
mass, spatial separation is usually provided in modern small scale combustion
devices between the fuel gasification process and the full oxidation of the pro-
duced gas into CO2 and H2O. The former occurs with primary air fed into the
glowing fire and the latter through secondary air fed into the burning gas, pre-
ferably in an after-burning chamber. To achieve low airborne emissions, good
mixing of air and combustible gas at high temperatures is necessary. Additional
design features assist in reducing particle emissions, including those for keeping
Biomass-based Green Energy Generation 99
Table 7.4 Typical combustion technologies and their characteristics.
Combustion Typical thermal
technology capacity Biofuels

Manually fed open/closed 2 to 15 kW wood logs,

systems chimney briquette
single stove 3 to 12 kW wood logs,
briquette
tiled stove 2 to 15 kW wood logs,
briquette
pellet stove 3 to 10 kW pellets
wood log stove 10 to 500 kW wood logs,
briquette
Automatic fed gasification firing 20 kW to 2 MW wood chips
systems system
under feed system 20 kW to 2 MW wood chips, wood
shavings and
filings
grate firing system 150 kW to 15 MW wood, bark
for wood
fluidized bed from 10 MW wood, bark, sewage
system sludge, black
liqueur
grate firing system 50 kW to 20 MW bales, chipped her-
for herbaceous baceous biomass
biomass
blow in firing 200 kW to 50 MW dust, shavings and
system filings

flue gas velocities low so that ash particles are not entrained. Table 7.4 gives an
overview of combustion technologies primarily used in industrialized countries.
Based on this a few major systems are discussed in more detail.

Pellet Combustor. Automatically fed combustion devices have been developed

for wood pellets with standardized fuel characteristics. On the reverse side of
such a device (Figure 7.5), a container is located to store fuel for automatic
operation over a certain period of time. The fuel pellets are transported from
this storage facility with a screw to a pipe from where the pellets fall into the
combustion chamber. Primary air is fed by nozzles through the bottom of the
combustion bowl. Secondary air is fed above the burning fuel via ring-shaped
nozzles to ensure the complete conversion of the gaseous fuel components into
CO2 and H2O. Additional air is fed into the system via the fall pipe to prevent
fire flash back into the fuel container. This well-developed air-feeding system
allows very low airborne emissions to be achieved. The ash produced during
the combustion of the wood pellets is normally removed manually. During
ordinary operation the combustion residues (i.e. ashes) contain less than 1%
carbon and can be used as a fertilizer or taken to a landfill.
The thermal efficiency of such systems can attain 95% or more. Emissions
are considerably lower compared to stoves fired with wood logs because
100 Chapter 7

Figure 7.5 Combustion device fired with wood pellets.4

the combustion device can be optimally adjusted to the standardized and

well-defined pellets. Such heaters can be operated over a wide range of power
settings, i.e. between approximately 30 and 100% of the rated capacity.

Oven for Wood Chips. A throw-charging system is used where wood chips
are transported from fuel storage with a stoker scroll and thrown with the
help of a centrifugal wheel into a combustion chamber equipped with a stiff
grate. Such a fully automatic feeding system allows the smaller fuel particles
to be combusted during the flight to the grate while more coarse fuel particles
are burned on the grate. The system also has the advantage that the fuel is
fed gently on the fire, thus reducing airborne emissions of particulate matter.
The primary air is blown with an automatic ventilator through holes in the
grate into the glowing fire. The secondary air is blown at the top of the burning
fuel. The air feeding system adjusts itself automatically according to informa-
tion from a sensor fixed in the flue gas outlet, minimizing pollutant emissions.
No additional flue gas treatment is needed and ash can be used as a fertilizer or
put on a landfill site.
The heat is extracted from the flue gas via a heat exchanger located on top of
the combustion device. Within the heat exchanger, the flue gas is cooled down
and water is heated up – depending on the heat utilization system – either close
to boiling point (to be used in hot water systems) or to steam for e.g. electricity
generation.
Biomass-based Green Energy Generation 101

Figure 7.6 Blow-in combustion unit for wood dust.4

Such combustion systems are characterized by a fully automatic operation.

They are available on the market in a range of thermal capacities from 300 up
to approximately 3,500 kW and can be used either for heat provision for a
single- or multi-family house or for industrial process heat.

Blow-in Combustion Units. Blow-in combustion units have been developed

for using dusty biomass residues (e.g. sawdust, shavings, filings) from the
wood-processing industry. The fuel particles are transported pneumatically
from the fuel silo directly into the combustion chamber or – as shown in
Figure 7.6 – into a pre-combustion chamber. Additionally, primary air is
blown into the pre-combustion or combustion chamber to ensure a full con-
version of the fuel into gas. Secondary air is blown into the combustion
chamber to ensure a complete combustion. To guarantee that the fuel parti-
cles ignite by themselves during their flight through the combustion chamber,
fuel water content has to be below 15 to 20%. To first ignite such a unit, a
burner based on light oil or natural gas is used to heat the pre-combustion
or combustion chamber to 450 to 500 1C.
Such a combustion system is characterized by relatively low emissions of
gaseous pollutants (such as NOx or CO). Because fuel is fed in very small
pieces, however, the particle content in the flue gas is relatively high. To meet
particle emission regulations, cleaning of the flue-gas is necessary in most
countries. Therefore such systems are often equipped at least with a cyclone or
102 Chapter 7
a multi-cyclone. In case cyclones do not sufficiently remove particle emissions a
fabric or bag house filter or even an electrostatic dust removal system is
additionally installed. Such combustion units are characterized by fully auto-
matic operation and low emissions at thermal capacities of several MW up to
some 10 and more MW and are mainly located at places where wood dust is
produced as a residue, such as e.g. the furniture industry.

7.3.1.3 Coalification
In this process, woody biomass is heated up in a nearly oxygen-free environ-
ment. Up to about 200 1C, drying occurs, followed at higher temperatures with
pyrolytic decomposition of the organic compounds. Substantial liquid and
gaseous residues such as tar and carbon monoxide are released in the course of
creating the final product, charcoal.
Such processes can be realized with quite different technologies. In devel-
oping countries, for example, charcoal kilns are usually made from earth or
brick, although simple metal kilns are sometimes found. The efficiency of such
devices is low (less than 25%) and the airborne emissions of volatile organic
compounds are high. Additionally considerable amounts of toxic liquid resi-
dues are produced under certain frame conditions. In industrialized countries,
charcoal is produced in large fully automatic devices. Here a differentiation is
made between retort and flush gas processes. Within the former the charcoal is
produced in a batch mode in a closed container (i.e. retort) where the thermo-
chemical conversion from wood to charcoal takes place. The heat necessary to
allow this process to take place is obtained from the combustion of the gaseous
and liquid by-product. There are also continuous charcoal production systems
where the wood is fed constantly through a reactor. Within such a reactor
different zones with various settings of reaction conditions ensure that the
charcoal is produced during the migration of the material through the reactor.
Also here the gas and liquids produced as by-products are used as a source of
energy to keep the coalification process going.
In general the importance of such processes is relatively low in industrialized
countries because charcoal plays only a minor role within the energy systems of
the countries of the western world. However, charcoal is used to a certain extent
as a raw material (e.g. to produce activated charcoal for filtering) and as fuel for
leisure. In developing countries charcoal is used as a clean fuel for heating and
cooking.

7.3.1.4 Pyrolysis
The pyrolytic decomposing processes realized during pyrolysis are similar to
those during charcoal production, but here the process conditions are set to
ensure that the main product of the thermo-chemical conversion process is
liquid rather than solid. There has been a broad variety of technologies
developed during the last decades attempting to make pyrolysis oil for use in
engines without any additional processing.
Biomass-based Green Energy Generation 103
Most promising is flash pyrolysis in which fuel particles are heated very
rapidly (more than 1,000 1C s1) and remain in the hot zone for a very short
time (in general less than 1 s). After this very short time period, the liquid
compounds produced from the solid biomass by decomposing the organic
compounds (i.e. lignin, celluloses) have to be removed and cooled rapidly to
avoid further decomposition into gases. To date, flash pyrolysis reactors have
reached laboratory stage development level and the first pilot plants are
available.
Reactors with ablative impact designs, for example, decompose the biolo-
gical raw material primarily into liquid components on the surface of a hot
rotation wheel (Figure 7.7). On the surface of this wheel the solid biomass is
‘‘melted’’. To avoid further decomposition, the produced components have to
be removed quickly from the hot zone close to the rotating wheel. After that
they are cooled down to produce the desired liquid energy carrier. Necessarily,
gaseous and solid components are also produced, which are used to heat the
wheel.
Pyrolysis oil is a mixture of different hydrocarbons (many of which are partly
oxygenated) along with charcoal, ash and water. The actual composition is
strongly dependent on the pyrolysis process as well as the specific process
conditions and the type of biomass. This is especially true for the average
composition and structure of the hydrocarbons (e.g. chain length, degree of

Wood chips

Filling
Rotating hot disc

Pressure
(ca. 30 bar)

Operation

Figure 7.7 Pyrolysis system based on a hot rotating wheel.7

104 Chapter 7
double bonding). This oily liquid can be toxic and is in most cases not stable in
air. Additionally the conversion efficiency of the available fast pyrolysis pro-
cesses is relatively low. The average heating value of pyrolysis oil is approxi-
mately 40% that of petroleum-based fuels.
The goal of pyrolysis is the provision of a liquid energy carrier that can be
used directly in engines for e.g. the provision of heat and electricity. But so far
the pyrolysis oil produced in the available plants cannot be used directly in
existing engines. Therefore upgrading of the produced oil is necessary. For
example, charcoal and ash particles need to be removed to ensure a sediment
free fuel and, to increase stability, double bonds need to be reduced by adding
hydrogen to yield saturated hydrocarbons which are then cracked or remain as
paraffin waxes in the pyrolysis oil. Additionally other measures have to be
taken to ensure the viscosity and combustion behaviour required by the
respective engine. Like the fast pyrolysis process itself, these upgrading tech-
nologies are not fully developed yet. Because of these technical and economic
constraints, there are no applications known for the provision of pyrolysis oil
as a source of energy on a fully commercial basis.
Nevertheless few industrial applications are realized to produce liquids to be
used as a raw material (e.g. as liquid smoke).

7.3.1.5 Gasification
Gasification describes the complete conversion of solid biomass at high tem-
peratures to a gaseous fuel by adding a small amount of oxidizing agents to the
gasification process. Unlike coalification and pyrolysis, gasification of biomass
is realized in the presence of a limited amount of oxygen. The main objective of
gasification is to transfer the maximum possible share of the chemical energy
within the feedstock into a gas.
This so-called ‘‘producer gas’’ can be used on the one hand as a fuel for the
provision of heat through direct combustion or used in engines, turbines or
even fuel cells. On the other hand the producer gas can act as a feedstock for the
production of liquid and/or gaseous fuels (like Fischer–Tropsch diesel, bio-
methane, methanol and hydrogen).
Biomass gasification consists of the following, more or less spatially dis-
tributed, steps: heating and drying of the biomass, pyrolytic decomposition of
the biomass (i.e. extracting the volatile components by heating) and gasification
(i.e. partial oxidation of the biomass, partial reduction of the oxidation pro-
ducts [CO2 and H2O to CO and H2] and simultaneous transformation of solid
carbon to CO).
The physical and chemical processes of biomass gasification are carried out
in a variety of different forms of equipment and technical concepts. Each of
them offers certain advantages and disadvantages concerning feedstock possi-
bilities, plant size and gas quality.
The gasification techniques can be distinguished related to different criteria
such as reactor type (fixed bed or fluidized bed), gasifying agent (air, oxygen, or
steam), heat supply into the reactor (directly or indirectly heated) and reactor
Biomass-based Green Energy Generation 105

Figure 7.8 Principle of an updraft gasifier (left) and a downdraft gasifier (right).4

pressure (atmospheric or pressurized). Over the years, a considerable variety of

biomass gasifiers has been developed.

 In fixed-bed reactors (Figure 7.8), the feedstock is exposed to the gasifying

agent in a packed bed that slowly moves from the top of the gasifier to the
bottom, where the ash is discharged. Fixed-bed gasifiers are dense-phase
gasifiers characterized by a relatively large amount of fuel exposed to a
limited amount of reactive gas. In fixed-bed reactors the feedstock occupies
most of the reactor volume.
 Fluidized-bed reactors are lean-phase gasifiers having a low ratio of solid
to reactor volume. Typically, the feedstock occupies only a small fraction
of the total reactor volume. Fluidized-bed gasifiers are classified,
depending on the intensity of fluidization, as bubbling fluidized-bed gasi-
fiers, circulating fluidized-bed gasifiers or entrained flow gasifiers.
 Gasifiers have also been developed that cannot easily be classified as
belonging to one of the former groups but have features of both.

Commonly, the goal of gasification is not to provide gaseous fuel itself but to
provide an easy to handle and environmentally sound intermediate energy
carrier with clearly defined characteristics that can be converted easily into
another, more valuable, energy carrier, for example electricity or biomethane as
one possible biofuel. To reach that goal, gas cleaning is usually necessary to
ensure a long lifetime of the downstream conversion device because the gas
produced within the gasifier does not usually match the fuel requirements in
terms of condensable organic compounds and/or particles.
106 Chapter 7
The gas leaving the gasification reactor is often called producer gas. The same
name is also used if this gas is cleaned to match the requirements for com-
bustion within e.g. an engine or a turbine for the provision of electricity (and
heat). If the gas is conditioned to fulfil certain requirements concerning the
composition and it is intended to use this gas for the synthesis of liquid or
gaseous biofuels it is called synthesis gas (or in abbreviated form ‘‘syngas’’).
For the provision of a gas to be used as a fuel for CHP-systems (e.g. engines,
turbines) a raw gas cleaning operation – either low temperature wet gas
cleaning or, alternatively, hot gas cleaning – can be applied. The effectiveness of
wet gas cleaning (e.g. cyclone and filter, scrubbing based on chemical or phy-
sical absorption and ZnO-bed) has been well proven for large-scale coal gasi-
fication systems. On the contrary, not all elements of hot gas cleaning (e.g. tar
cracking, granular beds and filters, physical adsorption or chemical absorption,
ZnO-bed, physical absorption) have reached technical maturity yet. Never-
theless, hot gas cleaning offers benefits for the overall energy balance and with
regard to the avoidance of contaminated waste water.
Additionally the producer gas can be conditioned to fulfil the required gas
characteristics especially for the conversion route to fuels (Figure 7.9). For that
different system components can be applied: hydrocarbons within the product
gas can be converted by means of an additional steam reforming step resulting
in a higher H2/CO ratio.
The cleaned producer gas can be used for the provision of electricity within
already existing gasoline engines or gas turbines. The former is demonstrated

Biomass (e.g. solid biofuels)

Gasification

Gas cleaning

Gas conditioning

Syngas (m CO + n H2 + o CO2)

Fischer- Dimethyl-
Methanol CO-shift
Tropsch ether Methanation
synthesis conversion
synthesis synthesis

FT-Diesel MeOH DME SNG H2

Liquid Gaseous

Figure 7.9 Possible routes to the production of liquid and/or gaseous fuels from
producer gas derived from biomass.
Biomass-based Green Energy Generation 107
within the gasification plant in Güssing, Austria, where wood chips are gasified
and the cleaned producer gas is then used within an engine-based CHP-plant
for the simultaneous provision of heat and electricity. Similar systems are in
operation and also under planning in other European countries. The next
development step will be biomass-based integrated gasification combined cycles
(IGCC).9
Alternatively the cleaned and conditioned gas can be used for the provision
of liquid and gaseous fuels. The necessary technology is currently under
development (see Chapter 8).

7.3.2 Physico-chemical Conversion

Based on physico-chemical processes vegetable oil can be extracted from biomass
to be used in the chemical and other industries and for energy generation.
Compared to solid biofuels vegetable oil has some outstanding advantages. It is
easy to store, has high energy content and can be used as an energy carrier e.g. in
some engines or combustion units without major problems. However, just like
crude oil is not generally useful in its raw or unprocessed form and thus needs
processing in a refinery to yield kerosene, diesel fuel or fuel oils for energy gen-
eration, fats and oils often need a chemical treatment in order to meet the fuel
characteristics of conventional diesel fuel to allow easy use in existing engines. The
physico-chemical biomass conversion comprises the oleochemical unit operations:

 extraction (pressing, solvent extraction, rendering);

 chemical and/or physical refining;
 conversion into fatty acid methyl esters

described in more detail in Chapter 9.1.

The final step, i.e. conversion of refined vegetable oil into fatty acid methyl
ester (FAME) is shown in Figure 7.10. According to this exemplarily shown
process the mixture of cleaned vegetable oil together with a catalyst and
methanol is pumped with a low velocity through a vertical pipe. The low
velocity of the liquid ensures that the glycerine produced during the transes-
terification process can settle in the reactor and can be removed for use as a raw
material. After the removal of the remaining methanol, the liquid is cleaned
by a multi-stage washing process. The produced FAME is now ready to be
used as a fuel either within power trains for cars and trucks or in engine-based
CHP-systems.
Pure vegetable oil can be used in some existing engines either for mobile
(e.g. in cars) or stationary application (i.e. in CHP-systems), but in most cases
it lowers engine lifetime and increases maintenance requirements. Therefore
only under very specific frame conditions could the use of crude vegetable oils
be a promising option for the transportation sector or to provide power (or
decentralized electrification and heat, if required) especially in rural areas. This
is true for developing as well as for industrialized countries.
108 Chapter 7

Figure 7.10 Continuously working transesterification process for FAME

manufacturing.4

Table 7.5 Selected properties of diesel fuel, FAME and rape oil (various
sources).
Diesel fuel/light
heating oil FAME Rape oil

Density (15 1C) in kg m3 820–845 875–900 900–930

Viscosity (40 1C) in 2.0–8.0 3.08 78.7
mm2 s1
Flash point in 1C 455 130 min. 220
CFPP-value in 1C max. 0 max. 0
(summer/winter) max. –20 max. –20
Sulphur content in max. 350 max. 100 max. 20
mg kg1
Cetan-value min. 51 55
Calorific value in MJ kg1 42.7 37.9 min. 35

FAME can be used directly as a substitute for diesel fuel in conven-

tional compression ignition engines (see Chapter 8) or in CHP-systems with
installed capacities from some tens of kW up to several MW (Table 7.5).
The prerequisite for this is that the produced FAME fulfils the existing
standards. Normally this is easily possible with FAME based on rape oil
but it might become difficult using other types of vegetable oil (like crude
palm oil).
Biomass-based Green Energy Generation 109
Besides the use of vegetable oil for the production of FAME also waste
cooking oil (waste grease) can be used under certain conditions. Due to limited
availability of waste grease this option is not playing a significant role in the
market so far.
Available experiences with FAME based on rape oil (RME) have shown
that there are no significant problems when using them in conventional diesel
engines although the higher solvency of RME compared to conventional diesel
fuel requires biodiesel compatible fuel lines.

7.3.3 Bio-chemical Conversion

Nearly all biomass is eventually decomposed naturally through biological
processes. Some of these processes can be harnessed to produce fuels.

 Composting occurs if oxygen is available. During composting the biomass

is degraded by bacteria mainly to carbon dioxide (CO2) and water (H2O)
while releasing low-temperature heat that can, in principle, be used via a
heat pump. But for the time being this option is only of theoretical
importance.
 Under anaerobic (oxygen-free) conditions, a variety of degrading pro-
cesses are employed by micro-organisms. Most relevant to energy are
ethanol production via alcohol fermentation and biogas (methane) pro-
duction via anaerobic digestion.

7.3.3.1 Alcoholic Fermentation

Sugar can be converted to ethanol based on micro-organisms. Because starch
and even celluloses can be converted more or less easily into sugar, such bio-
mass streams are also a potential resource for the production of bioethanol in
addition to naturally sugar-containing crops like sugar cane and sugar beet (see
Chapters 8 and 9.3).
In power trains for vehicles, ethanol can fully or partly substitute gasoline.
But a larger volume is needed compared to gasoline because the LHV of
ethanol is lower (Table 7.6). The combustion of ethanol, however, requires a
lower air volume. Therefore the heating value of the mixture pressed into the
cylinder is more or less the same for ethanol and gasoline. This is the reason
why an engine powered by ethanol produces the same power as an engine
driven by gasoline.
Internal combustion engines must be specially adapted to run on pure
ethanol, because it shows different combustion behaviour compared to gaso-
line. Therefore in most countries ethanol is mixed with gasoline to a maximum
of 10% in which form it can be used without any known problems in existing
engines. Bioethanol is also being considered for powering fuel cells in future
design and applications.
110 Chapter 7
Table 7.6 Selected properties of fuels (various sources).
Ethanol Gasoline

Composition in %
carbon 52 86
hydrogen 13 14
oxygen 35 0
LHV in MJ kg1 26.8 42.7
in MJ l1 21.3 ca. 32.0
Density (15 1C) in kg l1 0.794 0.72–0.78
Viscosity (20 1C) in mm2 s1 1.5 0.6
Boiling point in 1C 78 25–215
Flame point in 1C 12.8 –42.8
Ignition temperature in 1C 420 ca. 300
Evaporation heat in kJ kg1 904 380–500
Minimum air volume in kg kg1 9 14.8
Octane-value 107 93

7.3.3.2 Anaerobic Digestion

During anaerobic digestion, organic material is decomposed in an oxygen-free
atmosphere by bacteria that produce a gas, called biogas or, depending on
where it is produced, landfill gas (LFG) or digester gas and usually containing
methane (CH4) and carbon dioxide (CO2) plus some impurities of minor
importance. Such decomposition occurs in nature, for example at the bottom of
lakes within the sediments containing organic material, and takes place in
landfills and dumps where the organic fraction of the waste material is con-
verted into landfill gas.
In addition to degradable organic input and freedom from air, nutrients for
the bacteria and absence of harmful, pathologic and inhibiting substances are
needed for a successful biogas production. Also the organic material should be
easily accessible to the bacteria. Well-suited for anaerobic digestion are agri-
cultural residues (e.g. liquid manure, leaves from sugar beet), residues from the
food processing industry (e.g. slurry of fruit and potato processing, some types
of slaughterhouse residues) and sewage sludge. Only biomass containing lignin
such as wood cannot be degraded by anaerobic bacteria.
During anaerobic digestion, organic matter is degraded by three different
kinds of bacteria: fermentative, acetogenic and methanogenic. The first two
bacteria families degrade the complex organic compounds of biomass into
simpler intermediates (Figure 7.11). These intermediate products are then
converted to methane and carbon dioxide by the methanogenic bacteria.
Anaerobic digestion relies on a dynamic equilibrium among the three bac-
terial groups, which is affected by e.g. temperature. Most digesters operate in
the mesophilic temperature regime around 35 1C. Some operate in the ther-
mophilic regime around 55 1C. Up to the temperature of peak microbial
activity, higher operating temperatures produce greater metabolic activity
within either regime. Additionally the pH-value and the composition of the
Biomass-based Green Energy Generation 111

H2, CO2 methanogenic bacteria CO2

acetate CH4
biomass
protein fermentative
carbonhydrate bacteria
fat
propionate
butyrate acetogenic H2, CO2
succinate bacteria acetate
alcohol

1. and 2. step 3. step 4. step

hydrolysis and digestion acetate production methane production

Figure 7.11 Anaerobic digestion process scheme.10

Table 7.7 Yield targets of biogas for different substrates (various sources).
Yield of biogas in Yield of biogas in
m3  mto1 organic m3  mto1 organic
Material dry matter Material dry matter

Liquid manure from 250 Paunch content 420–520

beef
Liquid manure from 480 Rey straw 300–350
pork
Droppings from 450 Potato herbs 560
chicken
Sewage sludge 400 Sugar beet leaves 550
Organic waste from 170–220 Food residues 80–120
households
Waste fat 1040 Waste water from 500
brewing
industries
Roadside green 550 Waste water from 650
sugar industries

biomass in relation to easily degradable biomass compounds affect the bacterial

balance. For optimal fermentation, pH-values between 6.8 and 7.2 are often
maintained by use of buffers.
The composition of the produced biogas is typically about two-thirds
methane and one-third carbon dioxide. Additionally the biogas may contain
trace substances such as H2S, depending on the composition of the biomass, the
process conditions and other parameters. The LHV of biogas, which depends
mainly on methane content, ranges from 14 to 29 MJ m3.
Expected biogas yields for different substrates are given in Table 7.7. Already
within the animal stomach digested substrates like animal manure and drop-
pings show in general smaller yields than fresh material, e.g. maize silage or
waste grease.
112 Chapter 7
The bacteria use relatively little of the biomass energy for their own survival
and only a very small amount of heat is produced (this is the reason why biogas
plants have to be heated), making the conversion process of the organic
material into biogas fairly efficient. Slurries of organic matter in more than
66% water ensure optimal process conditions with a good access of the bacteria
to the organic material so that gas yield is maximized. To optimize production
rates, the slurry should be kept at temperatures of 28 to 35 1C or 50 to 70 1C,
which correspond to the ranges appropriate to different bacterial species.
Production will also occur at lower temperatures, but essentially stops at 10 1C.
Due to the low conversion rates such low temperature level has no importance
for technical processes optimized to maximize the space time yield.
Typical feedstock for biogas production is organic waste material available
with a high water content and/or – in some countries because of the feed-in laws
existing in these countries – energy crops (like maize silage). Examples for the
former are sewage sludge, animal manure and organic residues from some types
of agricultural production and the food processing industry.
Within biogas plants, preparation of the feedstock is needed that might
include short-time storage, sedimentation of mineral contaminants (like sand,
stones), reducing the material into small pieces, mixing of different types of
feedstock to maximize the gas yield and heating to the required temperature
level. Then the feedstock is pumped into the biogas reactor where anaerobic
fermentation takes place. For successful operation, the bacteria must always be
well mixed with the organic material. It is also important to realize a good
temperature distribution within the reactor. The biogas is removed from the
top of the plant and, after removal of impurities like water, stored before it is
used as a source of energy.
The digested material is removed from the reactor and stored in a tank where
a small amount of additional biogas is produced. Therefore this storage facility
should be covered gas tight to avoid the release of the produced gas into the
atmosphere because biogas is harmful to global climate. This digested slurry is
used as a fertilizer, because it contains the nitrogen that was originally part of
the feedstock. Since biogas technology helps to close the nutrient cycle, this is of
increasing importance in environmentally sound management of organic
material (Figure 7.12).
Biogas can be used in a boiler, stove or engine for the provision of heat,
mechanical power and/or electricity. A part of the heat and electricity produced
is often applied to warming up the feedstock and running of the plant. This is a
system layout most widely used in industrialized countries. Alternatively or
additionally, biogas can also be fed into the natural gas system. To do so
requires an upgrading of the biogas to fulfil the natural gas standards. This is
done in Switzerland, Germany and Sweden, for example. Based on such a feed-
in into the gas grid the use of the biogas – in the form of biomethane – as a
transportation fuel is then easily possible. Nevertheless the biomethane can also
be used for an environmentally sound and climate neutral high efficient heat
provision in very densely populated areas (i.e. downtown areas in big cities)
using e.g. existing condensing boilers.
Biomass-based Green Energy Generation 113
combined heat and power system

heat power

biogas

heat reservoir

stable

material flow
animal manure

pit for
material gas proof storage for
preparation digested material

Figure 7.12 Biogas plant using animal manure as feedstock and commonly used in
countries like Denmark, Germany and Austria.11

7.4 Biomass Use

The available biomass potentials discussed in Chapter 3 can be converted by
the options outlined in Chapter 2 into thermal energy, electric energy and/or
fuels. However, individual technologies for miscellaneous fields of application
are in different states of technological development; some are industrially used
or ready for the market and others are still at research or pilot plant level. This
technical variety combined with the expected increase of the potentials thereby
represents an ideal possibility for integrating biomass successfully into the
energy system.
Considering the potentials mentioned exemplarily for Germany and the
already realized energetic use of 675 PJ a1 in 2007,8 the available potentials
are already used to a considerable extent. While residues, by-products and
waste are the prior ranking biomass sources of energy at present, an increa-
sing amount of energy crops are used as feed for the German energy net-
work. Currently cultivated energy crops are mainly rape-seed and biogas
substrates (i.e. energy maize), which are grown on a land area of roughly 1.5
Mio ha. This corresponds to approximately 10% of the German agricultural
land area.
The current energetic use of biomass and the related requirements of area are
described in Table 7.2 and can be summarized as follows:

 Heat. Heat is mainly supplied by small-scale combustion systems in

households and (to a limited extent) by combined heat and power plants
(CHP) (approximately 311 PJ of fuel energy in 2007). It has to be noted
114 Chapter 7
that the bigger share of this wood is not covered within the official felling
statistics, but traded locally in an informal manner from various sources.
 Power. Electric energy is primarily produced via the direct combustion of
solid biofuels within power plants equipped with a steam cycle as well as by
making use of biogas in combined heat and power plants (e.g. gas engines).
Furthermore biogas from sewage plants and landfills as well as liquid
bioenergy carriers (mainly vegetable oil) is used within combined heat and
power plants (CHP). In 2007 approximately 23.4 TWh have been gener-
ated by the use of biomass (including electricity generated from organic
waste within waste incineration plants).
 Fuels. In 2007 mainly biodiesel (FAME) and to a minor extend bioethanol,
which was processed to ETBE, were produced. Overall roughly 156 PJ has
been sold on the German energy market.

The current use of biomass amounts to almost 783 PJ (primary energy

equivalent) in 2007, which is about 5% of the primary energy consumption
of Germany.12 If the present frame conditions persist in the future, primarily the
power production from biomass will increase in years to come. For the different
possibilities of using biomass the following tendencies are recognizable.

 A market expansion is expected for first-generation biofuels, e.g. biodiesel

and bioethanol, with the focus on bioethanol. Due to the given (land)
restrictions in Germany it is likely that increased imports could result from
this development. Assuming a consistent progress in technical develop-
ment, BtL-plants might be available for commercial use around the year
2020 at the earliest.13 And it is still not known to what extent gaseous
bioenergy carriers, e.g. synthetic natural gas (Bio-SNG) or biogas, could
gain importance within the traffic sector.
In this respect biomethane seems to be a very promising energy carrier,
because it can be fed into the existing natural gas grid and support the
security of supply especially for Central and Western Europe. For
the generation of biomethane two conversion pathways are available: the
thermo-chemical biomass conversion with gasification and methanation
(Bio-SNG) and the bio-chemical biomass conversion with anaerobic
digestion (biogas).
The conversion technologies for Bio-SNG and biogas differ significantly
concerning e.g. the biomass feedstock, the conversion principle, the
state of technology, the installed capacity per conversion unit, the avail-
able technical experiences and the R&D demand. But both conversion
routes allow the provision of biomethane fulfilling the requirements
for a feed-in into the existing natural gas grid. Therefore biogas as well as
Bio-SNG has to be upgraded to guarantee a similar calorific value
and chemical composition compared to natural gas. Only if this pre-
requisite is fulfilled can biomethane be used in a mixture with natural
gas by using the same gas grid infrastructure without creating problems for
the end user.
Biomass-based Green Energy Generation 115
Both biomethane production paths complement one another in an ideal
way. While the thermo-chemical route focuses on solid biofuels (e.g. wood,
straw) the bio-chemical route uses wet biomass (e.g. animal manure, maize
silage). The latter will be realized with plant capacities in the one-digit
thermal MW-scale and the former in the two- to three-digit MW-scale. The
provided product is basically similar and can be used together with natural
gas in any mixture. The erection of the biogas and Bio-SNG conversion
plants can be planned directly at the established gas grid.
 Based on the current support schemes for the generation of electri-
city, biogas from anaerobic digestion will increase further and might
contribute significantly more to the generation of electricity from biomass;
this will only happen if the support schemes are intensified and/or highly
efficient techniques for generating electricity (e.g. by gasification) be-
come market-ready and are available cost-efficiently. The use of liquid
biofuels (i.e. vegetable oil) for the provision of electricity will be of minor
importance in comparison with the transportation sector. Due to the
expected dynamic price development within the global vegetable oil
markets the market development is characterized by substantial
uncertainties.
 The further development of the provision of heat from solid biofuels
depends strongly on the energy price level of fossil fuels (i.e. crude oil price)
as well as on the given frame conditions (e.g. a renewable heat law cur-
rently under discussion within the German government, the financial
consequences of the carbon dioxide trading scheme, the carbon tax). Those
developments are very difficult to predict.
 Additionally biomass has to be made available for the ‘‘new technologies’’
for the conversion of biomass into liquid or gaseous secondary energy
carriers (synthetic biofuels (BtL) and synthetic natural gas (Bio-SNG)).
These technologies could be available from 2015 to 2020 onwards at a
(semi) commercial stage. In order to cover the upcoming biomass demand,
increasing build-up of short rotation plantations is expected.
Based on these developments the overall energetic use of biomass might
increase up to 850 to 950 PJ a1 until the year 2010 (depending on heat
utilization) in Germany, which is about 6 to 7 % of the expected primary
energy demand.

7.5 Final Considerations

Against the background of the growing biomass markets – and for this reason
an increasing use of the available potentials – competitions will necessarily
arise.14–18 These are expected on the following levels:

 Land area;
 Biomass;
 (End-)energy sources.
116 Chapter 7
The development in Germany as well as in other European countries
throughout recent years shows that all these possible competitions exist in
reality. Thus competitions so far influence prices on all different levels. While
land and biomass competition rather result in increasing prices due to estab-
lishing of additional demand, price increasing effects might be restrained in the
field of (end-)energy sources with an increasing substitution of fossil fuel energy
at a high energy price level because of reduced price volatility of fossil fuels. The
different levels of competition are analyzed in the following exemplarily for
Germany. But it is expected that the conclusions to be drawn are also true for
most industrialized countries of the western world.

7.5.1 Competition Areas

Competition can arise on the following levels or areas:
Level ‘‘Land area’’. An increase of the use of biomass can lead to conflicts
around the limited agricultural land area. Basically this kind of competition is
only solvable by an expansion (such as in Australia or Argentina) or by a raise
in the productivity of the already used agricultural land.
In Germany, for example, today there are already sporadic competitions
about agricultural land of good quality for the cultivation of rape seed (for
producing FAME) and biogas substrates (for electricity production); the con-
sequences are increasing land lease prices. Even if the agricultural land avail-
able in the years to come for energy crops is known roughly, locally adjustment
problems can occur and therefore lease prices could rise at least temporarily.
Additionally interactions with the international agricultural markets (and also
perhaps with the cost-attractive import options) can be expected.

Level ‘‘Biomass’’. The increased biomass use goes along with an additional
demand: in Germany, for example, bioethanol, biodiesel and biogas plants
demand an increasing amount of e.g. cereals and oil seeds from the regional,
national and global agricultural markets, which so far have been used mainly
for food and fodder as well as for chemistry. Additionally there is a demand
from the energy markets for forest and industry (residual) wood to be used
for the provision of solid bioenergy carriers; this stands in competition to the
markets for wood as a raw material to be used e.g. in the pulp and paper
industry as well as for the production of furniture. The results are – and this
appeared in the past on the cereals and oil seed markets as well as on the
wood markets – rising prices. Also, in the field of residues, by-products and
waste, the price structure has partly been changed significantly due to the
emerging new energy markets (i.e. for demolition wood or certain organic
waste fractions, which can be used e.g. in biogas plants). So, for biomass
resources national and even international markets were developed during the
last years, which answer the resource competitions by quantity-price pro-
blems (which means the desired quantities are not available at the intended
price at the market).
Biomass-based Green Energy Generation 117
Competitions for the biomass are basically solvable by an expansion of the
production, an import and a substitution with other (non-biogenic) products
(i.e. substitution of woody materials by plastics or stones). However, they differ
according to the organizational extent and the necessary time periods.

 Expansion of production. The (a priori limited) supply of products from the

agricultural and forestry primary production can be expanded only by an
expansion of production. This is possible by a more intensive production
(i.e. higher yield per hectare) and/or a production on land not used on a
commercial basis so far. For the latter option the needed land areas in
Europe are available (see above). In contrast to that, emerging competi-
tions about residues, by-products and waste can not be met by an
expansion of the agricultural and forestry primary production or only to a
very limited extent.
 Import. Since many products of the agricultural and forestry primary
production are already today traded on international markets, increased
imports to Germany are basically possible. This option can in principle be
realized quickly and on a large scale. However, increased imports lead
(from a global point of view) to an expansion of the land areas used for
agriculture and/or forestry somewhere else. And these additional land
areas are available on the long term only if they are managed in a sus-
tainable way (therefore they can not be established immediately). Addi-
tionally, due to the strong influence of the climate on the agricultural and
forestry yields, the international markets for wood and agricultural goods
are characterized by partly significant price fluctuations. If a new high
demander enters such a market (in this case the energy industry), the
already unstable market equilibrium will be additionally disturbed; the
expected result is a rise in the market prices. Due to such rising prices it is
worthwhile for the farmer and the forester to expand the production with
the consequence that the prices will probably fall again after a certain
period of time. If thus the additional demand of the energy industry rises
moderately, the prices could in the medium term move back to the original
level. For residues, by-products and waste international markets are of
clearly smaller importance.
 Substitution. Additionally substitution effects can appear (that means that
one kind of biomass is replaced by another; e.g. replacement of woody
biofuels by herbaceous biofuels). To what extent these options have an
effect on the markets depends on the available or to be developed technical
possibilities and the attainable respectively demanded prices on the
market.

Level ‘‘(End-)energy Sources’’. On the background of an approximately

stable energy consumption in Germany, (end-)energy sources provided from
biomass necessarily compete with other energy sources providing a compar-
able energy service. These competitions result in changing market shares of
118 Chapter 7
the different available alternatives. This could result in a stabilization of the
energy price level because of the declining demand for fossil energy sources.
The expansion of the use of biomass for heat provision in small scale units
today already leads to noticeable substitution effects in using e.g. light fuel oil
or even natural gas. This is intended by the government for environment and
climate protection reasons and supported by numerous laws and regulations.
Assuming a free energy market, the consumer will choose the most promising
option. Thus supply and demand will be adjusted over the respective market
price. Since the energy market is traditionally strongly influenced by political
measures e.g. for environmental reasons, the definition of an appropriate fra-
mework ensures that the politically desired options have good development
perspectives for the customer. Because the prices for energy for the final con-
sumer will remain orientated on the fossil energy price level, the prices for end
energy based on biofuels will also depend on the market. In Germany, for
example, this is so far only true for the prices for the provision of heat and
transportation fuels because within the field of electricity the prices are fixed
by the feed-in law and therefore so far not noticeably affected by the price of
the fossil energy sources. But even then the decoupling from the fossil energy
price – if at all – is to be expected only in the medium to long term. Nevertheless
it can come to effect in restraining increasing prices.

7.5.2 Effects on Competition

Altogether, there are wanted and unwanted competitions on very different
levels, which can result in very different – intended and unintended –
consequences. From this the following fundamental statements can be derived.

 Competitions do not lead per se to a lack of land areas or biomass. There

are various compensation possibilities (e.g. expansion of the culti-
vated land areas, import, substitution, higher yields). Additionally there
will be increasing price, which can be connected with appropriate
feedback effects and therefore do not have to be assessed negatively a
priori.
 Since the covering of the energy demand by biomass is supported by the
legal framework, the increase of prices must be kept as small as possible.
This is true because the markets for food, fodder and raw material (e.g.
wood) coupled with the bioenergy markets should not be disturbed in a
long lasting way.
 Presumably possible increase of prices can be kept small if the increase in
the demand (concerning bioenergy) corresponds with the increase of
supply (due to land areas no longer needed for food and fodder produc-
tion). The speed of the expansion of the use of bioenergy within the energy
system therefore should be oriented at the technical and organizational
possibilities for the expansion of the biomass production; internationally it
might be essential for the volatility of the markets.
Biomass-based Green Energy Generation 119
 At the same time the market expansion must allow for an increased
technical learning and must support as quickly as possible the development
and market introduction of (energy) efficient systems. On the one hand this
is necessary to allow the limited and valuable biomass to be used as effi-
ciently as possible and on the other hand the cost reduction potentials can
be exploited immediately. In parallel the development of a broad basis of
the used biomass fractions is necessary to compensate possible price
fluctuations of individual biomass fractions, for example as a result of
climatically indicated yield variations.
 The rising prices, which can be expected in the case of overheated
development of biomass and bioenergy use, could on the other hand
support price stabilizing effects for the general price level of energy
sources.

7.5.3 Configuration Approaches

The consequences of such competitions – and these are e.g. rising prices – can
be reduced (but not completely avoided) if the political frame conditions for the
further development of power production from biomass are set adequately. To
identify the competitions least wished from a socio-economic and national
point of view, appropriate goals for increased biomass use must be defined.
Such goals could e.g. be:

 protection of climate and finite resources;

 economic development of rural regions;
 development of conversion technologies for the global energy markets to
strengthen the national economy and to create (industrial) employment;
 security of supply (i.e. cost effective energy supply, sustainable energy
system).

Against the background of the multiplicity of partly contrary possible goals –

and therefore in the short term hardly possible definition of goals on which a
political consensus might be reached – the identification of a comprehensive
and widely acceptable strategy for the avoidance of unwanted competitions is
almost impossible from the current point of view. Such a strategy can only be
developed in the long term within a discourse throughout the overall society
and/or a political process, which adequately considers the entitled (conflicting)
interests of the groups concerned.
For the support of such a political process different indicators are presented
exemplarily in Table 7.8 to be used for the evaluation of different targets. The
indicators are limited to these material flows, for which from a present point of
view a substantial ‘‘potential for competition’’ is to be expected. It has to be
noted that the presented criteria are not final and not complete; certain aspects
(e.g. aspects of import) are not considered. Nevertheless it becomes obvious
that the different use paths show both strengths and weaknesses regarding
defined goals.
Table 7.8 Analysis of different options for the use of biomass exemplarily for Germany.14

120
Development of Security of
Usage path Economy Climate and resources protection Development of technology rural regions supply
Dependency from
oil (calculations,
Specific CO2- orientated at ‘‘oil
Specific actual Marginal costs on Level of fuel uti- equivalent- Specific invest- dependency indi-
costs(hct an oil basisa lization– netb savingsc (g Development ment costs Local processing cator’’ of the
Energy fuel** kWhoutput1)* (US$ barrel1) (%) kWhoutput1)* potentiald (h kWoutput1)* possible World Bank)

(‘‘Pure’’) heat solid biofuels 6–9 45–75 70–85 140–250. Low 300–1500 Energy provision Medium
and use
Power (CHP Biogas 10–25 No direct 40–55 480–550 Medium 2000–4500 Medium
plants solid biofuels 13–25 correlation 25–60 450–600 Medium 2400–7000 Energy provision
included) (combustion)
solid biofuels 12–27 45–55 500–600 High 4000–6000
(gasification)
vegetable oil 15–37 20–60 170–320 Low 950–2350 Energy provision
and use
f e
Fuel vegetable oil 4–6(42–69) 40–75 35–65 170–180(85–95) Low 40–380 High
biodiesel 5–7(52–73)f 55–80 50–60 185–250(95– Low 120–210 Biomass
125)e provision
bioethanol from 8–12(68–104)f 75–120 45–50 40–200(25–123)e Medium 2080–3740
starch (corn)
bioethanol from B12(108) f
B125 B45 210–360(100– High B2400 Very high
lignocelluloses 190)e
(straw)
synthetic biofuels 8–10(86–93)f 95–110 B45 200–205(100– High 1900–2100
(BtL) 150)e
biogenous 10–12(97–113)f 110–125 B55 215–260(100– High 6740–26,700
hydrogen 120)e
f
Natural gas sub- biogas 5–16(59–91) 60–100 45–85 160–245(100– Medium 1470–5160 Energy provision High
stitute (mainly 150)e
fuel) synthetic natural B7.4(74)f B80 B65 160–180(100– High B990
gas Bio-SNG 110)e

*for heat: kWhth respectively kWth (th: thermal); for power: kWhel respectively kWel (el: electrical); for fuels and natural gas substitute: kWhfe respectively kWfe
(fe: fuel equivalent).
**if not indicated differently, the conversion of the fuel is based on combustion technology.
a
for liquid biofuels the costs for the distribution until the filling pump are included, but no profit margins for producers and traders.
b
rate of fuel utilization relating to the biomass (solid biofuel, corn, oil seeds) respectively the biogas potential of wet biomasses (manure, silage).

Chapter 7
c
in relation to the appropriate references (heat: oil or gas burner/power: power mix in D; CHP is incorporated/fuel: petrol or diesel vehicles).
d
concerning an increase of the rate of utilization, CO2 and cost reduction; development potentials for the mitigation of emissions (e.g. particulate matter) are not
incorporated.
e
additional declaration in g km1.
f
additional declaration in hct lfe1.
Biomass-based Green Energy Generation 121
Regarding the political setting of the frame conditions within the (bio-)-
energy system for minimizing unintended competitions the different, partly
conflicting goals of an intensified biomass use for energy have to be evaluated
and assessed in order to derive appropriate priorities.
It is rather unlikely – regarding the high complexity of the goals and inter-
ests – that there is a silver bullet, which can avoid all use competitions on all the
different levels they might occur. This means that for the time being all pro-
mising pathways for the conversion of biomass into useful energy have to be
developed further. Such an approach is also supported by e.g. the following
considerations.

 Many biomass conversion pathways are still characterized by relatively

new conversion technologies. By an appropriate and target-oriented
research the costs and/or environmental effects, but also the used biomass
fractions, might be optimized and the areas of application might broaden
significantly. For example, the bioethanol production in Brazil, which has
been developed continuously throughout the last three decades, today uses
only a small fraction of the energy input and emissions compared to the
time of its market introduction. Such improvements in technology, eco-
nomics and environment are not fully foreseeable at the time, when deci-
sions regarding market introduction or even intensified R&D are taken.
Therefore the exclusion of certain technologies and/or conversion path-
ways is not recommended and thus a broad development of technologies
for an efficient biomass use is promising.
 In the future larger energy crop potentials will be available. Therefore for
the agricultural and – to a lesser extent – for the forestry primary pro-
duction, advanced and improved crops as well as innovative cultivation
systems are urgently needed. Presently discussed conversion pathways for
biomasses containing special substances therefore need a certain biomass
diversity and thus (compared with today) a larger range of energy crops
used – with all advantages exerted by it.
 The international and EU-wide agricultural commodities markets showed
in the past that – with certain restrictions – they can react flexibly to
changing frame conditions. This does not lead to basic supply problems,
but to increased prices for agricultural products. As a result the agri-
cultural production might increase and prices decrease again. Therefore it
should be possible in the future to serve growing markets by an expansion
of the agricultural and forestry production – however, with initially and
eventually durably higher prices.
 Finally the definition of acceptable political targets with high priority (e.g.
security of supply versus rural development) might take a very long time.
And the necessary discussion within society overall would slow down the
further development of an increased use of biomass within the energy
system. Furthermore the value of different political goals within society
could change – depending on the political development and special events.
Here the development of different goals in parallel, covering the majority
122 Chapter 7
of the targets currently on the political agenda, offers certain stability
against such changes and thus a better planning security for the players
involved.

7.5.4 Conclusions and Recommendations

For environmental and climate protection reasons biomass should contribute
significantly more to cover the demand for heat, electricity and fuels in the
future energy system. Parallel to that biomass is to be used increasingly as a raw
material (e.g. biorefinery) besides the raw material markets established for
generations (such as e.g. the use as building timber or within the pulp and paper
industry). And irrespective of that the globally increasing demand for food and
fodder due to a still increasing population on Earth must be secured globally
and locally. Therefore the question of whether biomass can fulfil all these
partially very ambitious and competing goals adequately in time gains
importance.

 By an increasing use of biomass – both as a source of energy and as a raw

material – potential and real competitions of use can be caused.
 A priori this competition can not be avoided but conversely can stimulate
innovative developments and hence help to exploit available efficiency
potentials.
 To promote a socially acceptable and politically enforceable development
path of an increased biomass use – under minimization of potential
competitions – a clear political goal definition for the global human
community would be helpful. Thereby the question has to be answered:
which political goals in energy, environment, agriculture, economy and
society can be realized with what priority under which frame conditions?
But it is likely that considerable time will pass before the prevailing opi-
nions converge in a certain direction.
 Therefore promising biomass conversion pathways should be developed
and improved in order to be able to assess different options on a sig-
nificantly improved database and, based on that, to propose political
priorities based on facts and not on visions. These priorities would have to
be updated regularly according to the latest technical developments and
system analytic findings.
 Against the background of expanding biomass markets it can be expec-
ted that prices tend to rise on short notice. As a consequence due to the
following national and international market adjustment processes more
biomass could be made available. Additionally rising prices of the bio-
mass help to exploit improvement potentials by the development of opti-
mized plants and systems. This again has an influence on the biomass
price.
 Finally price-stabilizing effects could be obtained on the use side by the
substitution of fossil energy.
Biomass-based Green Energy Generation 123
Altogether an expansion of the use of biomass as a source of energy leads –
due to the huge variety of possibilities to use biomass within our society –
inevitably to competitions on very different levels. This development thus
necessarily disturbs the established markets first. Thus it comes to adjustment
reactions and processes (e.g. prices rise on very different levels). This again
supports an expansion of the primary agricultural and forestry production as
well as the development of more efficient conversion systems and paths. In the
medium term this development results in new market equilibriums – eventually
even on, again, low price level. On the basis of such mechanisms, which can
additionally be overlaid by other effects, competitions could indeed support
and promote the further development of the use of biomass as a source of
energy. Market expansion rates adjusted to the development of the potentials
and political instruments supporting the market development aimed at plan-
ning dependability can help to reduce such increase of prices on the biomass
markets. However, the possibilities to influence these markets by political
measures are presumably significantly lower compared to oil price fluctuations
and effects initiated by it.

References
1. German Federal Ministry for the Environment, ed., Nature Conservation
and Nuclear Safety, Berlin, 2008, http://www.bmu.de/english/aktuell/
4152.php.
2. Ö. Gustafsson, M. Kruså, Z. Zencak, R. J. Sheesley, L. Granat, E.
Engström, P. S. Praveen, P. S. P. Rao, C. Leck and H. Rodhe, Science, 23
January 2009, 323(5913), 495.
3. M. Kaltschmitt, W. Streicher and A. Wiese, ed., Renewable Energy –
Technology, Economics and Environment, Springer, Berlin, Heidelberg,
2007.
4. M. Kaltschmitt, H. Hartmann and H. Hofbauer, ed., Energie aus Biomasse,
2. Aufl., Springer, Berlin, Heidelberg, 2009.
5. Fachagentur Nachwachsende Rohstoffe, ed., Biokraftstoffe, 3. Aufl., Gül-
zow, 2007.
6. D. Thrän, Personal communication, German Biomass Research Centre,
Leipzig, 2008.
7. PYTEC Thermochemische Anlagen, Personal communication, Hamburg,
2008.
8. F. Müller-Langer, Personal communication, German Biomass Research
Centre, Leipzig, 2008.
9. IEA Energy Technology Essentials, Biomass for Power Generation and
CHP, ETE03, http://www.iea.org/Textbase/techno/essentials3.pdf (retrieved
23.01.2009).
10. M. Kaltschmitt, Lessons taught at Hamburg University of Technology,
Winterterm, 2008/09.
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11. J. Daniel, Personal communication, German Biomass Research Centre,
Leipzig, 2008.
12. V. Lenz, M. Edel and M. Kaltschmitt, Erneuerbare Energien – Stand 2007
in Deutschland; BWK, 2008, 60(4), 106–117.
13. A. Vogel, F. Müller-Langer and M. Kaltschmitt, Chem. Eng. Technol.,
2008, 31(5), 755–764.
14. D. Thrän and M. Kaltschmitt, Biotechnol. J., 2007, 2, 1514–1524.
15. M. Thrän, M. Kaltschmitt, A. Kircherer and M. Piepenbrink, Kriter-
ienmatrix zur stofflichen und energetischen Nutzung nachwachsender Roh-
stoffe, Erich Schmidt Verlag, Berlin, 2008.
16. M. Kaltschmitt and M. Weber, Biomass & Bioenergy, 2006, 30, 897–907.
17. M. Kaltschmitt and D. Thrän, Energiewirtschaftliche Tagesfragen, 2008,
58(7), 8–13.
18. M. Kaltschmitt and D. Thrän, Zeitschrift für Energiewirtschaft, 2008,
32(2), 127–138.
CHAPTER 8

Green Fuels – Sustainable

Solutions for Transportation
ECKHARD DINJUS,a ULRICH ARNOLD,a NICOLAUS
DAHMEN,a RAINER HÖFERb AND WOLFGANG WACHc
a
Forschungszentrum Karlsruhe, Institut für Technische Chemie, Postfach
3640, D-76021, Karlsruhe, Germany; b Cognis GmbH, Rheinpromenade 1,
D-40789, Monheim, Germany; c Südzucker AG, Mannheim/Ochsenfurt,
Wormser Str. 11, D-67283, Obrigheim/Pfalz, Germany

8.1 Introduction
The importance of biofuels is growing rapidly and this is reflected in steadily
increasing research activities in both academia and industry as well as an
increasing number of joint ventures comprising several institutions. Thus, not
only is the extent of publications on this highly dynamic topic strongly
increasing but so too, due to its obvious socioeconomic relevance, is public
interest.
In the European Union (EU) the strategy with respect to the implementation
of biofuels is outlined for the member states in several directives and com-
munications such as the Renewable Energy Directive of the European Com-
mission from 2003 (2003/30/EC), the Communications from the Commission
Biomass Action Plan (COM(2005) 628 final), An EU Strategy for Biofuels
(COM(2006) 34 final), Towards a European Strategic Energy Technology Plan
(COM(2006) 847 final) and An Energy Policy for Europe (COM(2007) 1 final).
Most recently, the European Commission has enacted a Renewable Energy

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

125
126 Chapter 8
Directive due to boost EU renewable energy use to 20% by 2020. The latter
also aims for a substitution of 10% of transport fuels by biofuels in 2020 as a
mandatory target for the Member States. Furthermore, this directive also
defines minimum sustainability standards, e.g. a 35% reduction of greenhouse
gas emission and a focus on the type of land used for biomass cultivation.
A wide variety of biomass types based on vegetable organic materials can be
used for the generation of biofuels. Food and feed crops, e.g. wheat, other
cereals, rapeseed, sugar cane or sugar beet, and ‘‘energy crops’’ designed for
non-nutritional consumption, e.g. willow, short rotation trees or grasses, can be
used. To minimize competition with traditional applications, low-value mate-
rials such as agricultural residues and wastes, e.g. straw, bark, reclaimed wood,
bagasse or waste paper, are largely regarded as the preferable resource. Value
chain considerations, however, additionally credit value-added by-products
like energy-rich proteins in the case of certain food and feed crops.
The biomass volume available for biofuel production in Europe was reported
to be 95 Mio mto oil equivalent (MtOE) per year in 2005 with an estimated
increase to a value between 112 and 172 MtOE in 20201 and 243 to 316 MtOE in
2030.2 For comparison, predicted energy demands for the transport sector are
416.3 MtOE in 2020 and 437.2 MtOE in 2030.2 Biomass yields under average
conditions are assumed to be approximately 10 mto of dry biomass per hectare
and year in the case of willow.
The term biofuels is used for all types of biomass-derived fuels employed in
the transportation sector. Most biofuels can be applied either as a substitute for
common fossil fuels such as gasoline and diesel or in blends with these fuels.
Engines can need some modification as, for instance, in Flexible Fuel Vehicles
(FFVs). Other biofuels, e.g. biomass-based natural gas, require major changes
in both vehicle construction and fuel distribution infrastructure. Biofuels,
mainly for historical reasons, are assigned to three main categories, the so-
called first- and second-generation biofuels and the recently emerging third-
generation biofuels.3,4

8.2 First-generation Biofuels

First-generation biofuels are obtained from cereal and oil crops using estab-
lished technologies at commercial scales. Their CO2 emission reduction is
typically about half of the emission of fossil fuels. One reason for this is the
energy-intensive production of fuels and crops. These biofuels comprise bio-
diesel, pure vegetable oil, ethanol, ethyl-tertiary-butylether and biogas. For
historical reasons the use of wood gas as an alternative fuel might be men-
tioned. This was quite popular during and after the Second World War in
several European and Asian countries because the war prevented easy and cost-
effective access to oil. Wood gas (a mix of approximately 49 vol.% CO2, 34
vol.% CO, 13 vol.% CH4, 2 vol.% ethylene and 2 vol.% H2) is produced by
thermal gasification of wood in a wood gas generator.
Green Fuels – Sustainable Solutions for Transportation 127
5
8.2.1 Bioethanol
Utilizing ethanol as a fuel is not a recent invention, but has been practised for
almost a century and a half: Nikolaus August Otto developed his prototype of a
spark-ignition engine in the 1860s using ethanol and was sponsored by the
sugar factory of Eugen Langen envisaging an outlet for the mass production of
ethanol.6 Henry Ford expressed the vision ‘‘to build a vehicle affordable to the
working family and powered by a fuel that would boost the rural farm economy’’.
His 1908 Model T engine was originally designed to run on 100% ethanol. In
the 1930s Rhenania-Ossag, Monheim (later Deutsche Shell AG), sold Dynamin,
a blend of petroleum gas with 45% benzene and up to 10% ethanol from
potatoes (called ‘‘Spiritus’’ or Kartoffelsprit in German; German Reich-
skraftstoff [RKS] developed shortly after the First World War even contained
up to 25% Spiritus [95 vol.%] in a blend with 25% Tetralins [tetra-
hydronaphthalin, manufactured by hydrogenation of naphtha]7 and 50%
benzene8). Since the 1970s the Brazilian Proálcool initiative has become a kind
of bonfire for sustainability in automotive transportation.9,10 In Europe etha-
nol will also take a big share of the 10% minimum target set by the new EU
Directive on the use of biofuels in transportation by 2020. The usual approach
to meet requirements for biocomponents in the gasoline pool is to blend
bioethanol directly (low blends and high blends up to 95% ethanol, called E95)
with the effect of improved octane numbers of low blends. An alternative route
is the use of ethanol as a raw material for ethers such as ethyl-tertiary-butyl-
ether (ETBE), which can be blended with gasoline easily.11 The use of biofuel in
the transport sector in the form of bioethanol constitutes a cost-effective option
to achieve reduction in greenhouse gas emissions.12–14 In 2007 the worldwide
ethanol production had reached 64,126 Mio litres with sales of 49,531 Mio
litres for the fuel market.

8.2.1.1 Plant Raw Materials for Use in First-generation

Bioethanol Production
Creation of ethanol in fact does not start in the factory but on farmers’ fields
in planta via plant photosynthesis. Photosynthesis, which mainly takes place in
the green leaves of plants, leads to the final carbohydrates hexosephosphates.
Hexosephosphates are converted to sucrose, the first free carbohydrate, which
is the most important transport carbohydrate in plants.
The so called ‘‘storage organs’’ are very important parts of the plant which
are strictly dependent on the supply with sucrose and other metabolites. A
storage organ is generally any photosynthetic non-active part of the plant in
which excess of energy (generally in the form of sugars, proteins or lipids) and
nutrients are temporarily stored in order to release it again later – when it has
become necessary – and use the stored material for future growth.
Storage organs with their high amounts of accumulated energy are those
parts of the plants which are typically used as raw material in the bioethanol
fermentation process. According to the nature of yeast (Saccharomyces
128 Chapter 8
cerevisiae), which assimilates glucose or sucrose (after cleavage by yeast
invertase) as energy source, plant organs exclusively storing carbohydrates are
most suitable for fermentation. As a result – and also because hexose-storing
plants are scarce in nature – sucrose or starch accumulating plant organs are
the best raw materials for bioethanol production. Consequently, one can dis-
tinguish between starch- and sucrose-based substrates for bioethanol produc-
tion. Among the starch–based substrates the most important ones are the
cereals, whose grains contain high amounts of starch (e.g. wheat, triticale,
barley, maize, rice, sorghum). Indeed cereals are the most widely used sub-
strates for bioethanol production in the USA, Canada and Europe; whereas
maize (Zea mays) is predominant in the USA and eastern Canada, wheat
(mainly Triticum aestivum) prevails in western Canada and Europe. Other
starch-based substrates are tubers of potato (Solanum tuberosum) and taproots
of cassava (Manihot esculenta); however, both play only a minor role as raw
material for bioethanol production as compared to grains.
The most important sucrose-based plant raw material is sugar cane (Sac-
charum officinarum), which stores up to 15% of sucrose (w/w) in the stem
internodes. Bioethanol production in South America, eastern Asia and Aus-
tralia is almost exclusively based on the use of sugar cane molasses or sugar
cane juice as substrate. Other sucrose-based substrates of importance are on
one hand sweet sorghum (Sorghum saccharatum), which is closely related to
sugar cane and, similar to cane, stores up to 15% of sucrose in the stem
internodes. On the other hand there is sugar beet (Beta vulgaris), which store up
to 20% sucrose in the taproot. Thick juice of sugar beet plays a significant role
as a substrate in the European bioethanol production, since this crop has the
highest bioethanol yield per hectare as compared to any other crop. However,
difficulties in storage and the fact that sugar beet is not available over the whole
year prevent a much wider use of this crop in bioethanol production.

8.2.1.2 Production Processes for Bioethanol

The overall production process for bioethanol has a clear advantage over some
other industrial fermentation products. Due to the fact that all the input
streams are converted to products such as bioethanol, gluten or a protein-rich
feed stuff, so-called DDGS (distillers dried grains with solubles), fertilizer and a
readily biodegradable wastewater the process can be seen as a zero-waste-
concept.

8.2.1.2.1 Bioethanol Produced from Sugar Biomass. Production of bioetha-

nol from sugar plants is a straightforward process: after conditioning of
the feedstock an aqueous raw sugar juice (sucrose syrup) is extracted (see
Figure 8.1 and Chapter 9.3) and directly submitted to fermentation.

8.2.1.2.2 Bioethanol Produced from Starch-containing Biomass. In the

starch-producing process based on cereals the main components of the
 Green Fuels – Sustainable Solutions for Transportation
starting
material production of sugar containing substrate Production of ethanol

C6H12O6 → 2 C2H5OH + 2 CO2

sugar containing washing, extraction of fermentation

biomass crushing sugar-juice

starch containing washing, dry-milling separation

saccharification
biomass crushing wet-milling
yeast
distillation/
lignocellulose pretreatment acid/enzymatic rectification
saccharification
containing delignification hydrolysis
biomass mash
dehydration
by-products

CropEnergies 260.000 m3/year

bioethanol plant in Zeitz/D. Bioethanol ETBE

Figure 8.1 Bioethanol production processes (reproduced from J. Bigorra and R. Höfer, Comunicaciones, 38 Jornadas CED, Barcelona, 2008,
pp. 179–200).

129
130 Chapter 8
kernels, the endosperm containing starch granules, are separated from
the bran and the germ by dry- or wet-milling (see Section 9.1.4.2.10). Wet-
milling facilities are more flexible and have the ability to switch between the
production of ethanol and the production of syrup and/or fructose. How-
ever, virtually all of the new starch bio-ethanol facilities being built are less
costly dry-milling operations simply grinding the unprocessed heterogeneous
seed into granules preferably using hammer mills.15 Producing ethanol from
starch-containing biomass instead of sugar adds an extra step to the process.
This stage, called saccharification, consists in depolymerizing the amylose
and amylopectin structures, which compose starch by enzymatic reactions
into a glucose syrup or hydrolysate (see Chapter 9.2). In some concepts the
saccharification and the fermentation take place simultaneously.16,17

8.2.1.2.3 Bioethanol from Lignocellulosic Raw Materials. Ways to sustain-

ably produce ethanol without diverting agricultural production away from
food are seen in the utilization of lignocellulosic materials.18,19
Bioethanol from lignocellulosic raw materials is actually classified as bioe-
thanol of the so-called second generation. The idea to produce ethanol from
lignocellulose, however, is not new and a lot of work has been done since the
1920s. Most work and some industrial plants had stopped in the 1950s.20 Today
there are some demonstration plants with different new technologies especially
driven by modern biotechnological approaches under construction. There is a
strong agreement of all involved groups that technology will not be ready on an
industrial scale before 2015.21
Lignocellulosic feedstock is biomass mainly consisting of a complex com-
posite of the two structural carbohydrates, cellulose and hemicellulose, and
phenolic lignin.22 Cellulose is the most abundant organic compound on Earth
(see Chapter 9.4) The orientation of the linkages and the additional hydrogen
bonding make the cellulose polymer rigid. The crystalline structure of cellulose
makes it insoluble and resistant to attack. Hemicellulose on the contrary has a
branched, amorphous character and is relatively easy to hydrolyze. The name
hemicellulose encompasses all polysaccharides based on polymeric hexosans
generated from a variety of monomers (e.g. glucose, mannose, galactose) and
all polymeric pentosans based on monomers like arabinose or xylose. The
lignin, a non-carbohydrate polyphenolic substance encrusts the cell walls and
cements the cells together (see Figure 8.2). This protective sheet of hemi-
cellulose and lignin around the cellulose must be modified or removed by pre-
treatment processes.
In comparison to the grain-ethanol process typical cellulosic-ethanol process
steps require pre-treatment and enzymatic/chemical hydrolysis prior to fer-
mentation. Pre-treatment basically refers to the mechanical and physical
actions to clean and size the biomass, furthermore to destroy its cell structure
by chemical, physical and/or biological methods to make it more accessible to
further chemical or biological processes with the aim to increase the yield of
hydrolysis (see Figure 8.3).
Green Fuels – Sustainable Solutions for Transportation 131

Figure 8.2 Cellulose structure and hydrolysis challenges (Genomics: GTL Roadmap,
US Department of Energy Office of Science, August 2005, http://
genomicsgtl.energy.gov/roadmap).

Figure 8.3 Pretreatment (Genomics: GTL Transforming Cellulosic Biomass, US

Department of Energy, June 2006, http://genomicsgtl.energy.gov/biofuels/
and US DOE. 2006. Breaking the Biological Barriers to Cellulosic Etha-
nol: A Joint Research Agenda, DOE/SC/EE-0095).
132 Chapter 8
The surrounding hemicellulose and/or lignin are removed, and the cellulose
microfibre structure is modified. The hemicellulose polymer is hydrolyzed to a
large extent in the pre-treatment step whereas cellulose hydrolysis needs an
additional step (acid or preferably enzymatic).
Common chemical pre-treatment methods use dilute acid, alkaline, ammo-
nia, organic solvent, sulphur dioxide or other chemicals.23 Some pre-treatment
methods can use only water such as steam explosion or liquid hot water
(LHW).24 Steam explosion is one of the most promising methods to make
biomass more accessible to cellulose attack. The material is heated using high-
pressure steam (20–50 bar, 210–290 1C) for a few minutes; these reactions are
then stopped by sudden decompression to atmospheric pressure.
Several pre-treatment processes combine physical and chemical elements.
Addition of dilute acid in steam explosion can effectively improve enzymatic
hydrolysis, decrease the production of inhibitory compounds and lead to more
complete removal of hemicellulose.
In hydrolysis, the cellulose is converted into glucose sugars. This reaction is
catalyzed by dilute acid, concentrated acid or enzymes (cellulase). Two process
concepts have been investigated, more than others, regarding ethanol pro-
duction from lignocellulosic materials. On the one hand dilute sulphuric acid
and on the other hand the use of cellulolytic enzymes. In the dilute sulfuric acid
technology, which is mainly developed by NREL,25 the raw material is treated
with 0.1–3% (w/w) H2SO4 at temperatures normally ranging from 160 to
200 1C. It may be advantageous to perform dilute-acid hydrolysis in two steps
since the hemicellulose fraction is more easily degraded than is the cellulose
fraction. A disadvantage of the dilute acid process is the somewhat low ethanol
yield and the necessity of using expensive construction materials that are
resistant to corrosion by acid at high temperatures. The acid must also be
neutralized, which leads to the formation of large amounts of gypsum, CaSO4
or other compounds that have to be disposed of.
In the past the high costs of cellulolytic enzymes has been a major hurdle for
a successful process development. A lot of effort has been made within the last
five years from the world’s leading enzyme companies Novozymes and Danisco
Genencor during a funded US DOE project. Enzyme costs could be reduced
significantly and are no longer prohibitive (Figure 8.4).
An important process modification made for the enzymatic hydrolysis of
biomass was the introduction of simultaneous saccharification and fermenta-
tion (SSF). In this process, cellulose, enzymes and fermenting microbes are
combined, with the intention of reducing equipment and improving efficiency.
The lignin will remain during processing and is in most concepts foreseen as
solid fuel for power generation. Furthermore concepts to convert lignin into
higher value products such as organic acids, phenols and vanillin are followed.

8.2.1.2.4 Ethanol Production by Yeast Fermentation. Many organisms have

been exploited for ethanol production from saccharified starch or other
sugars, however, the yeast Saccharomyces cerevisiae still remains the most
important species.
Green Fuels – Sustainable Solutions for Transportation 133

Figure 8.4 Hydrolysis (Genomics: GTL Transforming Cellulosic Biomass, US

Department of Energy, June 2006, http://genomicsgtl.energy.gov/biofuels/
and US DOE. 2006. Breaking the Biological Barriers to Cellulosic Etha-
nol: A Joint Research Agenda, DOE/SC/EE-0095).

The chemical reactions are shown below:

C12H22O11 + H2O C6H12O6 + C6H12O6

Sucrose Water Fructose Glucose

C6H12O6 2 C2H5OH + 2 CO2

Fructose/Glucose Ethanol

Under aerobic conditions yeasts grow efficiently on sugar substrate making

lots of biomass and carbon dioxide. However, when oxygen is absent, yeasts
switch to the anaerobic metabolism. Under these conditions 1 mol of C-6
sugars are converted into 2 mol each of ethanol and carbon dioxide. Due to the
fact that Saccharomyces produces some side products such as glycerol (osmo-
protectant), acetic acid and other alcohols, the yield of ethanol is never 100%.
Important for a high ethanol productivity of the yeast cells are the genetic
composition as well as the amount and nature of fermentable sugars. Carbo-
hydrates such as glucose, maltose and maltotriose derived from liquefied and
saccharified cereal starch can be metabolized by Saccharomyces cerevisiae.
Further, sucrose or galactose can easily be fermented by that yeast; however,
large polysaccharides such as starch or oligo- and polysaccharides derived from
cellulose can not be taken up in that form.26 Additionally, Saccharomyces is not
able to ferment either lactose or C-5 sugars such as arabinose or xylose, which
134 Chapter 8
makes it unsuitable for the production of ethanol from whey or saccharified
biomass. Therefore a lot of R&D work on genetically modified micro-organ-
isms has the task to valorize the C-5 fraction of the hydrolyzed biomass.27
Due to the fact that the extracellular proteolytic activity of Saccharomyces is
negligible, high-molecular-weight nitrogenous materials can not be utilized by
the cells. Therefore the application of inorganic ammonium ions (e.g. ammo-
nium sulphate, di-ammonium hydrogenphosphate), urea, amino acids or small
peptides is necessary.28
At higher ethanol concentrations the intracellular alcohol interferes with
membrane organization, increasing its fluidity and permeability to ions and
small metabolites and inhibiting transport of nutrients.29 Especially Ca21 and
Mg21 ions are able to increase the plasma membrane stability. It has been
demonstrated that incorporation of unsaturated fatty acids and/or sterol(s) as
well as proteolipids into cellular membrane of yeasts helps to alleviate ethanol
tolerance.30,31 For the synthesis of the unsaturated fatty acids the presence of
traces of oxygen under fermentation conditions is required.32,33 Further to Ca
and Mg ions, other trace elements such as Co, Cu, Mn and Zn34 and vitamins,
e.g. pantothenate, thiamine, riboflavin, nicotinic acid, pyridoxine, biotin, folic
acid and inositol, are essential for the growth and ethanol production by
yeasts.35
During ethanol fermentations, yeasts suffer from various stresses. Ethanol as
the major metabolic product of yeast fermentation accumulates in the cell and
acts as a potent chemical stress towards the yeast cell. Further, temperatures
higher than 35 1C, pH values below 3.5, acetic acid produced either by the yeast
itself or by contaminants such as lactic acid bacteria or wild yeasts, lactic acid
and osmotic pressure have a negative impact on the ethanol production by
Saccharomyces cerevisiae.

8.2.1.2.5 Ethanol Fermentation with Bacteria. In the 1980s the use of ther-
mophilic bacteria for the production of ethanol was the focus of study for a
number of research groups. The idea behind it was the facilitated recovery of
ethanol at elevated temperature, the lower costs for heating a thermophilic
fermentation rather than cooling a mesophilic one, increased process stabi-
lity, lower contamination risk and the higher substrate versatility of thermo-
philic bacteria compared to that of the mesophilic ones.36 Thermophilic
clostridia such as C. thermocellum, C. thermohydrosulfuricum and C. thermo-
saccharolyticum are able to use a wide range of substrate, from polymeric
carbohydrates such as cellulose, pectin, xylan and starch to mono- and dis-
accharides such as glucose, cellobiose, xylose and xylobiose. A disadvantage
of these micro-organisms is the product pattern. Besides ethanol the side
products acetate, lactate, carbon dioxide and hydrogen are also formed in
various amounts.
Another promising micro-organism for the production of fuel ethanol is
Zymomonas mobilis.37 This facultative anaerobic, Gram-negative bacterium
degrades glucose by the so-called Entner-Doudoroff-pathway with the
consequence that only 1 mol of ATP is produced during the breakdown of
Green Fuels – Sustainable Solutions for Transportation 135
1 mol glucose. This means that less biomass than by S. cerevisiae is generated
and more carbon is converted to ethanol fermentation.38 It was reported
that the ethanol yield of Z. mobilis could be as high as 97% of the theoretical
yield of ethanol to glucose.39 However, despite these advantages Zymomonas
mobilis is not applicable for the ethanol industry. First of all the species
has a very specific substrate spectrum including just the three sugars glucose,
fructose and sucrose. Maltose or maltotriose – generated by the liquefaction
of starch by a-amylases – can not be converted by this bacterium. Another
disadvantage is that its growth on sucrose is accompanied by the formation
of extracellular fructooligosaccharides (levan) and sorbitol.21 Finally, the
use of Zymomonas mobilis is not commonly accepted as animal feed and this
generates problems for its biomass disposal if being replaced by Sacchar-
omyces cerevisiae in the industrial ethanol production. Therefore Sacchar-
omyces cerevisiae is still the workhorse for the industrial synthesis of fuel
ethanol.

8.2.1.2.6 Distillation/Rectification/Dehydration. After fermentation the

mash should contain more than 12% of alcohol (V/V) and virtually neither
sugars nor starches. The removal of the alcohol from the mash is performed
by distillation.
The setup of the distillation unit can vary significantly with the type of
process, raw material supplied and the desired product quality. Usually, the
unit consists of at least two steps:

 removal of the ethanol from the mash (distillation);

 purification of the raw alcohol (rectification).

The distillation and rectification is conducted in columns with a variable

number of trays, the construction and design of which vary significantly. The
setup of the distillation unit is directly linked to the quality requirements for the
ethanol produced. The distillation yields a raw alcohol with an alcohol content
of approximately 85–87%. The rectification is necessary to increase the alcohol
content and to remove so-called fusel oils, which are C3-C5 alcohols. In modern
distillation units, these two basic steps are integrated to optimize the energy
requirement for the process.
For the production of fuel-grade ethanol, the ethanol has to be ‘‘dried’’.
Anhydrous ethanol cannot be produced by simple distillation because ethanol
forms an azeotropic mixture with water. The maximum ethanol content
achievable by distillation is approximately 97.2 vol.%, which is usually not
sufficient for the application as fuel-ethanol. The residual water can be removed
either by azeotropic distillation by the addition of, e.g., cyclohexane or by the
application of molecular sieves. Today, state-of-the-art plants operate with
molecular sieves which provide considerable advantages in terms of investment
and operating costs.
Whereas the aqueous alcohol is further rectified and dried, the stillage is
separated in decanter centrifuges into a more liquid and a solid fraction.
136 Chapter 8
The liquid is partly recycled to the flour to be added together with fresh water
to get the slurry prior to liquefaction. The recycling degree must be as high
as possible to avoid too much freshwater consumption but is on the other
hand limited by the potential negative effect of components from back-stillage
on the yeast.
This recycling of the thin stillage and the reduction of freshwater con-
sumption are crucial to reduce energy consumption – besides other measures
such as multistage distillation and rectification. In today’s downstream pro-
cessing an additional means is applied to save energy: the vapours from the
consecutive stillage drying process are often used as an energy source for
concentration of the thin stillage prior to drying. The dried stillage – named
DDGS – is used as protein rich feed.

8.2.1.2.7 Genetically Modified Organisms. Traditionally, Saccharomyces

cerevisiae is used in industrial ethanol fermentation; however, S. cerevisiae is
not able to utilize pentoses, which present a significant fraction of the sugars
present in lignocellulosic material.
Due to their prokaryotic nature the genetic manipulation of bacteria is much
easier than that of yeasts. Nevertheless, much effort has been undertaken in the
last years to manipulate the more ethanol tolerant yeasts towards the ability
to metabolize C-5 sugars, especially xylose and arabinose.31–35,40–44 Further,
ethanol yields of about 20–30 g L1 are still too low to make these organisms
industrially profitable.

8.2.1.2.8 Ethanol Usage as Transportation Fuel. Energy content of ethanol

is approximately two-thirds that of petrol. Nevertheless ethanol is worldwide
the most used biofuel. Up to 20% of ethanol can be blended to fossil petrol
without the need for engine manipulations. However, Flexible Fuel Vehicles
(FFVs), tolerating ethanol, petrol and variable mixtures of both (more parti-
cularly the high blend E85 of 85% bioethanol and 15% petrol), have become
widely accepted and are offered by several automobile manufacturers. In
Brazil, as an example, 86% of cars and light commercial vehicles sold in
2006 were FFVs.
In Germany, however, bioethanol will mainly be used as low blend
of bioethanol and petrol (E5, E10) and for the production of ETBE (ethyl-
tertiary-butyl-ether). Similar to methyl-tertiary-butyl-ether (MTBE), ETBE is
used to enhance the octane index and improve knock-resistance and combus-
tion properties of gasoline.45 It is less challenging to handle, does not induce
evaporation of gasoline and does not absorb moisture like ethanol does. ETBE
is produced by reacting ethanol and isobutylene via acid catalyst:
Green Fuels – Sustainable Solutions for Transportation 137

8.2.1.2.9 Outlook for Bioethanol. Production of ethanol from starch-based

crops such as wheat and corn is a well-known technology and is reaching a
level of maturity. In contrast, processes using lignocellulosic raw materials
are still under development and significant technology jumps with reduc-
tions in ethanol production cost can be expected in the mid-term. Feedstock
infrastructure, pre-treatment and enzymatic processes have to be flexible
regarding feedstock and feedstock compositions. High ethanol yields need to
be reached. In the short term concepts with an integration of cellulose-to-
ethanol processes into first generation plants are rather promising.

8.3 Lipid-based Biofuels

Lipids, in the form of adipose tissue triacylglycerol, intramuscular triglyceride
and dietary-derived fatty acids from plasma triacylglycerol and very low-den-
sity lipoproteins, represent the largest store of nutrient energy in humans. As a
stored source of energy, fat has an advantage over carbohydrate: the energy
density is higher while the relative weight is lower. Fatty acids provide more
adenosine triphosphate (ATP) per molecule than glucose. Ultimately, more
energy can be derived per gram of fat (9 kcal gm1) than per gram of carbo-
hydrate (4 kcal gm1) or protein (4 kcal gm1). Although there is limited
capacity for fat oxidation during exercise, endurance athletes and dieters are
eager to burn more fat during exercise. Indeed, men and women with higher
levels of energy expenditure due to sport are claimed to show a better lipid
profile than their sedentary counterparts.46
The high energy density, the liquid character and the structural analogy to
hexadecane (cetane, the high-quality standard of the ignition quality of a diesel
fuel, i.e. cetane number ¼ 100) make lipids likewise suitable as an ‘‘alternative’’
diesel fuel source.47
The dual capacity as energy source for human nutrition and as fuel for
transportation emphasizes the important role of lipids on one side and reveals
the conflict relative to sustainable availability for both food and fuel applica-
tions on the other.

8.3.1 Vegetable Oils as Transportation Fuels

‘‘Oil from the Sun’’ has been envisaged as fuel since the very beginnings of
automotive transportation. When Rudolf Diesel presented the prototype
compression-ignition engine built by his French licensee Société Française des
Moteurs à Combustion Interne at the 1900 World Trade Show in Paris he was
awarded the ‘‘Grand Prix’’ because of the innovative concept, the efficiency, the
performance and the economics of the engine. Diesel demonstrated that all
kinds of (cheap) petroleum products like mineral oil, petroleum fuel, shale oil
or coal tar dust could be used to fuel the engine.48 He also reported a diesel
engine shown at the 1900 World Trade Show, working with peanut oil, and
138 Chapter 8
demonstrated himself the suitability of peanut oil as an alternative to petroleum
fuel in compression–ignition engines. When presenting the performance figures
of the test, Rudolf Diesel actually made the visionary statement:
‘‘The fact that fat oils from vegetable sources can be used may seem insig-
nificant today. But such oils may become in the course of time as important as
the petroleum and coal tar products of the present time’’ . . . ‘‘One cannot
predict what part these oils will play . . . in the future. In any case, they make
it certain that motor-power can be produced from the heat of the sun . . . even
when all our natural stores of solid and liquid fuel are exhausted.’’49
Interest in energy self-sufficiency of tropical colonies or other remote areas
and periodic petroleum shortages spurred research into vegetable oil as a pet-
roleum diesel substitute during the 1930s and the Second World War, and again
in the 1970s and early 1980s. However, the high viscosity of vegetable oils
(about 35–60 cSt compared to 4 cSt for diesel fuel at 40 1C) in fact leads to poor
atomization in the engine and incomplete combustion. As a result formation of
carbon deposits, injector coking and piston ring sticking may occur. Moreover,
high viscosity and low volatility risk give rise to poor cold starting, misfire and
long ignition delay.50 If Straight Vegetable Oil (SVO) also referred to as Pure
Plant Oil (PPO) (the term used in the biofuels directive published by the
European Commission is ‘‘pure vegetable oil from oil plants’’) is to be used in
conjunction with diesel in a dual-fuel mode,51–53 necessary modifications
include an additional fuel tank, a system to allow switching between the two
fuels and a heating system for the SVO tank and lines. If SVO is to be used
exclusively, modifications would include a preheating system, an upgraded
injection system and the addition of plugs in the combustion chamber.9
Although the 1970s already saw the formation of the first commercial enter-
prise, Elsbett, to allow consumers to run straight vegetable oil in their auto-
mobiles,54 R&D strategies started aiming at the adaptation of alternative fuels
to existing compression–ignition technologies instead of developing new
engines capable of being fuelled by vegetable oils instead of petroleum diesel.

8.3.2 Vegetable Oils as Biodiesel Feedstock

The most appropriate way to adjust the viscosity of vegetable oils or animal fats
for use in unmodified diesel engines is by converting the triacylglycerides into
lower molecular weight fatty acid mono-alkyl esters standardized as biodiesel,
when meeting the requirements of ASTM D 6751 and Euro norm EN 14214,
respectively. The term biodiesel refers to the pure biofuel (designed B100) before
blending with diesel fuel. Biodiesel blends are denoted as ‘‘BXX’’ with ‘‘XX’’
representing the percentage of biodiesel contained in the blend (e.g. B20 is 20%
biodiesel, 80% petroleum diesel).
The principles of biodiesel synthesis are relatively simple oleochemical
reactions (see Chapter 9.1) and have been known and applied for many decades
(Figure 8.5).47,55 The basic technology consists in a catalyst induced transes-
terification of a vegetable oil in a batch, semi-batch or continuous process to
create a fatty acid methyl ester (FAME). The catalyst used is a strong base,
Green Fuels – Sustainable Solutions for Transportation 139

starting material synthesis conditioning

Triglyceride + 3 MeOH → 3 FAME + Glycerine

KOH Methanol

crude
refining Glycerine
Glycerine

vegetable oil transesterification MeOH

recycling

crude
refining Biodiesel
Biodiesel
recycled greases
esterification
soapstock

diluted Methanol or
H2SO4 Glycerine

Figure 8.5 Production of biodiesel (reproduced from R. Höfer and J. Bigorra, Green
Chem. Lett. Rev., June 2008, 1(2), 79–97).

such as sodium or potassium hydroxide. Once the ester chains are broken off,
the leftover glycerine molecule is a valuable by-product of the reaction.56
Different feedstock can be used, such as more or less any vegetable oil,
including recycled oils and soapstock.57 Process improvements such as higher
reactivity, more complete conversion, less use of base initiator and faster
separation time to increase throughput are claimed when performing the
transesterification in the presence of a phase-transfer catalyst58 or when using a
stable ionic liquid as both solvent and catalyst.59 Technical feasibility of bio-
diesel synthesis by alcoholysis of vegetable oils catalyzed by commercial lipases
has also been described.60 Finally, a dramatic improvement in the rate of the
transesterification reaction has been demonstrated in selected micro-reactor
systems.61
Pure plant oils (PPO) can be used directly as a starting material for biodiesel
synthesis via transesterification. To reduce free fatty acids, raw materials con-
taining such are submitted to an esterification step prior to transesterification.
Composition of the oil feedstock, more particularly the fraction of saturated
fatty acids, has a decisive influence on biodiesel specifications and properties;
more particularly on viscosity, consistency and wax crystal settling, i.e. plug-
ging at low temperature. Fuel properties (Table 8.1) and performance as engine
fuel in comparison to petroleum diesel (PD) have continuously been studied
following the development of new motor generations and machine applications
including exhaust emissions and mutagenic potential of particulate matter as
well as exhaust-gas limit value requiremens.62 Compared with PD European
biodiesel based on rapeseed methyl ester (RME) has similar viscosities and
a remarkably higher cetane number. The caloric value of RME relative to the
140 Chapter 8
Table 8.1 Influence of saturated fatty acids fraction on specifications of
biodiesel.
Oil and ester characteristics
Saturated
Melting range (1C) Iodine Cetane CFPP fatty acids
Type of oil Oil/fat FAME value number (FAME) (%)

Rape seed –5 –10 110–120 55 –20; –10; 0* 7–8

Soy bean –12 –10 120–140 53 –4 12–15
Palm 30–38 14 44–54 65 10–14 45
Petroleum DIN EN 590:
diesel fuel min. 51 –20; –10; 0*
*seasonal:
Winter –20
transition –10
summer 0
CFPP ¼ cold filter plugging point, DIN EN 14 214, the temperature at which a fuel will cause a fuel
filter to plug due to fuel components, which have begun to crystallize or gel.

mass is 13.4% below that of PD, relating to the volume 7.9%. As RME con-
tains oxygen the minimal air consumption decreases by 13% regarding the
mass, and by 7% regarding the volume. The caloric value of the air-fuel mix-
ture, however, is almost identical in both cases.
RME is biodegradable and non-toxic. The flash point of 130 1C (compared
to Z 55 1C for PD) ensures a safe storage. Compared to petroleum fuels RME
has a more favourable combustion emission profile such as low emissions of
carbon monoxide, sulphur and particulate matter. As a consequence of the
so-called NOx-particle trade-off phenomenon, emissions of NOx are increased.
Mutagenicity of RME emissions, however, is much lower compared to PD
indicating a reduced health risk from cancer.63

8.3.3 Fats and Oils as BtL Raw Material

The hydrogenolysis of esters to alcohols is a reaction between esters and
hydrogen which selectively splits a C–O bond adjacent to a carbonyl group.
Hydrogenolysis of fatty acid methyl esters under methanol circulation and with
glycerine and methanol recovery is actually the preferred technology for
industrial manufacturing of natural fatty alcohols (see Chapter 9.1). Fatty
alcohol synthesis starting directly from natural fats or vegetable oils yields 1,2-
propanediol instead of glycerine as by-product. During fatty alcohol manu-
facturing reaction temperatures and choice of the catalyst are critical in order
to avoid over-hydrogenation to hydrocarbons.
Whereas the biodiesel synthesis from natural fats or vegetable oils does not
alter the ester structure of glycerolipids, the intentionally conducted over-
hydrogenation has recently created considerable interest as a new synthesis
Green Fuels – Sustainable Solutions for Transportation 141
Table 8.2 Fuel property comparison (reproduced from http://www.green-
carcongress.com/2006/03/neste_oil_and_o.html).
Fuel property comparison
Biodiesel Sulphur-
NExBTL GTL (RME) free diesel

Density at +15 1C 775 . . . 785 770 . . . 785 B885 B835

(kg m3)
Viscosity at +40 1C 2.9 . . . 3.5 3.2 . . . 4.5 B4.5 B3.5
(mm2 s1)
Cetane number B84 . . . 99 B73 . . . 81 B51 B53
Cloud point (1C) B–5 . . . –30 B0 . . . –25 B–5 B–5
Heating value B44 B43 B38 B43
(lower) (MJ kg1)
Heating value B34 B34 B34 B36
(MJ litre1)
Polyaromatic con- 0 0 0 0
tent (wt.%)
Oxygen content 0 0 B11 0
(wt.%)
Sulphur content o10 o10 o10 o10
(mg kg1)

route to Green Diesel. Catalytic hydro-treatment comprising a Group VIII and

Group VIB element catalyst (especially Pd, Pt, Ni, Ni-Mo or Co-Mo supported
on Al2O3, SiO2 or carbon) and conducted in a semi-batch or continuous pro-
cess in a (depending on process conditions) broad temperature and pressure
range of 300–360 1C and 6–80 bar results in a complete de-oxygenation, i.e.
cracking of the triacylglyceride structure and converting the glycerol part into
propane and the fatty acid moieties into linear hydrocarbon molecules similar
or even identical to cetane.

CH3 ðCH2 Þ7 CH¼CHðCH2 Þ7 CðOÞ  OH þ xH2

! nC17 H35 þ xH2 O þ yCO2 þ zCO

These are isomerized to branched paraffins in a second stage. The resulting

middle distillate is suitable for use as diesel fuel without particular specifica-
tions. Some commercial examples of vegetable oil hydrotreatment are NExBTL
(Neste), H-Bio (Petrobras), Ecofining (UOP) and the ConocoPhilips process.64
Neste Oil claims for its industrially very advanced NExBTL process that it
generates less life-cycle CO2 per kilogram oil equivalent than rapeseed-based
biodiesel: 0.5–1.5 kg CO2 kgoe1 fuel for NExBTL, versus 1.6–2.3 kg CO2
kgoe1 fuel for biodiesel and 3.8 kg CO2 kgoe1 for petroleum diesel.

8.3.4 Lipid-based Jet Fuels

Recently Boeing 747 test flights of Virgin Atlantic Airways and Air New Zealand
using ‘‘Biojet Fuel’’ blends have created public interest.65 Actually, jet fuel is
142 Chapter 8
based on either an unleaded paraffin oil (Jet A-1) or a naphtha-kerosene blend
(Jet B). It is similar to diesel fuel, and can be used in either compression ignition
engines or turbine engines. Indeed, a specially adapted biodiesel fraction (bio
kerosene) has been successfully tested already at the beginning of the 1980s in an
EMBRAER turbo-prop powered aircraft flying from São José de los Campos to
Brasilia.66 While Virgin Atlantic tested a 20% blend of biojet fuel derived from
babassu and coconut oil by transesterification, Air New Zealand used a 50%
biojet fuel blend based on jatropha oil. Major technical challenges faced by biojet
fuels up to now are propensity to freeze at normal operating cruise temperature
and thermal stability characteristics in the engine.67

8.3.5 Conclusions for Lipid-based Biofuels

Fuels based on biomass may be the only solution when fossil fuels gradually
become exhausted but a tremendous rift needs to be overcome before renewable
resources can completely substitute fossil fuels. If the emerging energy
gap and the fuel crisis are to be solved while at the same time providing suf-
ficient feedstock for the chemical industry and foodstuffs for humans and
animals then a well-organized, anticipatory cross-border cultivation policy
including water management is required. In this scenario, natural fats and oils
as biofuel sources offer well-established pre-treatment processes and energy
density, physico-/chemical characteristics and handling properties similar to
petro-fuel (Figure 8.6).

8.4 Methane via Anaerobic Digestion

Biomethane (biogas) is produced by anaerobic digestion or fermentation of
biomass, manure or biodegradable wastes, e.g. sewage sludge. The resulting gas
is predominantly composed of methane and carbon dioxide. Biomethane can
be used for electricity production or heating (see Chapter 7) and, if cleaned and
compressed, as fuel for combustion engines or fuel cells.68,69
Increasingly, it is aimed at feeding of biomethane to the natural gas grid as
green gas. Thorough cleaning is necessary to meet the demanding specifications.
In this context, biomethane is also used as a transportation fuel today; more than
5 Mio. methane-fuelled cars are in use worldwide today. Compared to all other
biofuels, biomethane provides the highest yield of fuel equivalent per area. On
the other hand long residence times of several days are required for biogas
formation using mainly wet feed material, meaning the use of huge reactors and
limited feedstock capacity by considering transport economics.

8.5 Second-generation Biofuels

Second-generation biofuels are produced from lignocellulosic materials, e.g.
low-value crops and residues from agriculture or forestry3,4 or purpose-grown
 Green Fuels – Sustainable Solutions for Transportation
Petroleum
Bio Diesel Green Diesel
Diesel
10 to 160 Mio years of Seed Fertilizer Fuel Chemicals Seed Fertilizer Fuel Chemicals
geological formation

Exploration

Energy crop
Crude oil Energy crop
farming
extraction farming

Crude oil transport Biomass transport Biomass transport

Vegetable oil Vegetable oil

Crude extraction extraction
refining: Cake/meal
Atmospheric
distillation/ Vegetable oil Vegetable oil
Vacuum distillation refining refining
Gas processing/
Hydrotreating
Methanol/ Transport Hydrogen
Isomerization/ LPG
Transport KOH or NaOH
Reforming/ Gasoline
Cracking/ Kerosene
Hydrocracking Fuel oils
Lubricating Transesterification Catalytic hydrotreatment
oils
Paraffin Glycerol Propane
wax Bio Diesel Green Diesel
Petroleum Diesel Asphalt

143
Figure 8.6 Flow diagram of lipid-based fuels compared to petroleum diesel.
144 Chapter 8
plants from short rotation forestry. Compared to first-generation biofuels,
extended raw material options offer a significantly improved production
capacity and CO2 reduction potential. Furthermore, such feedstock may be
considered more sustainable and does not compete directly with food.
Advanced production technologies are employed which have become available
now, even on a commercial scale. The most important second-generation
biofuels are hydrogen, synthetic natural gas (SNG), bioethanol from lig-
nocellulosic raw materials (Section 8.2.1.2.3), butanol and HTU diesel as well
as the extensive class of Biomass to Liquid (BtL) fuels based on synthesis gas
(syngas). The latter fuel type comprises methanol, ethanol, dimethylether, BtL
gasoline and BtL diesel.

8.5.1 Hydrogen via Biomass Gasification

Hydrogen can be produced via gasification of biomass,70 provided that the
gasification procedure is optimized to yield a high hydrogen content in the
resulting gas mixture. A downstream water gas shift reaction can be used to
reduce carbon monoxide contents and thus increase hydrogen yields. Further
options for hydrogen production from biomass are supercritical water gasifi-
cation71 and dark fermentation.72–80 Crude biohydrogen has to be cleaned,
compressed or liquefied, or stored in suitable storage media and can be used as
fuel for appropriate combustion engines or fuel cells.

8.5.2 Synthetic Natural Gas via Biomass Gasification

In addition to methane production by anaerobic biomass digestion, methane
can also be obtained by biomass gasification and the latter technology allows
for the use of a wider variety of biomass types compared to the former. Thus-
produced methane, so-called synthetic natural gas (bio-SNG), can be used,
after cleaning and compression or liquefaction, as fuel for modified spark
ignition engines and exhibits high octane numbers. Another option to produce
SNG is supercritical water gasification of biomass.78,79 Naturally, such a pro-
cess is highly attractive, since wet biomass can be employed.

8.5.3 Biobutanol
Acetone, butanol and ethanol can be produced in a ratio of approximately 3 : 6
: 1 from sugars derived from food crops or sugars obtained from the degra-
dation of cellulose using Clostridium bacteria (ABE fermentation). Butanol/
diesel and also butanol/gasoline blends can be used in unmodified or slightly
modified engines and represent another attractive option. However, as in the
case of ethanol, cellulose conversion to fermentable sugars and the following
fermentation have to be optimized.80
Green Fuels – Sustainable Solutions for Transportation 145
8.5.4 HTU Diesel
Conversion of biomass at a temperature of 300–350 1C and a pressure of 120–
180 bar within the so-called HydroThermal Upgrading (HTU) process yields a
mixture of hydrocarbons, carbon dioxide, water and dissolved organics, which
can be further processed in a catalytic HydroDeOxygenation (HDO) step to
yield diesel with characteristics similar to fossil diesel.81 A major advantage
is that wet biomass feedstocks can be employed without drying; in contrast,
water at hydrothermal conditions acts as a solvent and reactant at the same
time, leading to a product with less oxygen compared to biocrude prepared by
pyrolysis.

8.5.5 Pyrolysis Oil

Pyrolysis of biomass produces gaseous, liquid and solid products by thermal
cracking in an oxygen-free atmosphere. The burnable gas and the char may be
used internally for heating the pyrolysis reactor. Char is also a suitable sub-
stitute for coke produced from fossil fuels. By applying fast or flash pyrolysis,
high quantities of liquid condensates up to 60 wt.% on a water- and ash-free
basis are formed, which principally may be used as a fuel. However, pyrolysis
oil is not a suitable fuel being a mixture of ca. 400 different chemical com-
pounds, including substantial amounts of water (15 wt.% water formed during
fast pyrolysis reaction+the humidity of the biomass feedstock) and oxygenated
compounds lowering further the heating value. Having tested as a fuel for diesel
engines and turbines concerns arose in regard to fuel properties and in parti-
cular to corrosion, fouling and plugging of engine components.82,83 Upgrading
of bio-oils to fuel standards may be achievable, but requires expensive treat-
ment e.g. by hydrotreating. However, fast pyrolysis may be a suitable method
for biomass pre-treatment prior to efficient gasification (see Section 8.5.6.2).

8.5.6 Syngas-based Biofuels

Employing BtL technologies, almost every type of biomass, organic residue or
waste can be used for the production of so-called (bio)synfuels. Depending on
the respective process, these can be very similar or even superior to conven-
tional petroleum-derived gasoline or diesel and can serve as direct substitute
thus maintaining engine types and fuel distribution infrastructure. The tech-
nologies are similar to already established Gas to Liquid (GtL) or Coal to
Liquid (CtL) processes and proceed via gasification of suitable biomass-derived
materials to syngas. The gas is cleaned in the next step and the hydrogen/
carbon monoxide ratio is adjusted to the respective requirements strongly
depending on the desired product. The thus-obtained syngas is a valuable base
for the generation of a whole range of products and fuels,84–86 e.g. methanol,
ethanol, dimethylether (DME), olefins, gasoline and diesel (Figure 8.7). Several
catalytic processes are involved, e.g. the direct synthesis of methanol or ethanol
from syngas, the methanol-based processes MTO (Methanol To Olefins), MTG
146 Chapter 8

EtOH MTG (ExxonMobil)

(TOTAL) Oligomerization
Syngas MeOH DME Olefins Synfuel

MTO (UOP)
MTS (Lurgi, Südchemie)
Sasol
Shell
BASF
Fischer-Tropsch

Figure 8.7 Production of biosynfuels from syngas: catalytic processes and some
selected suppliers.

(Methanol To Gasoline) and MTS (Methanol To Synfuel), the production of

fuels by oligomerization of olefins (Conversion of Olefins to Distillate, COD) or
the synthesis of a wide range of hydrocarbons in Fischer–Tropsch processes.
Some main features of these processes are outlined in the following sections.
Diesel or gasoline produced from syngas may be tailored towards new
demands more easily than fuels produced from crude oil. This can be an
advantage to meet new emission standards as well as for the development of
advanced fuels for improved motor concepts e.g. for use in combined com-
bustion system (CCS), i.e. engine concepts which combine the advantages of
both diesel compression ignition and Otto spark ignition technologies.87

8.5.6.1 Syngas-based Products

Methanol. Methanol is produced from syngas at temperatures between 220
and 275 1C and pressures ranging from 50 to 100 bar using Cu/ZnO/Al2O3
catalyst systems. Today, the required syngas is obtained from natural gas in an
upstream steam reforming process and the underlying chemistry is summarized,
in a simplified way, in equations (8.1) and (8.2). Some major methanol tech-
nology suppliers are ICI, Lurgi and Mitsubishi.

CH4 þ H2 O ! CO þ 3H2 ð8:1Þ

CO þ 2H2 ! CH3 OH ð8:2Þ

As outlined above, biomass feedstock can also be employed for the pro-
duction of syngas and, thus, methanol produced from biomass-derived syngas
and fuels obtained through processing of biomass-based methanol can be
considered as typical biofuels. Blends with petrol containing up to 20% of
methanol can be used in combustion engines without elaborate modifications.
However, the comparatively low energy density and safety concerns have
limited so far broad applications of methanol as fuel. Another option is the use
Green Fuels – Sustainable Solutions for Transportation 147
88–90
of methanol in fuel cells, either directly in Direct Methanol Fuel Cells
(DMFCs) or indirectly as hydrogen source.

Ethanol and Higher Alcohols from Syngas. Direct synthesis of ethanol from
syngas is intensely investigated especially in North America.91,92 Another
approach in this context is the homologization of methanol, i.e. the reaction
of methanol with syngas to yield ethanol. Higher alcohols can also be
formed. The reactions are summarized in equations (8.3) and (8.4).

nCO þ 2nH2 ! Cn H2nþ1 OH þ ðn  1ÞH2 O ð8:3Þ

CH3 OH þ nCO þ 2nH2 ! Cnþ1 H2nþ3 OH þ nH2 O ð8:4Þ

However, ethanol selectivity is still moderate and there is lack of highly

efficient catalysts for these reactions.

Dimethylether. Several strategies for the production of dimethyl ether

(DME) are described, e.g. direct synthesis from syngas according to equation
(8.5) or via dehydration of methanol according to equation (8.6). From
a mechanistic point of view direct synthesis proceeds also via methanol
formation and subsequent release of water but without procedural isola-
tion of methanol. The process can also be designed to yield both
methanol and DME. Established methanol catalysts are employed for metha-
nol formation and typical dehydration catalysts are solid-acid catalysts,
e.g. alumina, silica-, phosphorus- or boron-modified alumina, zeolite, (sili-
co)aluminophosphates, tungsten–zirconia or sulfated-zirconia.93,94

3CO þ 3H2 ! CH3 OCH3 þ CO2 ð8:5Þ

Since DME characteristics are similar to those of liquefied petrol gas

(LPG),95 it can be used in typical LPG applications, e.g. power generation,
propellants, domestic cooking fuels or automotive fuels. If DME is employed
as admixture, LPG properties are not significantly affected up to a DME
content of around 20%. Compared to LPG, the cetane number is much
higher (55–60 in contrast to 5 and 10 for propane and butane) and DME is,
in principle, a suitable fuel for diesel engines. However, DME can not be
blended with fossil diesel and its energy density is much lower, so that
engines have to be adapted.

Gasoline via the MTG Process. Conversion of methanol to gasoline in the

so-called MTG process is accomplished over zeolitic ZSM-5 catalyst systems
either via fluidized- or fixed-bed technology. The former was demonstrated
by Mobil, Union Rheinische Braunkohlen Kraftstoff AG and Uhde in a
pilot plant at UK Wesseling and the latter was operated successfully by
Methanex in New Zealand licensed by ExxonMobil. The Mobil process
148 Chapter 8
yields around 38 wt.% of gasoline, 4 wt.% of LPG, approximately 58 wt.%
of water and a small amount of fuel gas.96,97
The underlying chemistry is complex and the multistage process is initiated
by the formation of DME through dehydration of methanol equation (8.6).
The following chain growth and cyclization reactions proceed via further
release of water and can be described, in a very simplified manner, by equations
(8.7) and (8.8). These reactions involve not only reactions of DME with itself
equation (8.8) but also reactions of DME with methanol equation (8.7).

2CH3 OH ! CH3 OCH3 þ H2 O ð8:6Þ

nCH3 OCH3 þ nCH3 OH ! ‘‘ðCH2 Þ3n ’’ þ 2nH2 O ð8:7Þ

nCH3 OCH3 ! ‘‘ðCH2 Þ2n ’’ þ nH2 O ð8:8Þ

The resulting hydrocarbon product mixture is free of sulphur as well as

nitrogen and exhibits low benzene content. Thus produced gasoline (Table 8.3)
complies with European gasoline regulations. Further advantages of the pro-
cess are minimal CO2 emission and high energy efficiency. However, direct
production of longer-chain alkanes for diesel and jet fuel using typical MTG
catalysts is not possible.
The MTG process can be combined with MTO technology as realized in the
so-called MOGD process (Mobil Olefin to Gasoline/Distillate). Employing this
process, olefins are synthesized in the first step followed by olefin oligomer-
ization to gasoline or diesel using a ZSM-5 catalyst. Hence, this route also
affords, unlike the MTG process, the production of synthetic diesel or jet fuel.96
A similar process is the TIGAS process (Topsøe Integrated Gasoline
Synthesis) developed by Haldor Topsøe A/S and demonstrated at a pilot plant
in Houston.96 It is, in principal, an improved MTG process combining
methanol, DME and gasoline production in a single synthesis loop thus cir-
cumventing intermediate production and storage of methanol. Different syngas
compositions can be employed since methanol/DME synthesis is flexible in
terms of syngas specifications.
Another approach is the MTS process (Methanol To Synfuel) introduced by
Lurgi GmbH, which is, in terms of process engineering, comparable to the
MOGD process. However, primarily diesel is produced – besides a smaller

Table 8.3 Typical MTG products and gasoline composition.97

Hydrocarbon products w/w% Gasoline composition w/w%

Light gas 1.4 Highly branched alkanes 53

Propane 5.5 Highly branched alkenes 12
Propene 0.2 Cycloalkanes 7
Isobutane 8.6 Aromatics 28
n-Butane 3.3
Butenes 1.1
C51 Gasoline 79.9
Green Fuels – Sustainable Solutions for Transportation 149
amount of gasoline – and therefore the process is, with respect to the product
distribution, more like the Fischer–Tropsch process, which is described in the
following section.

Fischer–Tropsch Diesel. Direct conversion of syngas to hydrocarbons suc-

ceeds in the Fischer–Tropsch (FT) process, discovered by Franz Fischer and
Hans Tropsch in the 1920s.98 The FT process is well established and cur-
rently operated e.g. by Sasol (Sasol Advanced Synthol, SAS process in
Secunda, South Africa) and Shell (Middle Distillate Synthesis, MDS process
in Bintulu, Malaysia). Coal and natural gas are employed in these processes
as feedstock for the generation of syngas and a biomass-based process is
already in an advanced stage (SunDiesels via the Choren Carbo-Vs Pro-
cess).99 FT syntheses can be conducted in slurry-phase, fixed- and fluidized-
bed reactors, mainly depending on the catalysts and reaction temperatures.
With respect to reaction temperatures one can distinguish between low- and
high-temperature FT technologies (LT-FT and HT-FT). The former operate
at temperatures around 220 1C and yield primarily long-chain hydrocarbons
such as paraffins and waxes whereas the latter, operating at temperatures
around 340 1C, produce mainly naphtha and olefins (Table 8.4). Long-chain
products obtained via LT-FT processes are hydro-cracked in the next step
to yield diesel in very high quality. Generally speaking, LT-FT syntheses
combined with slurry-phase reactors are, at present, the preferred
option.100,101
The Fischer–Tropsch reaction of carbon monoxide with hydrogen can be
described, in a simplified way, according to equation (8.9). Chain growth
proceeds at the surface of cobalt- and/or iron-based catalyst systems, e.g.
Fe-, Fe/Co-, Fe/Co-Spinel-, Co/Mn-Spinel- or Cu-doped Co-catalysts. Iron
catalysts, on the one hand, are cheaper than cobalt catalysts and more flexible
as well as resistant with respect to syngas composition and quality. Cobalt
catalysts, on the other hand, exhibit best performances at a H2 : CO ratio of

Table 8.4 Comparison of product spectra obtained from different Fischer–

Tropsch processes.102
LT-FT HT-FT
Compound Cobalt catalyst 220 1C Iron catalyst 340 1C

Methane 5 8
Ethylene 0 4
Ethane 1 3
Propylene 2 11
Propane 1 2
Butylenes 2 9
Butane 1 1
C51 Gasoline 19 36
Gasoil/Distillate 22 16
Heavy Oil/Wax 46 5
Oxygenates 1 5
150 Chapter 8
2 : 1 and feature longer lifetimes as well as higher selectivities than iron
catalysts.
nCO þ ð2n þ 1ÞH2 ! Cn H2nþ2 þ nH2 O ð8:9Þ

As mentioned above, high-quality diesel can be obtained via FT processing.

High cetane numbers of 4 70 are reached and the fuel is almost free of sulphur,
nitrogen or aromatic contaminants. Furthermore, engine tests revealed low
NOx, CO, hydrocarbons and particulate emissions. Compared to fossil diesel,
FT diesel shows superior characteristics and can be employed instead of, or in
blends with, fossil diesel without modification of engines and gas station
systems.
Current research in the field of FT catalysis focuses on improved selectivities.
Selectivities can be influenced not only by the catalyst but also by choice of the
process and reactor type as well as favourable reaction conditions such as
temperature, pressure, syngas composition, feeding of co-reactants into the
reaction zone, etc. As an example, FT synthesis can be modified to yield parti-
cularly a-olefins103 and these can be converted to diesel in a subsequent reaction.

8.5.6.2 Synthesis Gas Generation

Major uses of syngas, produced mainly from natural gas, coal or petroleum
fractions today, is for hydrogen generation, methanol production, hydro-
formylation, and Fischer–Tropsch synthesis. However, a broad range of pro-
ducts can be derived from syngas opening access to many biofuels (see above)
and platform chemicals.104 As a result of the increasing interest in syngas-based
products, many gasification methods, reactors and plant configurations are
available or under development. While the chemical syntheses are mainly well
established and commercially applied based on fossil feedstock, the front end
processes to convert biomass into synthesis gas are still under development.
The main chemical equilibrium reactions for complete gasification e.g. at
1200 1C are compiled in Table 8.5.
By gasifying biomass or biomass-based intermediates producer or synthesis
gas (or simply syngas) is generated with H2, CO, CO2 and CH4 as the main
components. The elemental composition of biomass feedstocks vary between
35 and 53 wt.% for carbon, 5 and 6 wt.% for hydrogen, 32 and 43 wt.% for
oxygen, 0.1 and 1.4 wt.% for nitrogen, 0.01 and 0.08 wt.% for chlorine and
0.02 and 0.5 wt.% for sulphur. Therefore, an H2/CO ratio in the order of 1 : 1 is
obtained, which cannot directly be used for all syntheses. By the water gas shift
reaction

CO þ H2 O ! H2 þ CO2 ð8:10Þ

as a separate process step the ratio has to be adjusted to the requirements of the
synthesis applied.
However, the gas produced by gasification contains impurities, depending
on the type of feedstock and conversion technology applied. Typical are the
Green Fuels – Sustainable Solutions for Transportation 151
Table 8.5 Main chemical equilibrium reactions for gasification.
Heterogeneous key reactions for complete gasification including C, CO,
CO2, H2, O2, H2O, CH4 at T 4 1200 1C DrH kJ mol1

R1 Combustion C+O2 - CO2 –394

R2 Hydration C+2H2 - CH4 –75
R3 H2O-gasification C+2 H2O - CO2+2H2 +119
R4 CO2-gasification C+CO2 - 2CO +173
Other important gasification reactions as linear combinations of R1–R4:
R5 Shift-reaction CO+H2O - CO2+H2 R4 – R3
R6 Partial oxidation 2C+O2 - 2CO R1+R4
R7 CO-oxidation 2CO+O2 - 2CO2 R1 – R4
R8 H2-combustion 2H2+O2 - 2H2O R1+R4 – 2R3

Table 8.6 Maximum contamination levels tolerated by methanol synthesis.105

Contaminant Level

Tars o0.1 mg Nm–3

CH4 o3 vol.%
NH3 10 ppm
HCN 0.01 ppm
Total sulphur 0.5 ppm
Halides 0.001 ppm

organic impurities like tar and BTX (benzene, toluene and xylenes), the inor-
ganic nitrogen-, sulphur- and chlorine-containing impurities NH3, HCN, H2S,
COS and HCl, as well as volatile metals (regarding biomass in particular Na
and K), dust and char or soot. Larger hydrocarbons, summarized as tars being
produced at low temperature gasification processes, may cause fouling of
downstream equipment, coat surfaces and plug pores in filters and sorbents.
Other impurities are corrosive or act as catalyst poisons in the subsequent
synthesis stages. Therefore, crucial toleration levels are set for contaminants;
Table 8.6 shows e.g. those for methanol synthesis.105
For gas cleaning, conventional technology is available. Tars and BTX may
be removed by either thermal or catalytic cracking, or by scrubbing with an oil-
based medium. The other above-mentioned impurities are removed by stan-
dard wet gas cleaning technologies, e.g. the well-established Rectisol process. In
that process, CO2 and sulphur compounds are removed in separate fractions,
resulting in a pure CO2 product (e.g. for urea production) and an H2S/COS
enriched Claus gas fraction suitable for sulphur production. In a multi-stage
process, the impurities are absorbed by cold methanol under elevated pressures
between 30 and 60 bar. The contaminants are then separated or even fractioned
by pressure release and temperature increase during solvent regeneration. In
advanced dry, hot gas cleaning, the residual contaminants are removed by
chemical adsorbents at elevated temperatures. However, for syntheses operated
between 200 and 300 1C there is only little energy advantage, if syngas
152 Chapter 8
compression is required prior to synthesis (compression require cold inlet gas).
In the case that gasification occurs already at pressures slightly above that of
the subsequently following synthesis, dry pressurized gas cleaning predicts
significant energetic benefits.
For biomass gasification, a variety of technologies exist.106 In view of large
scale production of high-quality synthesis gas as required for synfuel produc-
tion mainly two types of gasifiers have to be considered here. Direct or indirect
gasification using fluidized bed and entrained flow gasifiers is possible with
potential plant capacities of up to several hundred MW fuel input capacity.
Here, experience from commercially operated plants with coal and lignite as
fuels is available and has already been transferred to the use of biomass as a
feedstock for heat and electricity production via gasification.
For reasons of economy of scale, syngas production and further processing
demand large-scale facilities; for comparison, a crude oil refinery has an input
capacity in the order of 10 Mio mto a1. On the other hand, biomass usually
exhibits low volumetric energy densities, has to be harvested and collected from
wide areas of agriculture or forestry and does not constitute a uniform feed-
stock. Chemical composition and the content of minerals and other inorganic
material, usually denoted as the ash content, may vary significantly. There are
four major sources of biomass: agricultural and forestry residues, municipal
solid waste, industrial waste and purpose-grown bioenergy crops. The
technologies applied should be able to be fed by different kinds of biomass
(multi-feed) to achieve high throughput capacities improving economic viabi-
lity of the plants.
In fixed bed reactors, the feedstock is exposed to the gasifying agent in a
packed bed that slowly moves from the top of the gasifier to the bottom, where
the ash is discharged. By moving through the reactor, the biomass passes dis-
tinct zones of drying, pyrolysis, oxidation and reduction. Usually the different
types of fixed-bed reactors are characterized by the direction of the gas flow
through the reactor and consequently are denoted as updraft, downdraft and
horizontal (crossdraft) gasifiers. Depending on fuel and product gas applica-
tion, a multitude of fixed bed gasifier designs exist. In general biomass fuelled
fixed bed reactors are suited for district heat and power production up to fuel
input capacities of 20 MW. For syngas production, substantial gas cleaning
would be required, due to the relatively high amounts of tar, residual pyrolysis
products, ash and dust particles, depending on the type of reactor applied
(Figure 8.8).
In fluidized-bed gasifiers, biomass particles are rapidly mixed and heated by
hot fluidized sand. Air, oxygen or steam is used as fluidization and gasification
agent. The biomass is quickly decomposed into a combustible gas. In an
autothermal process, a part of the incoming biomass is burned in the bed to
maintain the reaction temperature at the desired value of typically 700–900 1C.
Due to the intense mixing, the gasification reactions cannot be distinguished in
local zones as in fixed-bed reactors, but occur throughout the whole bed leading
to a uniform temperature distribution. The degree of fluidization can be small
(bubbling fluidized bed, BFB) or high (circulating fluidized bed, CFB). BFB
Green Fuels – Sustainable Solutions for Transportation 153
Fixed bed Fluidized bed Entrained flow

Counter current Stationary Slagging

Solid fuel Raw syngas O2 (Air)

Solid fuel Raw syngas Pilot flame Steam

Bubbling bed Fuel

Ash (slag) Air (O2), Steam Ash Fluidization gas Molten slag Raw syngas

Co-current Circulating Slag bath

Air (O2)
- Raw-syngas Fuel
Solid fuel Steam Raw syngas

Recirculation Air (O2)

loop Steam
Bath of hot,
Ash
Fuel molten slag
Ash (slag) Raw syngas Fluidization gas

Figure 8.8 Commonly used types of gasifier.

gasifiers, having a well-defined interface between the reaction zone of the flui-
dized bed and the freeboard above the bed surface, are well known and com-
monly used because of their robust properties but show higher tar formation of
the order of 1–2 wt.%. In a CFB gasifier, there is no distinct interface between
the fluidized sand bed and the freeboard; the entrained media and char are
recycled back to the gasifier via a cyclone. The carbon conversion is con-
siderably better than in BFB gasifiers. In addition, a CFB gasifier can be
operated at high pressures, which is advantageous and more economic in
regard to hydrogen, liquid fuels and chemicals production.
In order not to poison the sensitive synthesis catalysts, synthesis gas must be
of high purity and free from dust and tar. Unlike most fixed-bed and fluidized-
bed gasifiers, entrained-flow gasifiers are able to generate a gas practically free
from tar with only little methane at the high gasification temperatures above
1000 1C. When the operating pressure in the gasifier is above the synthesis
pressure, there is no need for the technically expensive step of recompression of
the synthesis gas, and gas purification is facilitated. An entrained flow gasifier
can be slurry or particle fed using air, oxygen or steam as the gasification agent.
Any feed material which can be pumped and sprayed pneumatically, and which
has a heating value in excess of 10 MJ kg1 is suitable in principle for entrained
flow gasification. Also biomass powders can be transferred out of a pressurized
entrained flow into the gasifier by a so-called high-density flow feed system.
However, this requires periodic operation of a sophisticated system of locks,
which becomes more complicated as the pressure rises. By virtue of the short
residence time (about 1 s), high temperature (1200–1600 1C), high pressure
(20–40 bar) and high capacity (4100 MW), a tar-free synthesis gas with low
methane content is produced.
To use also biomass and biogenic waste with higher ash and alkali contents,
the gasifier type used may be operated at slagging conditions: depending on the
alkali content ash softening or melting already occuring below 1000 1C. The
154 Chapter 8
liquid slag can be handled e.g. by a reactor equipped with a cooling screen,
which originally had been developed for salt-bearing lignite at the DBI
(Deutsches Brennstoff Institut, German Fuel Institute) of Freiberg, Saxony
after 1976. This so-called GSP gasifier can tolerate high alkali chloride and ash
contents and rapid fluctuations of quantities and softening points typical of
straw and similar residues.

8.5.6.3 Current Developments

Depending on the plant size, the biomass feedstock used and the type of fuel to
be produced different concepts for syngas-based fuels are under development
today. However, other plant configurations and gasifiers up to 100 MW bio-
mass input capacity exist but which are related to heat and power production
today.106

SVZ, Sekundärrohstoff-Verwertungszentrum Schwarze Pumpe, Germany. At

SVZ three different types of gasifiers with a total fuel capacity of 420 MW
have been operated. The product gas was used for methanol (120,000 mto
a1), heat and power (75 MWe) production. The methanol plant consists of a
three-stage fine cleaning of the syngas, a catalytic reactor operated at pres-
sures up to 40 bar and a temperature about 250 1C with a recycling gas loop.
Methanol cleaning is performed by a two-stage distillation. Being applied to
town gas production from lignite, the gasification complex was turned to the
use of secondary raw materials such as plastics, sewage sludge, paper, con-
taminated wood or municipal solid waste since 1996. The gasifiers in use
were:

 SVZ fixed-bed gasifier for municipal solid waste and refuse derived fuels
(RDF) in mixtures with coal (24 bar operation pressure);
 BGL fixed-bed gasifier for solid waste/coal mixtures;
 Entrained flow gasifier (GSP-type) for oil slurries, pastes, fuel mixtures
from tar and sewage sludge etc. (25 bar operation pressure).

Coal was added to the secondary fuels to balance out the significant fluc-
tuations in fuel properties, e.g. heating value, and to provide residual char as
energy source for the endothermic gasification process (autothermal opera-
tion). In 2007 the Swiss Sustec Industries AG, then owner of SVZ, put the
gasification plant out of service and discontinued the waste conversion
operation because of insufficient profitability.

Värnamo demonstration plant, Sweden. Sycraft AB operated the pressurized

biomass IGCC (Integrated Gasification Combined Cycle) for combined heat
and power production (CHP). The circulating fluidized bed gasifier was oper-
ated between 1993 and 1999 for about 8000 hours, with a fuel capacity of
Green Fuels – Sustainable Solutions for Transportation 155
18 MW at 18 bar pressure. Wood as the main fuel aside from straw, RDF
and bark was collected in a radius of 50 km. Using air as the gasification
medium, about 50 vol.% of nitrogen is contained in the raw synthesis gas.
After 2000, in a new EU project (CHRIGAS) the production of a hydrogen-
rich synthesis gas was targeted. Therefore it is planned to refurbish the air-
blown gasifier to make an oxygen and steam-blown gasification process. In
addition, a hot gas filtration system will be used to improve the overall
energy balance.

Güssing, Austria. To demonstrate the production of bio-SNG from solid

biofuels, the existing 8 MW fuel-input biomass gasifier in Güssing is equip-
ped with a 1 MW (product capacity) methanation plant (construction start:
January 2008) within the EU Bio-SNG project. On the way to the final pro-
duct, bio-SNG, with the quality of natural gas that can be used for sta-
tionary and mobile applications, the synthesis gas has to be cleaned from
dust, tars, sulphur compounds and other impurities. Subsequently hydrogen
and carbon monoxide are converted into methane by the methanation reac-
tion. The gasifier at Güssing is an FICFB (Fast Internal Circulating Flui-
dized Bed) steam gasifier so far being operated for combined heat and power
production. Within its activities as an energy centre for the production of
heat, power, substitute natural gas and liquid biofuels (coordinated by TU
Wien) the gasification product gas has also been applied to fuel cells and to
Fischer–Tropsch synthesis. A small-scale 1 l h1 (10 Nm3 h1 syngas) Fischer–
Tropsch plant together with the required gas cleaning section for water,
chlorine and sulphur removal has been set up and operated in the frame of
the EU RENEW project. The syngas, delivered at atmospheric pressure from
the gasifier, had to be compressed before the synthesis by a two-stage com-
pressor. Scale-up of the Fischer–Tropsch plant for demonstration is planned.

ECN, The Netherlands. Another type of indirect gasifier, developed in

regard to bio-SNG production by the Energy Research Centre of the Nether-
lands (ECN), is the MILENA gasifier. A new installation with a fuel input
capacity of 1 MW has been commissioned in 2008. Indirect gasification
means that the char is internally recycled to the combustor with the bed
material. In the combustor (fluidized bubbling bed) the char is burned with
air and heats the bed material. The bed material is recycled back to a riser,
where the gasification takes place. Thus, a nitrogen-free product gas is
obtained. Next, the whole bio-SNG production process, already tested suc-
cessfully in lab scale (5 kg h–1 biomass input) will be scaled up to the 1-MW
size.

Choren CarboVs, Germany. In the BTL process of Choren Industries a

three-stage gasification process is applied to convert wood chips, waste
wood, etc. into a tar-free synthesis gas used for synfuel production. In the
156 Chapter 8
1-MW alpha-plant the principal technical feasibility was demonstrated. The
beta-plant, completed in 2008, is constructed for the production of
15,000 mto a1 synthetic fuel. In the first stage of gasification, the air dried
biomass (water content 15–20 wt.%) is carbonized through partial oxidation
with air or oxygen at temperatures between 400 and 500 1C into a tar-con-
taining gas and solid char (low temperature gasification). The tar-containing
gas is partially oxidized for tar decomposition by oxygen and steam at tem-
peratures of about 1400 1C in the second stage of the process. At that tem-
perature, in the third gasification stage, the pulverized char is blown into the
hot gasification medium to be converted to a tar-free synthesis gas. After
appropriate gas cleaning and conditioning, the syngas is converted to BtL-
synfuel (SunDiesel) by Fischer–Tropsch synthesis. Volkswagen, Daimler and
Shell are involved in the project.

bioliqs-process of the Karlsruhe Institute of Technology (KIT). Biomass is

distributed in many ways over large agricultural areas, pastures or forests. In
order to take into account the widespread distribution, the low energy content
and the very different properties of potential feed materials in a more effective
way, the two-stage process bioliqs has been developed at the KIT.107 Accord-
ing to the bioliqs concept, biomass is first liquefied in local facilities by fast
pyrolysis into a pumpable biosyncrude by mixing the char and liquid con-
densates formed during the thermal degradation. Any kind of dry lig-
nocellulose may be used for that process. The biosyncrude can be stored
stably in tanks and is capable of safe and economic transport. The volumetric
energy density of the biosyncrude in the case e.g. of straw is more than ten
times higher than that of the initial biomass. Out of several such regionally
distributed pre-treatment plants, a central large-scale facility is then supplied
with biosyncrudes, e.g. by railway tank wagons. Biosyncrude gasification, raw
syngas cleaning and conditioning are handled more efficiently, flexibly and
with less environmental pollution and, above all, more economically in large
facilities than in a large number of small-scale plants. For this type of chemi-
cal plant, the decremental cost exponent is on the order of 0.7, i.e. an increase
in throughput by roughly one order of magnitude reduces by half the specific
plant investment costs. For gasification, high pressure entrained flow gasifica-
tion has been selected and tested in the 3–5 MW pilot plant of Future Energy
in Freiberg (now Siemens Fuel Gasification Technology) in four gasification
campaigns with different slurries and at different conditions up to pressures of
26 bar and temperatures above 1200 1C. The feasibility of fast pyrolysis for
biomass pre-treatment by producing an intermediate suitable for efficient gasi-
fication was demonstrated in bench-scale plants (10 kg h1).
Based on the promising results a pilot plant covering the complete process
chain is about to be constructed in cooperation with Lurgi on the KIT site.107
The 2-MW (500-kg biomass input capacity) fast pyrolysis plant based on a
transported bed (twin screw) reactor was commissioned in 2008. A 5-MW
high-pressure entrained flow gasifier equipped with a cooling screen and
Green Fuels – Sustainable Solutions for Transportation 157
suitable for operation up to 80 bar at temperatures above 1200 1C is presently
under construction. The 1600 Nm3 h1 syngas obtained at pressures above
synthesis pressure will supply a methanol production unit without expensive
compression of the syngas. Subsequently, a methanol-to-synfuel plant will be
added, which is currently under design.

8.5.6.4 Conclusion for Second-generation Biofuels

Except for heat and power production, no biomass gasification process is
commercially established today. A variety of pilot and demonstration projects
are on the way to show the technical and economic feasibility of biomass-based
syngas processes. Benefit and experiences may be taken from already estab-
lished coal and gas conversion technologies. However, specific differences from
biomass conversion exist, demanding improved solutions. Issues to be
addressed concern the broad range of potential feedstocks differing in chemical
composition, consistency and availability. Many issues are related to the
integration of gasifiers, gas cleaning and conditioning with the syngas con-
version processes according to the requirements of the chemical syntheses
applied. It is nearly impossible to separate the fuels and chemicals business;
considering a BtL production complex, not only the most valuable mix of fuels
and chemicals has to be produced but also co-production of energy, heat and
power has to be included to achieve high thermal efficiencies. It is always more
costly to produce only liquid fuels! In that respect, synthetic fuels production
demands co-generation (polygeneration) of fuels, chemicals, heat and power
within an integrated bio-refinery.

8.6 Third-generation Biofuels and Beyond

Getting photosynthetic organisms to produce fuel directly has long been a
subject for researchers working with organisms that can absorb sunlight and
CO2 to produce plant oils or other fuels. Algae, such as Botryococcus braunii
and Chlorella vulgaris, are relatively easy to grow and create interest as feed-
stock for energy and fuel production (Section 9.1.4.2.25).108–110 Microalgae,
produced in open ponds or more efficiently in photobioreactors, may contain
up to 50 wt.% of lipids which can be converted to suitable fuels, meanwhile
denoted as third-generation biofuels. Instead of growing their algae outside in
the sunlight, researchers of Solazyme grow them inside dark stainless steel
fermenters, in which the organisms convert sugars to oils.
Actually, the search for fuel-producing microbes is one of the hottest areas in
synthetic biology today using synthetic biology to lend E. coli, yeast and other
easily grown micro-organisms the ability to create mixtures of compounds that
can be used to make various substances for use as fuels. A handful of start-up
companies have leapt into the field, some even teaming up with major energy
companies such as Chevron and BP. As an example, LS9, Inc. researchers are
reengineering E. coli and other organisms to make what they refer to as
158 Chapter 8
renewable petroleum focusing on a pathway that converts sugars to fatty acids,
which can then be converted to biodiesel. In another approach in San Francisco
the University of California is working with biosynthetic bacteria like E. coli to
make isobutanol.111
A recently discovered fungus, hidden within a stem from a scraggly tree in
northern Patagonia, produces dozens of the same midlength hydrocarbons,
which are also contained in gasoline, diesel fuel and jet fuel.112
Other approaches, already announced as fourth-generation biofuels, are
the conversion of spent vegetable oil to gasoline113,114 or the use of (modified)
micro-organisms to produce suitable feedstocks from CO2.115

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CHAPTER 9

Biomass for Green Chemistry

KARLHEINZ HILL AND RAINER HÖFER

Cognis GmbH, Rheinpromenade 1, D-40789, Monheim, Germany

Coal tar dyes mark the beginning of the chemical industry in the UK, in
France and in the Rhine Valley with chemists like August Wilhelm Hofmann
and William Henry Perkin and company names like Ciba, BASF, Hoechst
and Bayer. Since the last century crude oil and natural gas have become the
key raw material sources for the modern chemical industry yielding all base
chemicals like olefins, acetylene and more particularly aromatics. In the
future, as in the past, a reliable and economically reasonable supply of car-
bon and hydrogen as raw material source for basic chemicals and their deri-
vatives will be the basic requirement for the chemical industry.1
Fossil raw materials such as crude oil, gas and coal are limited, though. In
contrast, nature is producing 170 billion mto of biomass every year simply by
photosynthesis.2 Thereby nature provides a remarkably wide range of renew-
able raw materials from agricultural, marine and forestry production of varying
material properties and differing chemical compositions, which constitute a
substantial potential for industrial production and energetic use besides the
traditional areas of food, feed, construction and garments.3 The term biomass
means all organic materials of biogenic, non-fossil character and comprises also
matter living and growing in nature and waste materials resulting from both
living matter and organic matter that is already dead (Table 9.1).
While petrochemical feedstock in a modern national economy like Germany
accounts for 17 Mio mto of the chemical industry’s raw materials mix, the use
of renewable resources represents approximately 2.7 Mio mto, i.e. 14%.

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164
Biomass for Green Chemistry 165
Table 9.1 Agrarian raw materials for use in the chemical industry, Germany,
2006. For comparison: Petrochemical raw materials: 17 Mio. mto.
With the permission of Fachagentur Nachwachsende Rohstoffe,
Gülzow; source: FNR, VCI, meó Consulting Team, Mantau/
University Hamburg, BFH; http://www.fnr.de/cms35/Industrielle-
Nutzung.1709+M54721168da5.0.html#content3341 (retrieved
18.08.2008).
Raw material Consumption (mto)

Vegetable oils 800,000

Animal fats 350,000
Starch 630,000
Cellulose/dissolving pulp 320,000
Sugar 295,000
Natural fibres 176,000
Rosin and natural waxes 31,000
Other (incl. proteins) 86,000 (55,000)
Total 2,688,000

Actually, biomass is mainly used to complement petrochemicals in applica-

tions, where renewable products can display advantages due to their chemical
structure or properties. While fossil raw materials coal and crude oil are bio-
mass, which has been reduced over millions of years to carbon or hydro-
carbons, renewable raw materials are already composed of a universe of lower
and higher molecular weight structures. It is a formidable challenge for che-
mical research to use these pre-manufactured renewable moieties as starters for
alternative manufacturing processes eventually employing new green catalysts,
green solvents or white biotechnology; to develop degradable polymers for
packaging, bonding and de-bonding on command or agricultural purposes, for
example; to synthesize environmentally benign safer chemicals, and biode-
gradable or recyclable products.4 Alternatively, white biotechnology can
transfer complex biomass structures yielding platform chemicals like ethanol,
glycerol, succinic or lactic acid. Gasification technologies can convert biomass
into synthesis gas – short-cutting the millions of years of geological coal and
crude oil formation and subsequent gasification and cracking of these fossil
base-stocks. Last but not least, anaerobic digestion or fermentation of biomass
yields biogas (also called landfill gas or digester gas), which primarily comprises
methane and carbon dioxide.
With high oil prices the interest in alternative sources for hydrocarbon
feedstock has increased and technologies to convert bio-ethanol into ethene
(see Figure 9.1) are moving to commercial scale (see Chapter 9.3). In combi-
nation with new processes, renewable feedstock represents alternative routes to
petrochemical production which are becoming competitive at an oil price above
40 US$ per barrel.5
166 Chapter 9

renewable
resources carbohydrates

synthesis
gas

value-
natural ethene/ adding
gas crude olefins chains
coal oil

acetylene

lignin
aromatics

Figure 9.1 Basic raw materials yielding key intermediates for the chemical industry.

References
1. J. -D. Arndt, S. Freyer, R. Geier, O. Machhammer, J. Schwartze, M. Vol-
land and R. Diercks, Chem. Ing. Techn., 2007, 79(5), 521.
2. W. Umbach, in Perspektiven nachwachsender Rohstoffe in der Chemie, ed.,
H. Eierdanz, VCH, Weinheim, 1996, p. XXIX.
3. meó Consulting Team, Institut für Energetik und Umwelt, Faserinstitut
Bremen, Marktanalyse Nachwachsende Rohstoffe (Teil I+II), ed., Facha-
gentur Nachwachsende Rohstoffe, Gülzow, 2006.
4. J. H. Clark, Green Chem., 2006, 8, 17.
5. S. Andre, C. Günther, S. Sanghvi and A. Vogel, McKinsey on Chemicals,
2008, 1, 31.
CHAPTER 9.1

Natural Fats and Oils1

KARLHEINZ HILL AND RAINER HÖFER

Cognis GmbH, Rheinpromenade 1, D-40789 Monheim, Germany

9.1.1 Introduction
Depending on geography, climate and soil conditions, fish and venison from
wildlife, milk, butter, meat from domestic animals and vegetable oils are all
part of the human diet and are essential daily items for food and non-food
applications. Vegetable oils are frequently classified into two main groups,
according to their source: pulp oils (palm, olive, avocado) and seed oils (soy-
bean, cottonseed, peanut, sunflower, rapeseed, sesame, palm-kernel, coconut,
linseed, castor and other minor). The major edible animal fats, also termed as
meat fats, are lard and tallow, butter and marine oils. Lard and rendered pork
fat are produced from the fat of pigs. Edible tallow is produced mainly from the
fat of cattle (beef tallow) or sheep (mutton tallow). The importance of fats for
humans, animals and plants lies in their high energy contents. Their calorific
value is more than double that of carbohydrates and proteins. In addition, fats
allow humans and animals to consume fat-soluble vitamins and provide them
with essential fatty acids. Securing the consistent availability of fats and oils in
sufficient quantity with equitable geographic distribution is required to fight
hunger and under-nourishment on Earth.
Besides utilization for food and feed, fats and oils are one backbone for green
industrial chemistry and key components of bio-refinery concepts.2 Vegetable
oils and their by-products, cysts, shells, hulls and parings as well as waste and

RSC Green Chemistry No. 4

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Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

167
168 Chapter 9.1
recycling products can serve as energy sources for the generation of thermal or
electrical power and as raw material base for alternative fuels. Efforts to
manage production of fats and oils involving the entire crop and its biomass as
a zero waste operation throughout the value chain from sowing, harvesting and
processing, to shipping, trade and disposal are important elements of modern
industrial ecology3 and of the Chemical Industry Responsible Cares – Global
Charter.

9.1.2 Paradigm Changes in Global Fats and Oils

Production, Use and Trade
Vegetable and animal oils and fats actually represent the main portion of
around 43% of all renewable raw materials used in the chemical industry of a
country like Germany (see Chapter 9, Table 9.1).
Their production at a global level has undergone fundamental changes over
time. During the 1930s oils and fats were already traded globally; worldwide
oilseeds reached an average annual production of 49 Mio mto, and fat and oil
trade reached an average of 20 Mio mto including up to 540,000 mto (1938)
sperm whale oil.4,5 At that time, sperm oil was highly thought of as the finest
lubricant, and the cleanest burning oil. It was also the first source for saturated
and unsaturated fatty alcohols until catalytic high pressure hydrogenation of
fatty acid esters was established. After the Second World War efforts to protect
endangered whales evolved into one of the first wildlife campaigns and have
perhaps made greater progress than any other international effort to protect
endangered species. In 1946 the International Whaling Commission (IWC)
was formed to protect the future of whales. Commercial whaling has
been banned via an ‘‘indefinite moratorium’’ set down in 1986. The controversy
over whaling, however, is also an example of conflicting ideas about human-
environment relations, resource management and the very concept of sustain-
ability. This applies more particularly to Greenland, where whales have been a
part of the marine-based economy of Inuit people and their ancestors since
their expansion from the Canadian Arctic into Greenland over four thousand
years ago.6,7
By 1960, world production of oils and fats had reached 30 Mio mto. Driven
mainly by population growth, rising per capita requirements for human
nutrition, changing consumer behaviour regarding the fatty acid composition
of the diet, and also by increasing industrial demand major changes in fats and
oils production have occurred in the following decades. While most of the fossil
crude oil products serve for energy or transportation purposes and o10% for
chemical applications, natural fats and oils are mainly used for human food
and animal feed. In recent years, however, biofuels are creating additional
demand and have become a new segment of vegetable oil use creating
a noticeable impact on the applications for food and chemistry purposes
(Figure 9.1.2).
Table 9.1.1 World production of fats and oils.8

Natural Fats and Oils

Independ States ðCISÞ4

Oil; Total World ðmtoÞ

2006=2007 ðMio mtoÞ
Oilseed Production

Commonwealth of

World ðMio: haÞ

South America3

Harvest Area;
Total World
Uzbekistan

Philippines

ðMio mtoÞ
Other EU
Argentina

Indonesia
Malaysia
EU  27

Pakistan

Thailand
Ukraine

Oilseed;
Canada

Mexico

Turkey
Russia

Africa
Brazil

China
Total

Total

India
USA

Oil seeds & seed oils

Soybean 86.8 3.5 – 58.7 48.3 115.3 1.3 0.6 0.8 0.9 o0.1 1.8 – 16 8 – – – 0.7 0.2 1 237.2 36.6 94.3
Cottonseed 6.7 – 0.3 2.3 0.2 2.8 0.6 – – – 2 3 1.3 12.2 9.3 4.4 – – – – 2.7 44 5 34
Groundnut1 1.2 – – 0.2 0.5 0.7 – – – – – – o0.1 10 3.7 o0.1 – – 0.8 o0.1 5 23 4.1 22
Sunflower 1 0.2 – 0.1 3.5 3.8 6.3 0.5 6.4 5.5 – 12.5 0.8 2 1.4 0.3 – – – o0.1 0.7 30 11.2 24
Rapeseed2 0.6 9.0 – o0.1 o0.1 0.3 16.1 0.1 0.5 0.6 – 1.3 o0.1 12.7 6.2 0.3 – – – – o0.1 47.8 18.5 27.2
Sesameseed – – o0.1 o0.1 – 0.2 – – – – – – o0.1 0.7 0.7 – – – – – 0.9 3.4 0.86 7.5
Palmkernel – – – o0.1 – 0.3 – – – – – – – – – – o0.1 4 4 0.2 0.8 10 4.4 10.5
Copra, coconut oil – – 0.2 – – – – – – – – – – – 0.6 – 1.7 o0.1 1.4 o0.1 0.1 4.7 3 9
Linseed 0.3 1 – o0.1 o0.1 o0.1 0.178 – – – – 0.1 – 0.5 0.2 – – – – – o0.1 2.6 0.7 2.9
Castorseed – – – 0.1 – ca. 0.1 – – – – – – – 0.24 0.8 – – – – – – 1.2 0.52 1.3
Corn oil (maize oil) 1.2 o0.1 o0.1 o0.1 o0.1 o0.15 0.25 – o0.1 o0.1 – o0.1 o0.1 0.2 – – – – – – – – 2.32
Total seed & seed oils 97.8 13.7 0.6 61.5 52.5 123.6 24.73 1.2 7.6 7 2 18.7 2.1 54.54 30.9 5 1.7 4.2 7 0.7 10.2 405 87.3 2335

Pulp oils
Olive oil – – – – o0.1 o0.1 2.1 0.1 0.3 3
Palm oil 0.2 1.2 16 17.2 1 1.6 38
Total pulp oils 0.2 0.1 1.2 2.1 0.1 16 17.2 1 1.9 41

Grand Total oil 97.8 13.7 0.6 61.7 52.6 124.8 26.83 1.2 7.6 7 2 18.7 2.2 54.54 30.9 5 1.7 20.2 24.2 1.7 12.1 405 128.3
seeds & vegetable
oils

Animal Fats & Oils

Fish o0.1 – 0.5 0.14 0.1 1
Butter 0.5 o0.1 0.2 1.8 o0.1 0.2 0.45 0.1 2 0.5 6.9
Lard 0.5 0.1 0.4 2 o0.1 0.2 0.4 3.6 o0.1 7.6
Tallow & Greases 3.8 0.4 0.1 0.6 0.2 0.8 1.1 o0.1 0.1 0.2 0.9 0.2 0.1 8.5
Total animal 4.9 0.5 0.1 1 0.2 1.5 5.4 0.1 0.5 1.1 4.6 2.2 0.6 24.0
fats & oils

Grand total 405 152.3 233

oils & fats

Sources: ISTA Mielke, Oil World Annual 2007, private communication Thomas Mielke. mto ¼ metric tons; Mio ¼ Million; ha ¼ hectare (2.471 acres)
1
shelled basis, 70% of unshelled; 2including canola; 3Argentina, Bolivia, Brazil, Colombia, Ecuador, Paraguay, Uruguay, Venezuela; 4Russia, Ukraine, Kazakhstan,

169
Belarus, Moldova, Armenia, Aserbaijan, Georgia, Kyrgystan, Tajikistan, Turkmenistan, Uzbekistan; 5(for comparison 1983/84: 150 Mio. ha)
170 Chapter 9.1

Mio. mto
50
42,5
37,7 1960 2008
40
30 Mio. mto 159,4 Mio. mto

30

20 19,4 17,1

10,1
10 8,6 8,1 7,8 8,8
7,1
3,4 3,5 4,2 2,4 3,6
1,3 1,2 1,8
0
Soybean Palm Rapeseed Sun- Tallow Butter Laurics Other Other
flower (coconut veg- animal
+ palm etable* (incl.
*cotton, peanut, sesame, corn, olive, linseed, castor kernel) fish oil)

Figure 9.1.1 Development of world oils and fats production 1960/2008.8

Mio. 2004 Mio. 185 2010

mto mto
65%
131 86%
120
113

25%
14% 10% 45
18 20

Total Food & Chemistry Total Food & Chemistry Biodiesel

Feed Feed

Figure 9.1.2 World consumption of oleochemical raw materials 2004/2010. Forecast

for biodiesel in 2010: 45 Mio mto;9 a more conservative forecast envi-
sages 32 Mio mto in 2012;10 for comparison: world consumption of
mineral oils in 2004: approximately 4 bn mto.

On a global basis annual production of oil seeds reached 405 Mio mto in
2006/20078 (Figure 9.1.3, Table 9.1.1). In the 2007/2008 season, though, world
output of oilseed dropped back to 391 Mio mto. After more than 20 years of
more or less steady growth the global area devoted to ten oilseeds declined by
1 Mio ha to 232.6 Mio ha reflecting the high interdependence and growing
volatility of grain and oilseed farming and their respective outlets to the food,
dairy, livestock and biofuels markets. Production of fats and oils reached
152.3 Mio mto in Oct./Sept. 2006/2007, i.e. more than five-fold higher than
1960, and production is estimated to be 159.4 Mio mto in 2007/2008. World
production of oil meals was 255.8 Mio mto in Oct./Sept. 2006/2007 and reached
an estimated 261.5 Mio mto in 2007/2008.
Natural Fats and Oils 171

420

380

Production (Mio mto)

340

300

260 Area (Mio ha)

220

180

140
82/83 87/88 92/93 97/98 02/03 07/08

Figure 9.1.3 Oilseeds: world area and production8 (reproduced with permission of
ISTA Mielke Oil World, Hamburg).

Possibly even more dramatic than the sky-rocketing of overall production are
regional changes in cultivation and alterations in the types of fats and oils
which have occurred. In 1960 butter and tallow ranked number 1 and 2 in
world production, respectively. Since then they have been largely surpassed by
vegetable oils, i.e. soybean, palm, rape seed and sunflower oils (Figure 9.1.1).
Europe is only one example for these changes. Towards the end of
last century large areas of European landscape changed from the green of
grassland to the brown-yellow of rapeseed and sunflower crops. This alteration
in postcard colours reflects a fundamental change in agro-production in Cen-
tral and Northern Europe, which traditionally had been focusing on farmyard
products like milk, butter and beef tallow. Permanent grassland decreased
significantly, accentuated by the fall in numbers of livestock after the EU
imposed milk quotas in 1984 in order to stop subsidized overproduction of milk
(which had resulted in so-called milk-lakes and butter-mountains). This
released land that could be farmed for the production of crops. Areas sown
leapt from just a few thousand hectares in the early 1980s to 4.8 Mio ha by 1990
and 10.2 Mio ha by 2007. Additionally, the reformed Common Agricultural
Policy, CAP, and a considerable body of legislation and energy-related policies
have provided incentives to encourage the use of energy crops for the pro-
duction of renewable energy, in particular biofuels. Meanwhile the E-27
became the world’s largest producer of rapeseed oil and number 2 (behind the
CIS) in sunflower seed and oil, which is dominant in the southern European
countries.
172 Chapter 9.1
Regional changes of similar magnitude have happened in South America.
Enlarged production of soy beans and livestock farming of cattle for meat
production helped the Brazilian national economy to significantly improve its
international financial position and to participate in the dynamics of global
growth. Brazil succeeded in reaching record highs in exports, trade balance
and, since 2003, a consecutive yearly current account surplus resulting in a
significant improvement of Brazilian external sustainability indicators to the
best levels of the historical series.11
At the same time soya has overtaken illegal logging and ranching as the main
engine of deforestation of virgin rainforest to make room for the crop. It needs,
however, to be noted that the Brazilian Agro Energy Plan 2006–2011 envisages
optimizing the use of areas affected by human action on natural vegetation,
maximizing the sustainability of the production systems, discouraging unjus-
tifiable expansions of the agricultural frontier and encroachment upon sensitive
or protected systems.12
In Southeast Asia the ambitious expansions of oil palm plantations in the
tropical areas have made this region by far the main palm oil producing region
in the world outdistancing natural rubber cultivation as the key agro resource
in Malaysia (Figure 9.1.4).
The accelerated extension of oil palm plantations has also initiated discus-
sions about the social and environmental impacts, more particularly violation
of land rights of indigenous people, destruction of community-based econo-
mies, deforestation of rainforests, oil palm cultivation as false pretence for
illegal logging, biodiversity loss including risk of orang-utan, Asian elephant,
clouded leopard, Sumatran and Javan rhino extinction,14 fragmentation and
loss of Sumatran tiger habitat and climbing pollution levels due to forest fires
for land-clearance.15

Figure 9.1.4 Planted area for oil palm and natural rubber in Malaysia13 (reproduced
with permission of Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
Natural Fats and Oils 173
Petroleum oil reserves are concentrated in a relatively small number of
countries. World consumption has surged steadily upward. The rapidly
industrializing economies of China and India are projected to increase their
demand dramatically. The consumption of Asia including Japan is already at
the level of North America. The crude oil main streams flow from a few
countries in the Persian Gulf, West Africa, the Gulf of Mexico and the Car-
ibbean plus Russia to the highly industrialized regions in North America,
Europe and Asia16 (Figure 9.1.5).
Compared with crude oil, biofuels are expected to reduce many of the vul-
nerabilities associated with today’s highly concentrated energy economy.17
Developing countries will have a competitive advantage in biofuel production
due to lower land and labour costs, warm tropical climates and longer growing
seasons. International trade channels will follow those already established
between grain and oilseed exporting countries like Brazil, Argentina, USA and
palm oil exporters like Malaysia and Indonesia and consumers in Europe and
Asia (Figure 9.1.6).
Africa has enormous potential to become a grain and vegetable oil exporting
region if ever political and administrative frameworks become sustainable and
the concept of good governance18 is established within each country. However, it
needs to be noted that with growing importance of biofuels the markets for food,
fuel and energy, when based on biomass, will increasingly become inter-twined.
Downstream processing will eventually move away from historical centres
of technology to the sites of origin, a phenomenon which is happening already
for fatty acid, fatty alcohol and fatty acid ester production.20 Indeed, there
is no guarantee for low freight charges supporting global trade and global

Main world-wide oil transportation routes

533
186

1037 447 771 Former USSR

292
North America Europe

1186
251
Middle East

1091 380
441 124 Asia/Oceania
Africa
485
Production 307
millions of tonnes Latin America

Transport route

Consumption Source: Pétrole 2004, Comité Professionel Du Pétrole, Cedre, Agence Hippocampe

Figure 9.1.5 Global trade fossil oil.16

174 Chapter 9.1

Figure 9.1.6 Global trade grains and oilseeds (Reproduced with the permission of
Rabobank).19

transportation forever. On the contrary, increasing crude oil prices will sooner
or later impact on transportation cost. This could compensate the lower energy
density of biomass compared to fossil crude and further push towards decen-
tralized bio-refinery concepts.

9.1.3 Production of Oils and Fats

Sustainable production of oils and fats starts from sustainable crop plantations
and livestock husbandry. Based on Good International Industry Practice
(GIIP) as technical reference, Environmental, Health and Safety (EHS)
Guidelines for crop plantation and crop production regulate environmental
issues such as stress on water resources, soil erosion, pesticide use, eutrophi-
cation of aquatic environments, biodiversity impacts, crop residues and
atmospheric emissions. Additionally, EHS Guidelines for Vegetable Oil Pro-
cessing are applicable to facilities that extract and process oils and fats from
vegetable sources.21

9.1.3.1 Production of Vegetable Oils and Fats

Modern manufacturing of vegetable oils can be considered as a set of unit
operations, which are applied depending on the composition of the crop, local
or regional conditions and the intended end use. Because of the quick dete-
rioration of the fruit, pulp oils are processed immediately after harvesting close
to or on the oil fruit plantation.
Oilseeds, unlike pulp oil fruits, can easily be transported and stored over long
periods in ventilated silos. Industrial extraction usually takes place close to the
location where the crude oil is further processed. Preparatory steps prior to oil
Natural Fats and Oils 175
extraction comprise preparation and conditioning, i.e. conveying the seed from
the silos to the factory processing equipment; cleaning; drying; removal of
husks, hulls, shell or seed coat from the oilseed kernel; crushing, sometimes
followed by rolling to improve oil extraction by increasing the surface area of
the seed.
After pre-treatment of the seeds, the oil is extracted and separated from the
meal. Oil extraction can be performed mechanically (cold pressing or expelling)
or chemically by solvent extraction.
During solvent extraction, in the majority of cases hexane is used to wash the
conditioned raw materials, typically in a counter current extractor. Hexane is
removed from the oil through distillation, and from the cake through steam
stripping in a multi-stage counter current toaster and recovered for reuse. EHS
issues during solvent extraction are odour and volatile organic compounds,
VOC. Extraction plants and processes should in each case comply with the
solvent emission directives in force.22 Efforts to replace hexane as the solvent of
choice by aqueous enzymatic methods or supercritical fluids have not yet found
industrial acceptance.
Mechanical extraction does not use solvent extracts. It is made the traditional
way, i.e. separation of the oil from the solid particles by squeezing the oil out of
the crushed mass of seeds using several different types of mechanical extraction
often in small-scale operations.23 This method is typically used to produce the
more traditional oils (e.g. olive oil) and it is preferred by most health-food
customers.
Crude oils and fats, which are obtained by expelling, extraction or rendering
(in the case of animal raw materials) still contain components that are unde-
sirable for taste, smell, stability and appearance. The removal of these unde-
sirable non-triglyceride compounds is called refining. Physical and chemical
unit operations exist for refining (Figure 9.1.7), degumming being the first one.
Degumming removes hydratable (HP) and part of non-hydratable phospha-
tides (NHP). Crude oil containing a considerable amount of gums is subject to
water degumming immediately following extraction. Water or steam is added to
hot oil as a result of which a phosphatides-containing gum layer is formed. The
layer is separated from the oil by decantation (settling) or continuously by
centrifugation and – in the case of soybean refining – processed into com-
mercial lecithin. Dry acid degumming applies for low gum contents such as in
palm oil, palm kernel oil, coconut oil or animal fats. Phosphoric or citric acid is
added to pre-heated crude oil followed by vigorous agitation. The conditioned
gums are absorbed into bleaching earth and separated by filtration.
Enzymatic degumming was first introduced by Lurgi as the EnzyMaxs
technology.24 Reduced gum volume due to formation of water-soluble lyso-
phosphatide, avoidance of soap stock formation, hence increased oil yield, and
reduced environmental impact have made enzymatic degumming based on
phospholipase enzyme an alternative to conventional degumming with
increasing commercial interest (Figure 9.1.8).25
Chemical refining (reduction of free fatty acids and oxidation products of
free fatty acids, which would make the oil or fat rancid; removal of the residual
176 Chapter 9.1

harvesting

preparation
transport

preparation

conditioning

cold pressing/ expelling press cake

solvent extraction animal
mechanical extraction hot/screw pressing 7% oil
feed

extraction
oil cake
10 –13% oil
oil desolvation meal
crude vegetable oil
meal desolvation
animal feed

cold pressed oil gums (lecithine)

degumming acidulated
containing vitamins soap stock
& trace elements oils

refining
chemical (caustic) refining
(enzymatic)
physical refining/ esterification
bleaching
steam refining -
deodorization distillation
deodorization
solvent fatty acid
cristallization esters

steamer

derivatization
distillate

tocopherols,
refined sterols,
sterols,
vegetable oil sterol esters
squalenes

Figure 9.1.7 Vegetable oil processing unit operations.

Figure 9.1.8 Layout of enzymatic degumming (reproduced with the permission of

Novozymes).

phosphatides) comprises the dispersion of an acid, e.g. phosphoric acid in water

de-gummed oil or crude oil and the addition of slight excess of caustic soda
liquor. By this treatment soap stock is formed as a second phase. The soap
stock contains the free fatty acids originally present in the untreated oil, some
Natural Fats and Oils 177
triglyceride oil and other compounds such as sucrolipids and lipoproteins. The
alkali refined, so-called neutral oil is then bleached by heating under reduced
pressure with bleaching earth which is subsequently removed by filtration. The
alkaline neutralization process has major drawbacks: the yield is comparatively
low and oil losses occur due to emulsification and saponification of neutral oil.
In physical refining, (Figure 9.1.9) the fatty acids are removed by a steam
distillation (stripping) process similar to deodorization. In practice, a tem-
perature of 230–250 1C, a pressure of 2 mbar and sparge steam of 1 to 2% are
applied for 60 to 90 min to reduce the free fatty acid content of the refined oil to
a level of about 0.03–0.05%. As a prerequisite, special degumming processes
may be required for physical refining that phosphatides be removed to a level
below 5 mg phosphorus/kg oil. In physical refining the gas exiting the steam
distillation is made up of a mixture formed by stripping gas, malodorous
compounds and valuable by-products such as free fatty acids (FFA), trigly-
cerides, sterols, tocopherols and squalenes.26
After refining hydrogenation of the unsaturated fatty acids in the presence of
a nickel fixed bed or a (supported) nickel slurry phase catalyst transforms the
liquid oil into a (semi-)solid fat. When Wilhelm Normann invented the liquid
phase hydrogenation of oils,27 which he called fat-hardening (Fetthärtung in
German), he initiated a paradigm shift in the diet of industrialized nations.
Hardened fats became a storage stable and economic alternative to butter but

Figure 9.1.9 Physical refining, schematic diagram (reproduced with the permission
of Ma Manuela Prieto Gonzalez, Universidad de Oviedo, Departa-
mento de Energı́a; [email protected]).
178 Chapter 9.1
also, going beyond food applications, in the manufacturing of candles, indus-
trial lubricants, fabric softeners, thixotropes, mould release agents, cosmetics
and toiletries, and household and automotive polishes.

9.1.3.2 Production of Animal Oils and Fats

As in the processing of vegetable oils the extraction of fats and oils from animal
sources can be regarded as a sequence of unit operations (Figure 9.1.10).28
In modern economies milk and butter are predominantly used as dairy pro-
ducts29 (besides e.g. casein paints and glues) whereas tallow and marine oils are
used for food as well as for industrial purposes.
Milk can be regarded as a dilute O/W-emulsion of butter fat stabilized by
membranes of phospholipids and casein proteins. Changing whole milk to
butter is a process of transforming the diluted fat-in-water emulsion to a water-
in-fat emulsion (butter). Churning physically agitates the cream until it rup-
tures the fragile membranes surrounding the milk fat. Once broken, the fat
droplets can join with each other and form clumps of fat, or butter grains, and
coalesce. In the end, there are two phases left: a semi-solid mass of butter
and the liquid left over, which is the buttermilk. The buttermilk is drained off,
and the remaining butter is kneaded to form a network of fat crystals that
becomes the continuous phase with water dispersed in it. Butter oil is the fat
concentrate obtained primarily from butter or cream by the removal of prac-
tically all the water.
Animal fats are produced batch-wise with the use of manual techniques or at
industrial scale using batch, semi-continuous or continuous processes called
rendering. Rendering involves the splitting of the fat bearing raw material into

Milk
Animal fat Fish or sea
3,25 –5% fat
tissue mammelia
O/W emulsion
Skimmed milk
cooking
skimming sorting
Low fat milk pressing
mincing
Cream desintegration
18 –40% fat chopping Press Press
cake liquid
pasteurization
rendering
decanting
churning Butter milk
wet dry raking heating
Butter grains
rendering rendering
separation
kneading centrifuge
drying
Butter separation sieving
80 –85% fat milling/
W/O emulsion grinding

Butter oil Tallow Lard

Fish meal Fish oil
100% fat from beef from pigs

Figure 9.1.10 Animal fat processing unit operations.

Natural Fats and Oils 179
its three major components comprising water, fat and solid proteinaceous
meal in a rendering cooker. Edible rendering consists of heating ground fat
trimmings in a melting tank to about 43 1C, pumping the melted tissue in a
disintegrator, which ruptures the fat cells, followed by separation of the pro-
teinaceous solids from the melted fat and water by centrifugation. The melted
fat and water are heated to about 93 1C and in a second-stage centrifuge the
edible fat is separated from water.
Fish oil and fish meal are produced from fish that are caught specifically
for this market, by-catch from fishing activities and solid waste from filleting
and canning. Raw materials are transported by screw conveyors to a cooking
process which acts to coagulate the protein. The cooked mixture is screened,
and then pressed to remove most of the water from the mixture. The press cake
is shredded and dried. The pressed liquid generated from the previous processes
passes through a decanter to remove most of the sludge, which is fed back to
the meal dryer. Fish oil is separated from the liquid by centrifuges, polished and
refined.
Over-fishing of the oceans is a deep-rooted concern of ecologists and the
public. Although there is wide agreement between experts that fisheries must be
managed with the least impact on stocks, food-webs and habitats, under cur-
rent fisheries management most fish are taken as soon as they can be caught
regardless of size or age for use as both marine food and fish oil. Thus a
paradigm shift is requested and promoted by the marine stewardship council
(MSC) for world fisheries towards an ecosystem-based fisheries management,
EBFM.30 A recent study of the Leibniz Institute of Marine Sciences in Kiel,
Germany, the Rhodes University, Grahamstown, South Africa, and the
Aquatic and Fisheries Sciences Centre in Rennes, France, has shown that
fishing has much less impact on stocks if fish are caught after they have reached
the size where growth rate and cohort biomass are maximum. Such manage-
ment would allow juvenile and adult fish to better fulfil their ecological roles
and prevent an increase in over-fished or collapsed stocks.31

9.1.4 Chemical Composition of Fats and Oils

Chemically, natural fats and oils are triglycerides, also called acylglycerols; that
is fatty acid triesters of glycerine with different even-numbered, linear fatty
acids. The fatty acids may be saturated or unsaturated. There are very few
exceptions to this (Figures 9.1.11 and 13). The most well-known exceptions
are castor oil, glyceroltriester of 12-hydroxyoleic (ricinoleic) acid, vernonia oil,
sperm oil, jojoba oil and tall oil.
Unsaturated fatty acids containing double bonds may have the cis- or trans-
configuration (Figure 9.1.12). In cis-fatty acids, all the hydrogen atoms adja-
cent to the double bonds are on the same side of the longitudinal carbon axis.
In trans-fatty acids (TFA), the hydrogen atoms adjacent to the double bonds
occur on alternate sides of the main axis. The trans-configuration is chemically
more stable. With non-treated vegetable oils the cis-configuration prevails.
180 Chapter 9.1

natural oils and fats castor oil tall oil

O O HO
O C O C 15 – 55 % unsaturated fatty acids
O O
HO
O C O C 20 – 65 % rosin acids
O O HO
5 – 30 % unsaponifiables
O C O C

Figure 9.1.11 Chemical composition of oleochemical feedstock.

Cis-9-octadecenoic acid Trans-9-octadecenoic acid

(Oleic acid) (Elaidic acid)

Figure 9.1.12 Cis- and trans-configuration of unsaturated fatty acids.

Due to interaction with a hydrogenation catalyst the cis-configuration can be

transformed into the trans-configuration. This typically happens during partial
hydrogenation of polyunsaturated vegetable oils and (as a function of time and
temperature) during physical refining. In response to published human studies
that show that intake of TFA increases low-density lipoprotein-cholesterol
(LDL-C) in the blood and risk of coronary heart disease, health authorities
worldwide recommend that consumption of trans-fat be reduced to trace
amounts.
If natural fats and oils are solid or semisolid at 20 1C they are designated as
fats (‘‘edible fats’’ in food technology); if they are liquid at 20 1C they are
described as oils (correspondingly ‘‘edible oils’’ in food technology). Naturally
occurring oils and fats always contain minor constituents such as free fatty
acids, phospholipids, sterols, hydrocarbons, pigments, waxes and vitamins.
Careful extraction of by-products like tocopherols or sterols and addition to
foodstuff as industrially produced dietary supplements is the basis of modern
neutraceutical or functional food manufacturing. Such by-products are, for
example, extracted from soybean oil steamer distillate,26,32 from lecithin after
degumming33 or from crude tall oil, CTO.34
Natural Fats and Oils 181

Vernonia oil, is a triglyceride of vernolic acid, an epoxy oleic acid.

Vernonia oil is extracted from the seeds of Vernonia galamensis
(or ironweed), a plant native to Eastern Africa. Vernonia seed contains
about 40 to 42% oil of which 73 to 80% is vernolic acid.
O
COOH

Vernonia oil has been discussed as natural alternative

to epoxidized soya bean oil or epoxidized linseed oil for
applications such as reactive diluent for low VOC alkyd paints.

Tall oil is a by-product of

sulphate pulping; Crude Pine Tree
tall oil (CTO) mainly
consists of a mixture of Lumber
unsaturated fatty acids
(TOFA), rosin acids and Kraft Sulphite
insaponifiables. Sulphate Pulping
Pulping

Paper Pulp Pulp Paper

Crude Tall Oil Lignosulphonate

Tall Oil Fractionation

Tall Oil TOFA (Tall Tall Oil Distilled Pitch (incl.

Heads Oil Fatty Acid) Rosin Tall Oil Stereols)
10% 35% 30% 5% 20%

Jojoba oil is a vegetable oil obtained from the crushed bean of the jojoba shrub. The jojoba
shrub is native to the Sonoran Desert of Northwestern Mexico and neighbouring regions in
Arizona and Southern California. Jojoba has flat gray-green leathery leaves and a deep root
system that make it well adapted to desert heat and drought. It has a life span of 100 – 200
years. Like sperm whale oil, jojoba oil is composed almost entirely of liquid wax esters of
straight chain mono-unsaturated cis C20 – C24 fatty acids and unsaturated higher fatty alcohols.
Main component is Docosenyl-eicosenoate (C42) and it's chemical structure is

CH3(CH2)7CH=CH(CH2)9C(O)O(CH2)12CH=CH(CH2)7CH3(37%).

Jojoba oil is similar to, and miscible with, sebum, which is secreted by human sebaceous
glands to lubricate and protect skin and hair. Obtained by cold pressing, its peculiar chemical
properties make it the only vegetable oil in nature having the same characteristics as sperm oil.

Sperm oil occurs in the blubber and in the head cavities of the sperm whale (this cavity helps
the whale keep part of his head above water to breathe). The oil contains a solid fraction
(spermaceti, cetin, cetylpalmitate) which can be cristallised. The liquid fraction mainly contains
oleyloleate and higher mono-unsaturated fatty acid monesters of unsaturated fatty alcohol.

Figure 9.1.13 Natural oils with unusual chemical composition.

182 Chapter 9.1
Essential oils are usually derived from the non-seed parts of the plants with
chemical composition other than the triglyceride structure of natural fats and
oils. They refer to the subtle, aromatic liquids extracted from the flowers, seeds,
leaves, stems, bark and roots of herbs, bushes, shrubs and trees through dis-
tillation. Essential oils are concentrated liquids containing volatile aromatic
compounds. They are used in perfumery, aromatherapy, cosmetics, incense,
medicine, household cleaning products and for flavouring food and drink.
Their use in aromatherapy and other health care areas is growing.
Natural waxes may be secretions of plants or animals with properties between
those of a fat and a resin, namely plastic (malleable, pliable) behaviour at
ambient temperatures, polishable under slight pressure, insoluble in water,
hydrophobic. They consist mainly of esters of long-chain alcohols and acids
(>C22), free primary straight chain aliphatic C24 to C36 alcohols, free fatty
acids and other components like paraffins, sterols or neutral resins. Natural
waxes include those of animal origin like beeswax, woolwax (lanolin), shellac
and spermaceti as well as vegetable waxes like carnauba wax, candelilla wax,
sugar cane wax, orange peel wax and floral waxes, i.e. by-products of the
extraction of fragrance oils from flowers such as jasmine, rose and lavender.35

9.1.4.1 Animal Fats and Oils

Animal derived fats can be categorized as milk, rendered fats and marine oils.
Milk fats have an unusually broad fatty acid distribution ranging between C4
and C20/22, mainly C16 and C18. Land-animal fats mainly have a fatty acid chain
length of C16 or C18 and ruminant fats contain 5–10% trans-fatty acids, which
are produced from linoleic and linolenic acid in the rumen. Marine oils of
industrial importance mainly come from three different species: herring, pil-
chard and menhaden. Fish oils are distinguished from land-animal fats by their
high content of highly unsaturated (4–6 double bonds) C20, C22 and C24 fatty
acids including o-3 fatty acids. However, fish do not actually produce omega-3
fatty acids, but instead accumulate them by either consuming micro-algae
(phytoplankton) that produce these fatty acids, as is the case with prey fish like
herring and sardines or, as is the case with fatty predatory fish, by eating prey
fish that have accumulated o-3 fatty acid from micro-algae (Table 9.1.2).

9.1.4.2 Vegetable Fats and Oils

Vegetable oils according to their major fatty acid composition can be sub-
classified into laurics and oleics. Laurics comprise coconut oil and palm-kernel
oil. Laurics mainly contain saturated C12 and C14 fatty acid triglycerides, the
raw material basis for surfactants. Oleics mainly contain unsaturated C16 and
C18 fatty acid triglycerides. Apart from food, which is the predominant use,
they deliver lubricants and base oils, which can be used for energy generation,
fuel, nutrition and specialty chemical derivatives.
Table 9.1.2 Fatty acid compositions of natural oils and fats.*
vegetable animal sea animal

rape seed high erucic

rape seed low erucic

HO sun-flower oil
systematic name

sperm whale oil

palm kernel oil

cotton seed oil

sun-flower oil
double bonds

trivial name

soy bean oil

coconut oil

linseed oil
peanut oil

hering oil
castor oil

Jatropha
palm oil
formula

tallow
lard
hexanoic acid 0 caproic acid C6H12O2 0.5 0.3
0.2–0.8 0–1
octanoic acid 0 caprylic acid C8H16O2 8 3.5
6–9 3–5
decanoic acid 0 caprinic acid C10H20O2 6 3.5 3
4–8 3–5 1–3
dodecanoic acid 0 lauric acid C12H24O2 48 48 0.2 0.2 0.2 16
46–52 46–50 0–0.4 0–0.5 0–0.5 14–18
tetradecanoic acid 0 myristic acid C14H28O2 18 16 1.5 1 o1.4 1.5 2.5 13 8
15–20 14–17 0.5–3 0.5–2 0–3 1–4 12–14 6–10
hexadecanic acid 0 palmitic acid C16H32O2 2 9 8 44 10 21 10 6 4 7 3 4.5 14.7 26 28 9 12
1–2 8–10 6–9 40–47 7–12 20–27 9–11 5–7 3.5–4.5 6–7 2–4 4–5 10–17 21–29 21–29 8–10 10–14
octadecanoic acid 0 stearic acid C18H36O2 1 2.5 2 4 3 2 4 4 4 4 1 1.5 6.1 16 20 2 1
1–2 1–3 1–3 2–7 2–6 1–3 3–5 3–6 3.5–5 3–5 0.5–2 1–2.5 5–10 13–18 15–24 1–3 0.5–1.5
eicosanoic acid 0 archidic acid C20H40O2 0.1 0.1 0.3 3 0.5 0.5 0.7 0.5 0.1 0.3 0.3
0–0.4 0–0.4 0–0.5 2–4 0.2–1 0.3–1 0.5–1 0.1–1 0–1 0–0.5
docosanoic acid 0 behenic acid C22H44O2 2 1 1 o0.1
0.1–3 0.4–1.5 0.4–1.5
tetracosanoic acid 0 lignoceric acid C24H48O2 o0.1 2 o0.1
1–3
dodecenoic acid 1 lauroleic acid C12H22O2 4
3–5
tetradecenoic acid 1 myristoleic acid C14H16O2 0.3 0.5 12
0–1 0–1 11–13
hexadecenoic acid 1 palmitoleic acid C16H30O2 0.2 Sp. 0.5 o0.5 Sp. Sp. o1 3 3 14 9
0–0.4 0–2 2–4 2–4 12–16 7–11
octadecenoic acid 1 oleic acid C18H34O2 3 6.5 16 38 50 29 28 24 83.5 22 15 60 40.7 41 38 17 10
2.5–4 5–8 13–19 36–42 35–70 20–35 20–35 18–28 82–90 12–34 11–24 50–65 36–64 39–45 33–46 15–18 9–11
eicosenoic acid 1 gadoleic acid C20H38O2 0.1 9 1.5 1 0.5 7 13
0–0.4 8–11 1–2.5 0–2 0–1 5–8 11–15
docosenoic acid 1 erucic acid C22H42O2 47 o0.1 18
41–52 15–21
12-hydroxy-octadecenoic acid 1 ricinoleic acid C18H34O3 87
86–92
9,12 octadecadienoic acid 2 linoleic acid C18H32O2 3 1.6 2.5 11 30 45 53.5 64 5 17 13 21 36 7.5 4 1
3–8 0–2.5 1–3 7–2 20–35 42–54 50–56 60–68 2–10 14–26 10–15 18–25 18–45 4–9 2–7
9,12,15 octadecatrienoic acid 3 linolenic acid C18H30O2 0.5 0.3 1 8 52 8 10 0.2 0.7 0.7 0.5
0.2–0.8 0–0.5 0.1–2 7–10 35–65 7–13 8–11.5 0–2 0–1.5 0–1
5,8,11,14,17 eicosapentanoic acid 5 C20H32O2 10
0–1 0–0.5 8–12
4,7,10,13,16,19 docosahexanoic acid 6 C22H34O2 7
6–8
Analytic numbers of oils iodine value (after Wijs) 81–91 7.5–10.5 14–23 44–54 84–100 99–113 120–140 126–136 80–100 155–205 97–108 110–120 96 53–57 40–48 70 123–142
saponification value 177–197 250–264 245–255 195–205 188–195 189–198 189–195 186–194 186–194 188–196 170–180 180–190 196 190–202 190–200 140–144 179–194
melting point 1C 10t.–15 23–26 24–26 30–40 –2 2 to.+2 10 15 10 20 9 5 33–46 40–46

* Source: Henkel KGaA, Hrsg., Fettalkohole, Düsseldorf, 1983; R. Höfer, D. Feustel, M. Fies, Welt der Farben 11 (5/1997), updated, based on proprietary analysis and
C. Thywissen, Neuss/D, K. Becker, G. Francis, Univ. Hohenheim/D for Jatropha, bold figures are average values, natural figures indicate the range of fatty acid composition in %.
Analytical methods: DGF C6 10A + 11D
184 Chapter 9.1
9.1.4.2.1 Soya Bean Oil, Soybean Oil
Historical Development and Economic Importance. Since 1965 global soybean
production has increased from 30 Mio mto to 237 Mio mto and soya oil pro-
duction from 5 Mio mto to 37 Mio mto in 2007. This change in the pattern of
soya seed production is reflecting both the growing importance of soybean oil
and also the growth in importance of oilcake and meal as a protein source for
human nutrition and animal feed.
Soya beans originate from China (Figure 9.1.14). Since the 1930s they have
been grown in the Midwest, the Corn Belt of the USA. In 1996 the United
States produced about 49% of the world’s soybeans. To feed growing demand,
new agricultural frontiers have been opened up in Brazil and Argentina and
meanwhile MERCOSUR countries have become by far the largest regional
producers. Although Chinese soybean acreage ranks fourth in the world, its
productivity is still lower than in the other soya-growing regions. This makes
China actually a net importer for soybean oil – imports in 2007 actually dou-
bled national production.

Genetic Modification. The soya bean success story would not have been pos-
sible without weed control pesticides on one side and modern genetic engineer-
ing technologies on the other. In 1995 Monsanto introduced Roundup
Readys (RR) soybeans that are genetically modified.36 RR soybeans have
greatly improved agricultural efficiency allowing a farmer to spray widely the
herbicide glyphosate in soya plantations in order to kill unwanted plants like
annual grasses, perennial weeds and other pests, to reduce tillage or even to
sow the seed directly into an unploughed field. The transgenic RR plant is
resistant against glyphosate, N-(phosphonomethyl)glycine. Glyphosate is a
non-selective, post-emergence, systemic broad-spectrum herbicide, absorbed
through the leaves, and was first sold as the isopropylammonium salt (IPA
salt) under the trade name Roundups.
O O
HO – C – CH2 – N – CH2 – P– OH
H OH

glyphosate, N-(phosphonomethyl)glycine

Glyphosate is only effective on actively growing plants and is not effective as

a pre-emergence herbicide. The herbicidal mode of action is to inhibit the
shikimate pathway enzyme 5-enolpyruvylshikimate 3-phosphate (EPSP) syn-
thase, the functionality of which is absolutely required for the biosynthesis of
aromatic amino acids and the survival of plants.37 Like weeds and grasses
conventional soya would thus not withstand treatment with glyphosate. RR
plants carry the gene coding for a glyphosate-insensitive form of this enzyme,
obtained from Agrobacterium sp. strain CP4. Once incorporated into the plant
genome, the gene product, CP4 EPSP synthase, confers glyphosate-tolerance to
the crop. Adoption of genetically modified (GM) soya has been extremely rapid
Natural Fats and Oils 185

Figure 9.1.14 Soybeans.

and now makes up approximately 90% of all soya crops in the USA.38 Also
Brazil and Argentina are going towards 90% adoption of GM soya crops.
Soybean tolerant to glyphosate has also been approved for use, import and
processing in Europe since 1996 under Directive 90/220/EEC.39

Crop Protection. Already by the early 1900s, a serious fungus disease,

caused by the pathogen Phakopsora pachyrhizi, had been taking hold in var-
ious soybean producing countries.40 This disease was first discovered in 1902
in Asia (China, Japan, etc.), which gave rise to the name ‘‘Asian Rust’’. As a
result of the windblown transport of spores by means of powerful currents of
air, the disease spread from Asia to various African countries. From Africa
it spread to South America, and lastly to Middle and North America. Pha-
kopsora pachyrhizi is a bound pathogen (it does not survive outside a vege-
table host) capable of infecting, in addition to soybean, about a hundred
species of plants belonging to the same family as the soybean. This allows it
to survive in the period when crops are not present, thus becoming a source
of infection to be feared all year round. Although genetic research is
attempting to develop new soybeans that are resistant to the disease, cur-
rently the only instrument of defence is the use of fungicides belonging to
different chemical categories, more particularly the triazole category (e.g.
cyproconazole, tebuconazol, tetraconazole), the strobilurine category, chlor-
onitriles (like chlorothalonil) and/or carboxamides.

Composition and Uses. Soybeans are distinguished from other oil crops in
that they only yield approximately 21% oil but 40–50% protein. Because of
the high content in proteins soybeans historically have been a protein rather
than an oil seed crop. The market for soybean products is largely driven by
soy meal applications, more particularly by the food and the livestock feed
industries (Figures 9.1.15 and 9.1.16). The majority of soy protein is a
186 Chapter 9.1

Soya bean seed

Kernel 93% Hull 7%

Protein
Protein 41%41%

Oil 21%
Oil 21%

Fibre 6%
Fibre 6%

OtherOther
25% 25%

Figure 9.1.15 Composition of soya bean seed.

Oil Baking & frying

19% fats 36%

Food Meal Soy protein 7%

1% Margarine 5%
20% (Soy milk, Tofu, other)

Whole Salad & cooking oil

beans 51%

Other 1%
Soya Feed Oil
beans 77% 0%
Meal
Poultry 51%
77%
Swine 26%

Industrial Oil Coatings, inks, Beef 10%

3% 3% plastics 19%
Dairy 5%
Amines/amides
Soya fatty acid Pet food 3%
Oleochemistry 11%
Aquaculture 1%
Biodiesel 68% Other 2%

Biolubes & metal

working fluids 1%

Green solvents, carrier

oils, other 1%

Figure 9.1.16 Soybean applications, regional US market.42

relatively heat-stable storage protein held in discrete particles called protein

bodies. This heat stability enables soy food products requiring high tempera-
ture cooking, such as tofu, to be made. Soya increases the protein content
of processed meat products. It replaces them altogether in vegetarian foods.
Natural Fats and Oils 187
In the USA 77% of soybeans are used in agricultural feeds for open land
animal husbandry. Indeed, soy protein is what has made the global factory
farming of livestock such as poultry, swine and cattle a possibility. More
recently soy protein is increasingly used as a supplement to fish meal in
aquacultures.41
20% of soybeans are used as oil for human consumption and 3% for
industrial applications.42 Soya oil has moved into markets once served by
cottonseed oil, peanut oil and animal fats. Among the food uses, baking and
frying fats plus salad and cooking oils are the main applications. Among the
11 Mio mto soya oil applied to non-food purposes about 19% are employed in
coatings, inks and plastics applications in the form of:

 soya alkyd resins, urethane oils, oil-modified phenolic or urea resins;

 epoxidized soybean oil (ESO) applied as plasticizer for PVC and nitro-
cellulose or as sticker in agrochemical formulations;
 soya polyols (Sovermols) as building blocks for polyurethanes and as
radiation curing monomers (Photomers).

About 11% are processed to yield soya fatty acid, amines, amides, esters,
soaps and other oleochemical derivatives.
The production of methyl soyate for environmentally friendly solvents
and for biodiesel fuel (in the USA) is becoming a significant outlet for soy
oil in non-food applications. Further progress in the demand for soy
biodiesel will result in additional soybean meal supplies, which will con-
siderably increase soy meal competitiveness as feedstock for livestock farming
and aquaculture.

9.1.4.2.2 Palm Oil and Palm-kernel Oil

Historical Development and Economic Importance. Even more impressive
compared to soya is the growth development of palm oil. The oil palm43 is a
native of West Africa. From the beginning and throughout the twentieth
century oil palm cultivation and development efforts in Zaire (formerly Belgian
Congo, now Democratic Republic of the Congo) had achieved significant
increases in yield and oil quality. Congo oil palm plantations did expand to a
peak of 250,000 ha in 1958. Later, political unrest and mismanagement of the
country’s economy following the army coup in 1960 led to stagnation and
decline in the industry. This is in marked contrast to developments occurring at
the same time in Southeast Asia. The optimal soil, rainfall and sunshine con-
ditions of Southeast Asia resulting in high yields and uniform quality and the
strong-willed support of local governments especially in Malaysia helped the
industry to grow quickly, more particularly during the last 30 years. Since
2004 palm oil surpassed soybean oil as the leading vegetable oil and reached
annual production of 41Mio mto in 2008 spearheaded by Malaysia and
188 Chapter 9.1
Table 9.1.3 Comparison of oil yield per hectare of five major oilseeds (plus
Jatropha).
Oilseeds Oil Yield (mto ha1 annum1)

Palm oil (Malaysian) 3.93a

Rapeseed (EU) 1.33b
Soybean (USA) 0.46b
Sunflower (Argentina) 0.66b
Jatropha 3.00c
Coconut (Philippines) 0.66d
Source: aMPOB (2006); bKhoo (2001); cH. A. Khoo (2007), Steffan Preusser (2006); dOil World
(2006).

Indonesia. The leading role of palm oil compared to other oil crops arises from
the high yield of oil per hectare.44,45
Further increase of palm oil production by yield increase, e.g. by better seed
material, as an alternative to land expansion, is one of the challenges faced by
the palm oil growing industry (Table 9.1.3).

Sustainable Palm Oil Cultivation. For a number of reasons palm oil has
become the focus for concerns dealing with the basic means of sustainable
development:

 The oil palm flourishes in the humid tropics between 7 or eventually

10 degrees north and south latitude, in other words in the central belt of
tropical rainforests. Rainforest destruction with its attendant elimination
of wildlife and biodiversity is a concern not only of environmentalists but
of large parts of the world community.
 Palm oil production has been a basic source of income of the rural poor
and their indigenous community-based economies; large-scale palm oil
plantations operated by multinational companies and financed by globally
operating financial institutions are regarded as a threat for the survival of
smallholder operations and are suspected of the alienation of indigenous
people who often do not have the formal government-recognized doc-
umentation to prove their ownership of the land.46
 Large oil palm plantations and intense palm oil production are accused of
polluting the environment, of using unsafe fertilizers and pesticides in
excess and of paying poor attention to workers’ health and safety.
 Palm oil, when traded and used as a transportation fuel and in electrical
and thermal power generation risks provoking a conflict with the tradi-
tional role as foodstuff.

In order to address these concerns without creating difficulties for the

developing nations to continue their economic and social progress, to promote
the sustainable production and use of palm oil and to meet the challenges from
NGOs and corresponding demands from consumers the Roundtable on
Natural Fats and Oils 189
Sustainable Palm Oil (RSPO) was formally established in 2004. The RSPO is a
global initiative having organizations carrying out their activities in and around
the entire supply chain for palm oil as stakeholders. Palm oil producing
countries, companies and organizations like the Malaysian Palm Oil Council
(MPOC) are well aware that ‘‘sustainable palm oil is now a business require-
ment, which no company can overlook’’ (Dato’ Seri Lee Oi Hian) and is
turning into a key trade issue.47 As a consequence, pursuing certification
of sustainably produced palm oil to a globally accepted standard with full
traceability has been recommended.44,48 Accordingly, the RSPO Verification
Working Group has elaborated and launched an Audit Programme and a
roadmap.49
The RSPO Principles and Criteria for Sustainable Palm Oil Production50
stipulate:

 public availability of health and safety plans, land titles and user rights;
 compliance with local, national and international laws and regulations
including the UN declaration of indigenous people;
 business plans to achieve long-term economic and financial viability;
 water management programs to minimize peat soil subsidence;
 appropriate integrated pest management (IPM) techniques;
 development, implementation and monitoring of plans to reduce pollution
and emissions, including greenhouse gases;
 a minimum age of workers, which should be not less than 15 years;
 involvement of governments with the problem of stateless persons.

The RSPO multi-stakeholder process has gained recognition as a valid

mechanism to develop and implement social and environmentally responsible
management practices towards sustainable development and could eventually
serve as a blueprint for multi-stakeholder production and supply-chain pro-
cesses for other critical regionally or globally traded commodities.51

Distinctive Features of Palm Oil and Palm-kernel Oil Production. The oil
palm is a perennial crop. It bears fruit 30 months after planting and is eco-
nomically viable for up to 30 years. The oil palm bunch is harvested manu-
ally using a knife attached to a pole which dissevers the stalk of the fruit
bunch from the palm (Figure 9.1.17). The harvested bunches are termed
fresh fruit bunches (FFBs). The oil palm is distinguished from other oil crops
as it delivers two vegetable oils with different chemical composition: palm oil
and palm-kernel oil (Figure 9.1.18).
Palm oil is the pulp oil extracted promptly after harvesting from the fleshy
mesocarp of the oil palm fruit using continuous screw presses. The liquid
coming from the press is a mixture of oil, water and non-oily solids
(NOS). After separation from sludge in a settling tank, clarification, purifica-
tion and vacuum drying, crude palm oil (CPO) is yielded from the press liquid.
Palm-kernel oil is the seed oil contained in the kernel of the palm fruit. The
kernel is the endosperm of white cellular mass coated with a tough black
190 Chapter 9.1

Figure 9.1.17 Oil palm and palm fruit.

Oil palm fruit bunch

Trunk, empty fruit

Fruit Nut
bunch, EFB
African oil palm 30% African oil palm 35%
African oil palm 35%
Asian oil palm 60% Asian oil palm 11%
Asian oil palm 29%

Water 41%
Kernel 45% Shell 55%
Fibre 20%
Protein 4,5%
Palm oil 39%
Palm-kernel oil 22,5%

Other 18%

Figure 9.1.18 Composition of oil palm fruit.

membrane or testa, which is encased in a thick shell or endocarp of the oil palm
seed nuts (Figures 9.1.17 and 9.1.18). When extracting the palm oil, nuts and
fibres remain in the press cake. Nuts are separated from the fibres and cracked.
After separating kernel and shell the palm-kernel oil is extracted from the
kernels by unit operations employed for vegetable seed oil extraction.
Natural Fats and Oils 191
Palm oil is traded as CPO and, increasingly, after physical/steam refining or
chemical/alkali refining as processed palm oil (PPO).

PPO ¼ processed palm oil, stands for different categories of treatment, i.e.
neutralized, bleached, deodorized and/or fractionated; according to the
degree of processing different export duty tariffs may apply: N/RPO ¼
neutralized/refined palm oil, BPO ¼ bleached palm oil, CPL ¼ crude palm
olein, N/RBPO ¼ neutralized/refined bleached palm oil, N/RPL ¼
neutralized refined palm olein, BPL ¼ bleached palm olein, N/RBDPO
¼ neutralized refined bleached deodorized palm oil, N/RBPL ¼
neutralized refined bleached palm olein, N/RBDPL ¼ neutralized/refined
bleached deodorized palm olein, Dp ¼ duty on PPO and Dc ¼ duty on
CPO; source: A. Mohd Nasir.52

Because of its fatty acid composition, which includes 50% saturated and
50% unsaturated fatty acids, palm oil is a semi-solid oil, which sediments at
room temperature even in tropical countries. Fractionation of CPO or RBDPO
by separating palm oil into a low melting fraction (palm olein) and into a higher
melting fraction (palm stearin) significantly extends the application. One of the
main objectives of fractionating palm oil is to obtain palm olein of low cloud
point for cooking oil or further processing, whereas palm stearin is used as a
component of harder frying fats or for the production of shortening, margarine
and vanaspati.
Three different technologies can be applied for palm oil fractionation:53

 winterization or dry fractionation;

 hydrophilization or rewetting, also called wet fractionation or detergent
process;
 solvent fractionation.

Winterization is claimed to be the cheapest technology in terms of cost

per unit of oil fractionated followed by the rewetting process. Due to the
continuous development of the dry fractionation process, a whole variety
of products formerly produced by solvent fractionation with hexane can
now be obtained with a high degree of selectivity with winterization. As the
crystallization operates in the bulk, viscosity problems limit the degree of
crystallization in one single step, and multi-step operations are currently used.
Additionally, combining proper crystal development with highly efficient
separation by using membrane press filters allows compression of the stearin
cake to obtain as much occluded liquid olein as possible.
Solvent fractionation is the most expensive process, and has been almost
abandoned, except for the production of high-premium mid-fractions for cocoa
butter replacers using an acetone-based double-stage process.
192 Chapter 9.1
In a well-run palm oil mill, it is expected that each 100 mto of FFB processed
yields 20 to 24 mto of crude palm oil and about 3 mto of palm-kernel oil. Thus
between 72 and 76% of the FFB comes out at various stages of the process as
waste. The solid wastes that result from the milling operations are empty fruit
bunches, palm fibre and palm kernel shell. With the aim of achieving zero-waste
operations the waste products are all put to economically useful purpose:54 wet,
empty bunches are dried and used as fuel. Another economic use for the empty
bunches is to return them to the plantation as a mulch to enhance moisture
retention and organic matter in the soil. Residual shell is disposed of as gravel
for plantation roads maintenance. The fibre recovered from the nut/fibre
separation stage constitutes the bulk of material used to fire the large boilers
that deliver superheated steam for electrical power generation. Boiler ash is
recycled as fertilizer and factory floor cleaning agent. Large- and medium-scale
mills produce copious volumes of liquid waste from the sterilizer, clarifying
centrifuges and hydro-cyclones. This effluent must be treated before discharge
to avoid serious environmental pollution. Liquid waste treatment involves
anaerobic fermentation followed by aerobic fermentation in large ponds until
the effluent quality is suitable for discharge. In some of the mills the treated
effluent is used on the farm as manure and as a source of water for irrigation.
The sludge accumulating in the fermentation ponds is periodically removed and
fed to the land.

Composition and Uses. Palm oil is an oleic oil, which is distinguished by its
high percentage of the saturated palmitic acid. Palm-kernel oil is a lauric oil
and to some degree exchangeable with coconut oil due to a similar fatty acid
composition.
Traditionally, about 80% of palm oil has been for edible use and 20% for
non-edible applications. Products for food are used as a medium for frying; as a
major component of non-dairy shortenings, margarines and vanaspati; in tai-
lored applications for bakery products and confectionery fats; and in reduced
fat spread, mayonnaise and salad dressings.55 Non-food applications comprise
the direct use of the triglyceride yielding palm oil polyols for polyurethane
foams.56 CPO is processed to yield glycerine, palm oil or hydrogenated palm oil
fatty acids, soaps, amides, esters and other oleochemical derivatives for
industrial and human care chemicals.57 The global trend associating ‘‘natural’’
with plant-derived products and belief that these are milder and healthier has
created a special Asian lifestyle favourable for palm oil derived cosmetics.
Religious considerations also mean consumers prefer plant-derived products
since they are regarded as kosher or halal.
This applies, of course, also for palm kernel oil (PKO), which is used either on
its own or in combination with palm oil products in the manufacture of spe-
cialty fats. Incorporation of palm kernel oil or its derivatives, particularly in
table margarine and spreads, improves the melting characteristic of the pro-
ducts. Non-food applications include soaps, which in Southeast Asia are pri-
marily made from palm oil and PKO or coconut oil. A typical blend of soap
noodles would be 80% palm oil and 20% PKO, giving about the right balance
Natural Fats and Oils 193
of lather, cleansing ability and hardness. PKO may also be used in a multitude
of other cosmetic and body-care products for its moisturizing properties. Palm-
kernel oil and coconut oil are distinguished from other vegetable oils because of
their high content in lauric and myristic acid. Both oils have a relatively sharp
melting point at 24–26 1C. It may be noted, however, that coconut oil has more
of the short-chain fatty acids while PKO has more of the longer-chain fatty
acids. Hydrogenation and fractionation of PKO fatty acid methylester yields
lauryl alcohol and lauryl alcohol-based plant-derived surfactants for cosmetic,
detergent and industrial applications.
Although actually (2007) only 1% of world biodiesel is based on palm oil,
because of the high yield per ha palm oil could become a highly competitive raw
material for biodiesel manufacturing.45,58 Palm biodiesel obtained by transes-
terification of CPO has a pour point of 15 1C. The relatively high pour point
and poor cold stability hamper the use as fuel and as a green solvent or carrier
oil. Using winterization as well as rewetting of palm biodiesel a palm olein
methyl ester with properties comparable to methyl soyate or methyl canolate is
yielded, besides palm stearin methyl ester. Economies of palm biodiesel are
improved, when sulphonating the palm stearin methyl ester by-product with
sulphur trioxide to yield a-sulphonic fatty acid methyl ester surfactants
(MESs). MESs based on palm stearin methylester are light-coloured washing
detergents, which provide good cleaning ability, are less sensitive to water
hardness and have better biodegradability characteristics compared to other
detergents like linear alkyl benzene sulphonates.59
Non-refined cold pressed crude palm oil, also called ‘‘Red Palm Oil’’, has
been consumed in Central and West Africa since time immemorial, as it has
also been in Central America and Brazil. Red palm oil has a wonderful rich
flavour; it is the richest known natural product in tocotrienols and carotenes,
which give rise to the red colour. Development of techniques like integrated
extraction technologies to recover these functional components from palm oil
has contributed to the emergence of the nutraceutical industry in Malaysia that
produces tocopherol and tocotrienol capsules, carotene-rich palm oil and palm
carotene concentrate.60

9.1.4.2.3 Coconut Oil

Perhaps more than anything else, the coconut palm has contributed in creating
the image of the islands in the Pacific Ocean and their beauty.
An adult coconut palm reaches 30 m or more in height. In some areas of the
tropics, the palm grows with a minimum of attention through a lifespan of
more than 50 years. About 96% of coconuts are grown by smallholders tending
small farms. Every part of its fruit can be utilized, including the fibre for coir
products, the shell for charcoal, the milk as a beverage and the meat as food.
However, its most important product is copra, the meat after drying. Copra is a
source of food, edible oil and protein meal (Figures 9.1.19 and 9.1.20).
Together with palm kernel oil and babassu oil, coconut oil forms the group
of important lauric oils. They contain 440% of lauric acid and ca. 15% of
194 Chapter 9.1

Figure 9.1.19 Coconut palm, coconut botanical.

Coconut fruit

Coconut 59% Fibrous mesocarp 41%

Water 27%

Copra 32%

Protein 2%

Oil 22%

Other 8%

Figure 9.1.20 Composition of coconut fruit.

myristic acid besides a significant fraction of shorter-chain fatty acids. Fatty

acids with 8 to 12 carbon atoms are classified as medium-chain fatty acids
(MCFA, in German Vorlaufffettsäuren; to distinguish from short-chain fatty
acids, SCFA, with carbon atom range from 2 to 6). With 415% C6, C8 and
C10 fatty acids, coconut oil is the richest source of MCFA.
The intrinsic qualities of coconut oil make it very suitable for household
culinary preparations, as frying oil, in non-dairy products, coffee whiteners and
Natural Fats and Oils 195
as spraying oil for biscuits and breakfast cereals. The cosmetic applications of
coconut oil include hair and skin oil (when mixed with herbal oils and different
scents), natural shampoos and skin and massage oils. The industrial use as
oleochemical base-stock absorbs up to 60% of coconut oil. The oleochemicals
sector comprises a myriad of acid, ester, alkanolamide and surfactant appli-
cations like isopropyl laurate (oil with solvent properties and wetting capacity
for aerosols, decorative cosmetics and hair-care preparations), coconut fatty
acid monoethanolamide (booster for detergents, foam stabilizer and thickening
agent for shampoos and bubble baths), sodium lauryl sulphate (foaming agent
for toothpaste, emulsifier for emulsion polymerization), sodium lauryl ether
sulphate (base for manufacture of liquid shampoos, bubble bath, high-quality
dishwashing agents) to name but a few.

9.1.4.2.4 Babassu Oil 61

The 20-m high babassu palm covers extensive areas of Brazil’s pre-Amazon region
and is an inherent part of the regional economy of north-central Brazil. The nuts
consist of a stone-hard protective shell that can be cracked only with immense
efforts. As a result babassu nuts are gathered in the traditional way without any
mechanization, and for the production of one mto of babassu oil nearly ten tons
of stone-hard nutshells have to be removed and disposed of. Thousands of
households derive a simple livelihood from collecting and processing babassu
nuts. Babassu oil is very similar to coconut oil and had long been regarded as a
promising alternative until palm oil took off even in the remote north of Brazil. As
a consequence palm-kernel oil took over as the leading lauric oil.

9.1.4.2.5 Cuphea Oil

Like coconut, palm kernel and babassu, many species from the genus Cuphea
have potential as sources of medium-chain triglycerides. These plants are native
to the New World, from southern USA to northern South America. Most are
herbaceous annuals that will grow in many locations. Table 9.1.4 illustrates the
diversity in fatty acid composition available in Cuphea germplasm.

9.1.4.2.6 Rapeseed Oil, Canola Oil

Historical Development and Economic Importance. Oilseed rape (also called
rape or rapeseed) due to its ability to germinate and grow at low temperatures is
one of the few edible oil crops that can be cultivated at northern latitudes.
In agriculture the crop is also grown as a winter-cover crop. It provides good
coverage of the soil in winter, and limits nitrogen run-off. The plant is ploughed
back in the soil or used as bedding. Rape is likely to have been among the
earliest domesticated food and fodder crops known since prehistoric times and
cultivated in Europe since the thirteenth century (Figures 9.1.21 and 9.1.22).
196 Chapter 9.1
Table 9.1.4 Fatty acid composition of some Cuphea seed oils in comparison to
coconut oil.62
Distribution (% of total fatty acids)
Species 8:0 caprylic 10:0 capric 12:0 lauric 14:0 myristic Others

C. painteri 73.0 20.4 0.2 0.3 6.1

C. hookeriana 65.1 23.7 0.1 0.2 10.9
C. koehneana 0.2 95.3 1.0 0.3 3.2
C. lanceolata 87.5 2.1 1.4 9.0
C. viscosissima 9.1 75.5 3.0 1.3 11.1
C. carthagenensis 5.3 81.4 4.7 8.6
C. laminuligera 17.1 62.6 9.5 10.8
C. wrightii 29.4 53.9 5.1 11.6
C. lutea 0.4 29.4 37.7 11.1 21.4
C. epilobiifolia 0.3 19.6 67.9 12.2
C. stigulosa 0.9 18.3 13.8 45.2 21.8
Coconut 8 7 48 18 19

Figure 9.1.21 Rapeseed.

The oil pressed from the seed historically has been used in oil lamps and
(because of the bitter taste) as poor people’s cooking oil, later as lubricating oil
in steam-powered ships and trains.63 For two reasons, the nutritional aspects of
rapeseed have been questioned: for the high fraction of eicosenoic and erucic
acids in the oil on one hand, and the high glucosinolate content in the meal on
the other. Glucosinolates (Figure 9.1.23) are thioethers, which contribute a
bitter, ‘‘hot’’ taste to condiments (mustard, horseradish) and give flavour and
Natural Fats and Oils 197

Rapeseed

Kernel 85% Hull 15%

Protein 20%

Oil 35%

Other 30%

Figure 9.1.22 Composition of rapeseed.

OH O-

O S
HO O
HO S O
OH N O

Figure 9.1.23 Glucosinolate, chemical structure.

odour to cabbage, broccoli, cauliflower and turnips. They act as defence

compounds against herbivores. The high levels of erucic acid in traditional
rapeseed oil were blamed, inter alia, for producing health concerns like fatty
deposits in the heart.
Production of rapeseed took off in North America, when Canadian plant
breeders at the University of Manitoba by 1974 succeeded in developing a new
rapeseed cultivar, 0-rape or CANOLA, from the original high erucic acid
rape seed, HEAR (Canola is a syncopated form of the abbreviation ‘‘Can.O.,
L-A.’’, Canadian Oilseed, Low-Acid, now a trade name of the Canola Council
of Canada; ‘‘canola’’ is mainly used in the American continent and in Australia,
whereas Europe and other countries use the term ‘‘rapeseed’’). The improve-
ments later resulted in ‘‘double low’’ (‘‘double zero’’, ‘‘00-rape’’, LEAR)
varieties, i.e. reduction in erucic acid level to o2% of the measured fatty acid
composition and a glucosinolate level less than 30 mmol g1 of air dried, oil-free
meal. By 1980 Canada had largely converted to the double-low varieties. It was
more difficult and took nearly a further ten years to introduce the low erucic
acid trait into European rapeseed lines of the winter type and to overcome the
original problems of lower yield. Nonetheless, since 1991, virtually all rapeseed
production in the European Union has shifted to 00-rape. Genetically modified
(GM) herbicide resistant rapeseed, which enables a more efficient and effective
approach to weed control, has been grown in Canada since 1996 and made up
three-quarters of Canada’s rapeseed crop in 2005. Although many field trials
have been conducted, GM rapeseed is not yet being grown commercially in
Europe.
198 Chapter 9.1
Composition and Uses. The traditional brassica variety (HEAR) is dis-
tinguished by the high fraction of 460% unsaturated gadoleic (C20:1) and
erucic (C22:1) acids, besides 435% oleic, linoleic and linolenic acids. The
long-chain fatty acids limit the usefulness as food but have preserved an
important niche market for HEAR in technical applications. At present,
world consumption is estimated to be 57,000 mto per year. The plastics
industry consumes a major part in the form of erucamide, a high melting
wax, applied as lubricant for PVC processing and as slip and anti-blocking
agent for polyolefin film. Hardening of erucic acid or splitting of hydro-
genated HEAR oil with subsequent fractionation yields behenic acid. Hydro-
genation of methyl behenate yields behenyl alcohol.
In the modern 00-rape the Z C:20 fatty acids have been reduced to trace
fractions in favour of oleic, linoleic and linolenic acids, resulting in a fatty acids
spectrum similar to olive oil. Characteristics of 00-rape are the most appro-
priate to fulfil the European biodiesel standards. As a result, the EU-27 are
now the by far largest rapeseed oil consumers, and the astounding growth in
European demand has been driven almost exclusively by the expansion of the
biofuels sector over recent years. Fifty percent of European rapeseed produc-
tion in 2005 has been turned into biodiesel, 37% has been used for human
consumption, 7% for oleochemical products and lubricants; 6% has been
exported. In 2007 the rape oil demand for biofuels has accounted for 60% of
rape oil consumption. Rape-based biofuels include biodiesel and direct use as
refined oil.

9.1.4.2.7 Sunflower Oil

Historical Development and Economic Importance. Sunflowers grow best in
fertile, moist, well-drained soil in a moderate climate with temperatures mainly
between 20 and 25 1C and full sun. The plant originates from the Americas. The
seed was introduced into Europe by the Spanish explorers returning to the
continent at the beginning of the AD 1500s. In Russia, it was introduced by Czar
Peter I the Great, who, having seen sunflowers in the Netherlands, took seeds to
Russia. Originally mainly regarded as a decorative flower, it was in Russia
where the most important development took place in the use of sunflower as
both a food and oil source (Figure 9.1.24). Starting from these origins Russia
has built a leading position in sunflower growing. Including Ukraine and
Russia the CIS States produce 40% of sunflower seed worldwide, followed by
the EU-27 (20%) and Argentina (11%).

Composition and Uses. The sunflower kernel represents 75% of the seed,
with an oil content of approximately 55%, amounting to 41% with respect
to the whole seed (Figure 9.1.25). Sunflower oil contains 485% unsaturated
fatty acids with linoleic acid accounting for 60%. The linoleic acid content in
the original ‘‘linoleic sunflower oil’’ is very much dependent on climatic con-
ditions and can deviate as much as 20% from the average. Selected parcels
Natural Fats and Oils 199

Figure 9.1.24 Sunflower plant, sunflower botanical.

Sunflower seed

Kernel 75% Hull 25%

Protein 19%

Oil 41%

Other 15%

Figure 9.1.25 Composition of sunflower seed.

of oil, also called high-PUFA, contain 469% linoleic acids. Sunflower is one
of the most important edible oils and is generally considered to be premium
oil compared to most other natural oils because of its light colour, flavour,
high level of linoleic acid and absence of linolenic acid.
High oleic sunflower oil (HOSO) is a cultivar, which has been developed
through conventional breeding. Introduced in the mid 1980s, it is usually
defined as having a minimum 80% monounsaturated oleic acid. The oil has a
very neutral taste and provides excellent stability towards oxidation without
hydrogenation. Demand for HO sunflower oil has been increasing as con-
sumers look for healthier vegetable oils in response to concerns over saturated
fats and trans fats in traditional edible oils and in part because of requirements
for labelling of trans fats. A diet rich in high-oleic-acid sunflower oil favourably
alters low-density lipoprotein cholesterol.64
NuSun is the name chosen by the US National Sunflower Association (NSA)
to represent an entirely new class of sunflower seed and oil to meet the needs of
the food industry.65 Needs were identified as ‘‘oil that had a pleasing taste,
200 Chapter 9.1
stability without needing partial hydrogenation and low saturated fat levels’’.
Initial testing of the new sunflower type (also developed through conventional
plant breeding methods) began in 1996. In 2007, it is estimated that 85 to 90%
of the sunflower acreage was NuSun with the rest equally divided between high
oleic and traditional linoleic sunflowers. NuSun, also called mid-oleic sunflower
oil, is lower in saturated fat (9%) than linoleic sunflower oil and has higher oleic
levels (55–75%) with the remainder being linoleic.
Besides food uses the original linoleic sunflower oil as well as HOSO are used
in industrial applications because of their specific properties.66 For example, in
view of the higher oxidative stability high-oleic sunflower oil is used as diesel
and gasoline engine lubricant. Containing around 70% linoleic acid, sunflower
oil is a semi-drying oil. Insofar as is economically feasible, sunflower oil may
replace soybean oil in the manufacture of resins or carrier oils for paint and ink
formulations.67

9.1.4.2.8 Cottonseed Oil

Cotton is a crop which delivers food (cottonseed oil), feed (meal) and fibre
(cotton lint). In analogy to the importance of cotton for the development of the
textile industry (see Chapter 9.6), cottonseed oil dominated the United States
vegetable oil market for almost 100 years until the Second World War. On a
global scale cottonseed oil production has been growing from 3.5 Mio mto in
1985 to 5 Mio mto in 2007. Cottonseed oil is mainly used for cooking, frying
and in salads and as an alternative to lard in shortenings. Cottonseed oil has
also been selected by Procter & Gamble to create Olestra, a sucrose-based
artificial fat that isn’t broken down by the body, and, as a result, adds no
calories to foods.

9.1.4.2.9 Peanut Oil

Peanut oil (also known as groundnut oil, arachis oil or earthnut oil) is obtained
from the seed kernels of the peanut plant, native to South America (Figure
9.1.26). Crude peanut oil has a nutlike flavour, which is removed by refining. It is
mainly used for edible purposes in the preparation of shortening, margarines and
mayonnaise, and as a salad-, cooking- and frying oil. Peanut butter is made by
grinding specially roasted peanuts and homogenizing the mash with addition of
liquid and possibly also hydrogenated peanut oil. Because of the high smoke
point (229 1C) refined peanut oil is often used in deep-fat frying. Besides food,
peanut oil is used as carrier oil in crop protection and in mineral oil-free pulp and
paint defoamers.68 Admixture of grain or seed with edible oil such as peanut oil
is recommended to protect maize, sorghum, wheat or rice from insect damage.69

9.1.4.2.10 Corn Oil, Maize Oil

70
Maize is, after wheat and rice, the most important cereal grain in the world
(Figure 9.1.27). As food, the whole grain may be used or the maize may be
Natural Fats and Oils 201

Peanut

Kernel 55% Shell 45%

Protein 16%

Oil 25%

Other 14%

Figure 9.1.26 Composition of peanuts.

Corn (maize)

Germ 12% Endosperm 80% Hull 8%

Protein 2% Protein 6%

Oil 5% Starch 71%

Starch 1% Fibre 2%

Sugar 2% Other 1%

Other 2%

Figure 9.1.27 Composition of corn.

processed by two basic methods known as ‘‘dry milling’’ (to produce bio-
ethanol, see Chapter 8) and ‘‘wet milling’’. In the wet milling process the
cleaned corn is conveyed to steep tanks where it is soaked for 30–50 h at ele-
vated temperature in an aqueous sulphurous acid solution resulting in the
softening of the corn kernels. The corn germs can now be removed from the
water-soaked kernels by a series of mills and cyclone germ separators. While
the corn kernel is further processed yielding starch (see Chapter 9.2), syrup,
corn gluten feed and sweeteners, the germ is dried and cold pressed through
screw presses or expellers before solvent extraction with hexane.
The golden yellow corn oil has a distinctive musty flavour and odour and a
composition similar to sunflower oil. However, it has a different tocopherol
composition with mainly g-tocopherol, which makes it more heat stable. Corn
oil is used especially as a salad oil and in salad dressings as well as in cooking,
where its high smoke point (unrefined 160 1C, refined 232 1C) makes it valuable
as frying oil.
202 Chapter 9.1
9.1.4.2.11 Rice Bran Oil
Rice oil, also called rice bran oil, has been used extensively in Asian countries.
It is the preferred oil in Japan as frying oil for its subtle flavour and odour.
During rice milling bran and germ are separated from the starchy endosperm
(Figure 9.1.28).71 The bran has an oil content of 12–18%. This means that the
potential volume of rice bran oil is 0.8% of the total rice produced.
The fatty acid spectrum of rice bran oil is 22–25% palmitic acid, 37–41%
oleic acid and 37–41% linoleic acid. More recently, interest in rice oil escalated
with its identification as a ‘‘healthy oil’’ that reduces serum cholesterol. Rice
bran is a good source of antioxidants including vitamin E and oryzanol (ferulic
esters of sterols and triterpene alcohols), cholesterol-lowering waxes and anti-
tumor compounds like rice bran saccharide.72 Besides applications in nutrition
and in phyto-chemicals, rice bran oil has traditionally been used for industrial
applications, such as dimer acid manufacturing, depending on pricing for
alternative vegetable oils.

9.1.4.2.12 Sesame Oil

Sesamum indicum is an herbaceous annual that reaches about 1 m in height
(Figure 9.1.29). Sesame oil, with an annual production of 860,000 mto in 2007,
is higher in quantity than linseed oil and safflower oil. Traditionally, China,
India, Sudan, Burma and Uganda are the world’s major sesame seed producing

Figure 9.1.28 Rice kernel structure adapted from Orthoefer.71

Natural Fats and Oils 203

Figure 9.1.29 Sesame indicum. Sources: Sesame plant, Koeh-129.jpg from Wikipe-
dia. Sesame flower (reproduction with permission of Karlheinz Knoch
Botanik-Fotos, Bruchsal).

countries. Sesame oil is one of the most stable edible oils despite its high degree
of unsaturation: oleic acid and linoleic acid constitute more than 80% of the
total fatty acids in sesame oil with the percentages of oleic acid (36–42%) and
linoleic acid (42–50%) close to each other. The presence of lignan type natural
antioxidants (sesamin, sesamolin and their transformation products sesamol
and sesaminol, respectively73) accounts for both the superior stability of sesame
oil and the beneficial physiological effects of sesame.
More than any other vegetable oil crop, sesame is embedded since ancient
times in a mythological background that lasts until today. Accounts
from ancient history document early recognition of sesame seed as a source of
high-quality food. Sesame was the symbol of immortality in early Hindu
legend. Women of ancient Babylon would eat halva, a mixture of honey and
sesame seeds to prolong youth and beauty. ‘‘Open sesame’’, the magic words
used by Ali Baba to open the treasure cave in ‘‘The Thousand and One Nights’’,
reflects the distinguishing feature of the sesame seed pod, which bursts open
when it reaches maturity. As part of modern lifestyle, sesame is applied in food
and cuisine, cosmetics and wellness treatment and in alternative medicine.74
Sesame oil plays a prominent role in Ayurvedic medicine. The oil absorbs
quickly, penetrates through the tissues and keeps the skin supple and soft. This
makes sesame oil an outstanding massage oil and carrier oil for cosmetic and
therapeutic activities and explains its use during abhyanga, a form of Indian
massage. Abhyanga is believed to improve energy flow and help free the body
204 Chapter 9.1
of impurities. Used on baby skin, sesame seed oil will protect the tender skin,
and more generally will cause young facial skin to have and display natural
good health.

9.1.4.2.13 Safflower Oil

Safflower oil is the seed oil of the thistle-like safflower plant, thriving in the west
of the USA, Mexico, North Africa and India. The plant can be grown under
fairly arid conditions. The seeds resemble small sunflower seed kernels and can
be harvested mechanically. Like corn oil the fatty acid composition is similar to
that of sunflower oil. Safflower oil has a high oxidative stability and is being
used increasingly in salad oils and dietetic margarines because of its high
content of linoleic acid.

9.1.4.2.14 Cocoa Butter

Cocoa75 is the dried and partially fermented fatty seed of the cacao tree from
which chocolate is made. Cocoa production has increased from 1.5 Mio mto in
1983/1984 to 3.5 Mio mto in 2003/2004. Over 90% of the world’s cacao is
grown by smallholder farmers. Main producing countries are Côte d’Ivoire,
Ghana, Indonesia, Cameroon, Nigeria, Brazil, Ecuador and República Dom-
incana. Cocoa butter, as the fat is called, becomes available during further
processing of cocoa beans by fermentation (to develop the cocoa flavour),
roasting, dehulling, grinding and expelling. The fat content of dehulled kernel is
about 55–60% in dry matter (Table 9.1.5).
Cocoa butter is used extensively in the production of chocolate and other
confectionery products, and to a lesser extent in the pharmaceutical and cos-
metics industries.

9.1.4.2.15 Shea Butter

The shea or karité nut tree is found in the savannahs of West and Central
Africa known as the Sahel region and produces its first fruit when it is about
20 years old, reaches its full production when the tree is about 45 years old and
produces nuts for up to 200 years after reaching maturity. The fruit resembles
large plums with a mucous pericarp generally containing only 1 seed, the shea

Table 9.1.5 Fatty acid composition of cocoa butter in %.

Typical Range

C16:0 26 22–30
C18:0 36 30–37
C18:1 33 30–36
C18:2 3 1.5–4.0
Iodine value 37 34–40
Natural Fats and Oils 205
Table 9.1.6 Fatty acid composition of shea butter in %.
Typical Range

C16:0 4 3–6
C18:0 42 36–44
C18:1 44 42–52
C18:2 7 4–8
Iodine value 57 55–65

nut, source of shea butter. Shea butter is similar to cocoa but somewhat higher
in oleic acid content. Shea butter has up to 11% unsaponifiable matter con-
taining 4–10% kariten [(C3H8)n, mp 63 1C], mainly a trans-1,4-polyisoprene like
gutta-percha (Table 9.1.6).
Shea butter is one of the most affordable and widely used vegetable fats in the
Sahel and an important ingredient for indigenous medicine and body care. The
refined fat is sold as baking fat, margarine and other fatty spreads. Shea butter
is traditionally used in medicines, particularly for the preparation of skin
ointments, as a rub for rheumatism and to treat inflammation, rashes in chil-
dren, dermatitis and sunburn. The kariten latex in shea is responsible for the
sealing property that shea butter has and that may aid in protecting skin and
preventing sun allergies. In cosmetics shea butter serves as a moisturizer and
emollient and as a base for cosmetics that prevent skin drying; good-quality
lipsticks also use shea butter. As a result, cosmetic industries in the Sahel and
elsewhere market this ingredient in many soap, shampoo and skin-cream
preparations.

9.1.4.2.16 Evening Primrose Oil

Evening primrose is a North American native biennial plant. With an estimated
90% of global supply, China has actually become the major producer of
evening primrose seed worldwide. Evening primrose oil has a long history
of use as an alternative medicine and is offered for healthy, active-lifestyle diets.
It contains up to 10% of g-linolenic acid (GLA). Formulations of GLA apply
for a range of nutritional, cosmetic and pharmaceutical products, including
some used in the treatment of rheumatoid arthritis (Table 9.1.7).

9.1.4.2.17 Olive Oil

Olive oil is obtained from the fruit of the olive tree. It is an important com-
ponent in the diet of Mediterranean people and in Mediterranean cuisine.
About 80% of total olive oil production comes from the European Commu-
nity, with the Near East contributing ca. 7% and North Africa supplying about
11%. The cultivation of the olive tree is known since biblical times. It is one of
the oldest signs of civilization in the world. The Mediterranean world has
regarded the olive as sacred for thousands of years. In many religions and
206 Chapter 9.1
Table 9.1.7 Fatty acid composition of evening primrose oil in %.
Typical

C16:0 8
C18:0 2
C18:1 11
C18:2 69
C18:3n–6 9
Iodine value 150
Adapted from N. A. M. Eskin, Eur. J. Lipid Sci. Technol., 2008, 110(7), 651–654 and P. Clough,
Lipid Technol., 2001, 13, 9–12.

cultures, the olive tree or its branches have been a symbol of peace, life and
salvation. Besides food, olive oil has been used for religious rituals and medi-
cine, as fuel in oil lamps as well as in skin care applications. In Ancient Greece,
athletes ritually used olive oil to rub over their bodies. The Bible, the Quran and
Hadith contain manifold references to olive oil. Still today the King of Saudi
Arabia gives it as a traditional gift to pilgrims to Mecca.
The olive fruit contains oil of very similar composition in the pulp
(approximately 20%) and in the kernel (approximately 12%). Genuine olive oil
contains up to 83% oleic acid, between 4 and 21% linoleic acid and 8 to 25%
saturated palmitic and stearic acids. The proportion of polyunsaturated fatty
acids is low. Olive pomace oil is the oil obtained by solvent extraction of olive
pomace. Pomace is the ground flesh and pits after pressing.
Internationally recognized quality definitions were promulgated by the
International Olive Oil Council (IOOC) and have been adopted in the Joint
FAO/WHO Food Standard Programme. The best virgin oils (those called extra
virgen in Spanish) are cold-pressed, which produces a natural level of low
acidity (under 1%) and a minimum organoleptic rating of 6.5 or more as
determined by the IOOC method. Extra virgin olive oil can be used in endless
ways in the kitchen, and has been a traditional ingredient in everything from
antipasti to desserts. It is best used raw in salads, in order to enjoy its real
flavour.

9.1.4.2.18 Linseed Oil, Flax Oil

Flax is a versatile, blue-flowered crop. It is most likely one of the oldest cul-
tivated plants, grown either for the oil extracted from the seed or for fibre from
the stem (Figure 9.1.30). There is well-documented evidence of the use of flax
fibres for textiles going back to prehistoric times (see Chapter 9.6). However, in
contrast to olive oil, no precise indication of the traditional use of linseed and
linseed oil for nutrition or other applications may be found. Indeed, the first
reliable source for utilization of linseed oil, namely for paintings, dates back to
the eleventh century, when the German monk Theophilus in his ‘‘Schedula
diversarum artium – De diversibus artibus’’ described the use of linseed oil for oil
paints and amber varnishes.76
Natural Fats and Oils 207

Figure 9.1.30 Linseed, flax. Sources: flax botanical, Koeh-088.jpg; Linum usita-
tissimum, released under the GNU Free Documentation Licence,
both from Wikipedia.

Flax seed has a warm, earthy and subtly nutty, butter flavour. The seed can be
eaten entirely, and has traditionally been used as an add-on to cereal or bread.
Today flaxseed is experiencing a renaissance among nutritionists, the health
conscious public, food and feed processors (see Chapter 6) and chefs alike. It is
one of the richest sources of lignan and a-linolenic acid (450%), one type of
fatty acid in the polyunsaturated o-3 fatty acid (PUFA) family, considered
essential fatty acids. Lignans, like isoflavones, are one of the major classes of
phytoestrogens, which are estrogen-like chemicals and act as antioxidants.
Linseed oil, or flax seed oil, is cold-pressed from the dried ripe seeds of flax.
For medicinal purposes recently expressed linseed oil, oleum lini, is preferable.
In order to enlarge the breadth of the linseed application profile crop breeding
efforts have led to new flax species, called Linolat and NuLint. Linola is high in
oleic and linoleic acid (485%) and low in linolenic acid (approximatley 2%).
Linolat received GRAS status from the US FDA. It is a substitute to sunflower
oil, to be used in margarines and in salad and cooking oils. NuLint on the
contrary is a high o-3 fatty acids flax (465% linolenic acid, IV 4205) and targets
industrial applications and health food such as bakery products.77

9.1.4.2.19 Camelina Oil

Camelina sativa, usually known in English as gold-of-pleasure or false flax,
also occasionally linseed dodder and Siberian oilseed, is a flowering plant in
the family brassicaceae, which also includes rapeseed. The crop is now being
208 Chapter 9.1
researched due to its exceptionally high level of o-3 fatty acids. Over 50% of
the fatty acids in cold-pressed camelina oil are polyunsaturated. The major
components are a-linolenic acid – C18:3 (o-3 fatty acid, approximately
35–45%) and linoleic acid – C18:2 (o-6 fatty acid, approximately 15–20%). The
oil is also very rich in natural antioxidants making this highly stable oil very
resistant to oxidation and rancidity. It has an almond-like flavour and aroma
and is well suited for use as cooking oil. Because of apparent health benefits and
its technical stability camelina oil is being added to the growing list of foods
considered as functional foods.

9.1.4.2.20 Calendula Oil

Calendula, also known as Pot Marigold, has historically been grown as an
ornamental and medicinal plant. Its seed oil contains up to 60% calendic acid
an (8t,10t,12c-18:3) o-6 trienoic acid synthesized in the plant from linoleate by
a D12-oleate desaturase:

Historically, calendula flowers were considered beneficial for reducing

inflammation, wound healing and as an antiseptic. Calendula oil is used as a
soothing therapeutic oil. It is a popular element of aromatherapy massage and
as an ingredient in homemade skin care products. Calendula is a drying oil and
considered as a replacement for tung oil in the coating industry.

9.1.4.2.21 Tung Oil

Tung oil, also called China wood oil, comes from the pressed seed from the
nuts of the Tung tree, a deciduous shade tree native to China. Tung oil
is a drying oil. When applied as wood surface coating, it provides a tough,
highly water-resistant finish which does not darken noticeably with age, as
does linseed oil. In fact, the ‘‘teak oil’’ sold for fine furniture is usually
refined tung oil. Some woodworkers consider tung oil to be one of the
best natural finishes for wood. Tung oil is composed primarily of (9c,11t,13t-
18:3) a-elaeostearic acid, with smaller amounts of oleic, linoleic and palmitic
glycerides.
Natural Fats and Oils 209
Table 9.1.8 Approximate fatty acid composition of selected nut oils compared
to olive oil.
Mono- Poly-
unsaturated unsaturated Linolenic Linoleic
Saturated fatty acid % fatty acid % fatty fatty
Oil fat % (MUFA) (PUFA) acid % acid %

Almond 8.2% 69.9% 17.4% 0.0% 17.4%

Brazilnut 24.4% 34.8% 36.4% 0.0% 36.0%
Cashew 19.8% 58.9% 16.9% 0.0% 16.5%
Hazelnut 7.4% 78.0% 10.2% 0.0% 10.1%
Macadamia 15.0% 78.9% 1.7% 0.0% 1.7%
Olive 13.5% 73.7% 8.4% 0.6% 7.9%
Peanut 16.9% 46.2% 32.0% 0.0% 32.0%
Pecan 8.0% 62.3% 24.8% 1.0% 23.6%
Walnut 9.1% 22.8% 63.3% 10.4% 52.9%
Source: USDA nutrient database; http://www.netrition.com/nuts.html.

9.1.4.2.22 Nut Oils

The latest of the different oils to be the darlings of the cooking world are cold or
expeller pressed tree nut oils, more particularly hazelnut oil, walnut oil and
almond oil. Most nut oils taste like the nut from which they were extracted.
They make a delicious, tasty, unique flavour statement, even when blended in a
small amount to mild-flavoured food oil such as canola. Not only do the nut
oils add great flavour to food, they also carry health benefits because of a
similar o-fatty acid balance as olive oil. Nut oils in general are excellent used in
salad dressing, over pasta with some cheese, in baked goods or for dipping
French bread into (Table 9.1.8).
Refined nut oils, when used as massage oils, maintain a faintly nutty aroma.
They are highly penetrative, have great moisturizing qualities and are heralded
as helping to tone and tighten the skin while strengthening capillaries and
assisting in cell regeneration.
Walnut oil has early been favoured by medieval oil painters like Jan van
Eyck and Peter Paul Rubens for its drying properties, since it dries quickly and
evenly throughout, has a light colour, has excellent endurance and yellows less
with age than other drying oils such as linseed oil.

9.1.4.2.23 Castor Oil

Castor oil is obtained from the seed of the castor plant, Ricinus communis. The
seeds of castor plants are the size of kidney beans and have beautiful and
intricate designs (Figure 9.1.31). Harvesting castor beans is not without risk.
Allergenic compounds found on the plant surface can cause permanent nerve
damage. Castor beans also contain two toxins that are poisonous to people,
animals and insects. One is ricin, a water-soluble protein. Ricin is a potent
cytotoxin. The other toxic protein in the castor bean, RCA (Ricinus communis
210 Chapter 9.1

Figure 9.1.31 Castor oil plant, castor seed. Sources: Ricinus communis, botanical
Koeh-257.jpg, from Wikipedia.

agglutinin), is a powerful hemagglutinin, i.e. it agglutinates red blood cells. Both

RCA and ricin fully remain in the meal or cake after castor oil extraction.
The castor plant is also known as ‘‘Palma Christi’’ for its palm-shaped leaves
and the magic healing power castor oil has been credited with in folk medicine.
A large part of world production and development of castor oil is by
members of the International Castor Oil Association (ICOA). India (besides
China, Brazil, Russia, Thailand, Ethiopia and the Philippines) is the world’s
largest producer of castor seed and meets most of the global demand for castor
oil, contributing over 60% of the entire global production.
The most difficult and labour-intensive operation in the growing of castor
was for many years and still is that of harvesting. Although newer dwarf-sized
cultivars with dehiscent fruits enable mechanized harvesting, fruit collection
and de-hulling is mainly done manually from wild or naturalized plants by
women and children.

Uses. Medicinal castor oil is prepared from the yield of the first pressing.
The oil is classified as an oleaginous vehicle. It is present in some topical
pharmaceuticals and is used as a purgative and laxative. The castor bean
contains 50–55% oil. Among vegetable oils, castor oil is distinguished by its
high content (485%) of ricinoleic acid. As a result, in contrast to other
vegetable oils castor oil is highly reactive for derivatization in the hydro-
carbon moiety of the acylglycerol molecule.78 It reacts with isocyanates to
form polyurethanes, especially in the field of surface coatings, potting and
Natural Fats and Oils 211
encapsulation compounds. Ethoxylates of castor oil are well known as emul-
sifiers for cosmetic and technical emulsions. Rather than alkali catalyzed
alkoxylation, castor oil alkoxylates suitable for PUR slab stock foams for
mattresses require special ‘‘double metal cyanide’’ (DMC) catalysis.79
Hardening of castor oil yields hydrogenated castor oil (HCO, glycerol
12-hydroxy tristearate also known as castor wax). HCO has a broad applica-
tion profile covering cosmetic applications like hair wax,80 topical ointment
compositions perceived as pharmaceutically elegant,81 internal lubricants for
PVC and other plastics;82,83 saponification of HCO yields Li-, Ca- or Al-soaps
which have been known for many years as thickeners or gelling agents for
the preparation of lubricating greases and biodegradable oleogels;84 when
micronized, castor wax acts as thixotropic agent for organic surface coatings
and sealants.85
Non-drying castor oil is converted into a drying oil when the hydroxyl group
and adjacent hydrogen are removed from each ricinoleic acid chain by action of
an acid catalyst at 230 to 260 1C. An additional double bond is created,
resulting in two double bonds on each chain, of which 25% are in the con-
jugated position. The result is a light-coloured, odourless drying oil known as
dehydrated castor oil (DCO). Varnishes, alkyds and resin systems based on
DCO are noted for fast-drying, flexibility, excellent chemical resistance, adhe-
sion to metals, high gloss and water-resistance.

O
O O
O
O O

Dehydrated castor oil, DCO

Sulphation of castor oil with sulphuric acid or oleum yields an easily water-
soluble or dispersible sulph(on)ated castor oil also called Turkey red oil, one of
the first synthetic detergents, which has been used for textile dyeing, softeners
and metal working.86
Castor oil is also a raw material for the ‘‘green polyamide’’ PA 11, Rilsans.

9.1.4.2.24 Jatropha Oil

Jatropha is a very diverse genus which includes herbaceous perennials like
Jatropha integerrima, a widespread ornamental garden plant, and Jatropha
curcas, a multipurpose plant with many attributes and considerable potential.
It is a genus of crops like the castor plant belonging to the family euphorbiaceae
(Figure 9.1.32). Jatropha curcas generates seeds containing from 36% up to
40% oil and may produce for over 35 years. Its frugality and durability even
with poor soil and unfavourable climatic conditions has created interest as a
crop that could combat desertification, provide employment in remote areas,
improve the environment and enhance the quality of rural life.87 The jatropha
seed provides an oil similar to cotton seed and soybean oil. This has made
212 Chapter 9.1

Figure 9.1.32 Jatropha.

jatropha interesting as an energy crop, for example when grown for biofuel
production thus satisfying local needs for farm machinery and even for export.

9.1.4.2.25 Algal Oil

Algae range from small, single-celled organisms to multi-cellular organisms,
some with fairly complex form. Algae are common in terrestrial as well as
aquatic environments. Their cultivation does not impact freshwater resources.
Crop growing can use ocean and wastewater and can be done without dis-
placing arable land currently used for food production.88
Macro-algae, commonly known as seaweed, can reach sizes of up to 60 m in
length. Commercial farming of seaweed has a long history, particularly in
Asian countries. Macro-algae have been used for some time as food and for the
extraction of hydrocolloids, i.e. as an excellent source of thickening, emulsi-
fying and gel-forming agents (agars, alginate, carageenan).
However, the majority of algae that are intentionally cultivated fall into the
category of micro-algae. Micro-algae are microscopic photosynthetic organ-
isms, 1 to 5 mm in size and also referred to as phytoplankton. Micro-algae
contain anywhere between 2% and 40% of lipids. They have much faster
growth-rates than terrestrial crops, which makes them interesting as an energy
feedstock. For that reason algae have been exhaustively studied during the US
Department of Energy’s Aquatic Species Program (ASP) initiated by the Carter
administration in 1978. At that time algae species, which looked promising in
Natural Fats and Oils 213
the laboratory for biodiesel production, were not robust under conditions
encountered in the field. Nonetheless, the potential of algal oil appeared highly
attractive, and in the 2008 US Department of Energy Biomass and Biofuels
Update to Congress89 and other R&D programs algae reappear as a potential
non-food feedstock (see Chapter 8).
Marine micro-algae provide the food base which supports the entire animal
population of the open sea. They are sourced for nutritional and pharmaceu-
tical use because of their nutrient-dense components including: carotenoids
(b-carotene), sterols (4-a-methyl sterols, 5-a-stanols), lipids, polyunsaturated
fatty acids (PUFAs) and polyphenols. Micro-algae contain a wide range of
fatty acids in their lipids.90 Of particular importance is the presence of sig-
nificant quantities of the essential polyunsaturated fatty acids, o-6 linoleic acid
(C18:2) and o-3 linolenic acid (C18:3), and the highly polyunsaturated o-3 fatty
acids, octadecatetraenoic acid (C18:4), eicosapentaenoic acid (EPA, C20:5) and
docosahexaenoic acid (DHA, C22:6), which are found in fish oils, and which
have been shown to lower blood pressure and ultimately lead to the reduction
of cardiovascular disease risk. Concern about depletion of fish stocks could
be addressed by alga-culture of micro-algae and extraction of algal oil as a
sustainable alternative to fish oil production.

9.1.5 The Value Chain of Fats and Oils – Industrial

Non-food Uses
The main biological functions of lipids include energy storage and acting as
structural components of cell membranes. More particularly glycerolipids serve
as a reserve or long-term source of energy. Fats also serve as an insulation
material to allow body heat to be conserved. In addition, fats are essential to
the proper maintenance of cell membranes in the body. Since an unsaturated
fat contains fewer carbon–hydrogen bonds than a saturated fat with the same
number of carbon atoms, saturated fats will yield more energy during meta-
bolism than unsaturated fats with the same number of carbon atoms. Saturated
fats can stack themselves in a closely packed arrangement, so they can freeze
easily and are typically solid at room temperature. The combination of satu-
rated and unsaturated moieties in the hydrocarbon chain of naturally occurring
fats imparting a ductile, malleable solid texture such as in lard or tallow
eventually represent the best compromise to fulfil the different biological tasks.
Additionally, certain glycerolipids like polyunsaturated conjugated fats exercise
useful physiological activities.
Based on this role in the metabolism of living organisms, glycerolipids and
their derivatives offer unique structure/performance profiles for industrial
purposes as well, namely:

 the low volatility combined to ready biodegradability and ability to compost;

 the polar molecular structure resulting in plasticizing and lubricating
properties;
214 Chapter 9.1
 their ability to protect and lubricate the skin, leaving a pleasant after-feel;
 the long, hydrophobic, chemically nearly inert and water insoluble
hydrocarbon chain of saturated fatty acids;
 the facility for functionalizing or splitting the hydrocarbon chain via
reaction at the double bond of unsaturated fatty acids;
 the hydrophilic/lipophilic structure hydrolyzing to yield fatty acid mole-
cules as precursors for soaps and surfactants;
 the glycerol group as a C3-building block.

9.1.5.1 Fats and Oils as Precursors for Biopolymers

The capability of highly unsaturated oils to dry and form a polymer film by
simple action of atmospheric oxygen explains the historic importance and
traditional usage of drying oils in lacquers and varnishes. The actual chemical
reactions involved in the drying process are still incompletely understood;
they do, however, involve oxygen attack on the fatty acid chains at or near the
double bonds, catalyzed by certain organic salts of multivalent metals, called
dryers or siccatifs. Similar chemical reactions are involved with operations like
manufacturing of stand oils, blown oils and conjugated oils, as well as with
formation of linoleum from linseed oil.
Oxidation of unsaturated triacylglycerides by action of performic or per-
acetic acid means, to a certain degree, incorporating reactive oxygen in the
molecular structure of the oil. By this, the polarity and the reactivity of the
molecule increase significantly. Whereas the natural oils themselves have
mainly solvent properties, epoxidized natural oils are well known as phthalate-
free, non-volatile, extraction and migration resistant plasticizers.83,91 Due to
the reactivity of the oxirane group and due to the high degree of oxirane
functionality, epoxidation of oils or oleic acid esters and (partial) ring opening
of the oxirane group reacting with water, mono- and polyfunctional alcohols or
acids yield so-called oleochemical polyols used as polymer building blocks for
plastic and coating applications (Figure 9.1.33).92
Oleochemical polyols have been commercial since the 1980s. They are used
for polyurethane foams,93 for solvent-free heavy duty multilayer coatings in
concrete protection (Figure 9.1.34) and for high-performance anticorrosion
coatings. Alternatively, hydroformylation of biodiesel followed by hydro-
genation yields a hydroxymethylated fatty acid methylester (FAME) monomer,
which can be transesterified with polyfunctional alcohols to yield natural oil-
based polyesters useful for the manufacturing of flexible moulded PUR
foams.94 Reaction of epoxidized oils with acrylic acid yields radiation curable
oleochemical polyols, e.g. Photomers 3005. Acrylated vegetable oils serve also
as matrix resins for natural fibre reinforced biopolymer composites.95
Unsaturated and saturated short-chain dicarboxylic acids such as maleic,
succinic and adipic acid are well-known industrial chemicals manufactured on
a petrochemical basis.96 Besides hydrogenation of maleic anhydride or oxida-
tion of tetrahydrofuran, white biotechnology additionally opens a new route to
Natural Fats and Oils 215
O
C(O)O

O O O HOH OH
C(O)O C(O)OR C(O)OR
OH
O O HO – X – OH
C(O)O OH OH OH OH
C(O)OR
O
OH
C(O)OR X
O O
OH C(O)OR
OH OH
+
O OH
C–O C(O) – O C(O)OR
OH O
O (X)–OH
OH
C–O
from castor oil C(O) – O
O
OH OH
C–O OH

Figure 9.1.33 Schematic pathways to oleochemical polyols. (Source: T. Roloff,

U. Erkens and R. Höfer, Polyols based on renewable feedstocks: A
significant alternative, Urethanes Technology, August/September
2005, 29.)

Figure 9.1.34 Self levelling multilayer PUR-flooring.

succinic acid from fermentation of agricultural carbohydrates.97 Natural oils

supplement these to provide longer-chain diacids or o-functional long-chain
monoacids using the double bonds of unsaturated acids as reaction centre or
Sollbruchstelle (Figure 9.1.35). For example, pyrolysis of castor oil or ricinoleic
acid methyl ester under reduced pressure yields heptaldehyde and undecylenic
acid.78 Alternatively, o-unsaturated monocarboxylic acids can be synthesized
by metathesis of sunflower, HOSO or rapeseed fatty acid methyl ester and
ethen yielding 9-decylenic acid methylester.98 Bromination of the o-double
216 Chapter 9.1

castor oil vegetable oils epoxydation/epoxy ring opening

ricinoleic acid oleic acid oleochemical

polyols

caustic
pyrolysis ozonolysis dimerization biooxidation
oxidation

pelargonic monomer
n-heptaldehyde 2-octanol
acid acid/iso
enantic acid/ stearic acid
n-heptanol

10-undecenoic octa-
sebacic acid azelaic acid
acid decan-
dioic acid
11-bromoundecanoic acid
dimer acid
11-aminoundecanoic acid

Figure 9.1.35 Polymer building blocks based on vegetable oils.

bond in undecylenic acid yields 11-bromoundecanoic acid, which reacts with

NH3 yielding o-aminoundecanoic acid. Sebacic acid and 2-octanol are pro-
duced from ricinoleic acid or castor oil by oxidative cleavage in an alkaline
medium. Oleic acid reacts with ozone forming azelaic acid and pelargonic
acid.99 However, oleic acid can also be oligomerized catalytically under heat.
This industrial process leads to a mixture of branched C18 monomer fatty acids
(the raw material for isostearic acid100), C36 dicarboxylic acid, C54 trimer fatty
acids and higher oligomers from which the dimer fatty acids can be separated
off by distillation.99,101 Azelaic acid, sebacic acid, o-aminoundecanoic acid
and dimer fatty acids serve as polymer building blocks for polyamide-based
high-performance engineering plastics, high-speed assembling, shoe hotmelt
adhesives, printing inks and coating resins. They are marketed as green alter-
natives to the butadiene-derived dodecandioic acid and laurolactam. Bio-
technological processes to manufacture higher molecular weight dicarboxylic
acids as an alternative to these, in part, highly energy-intensive syntheses
are under development. o-Octadecandioic acid is to date only available via
biooxidation technology,102 whereas dimethyl 9-octadecylendioleate can also
be synthesized by cross-metathesis of methyloleate with methylacrylate.103

9.1.5.2 Fatty Acids – Keystones of Oleochemistry

Historically, industrial oleochemistry began when Ernst Twitchell at Emery
(now Cognis and Emery Oleochemicals) in Cincinnati successfully performed
Natural Fats and Oils 217
104
the first catalytic acid cleavage of fat. Likewise, enzymatic fat splitting has
been known since the beginning of last century. By catalytic fat splitting the
chemically reactive fatty acids were readily available, in contrast to alkaline
saponification which only provided lard soaps of low chemical reactivity
(Figure 9.1.36).
Fat splitting can be done batch-wise or continuously in counter-current
splitting columns. Crude fatty acids from splitting are still contaminated with
colour bodies, partial glycerides, oxi- or partially polymerized fatty acids,
unsaponifiable materials, free glycerine, etc. They may be purified by batch-wise
or continuous distillation or separated into their component fatty acids by high-
vacuum fractional distillation. Tall oil fatty acids are obtained by fractional
distillation of crude tall oil (CTO). Industrially, fatty acids derived from palm oil
and tallow represent the lion’s share with coconut and palm-kernel coming next,
followed by tall oil, soya and sunflower oil. These seven oils represent 497% of
fatty acid feedstock. Global fatty acid production capacity grew from 2.5 Mio
mto in 1985 to 7 Mio mto in 2006 with 60% now in Asia.20,105
Fatty acids are predominantly used as intermediates. Main applications are
water soluble soaps for household cleaning, personal care, industrial and
institutional (I&I) cleaning and synthetic rubber manufacturing by emulsion
polymerization. Soaps are made by reaction of fatty acids with caustic alkalis,
alkali carbonate or ammonia or (490%) by direct saponification of
the triglyceride oil.106 Another important group of fatty acid soaps are dry,
water-insoluble metal soaps used as lubricants or stabilizers for PVC and other
plastics and aqueous calcium stearate dispersions applied as paper coating

CH2 – O – C(O) – R

CH – O – C(O) – R

CH2 – O – C(O) – R

transesterification splitting saponification

+ CH3OH - glycerin + H2O - glycerin + KOH - glycerin

O O
R – C(O) – O – CH3 R–C R–C
OH O] − K+

fatty-acid-methyl-ester fatty acid fatty acid soap

+ CH3OH -H2O + HCI

Figure 9.1.36 Processing of fats and oils.

218 Chapter 9.1
lubricants and as friction agents to avoid dusting and picking during calen-
dering and printing processes.
Fatty acids are raw materials for fatty amines, ethoxylated fatty amines,
quaternary ammonium compounds (Quats), fatty acid-polyamine condensates,
fabric softeners based on esterquats, fatty acid amides, alkyl keten dimers for
paper sizing and amphoteric surfactants. Binding of oleic acid anhydride to
cellulose fibre by chemical grafting is a recently introduced sustainable process
to protect construction timber for outdoor use, such as pinewood shutters,
from moisture and outside attack. Impregnation of the wood involves two
stages: firstly in an autoclave, where vacuum and pressure ensure its penetra-
tion, and then in a tank where the wood is soaked in a bath of anhydride, to
encourage grafting of the anhydride on the wood.107

9.1.5.3 Fatty Acid Esters

Fatty acid esters of mono- and polyfunctional alcohols are the workhorses of
oleochemistry. In many fields of application fatty acid methyl esters replace
fatty acids because they are less corrosive. Chemical reactions can often be
carried out under milder conditions. They have lower boiling points and require
less energy to distil and to fractionate than the corresponding fatty acids. The
elimination of methanol from the reaction products can be more easily achieved
than that of water. Therefore fatty acid methyl esters are primarily used for
the production of saturated and unsaturated fatty alcohols. Methyl esters are
manufactured by acid catalyzed esterification of fatty acids in counter-
current reaction columns or by alkaline transesterification starting directly
from the triglyceride oils in a batch, semi-batch or continuous process
(Figure 9.1.37).108,109
Together with fatty acids and glycerine, they form the raw material base for
the oleochemistry value chain (Figure 9.1.38).
Methyl esters of soya, rapeseed and palm oil fatty acids used as biodiesel
(Chapters 7 and 8) are preferentially manufactured by transesterification.110
The acid catalyzed esterification and the alcoholysis of triacylglycerides
apply also for the manufacture of higher alcohol monoesters as well as for fatty
acid polyol esters. Due to their oily consistency and to their solubilizing
properties fatty acid esters of low Mw alcohols are components in odorous
substances like perfumes, and cosmetic and drug formulations such as oint-
ments, creams or lotions.

9.1.5.4 Green Lubricants and Carrier Oils

The increasing prices of mineral oils mean that the substitution of mineral oils by
fatty acid esters is becoming economically viable. This applies especially to the
lubricant sector, where rising economic competitiveness on the one hand and
ecological safety on the other have helped biogenic lubricants achieve the
Natural Fats and Oils 219

Ester splitting/esterification/transesterification

O
R2
R1 OH + O

O
[cat] R1
O + R2 OH

ester splitting esterification transesterification

R1 = H, R2 = alkyl R1 = alkyl, R2 = H R1 = alkyl1, R2 = alkyl2

Hardening

O H2 O
HO [cat] HO
unsaturated fatty acid saturated fatty acid

Hydrogenation

O H2
RO [cat] HO
saturated fatty acid (ester) saturated fatty alcohol
O
H2
RO [cat] HO

unsaturated fatty acid R = H or alkyl unsaturated fatty alcohol

Figure 9.1.37 Value adding basic reactions of oleochemistry.

breakthrough.111 Lubricants form a film on metal surfaces to reduce or prevent

friction between machinery parts in motion and minimize wear between inter-
acting surfaces. Synthetic esters based on renewable sources have outstanding
tribological properties which can, among others, be seen from the very good
viscosity-temperature behaviour. The evaporation loss of such biolubes is much
lower than the evaporation loss of mineral oils. Lubricants and functional fluids
are omnipresent. Because of their widespread use in industrial machinery,
in mining, metal working, fibre and textile manufacturing, agriculture, forestry,
in construction, road construction and automotion, they pollute the environment
in small, widely-spread quantities and rarely in large, locally fixed amounts.112
Thus the selection of rapidly biodegradable lubricants20,113 inter alia will reduce
the expenses of oil spillage or disposal.
Esters of saturated, long-chain fatty acids with long-chain fatty alcohols,
such as stearyl stearate, have a waxy characteristic. These waxes develop
lubricating effects in plastics processing;82,83 which means they prevent friction
between plastic molecules and thus permit faster transport of the molten plastic
mass through the processing machines (internal lubrication). At the same time
they reduce the friction of the molten plastic with the surrounding machine
parts (external lubrication).
220 Chapter 9.1

Partial
Esterification Glycerides
Gly-
cerol Polyether
Alkoxylation polyols
Splitting
Fatty Acid
Esterification Esters

Epoxidation Alkyl Epoxy

Esters
Fatty Fatty Acid
Ethoxylation Ethoxylates
Acids
Conjugation Conjugated
Fatty Acids
Saturated
Hardening Fatty Acids
Guerbet Guerbet
Reaction Alcohols
Ester-
ification Alkyl
OILS Glycosidation Polyglycosides
Hydro - Fatty
and Fatty Alco - Fatty Alcohol
genation Ethoxylation
FATS Acid hols Ethoxylates
Transester - Methyl
ification Sulphation Fatty Alcohol
Esters Sulphates
Esterification Esters
α-Sulpho Fatty
Sulphonation Acid Esters

Amidation Fatty Acid

Alkanolamides

Epoxidation Epoxidized
Vegetable Oils
Ethoxylated
Ethoxylation Triglycerides
Hardened
Hydrogenation Triglycerides,
Hydrogenated
Castor Oil, HCO
Sulphation/ Fat liquors/
Sulphitation Turkey Red Oil

Figure 9.1.38 Oleochemistry value chain.

In industrial applications liquid fatty acid esters are well known as plasti-
cizers for pyroxyline varnishes and as secondary plasticizers for PVC.91
They are used as thinners and carrier oils and have become established as
green solvents (see Chapter 10) for printing inks (Table 9.1.9) and for industrial
surface cleaning due to their low volatility, environmental compatibility and
contribution to work hygiene and industrial safety.20,67
As green carrier oils or solvents – together with green surfactants – they also
play a key role as ‘‘inerts’’, i.e. non-active, inert formulation aids in modern
crop protection, such as pesticide microemulsions or emulsifiable con-
centrates.114 Besides fatty acid esters, certain liquid fatty acid amides, more
particularly capryl dimethylamide, are also increasingly creating interest as
green solvents and carrier oils.
 Natural Fats and Oils
Table 9.1.9 Specifications of oleo-based oils in comparison to mineral oil based printing ink distillates.
Titer (pour Flash Boiling Visc. At Kauri butanol Anilin Iodine value
point) (1C) point (1C) point (1C) 25 1C (Mpas) value point (Wijs)

Short-chain fatty acid methylester –28 75 204–244 2.7 107 o –20 o1

Rapeseed fatty acid methylester –3 155 335–365 6 66 –1,7 90–100
Soybean fatty acid methylester –6 170 335–365 10 67 3.69 115–135
n-Butylstearate 22 190 344–385 8.7 42 10 o1
Isobutylstearate 19 4170 341–381 8.4 41 10 2
Soybean fatty acid-2-ethylhexylester –13 180 369–389 9.9 46 –7 85–95
Epoxy stearic acid methylester – – 348–386 13.5 4150 –19 –
Di-n-octylether 7 139 298 3.5 41 27 o1
Capryldimethylamide – – 294 6.6 4150 o –20 –
Propylene glycol monooleate – 210 284 30 – – 76
Printing ink distillate PKWF 4/7 af new1 –12 4100 n.d. 25 84 –
Printing ink distillate PKWF 6/9 af new1 –9 4110 n.d. 23 90 –
1
Fa. Haltermann, Hamburg

221
222 Chapter 9.1
9.1.5.5 Glycerine as C3-Building Block
The manufacturing of fatty acids by fat splitting and of fatty acid methylesters
by alcoholysis of fats and oils yield approximately 10% to 13% of glycerine
(glycerol) as by-product. Established glycerine markets are applications as
hydrotrope, humectant, solvent, solubilizer, antifreeze and plasticizer for
aqueous systems in cosmetics, pharma, food and industrial markets; as
humidity stabilizer and preservative for tobacco; as raw material for glycerol
esters, for polyetherpolyols, for synthetic resins, and nitroglycerine.115
The emergence of biodiesel had a major impact on the glycerol market. In the
European 300 to 400,000 mto a1 glycerol market appeared an additional offer
of 200 to 400,000 mto a1 crude glycerol. Glycerol price was cut to half between
2003 and 2006 reaching the level of ethylene glycol or below and one-third
approximately of propylene glycol. As a result glycerine became of interest as a
commodity solvent and C3-building block. More particularly, synthetic glycerine
made in a three-step process by oxychlorination of propene and hydrolysis of the
epichlorohydrin intermediate nearly disappeared from the market. Glycerine was
cheap enough to make epichlorohydrin in an alternative way, i.e. starting from
glycerine instead of propene (Epicerols process, Solvay; GTE process, DOW).
Similarly, hydrogenolysis of glycerine to manufacture 1,2-propylene glycol is
being explored by several companies. Glycerol formal, glycerol butyral or gly-
cerol carbonate as green solvents, glycerol tert.-butylether (GTBE) as a gasoline
additive, triacetine as a plasticizer, dihydroxyacetone as a sunless tanner and 1,3-
propanediol (1,3-propylenglycol) by bioconversion (as alternative to the acro-
lein-3-hydroxypropionaldehyde route116) are other existing or potential appli-
cations for a low-cost glycerol feedstock. Meanwhile a recovery in glycerine
quotations can be noticed. These fluctuations of glycerol pricing in fact are
indicating the upcoming dependency of glycerine valuation on tax regulations
and state policies for the transportation and energy sectors.

9.1.5.6 Fatty Alcohols

While fatty acids are cornerstones for soaps, oleochemical esters, oils and lubri-
cants, medium-chain fatty alcohols (C6–10) are the basis for oleochemical solvents
and plasticizers and C12–18 fatty alcohols since their discovery have laid the
ground for green surfactants and detergents (Figure 9.1.39). Natural fatty alco-
hols are monobasic, straight-chain, primary, saturated or unsaturated, which
explains the favourable ecotox-profile of fatty alcohols and fatty alcohol derived
surfactants.117 Approximately 75% of all consumed C12–18 fatty alcohols are used
for the manufacturing of surfactants with household detergents covering the
lion’s share. Alkylpolyglycosides and polyglycolethers of natural fatty alcohols
and their sulphates, phosphates and sulphosuccinates follow a rapid and com-
plete degradation mechanism under aerobic and anaerobic conditions leading to
the conclusion that they form a sustainable base set of green surfactants.
Natural Fats and Oils 223

FAES · FAEP APG®

FAE · SUS FAS surfactants α-OS

FA · EO FA α-Olefine

Ethylene n-Paraffine SAS

EO
FS · EO

Fats; Crude oil

Soaps FS FSME Benzole ABS
vegetableOils coal

Phenole

Sorbitan
esters Naphtalene Propylene
NP OP DP
Butylene

Fattyamine FSS FSES ANS APES · APEP AP · EO

APE · SUS

Turkey Red
Oil (SCO)
QAC AEO Dowfax®

Figure 9.1.39 Fossil vs. renewable base stocks for surfactants.

Legend: aOS alpha olefin sulphonates, SAS sec. alkane sulphonates,
ABS alkyl benzene sulphonates, NP nonylphenol, OP octyl phenol,
DP dodecyl phenol, AP.EO alkylphenol polyglycolethers, APES
alkylphenol ethersulphates, APEP alkylphenol etherphosphates,
APE.SUS alkylphenolpolyglycolether sulphosccinic acid monoesters,
ANS alkyl naphthalene sulphonates, SCO sulphated castor oil
(Turkey Red Oil), FSME fatty acid methylester, FS fatty acid, FSS
fatty acid sulphonates, FSES fatty acid methyl ester sulphonates,
QAC quaternary ammonium compounds, AEO fatty amine ethox-
ylates, FS.EO fatty acid polyglycol esters, FA fatty alcohols, FA.EO
fatty alcohol polyglycolethers, FAS fatty alcohol sulphates (f. ex.
sodium lauryl sulphates), APGs surfactants alkyl polyglycosides,
FAES fatty alcohol ethersulphates, FAEP fatty alcohol etherphos-
phates, FAE.SUS fattyalcoholpolyglycolether sulphosuccinic acid
monoesters, Dowfaxs alkyldiphenyloxide disulphonate.

Since 1931 Deutsche Hydrierwerke AG (DEHYDAG, now part of Cognis’

company history) has been the first to synthesize natural fatty alcohols at an
industrial level. Manufacturing today is realized by catalytic high-pressure
hydrogenation of fatty acid methyl esters yielding saturated or unsaturated
fatty alcohols depending on process conditions. Starting from wax esters, long-
chain fatty alcohols (C422 fatty alcohols) such as lanolyl alcohol (also called
hydrogenated wool fat) can be made by hydrogenolysis in a continuous flow
process using n-decanol as reaction medium.109 Alternatively, synthetic fatty
224 Chapter 9.1
alcohols have been produced since the 1950s according to:

 Ziegler-technology based on organic aluminium compounds in a hydro-

carbon solvent (K. Ziegler, 1953; Alfol-Process, Conoco; Epal-process,
Ethyl Corp);
 Hydroformylation (Oxo-process, O. Roelen, Ruhrchemie, 1938; world-
wide there are three variants of the Oxo-process: 1. the classical synthesis
using HCo(CO)4 as catalyst; 2. Shell’s SHOP-process, based on a cobalt
carbonyl – phosphine complex; 3. UCC’s process, using a rhodium
catalyst).118

The Ziegler technology produces a broad Poisson-distribution of more

or less even-numbered fatty alcohols which are fractionated into blends and
single cuts. The Oxo-process results in more or less highly branched, even- and
odd-numbered alcohols.
Based on easily available cheap ethylene or olefins, the Oxo- and Ziegler
technologies have shaped the global fatty alcohol market until the 1990s. They
are still the predominant technology for short- and medium-chain fatty alco-
hols. The fact that Asian nations have started to process their indigenous
vegetable oils into fatty alcohols, though, has originated a significant increase
in global fatty alcohol capacities and has clearly shifted the balance between
synthetic and natural fatty alcohols to the renewable resources side.20

9.1.5.7 Green Surfactants

Bathing in ass’s milk and honey like Cleopatra did in Roman times was the
precursor to modern skin-care baths. Today’s modern-trend cosmetics include
natural oils such as olive, evening primrose and almond oil as well as natural
waxes such as beeswax and carnauba wax. Emulsifiers in bath-oil concentrates
distribute fatty substances or oils in water and prevent them being deposited on
the bathtub. Bath oils are enriched with essential oils and aromatic substances
for aromatherapy. Depending on the type of essential oil or corresponding
mixtures, relaxing, invigorating or antispasmodic effects can be achieved.
Essential oils must be well distributed in water by the surfactant components
since they can irritate the skin in concentrated form. Natural surfactants based
on renewable raw materials119 combine a high emulsifying power with good
electrolyte stability and extremely good skin compatibility. Examples for such
natural surfactants are acylated proteins and amino acids (protein–fatty acid
condensation products, Figure 9.1.40), which can be obtained from both ani-
mal source (e.g. leather waste) and from plants, such as wheat, rice and soy-
bean, with the protein part representing the hydrophilic moiety in the
surfactant structure whereas the hydrophobic part is formed by a fatty acid
group. They favourably interact with the collagen in the skin, feel especially
mild even in the smallest amounts and reduce any irritant effects of other
Natural Fats and Oils 225

O
HO – C – CH – NH2
O
CH2
+ Cl
CH2
O C
OH
NaOH - HCl

O O
HO – C – CH – N
H
CH2
CH2
O C
O-Na+

Figure 9.1.40 Protein-fatty acid condensates.

constituents of the formulation. The products are obtained industrially by

aminolysis according to ‘‘Schotten-Baumann’’.120
Other than proteins, carbohydrates are also able to build up the hydrophilic
part of surfactants,121 for example glucose is derivatized selectively by acet-
alization with fatty alcohols to produce alkyl glucosides; N-methylglucamides
are prepared by reductive amination with methylamine and subsequent
acylation. Both products have proved to be highly effective surfactants in
washing and cleansing agents, but only the alkyl glucosides are produced on an
industrial scale at present122 (Figure 9.1.41).
Special combinations of tensioactives are aimed at producing a feeling of
mildness, relaxation, care, health and the modern term wellness in skin-care
concepts.123 The development of new surfactants and new formulations that
conform to these demands require application technology testing but also
toxicological and sensory testing to ensure skin compatibility and to rule out
skin and mucous membrane irritation. In order to protect living beings,
testing methods on alternative membranes including those of red blood cells
and chicken egg yolk membranes or skin models are being developed to partly
or completely replace the conventional animal tests of the past.124
Besides personal care and fabric care, surfactants are also key ingredients in
industrial and institutional cleaning processes on glass, ceramic, plastic and
metal surfaces. The chemical stability of surfactants against acids, alkalis and
oxidizing agents is a determining factor for particular cases like bottle-cleaning
installations. Here specially designed surfactants, so-called end-capped non-
ionic tensides, manufactured by Williamson-etherification of fatty alcohol
polyglycol ethers with linear short-chain alcohols, combine key performance
properties like alkali stability, low foaming and biodegradability.125 In addition
to the specific cleaning function in metal working operations surfactants are
226 Chapter 9.1

OH

O
HO H+
HO OH + H O
OH -H2O
Glucose Fatty alcohol
OH

OH O
HO
HO O
O
HO OH
HO
OH O
+
O
HO
HO
OH O
n

hydrophilic hydrophobic

Figure 9.1.41 Synthesis of APGs surfactants.

applied in cooling lubricants, tempering oils, hydraulic emulsions, polishing

pastes and mould release formulations.
Cleaning operations under highly complex conditions are required in crude
oil extraction. In the lines leading from the wells to the central processing
facility over a period of time, deposits of heavy hydrocarbonaceous materials
and finely divided inorganic solids, referred to as ‘‘schmoo’’, deposit on the
inner surfaces of the lines. The schmoo is a slimy, oily substance which adheres
to almost any surface with which it comes in contact, and is difficult to remove.
Removal of such deposit can be achieved by the use of a surfactant composition
consisting essentially of a caustic aqueous solution of alkyl polyglycoside,
ethoxylated fatty alcohols and an alkyl alcohol as solubilizer.126 Their high
pH tolerance and their surfactant activity at high temperatures under the
specific conditions of crude oil extraction have made APGs surfactants a very
appropriate component in tenside blends for well operations in general. Their
excellent wetting action at pH 4 or less makes alkyl polyglycosides applicable in
acidic cleaning solutions capable of dissolving carbonate and calcite scales. On
the other hand, in combination with caustic material they are particularly
effective in removing oil-based drilling fluids and other oil-based materials
found in well bores. Additionally their stability at high pH makes APGs
surfactants effective wetting, dispersing and emulsifying agents for cement
slurries used in well-bore operations enhancing cement hydration and adhesion
to the well-bore walls.127
Since the 1970s polymer dispersions manufactured by emulsion poly-
merization have increasingly substituted solvent-borne paints, coatings, adhe-
sives and inks. Water-based emulsion systems have made a significant
contribution to VOC-reduction in corresponding industries. The emulsifier in
Natural Fats and Oils 227
emulsion polymerization has three key functions, namely: stabilizing the
monomer droplets during the first stage of the emulsion polymerization, sup-
plying surfactant micelles as the site of the polymerization reaction (literally the
micelles can be regarded as some kind of micro-reactors) and stabilizing the
latex particles at the end of the emulsion polymerization process pending
transportation, storage and handling until the latex is intentionally destabilized
by evaporation of water and formation of a polymer film (Figure 9.1.42).
Whereas the world of surfactants for emulsion polymerization 25 years
ago mainly consisted of petrochemical species, the growth of renewable raw
materials in general, and the growing importance of vegetable oils in particular,
hand in hand with a growing sensitivity for sustainability initiated a move away
from petrochemical emulsifiers towards surfactants derived from natural fats and
vegetable oils. In the meantime green surfactants clearly dominate the emulsion
polymerization technology. The breakthrough of green surfactants for emulsion
polymerization happened when equally performing alternatives to alkylphenol
ethoxylates (APE) and alkylphenol ether sulphates – until then the workhorses in
emulsion polymerization technology – became available and since the FDA
approved Disponils FES-type surfactants according to FDA y 178.3400. Mod-
ern surfactant systems for polymer dispersion manufacturing consist of anionic
fatty alcohol sulphates or fatty alcohol ethersulphates and green non-ionic sur-
factants like Disponils A or Disponils AFX.128 To a lesser extent fatty alcohol
ether sulphosuccinates and fatty alcohol ether phosphates are used.129 Monomer
emulsion stability is improved when Dowfax 2A1 is added.
Surfactants become a problem when they are discharged into the environ-
ment if they are not readily biodegradable. There are practically no

Nitrogen

Water

monomer solubilisation M
in the micelle M M
micelle
M M 103 nm
M M M

3,5 nm 5 nm
momomer droplet
. .
.
I+ I I

swollen micelle
102 nm
.
I = initiator radical
M = monomer molecule latex particle
= surfactant molecule

Figure 9.1.42 Emulsion polymerization process.

228 Chapter 9.1
applications for surfactants in which they are recovered and recycled. Besides
the use in detergents, direct release into the environment happens when sur-
factants are used as inerts in agrochemical applications. Modern crop protec-
tion aims at releasing the active pesticide straight at the point of action,
improving its activity and reducing the dose rate and wastage of the active.
Adjuvants in a pesticide formulation should be readily biodegradable, and
should allow safe handling without causing damage to the environment or
creating a health risk for the workforce or for untrained people, who risk
coming into contact with crop protection chemicals when applied. Green sur-
factants such as (alkoxylated) alkyl polyglycosides are particularly qualified to
meet this demand.130

9.1.6 Perspectives
Natural fats and oils are extremely well positioned to produce environmentally
compatible and powerful products in the sense of a sustainable development.
Oil crops are a unique combination of useful base stock materials. They supply
essential protein for human food and animal feed. They need neither refining
(in the sense of crude oil refining) nor cracking, before being processed for food
or feed or being transferred into useful oleochemical specialties. The high
biocompatibility of oleochemical surfactants, solvents and biolubes will even
further increase their importance for all applications, which come into direct
contact with the environment be it as fabric or body care detergents, additives
for paints, inks or adhesives, lubricating oils, agrochemicals and even oil-well
drilling adjuvants. Hulls, shells and other by-products are biomass for energy
generation. They eventually carry extractives, which can be used as specialty
chemicals, and their potential to be converted in new chemical products via
biochemical technologies is by far not exploited. It can clearly be assumed that
in future further possibilities for using renewable resources will be intensely
investigated. Here the combination of different types of vegetable raw mate-
rials, such as vegetable oils, carbohydrates and proteins, to form new products
and intelligent product concepts in order to meet market and consumer needs
will be a challenge for research and development.

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CHAPTER 9.2

Starch: A Versatile Product

from Renewable Resources for
Industrial Applications
ANDREA GOZZOa AND DETLEV GLITTENBERGb
a
Cargill R & D Centre Europe, Havenstraat 84, B-1800 Vilvoorde, Belgium;
b
Cargill Deutschland GmbH, Düsseldorfer Strasse 191, D-47809 Krefeld,
Germany

9.2.1 Markets
Starch and its derivatives can be produced from several raw materials including
corn, wheat, pea, potato, and tapioca and, in general, its production follows
local raw material availability. In 2006 European (EU-25) production of
starches, modified starches and refinery products was approximately 8.6 Mio
tons.1 The main consumer, accounting for 4.5 Mio tons, was the food industry,
followed by the paper and board sector with 2.4 Mio tons, the pharmaceutical
and chemical sector with 1.2 Mio tons and the industrial bindersi sector with 0.6
Mio tons (Figure 9.2.1).
The botanical source of the primary starch products, from which also
refinery products are derived, has been roughly as follows: corn starch 4.0 Mio
tons, wheat starch 2.9 Mio tons, potato starch 1.8 Mio tons.2

i
Industrial Binders includes the adhesives, gypsum boards and textile industries.

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

238
Starch: A Versatile Product from Renewable Resources for Industrial Applications 239
The total raw material processed to produce these starches and derivatives
has been estimated at 12.5 Mio tons of potatoes and 10 Mio tons of cereals
(corn and wheat).3
The perishable nature of potatoes limits the market of this raw material to
the region of production: what is produced in Europe is predominantly con-
sumed in Europe. On the other side, cereals are commodities traded globally
and therefore subject to the dynamics of a global market. A recent demon-
stration of these global dynamics was the temporary shortage of cereal on the
market caused, among others, by an increased demand for food coming from
China and India, bad weather conditions and the use of cereals as feedstock for
‘‘bioethanol’’ production.
It is worthwhile noting that there are regional differences in the use of crops
for bioenergy. In the USA, bioenergy is mostly bioethanol, which reflects on the
high share (B25%) of corn crop used for energy production.4 In Europe,
bioenergy mainly comes from biodiesel, which is derived from oilseeds and has
no impact on corn availability. According to the forecast of the European
Commission the use of corn for bioethanol production in Europe will be very
limited (see Figure 9.2.2 and Table 9.2.1).

9.2.2 Starch and Derivatives

Native Starch: Structure and Properties
Starch is the material used by Nature to store and provide energy for plants in
the form of a glucose polymer. It is synthesized and stored by all plants, but it is
industrially extracted mainly from cereals and tubers such as corn, wheat,
potato and tapioca.
Starch occurs as discrete granules whose size and shape depends on its
botanical origin. However, all starch granules have a semi-crystalline structure,
hydrated only to a very small extent, insoluble in cold water, and very dense.
The term ‘‘starch’’ identifies a mixture of two different polysaccharides:
amylopectin and amylose (Figure 9.2.3). Both are homopolymeric a-1,4-glu-
cans based on D-glucose as monomeric unit, but they differ in molecular weight
and in the ramification of the polymer.
Amylose has a molecular weight in the range 100,000–1,000,000 Daltons, is only
lightly branched and in aqueous solutions assumes the shape of a random coil
consisting of helical segments joined by segments with no specific conformation.
Amylopectin has a molecular weight in the range 1,000,000–10,000,000
Daltons, and is highly branched. According to Manners,6 amylopectin has a 1,6
branch point every 5 to 9 glucose units.
While amylopectin constitutes the backbone of the granule and contains
sections in which neighbouring chains within clusters intertwine into parallel
double helices to form crystals, amylose has a largely amorphous structure.7
These two polymers are held tightly together via a dense network of internal
hydrogen bonds that optimizes the spatial arrangement and guarantees efficient
storage and availability of energy reserves, as glucose, to the plant.
240 Chapter 9.2

Industrial
Binders
6%
Pharma &
Chem.
13%

Food
53%

Paper &
Board
28%

Starch consumption Tons

EU 2006
Food 4,500,000
Paper & Board 2,400,000
Pharma & Chemicals 1,150,000

Industrial Binders 550,000

Figure 9.2.1 Starch products consumption by sector. Europe 2006.

300
250
Mio Tons

200
150
100
50
0
2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014

Feed Food & Industrial Bioenergy

Figure 9.2.2 Total cereal market projections –EU-27.5

The internal hydrogen bond network also provides a barrier to water pene-
tration inside the granules that are therefore insoluble in cold water. However,
when heat is applied, the surrounding water molecules acquire enough energy to
massively penetrate the network of hydrogen bonding and start competing with
it, resulting in the hydration and dissolution of the polymer chains. This process
is called gelatinization because it eventually leads to a starch gel (or paste) with
Starch: A Versatile Product from Renewable Resources for Industrial Applications 241
Table 9.2.1 Total cereal market projections – EU-27.
Total cereal market projections for EU-27 (Mio MT)
2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014

Feed 153.2 154.9 153.7 165.2 166.5 167.8 167.9 168.6 168.8 168.6 168.5
Food & Industrial 78.4 76.9 78.6 86.6 87.9 88 88.1 88.1 88.2 88.3 88.3
Bioenergy 0.7 2.7 2.5 1.9 4.8 4.5 5.5 7.5 10.3 15.7 18.4

Amylose Amylopectin

Figure 9.2.3 Amylose and amylopectin structures.

marked viscosity. Even after gelatinization, starch polymeric chains surrounded

by water molecules have a strong tendency to form new hydrogen bonds among
themselves. This results in a further increase in viscosity, which ultimately leads
to a strong gel. The process is called retrogradation, which literally means ‘‘move
backwards’’ and consists of a sort of re-crystallization of the polymeric chains
that brings the polymer into a more crystalline state. Amylose is the main
polysaccharide responsible for the retrogradation of starch paste as its structure
facilitates the formation of pseudo-crystalline structures, which, linked to amy-
lopectin, are widely responsible for the massive increase in viscosity and for-
mation of strong gels. Conversely, the branched structure of amylopectin induces
the formation of soft gels characterized by a relatively stable viscosity over time.
The length of the chains helps to create an extended network of internal
hydrogen bonds and, at the same time, the ramification of the polymer prevents a
real crystallization of the amylopectin structure.
Retrogradation is strongly influenced by factors such as the amylose/amy-
lopectin ratio, temperature and its variation, and the interaction between starch
and other materials (proteins, lipids, etc.).
The functionalities of starch and its derived products that can be exploited in
industrial applications are directly linked to its chemical structure and can be
summarized as follows:

 Polymeric structure;
 Fermentation feedstock (glucose source);
242 Chapter 9.2
 Chemical intermediate for synthesis;
 Protective colloid;
 Binder;
 Humectant;
 Carrier;
 Rheology modifier.

Modified Starches
Even though native starch can be used for some applications, chemical mod-
ifications of its structure are generally necessary to optimize a particular func-
tionality and to obtain a product that can be handled on an industrial scale.
Even relatively low-level modifications in the chemical structure of starch
have a significant impact on its properties such as:

 Viscosity;
 Paste viscosity stability;
 Retrogradation;
 Rheology;
 Water retention;
 Film formation capacity and film flexibility;
 Ionic charge;
 Affinity with hydrophobic molecules.

Chemical modifications are generally carried out on the starch granules

dispersed into water as starch slurry. The reactants are dissolved into the slurry
and the mixture is heated until the reaction is completed. After separation of
the remaining reagents, water is removed. At the end of the process, modified
starch is still in granular form and can be handled as a powder. The reaction
conditions have to be carefully chosen to avoid the gelatinization of starch
during the process. When a high degree of modification is required, gelatini-
zation cannot be avoided and the final product is sold as a liquid.
Chemical modifications of starch include derivatization (also known as
substitution), oxidation, cross-linking, hydrolysis (also known as thinning) and
hydrolysis combined with internal rearrangements of the glucosidic bonds.
Derivatized starches are obtained by reaction with a-chloroacids, epoxy
derivatives or anhydrides in alkaline conditions. In general, they have lower
gelatinization temperature, better film-forming properties and tend to give
softer gels. Typical products used in oil drilling fluids, adhesives and paper
applications are carboxymethylated starches, hydroxypropylated starches,
cationized starches and acetylated starches.
Oxidized products are normally prepared by treatment with an alkaline
hypochlorite. This treatment results in two chemical reactions taking place
simultaneously: a partial depolymerization that lowers molecular weight, and
the introduction of some carbonyl and carboxyl groups.
Starch: A Versatile Product from Renewable Resources for Industrial Applications 243
After gelatinization, these starches form pastes with low viscosity at a relatively
high concentration and with very stable viscosity. The resulting products are well
suited for use in pigmented coating colours, adhesives and textile warp sizing.
Thinned products are the result of acid treatment of the granular starch that
essentially produces depolymerized starches with lower molecular weight. Two
straightforward consequences of this modification are: increased solubility
compared to the native starch and a more pronounced retrogradation ten-
dency, which results in a strong increase in viscosity of the gelatinized starch
upon cooling. Thinned starch can be used at relatively high concentrations
providing good binding properties as well as high film strength. Typical
applications for such starches are as a binder in gypsum boards and in textile
and paper-making applications.
Dextrins are produced by a severe thermohydrolytic action in conditions of
low moisture (1–5%), acid pH and very specific ranges of temperature and
time. Under appropriate conditions, two main chemical reactions occur: the
hydrolysis of the 1,4 glucosidic bond and the rearrangement (or transglucosi-
dation) of the 1,4 bond to 1,3 or 1,2 or 1,6 bonds. This rearrangement produces
an amylopectin-like structure that is responsible for the superior viscosity
stability of dextrins compared to the thinned products.
Dextrins’ solubility in water varies from low (20%) to high (90%). The
corresponding solutions are tacky and dry quickly, providing an excellent
solution for adhesives.

Refinery Products: Maltodextrins, Glucose Syrups, Dextrose and

Polyols
Hydrolysis of aqueous solutions of starch by acid or enzymatic reactions yields
a mixture of different products, mainly consisting of D-glucose, maltose,
maltotriose and higher oligosaccharides. Because of their complex composi-
tion, these hydrolyzed products are best characterized in terms of their
‘‘dextrose equivalent’’ (DE) value, which is a measure of the total reducing
power of the saccharides relative to glucose taken as 100 and expressed on a dry
weight basis.8 The higher the DE, the higher the degree of hydrolysis of the
product.
Starch hydrolysis products with a DE lower than 20 are defined by food
legislation as maltodextrins, while those with a DE value higher than 20 are
classified as glucose syrups.
A typical enzymatic production process for these products involves mixing
enzymes and starch slurry, gelatinizing the starch by heating the mixture up to
B75 1C, holding it at that temperature to allow for enzymatic cleavage and
then heating it again or acidifying the mixture to inactivate the enzymes. After
separation of the insoluble material, the product is stored as a liquid, or spray-
dried to obtain a white powder. There are several versions of this process, and
combinations of acid hydrolysis and enzymatic cleavage are also used. A good
overview of such processes can be found in Howling’s work.9
244 Chapter 9.2
Table 9.2.2 Functional properties of glucose syrups as function of DE.
Adapted from Howling.9

Property Low DE High DE

High Average Low Average
Molecular Weight Molecular Weight

Colour formation

Crystallisation control

Emulsion stabilisation

Fermentability

Foam stabiliser

Hygroscopicity

Osmotic pressure

Viscosity

Glucose syrups are produced via the same process described for mal-
todextrins but the hydrolysis reaction is run more extensively, resulting in
products with higher DE. In general, the properties of syrups produced using
the same process can be related to the DE value (Table 9.2.2).
Hydrolysate is a special type of glucose syrup in which starch has been
hydrolyzed to obtain a D-glucose content of at least 90% on a dry basis, with a
typical value ranging between 95 and 96%.
Hydrolysate is the starch-based product most widely used as a carbon source
for fermentation processes. It is also the product used as feedstock to produce
dextrose.
Dextrose is the common name of the monosaccharide D-glucose (CAS
50-99-7). It is an aldohexose that, when crystalline, assumes a hemiacetal form
(a or b) of the six-membered ring (pyranose) while in solution it reaches
equilibrium between the hemiacetal forms and the aldehyde open form (see
Figure 9.2.4). The open form of D-glucose has the typical reducing property of
the aldehyde group. It is worth mentioning that every amylose and amylopectin
molecule at the end of the chain has one and only one glucose unit that is in
equilibrium between the pyranose and the open form. This is normally called
the reducing end.
Catalytic hydrogenation of an aqueous solution of glucose leads to the main
polyol used in industrial applications: sorbitol. The aqueous solution of sor-
bitol is purified by ion exchange chromatography, decolourized and con-
centrated to give a 70% solution that is sold as such or further processed to give
a crystalline powder (Figure 9.2.5).
Starch: A Versatile Product from Renewable Resources for Industrial Applications 245

H OH

H O
HO
HO H
H OH O H
H OH

α-D-glucose H OH

HO H

H OH
H OH
H OH
H O
HO CH2OH
HO OH
H OH

H H

β-D-glucose

Figure 9.2.4 Equilibrium between hemiacetal and aldehyde forms of D-Glucose.

O H
CH2OH

H OH H OH

HO H H2, Δ HO H
Catalyst
H OH H OH

H OH H OH

CH2OH CH2OH

Sorbitol

Figure 9.2.5 Sorbitol from D-glucose.

9.2.3 Food Applications

The market for starch-derived products in the food industry is generally seg-
mented into the following application areas: confectioneries, processed food,
beverages, dairy products and baked foods (see Figure 9.2.6).
246 Chapter 9.2

Baked Foods
Dairy Products 5%
11%

Starch for Food Applications Tons

EU 2006
Beverages Confectioneries Confectioneries 2,155,500
14% 48% Processed Foods 994,500
Beverages 639,000
Processed Dairy Products 508,500
Foods
22% Baked Foods 202,500

Figure 9.2.6 Starch products conumption in the food sector. Europe 2006.10

Confectioneries
Starches are widely used in confectioneries as binding or gelling agents. They
provide quick gelling action upon cooling and texture-stabilizing properties.
Starch-containing gum candies are typically prepared with thinned starches
that ensure a relatively low viscosity when cooked but then quickly form a gel
upon cooling. This rapid gel formation is also appreciated in gelled con-
fectioneries such as jelly beans and orange slices.
Maltodextrins are also used as a source of energy with sweetening activity in
the so-called ‘‘energy bars’’.
Glucose syrups are mainly used to control crystal size and texture in various
products.

Processed Foods
This market segment includes a wide variety of products with a very diverse set
of requirements on starch functionality. In dressings and sauces, starches have
to be stable at acidic pH and compatible with hydrophobic components such as
oils and fats.
The use of harsh processing conditions, food safety and the long-shelf-life
requirements are the major challenges for the starch product used in this segment.
In sauces and soups starch is used as a thickener that provides also a specific
texture and mouthfeel. Those functionalities are particularly critical in low-fat
products where starches are expected to provide the same textural and
mouthfeel experience commonly associated with conventional products.

Beverages
A significant amount of glucose syrups are used in this segment as sweeteners.
High Fructose Corn Syrup (HFCS), a glucose syrup with high concentration
Starch: A Versatile Product from Renewable Resources for Industrial Applications 247
of fructose, is used in soft drinks as sugar (saccharose) replacement with very
similar sweetness profile.
Glucose syrups are also used as fermentables in beer and alcohol production.
Finally, modified starches are used to encapsulate vitamins that are frequently
added to juices.

9.2.4 Pharmaceutical and Chemical Applications

The Pharmaceutical and Chemical Applications sector covers a wide range of
different uses of starch and is one of the most promising development areas for
carbohydrate chemistry in the future.
The following paragraphs give an overview of current industrial applications
of starch-related green chemistry in this area.

Drug Formulations
Starch is used in many solid formulations as binder, diluent and disintegrant.
A special grade suitable for direct compression has been developed for tablet
formulations.
Polyols and dextrose are used to impart a sweet taste to chewable tablets and
syrups.

Active Ingredients
Dextrose is an essential ingredient of intravenous and dialysis solutions. In
addition to its nutritional value, it allows the control of the liquid osmotic
pressure.
Maltodextrins develop lower osmotic pressure than low-molecular-weight
carbohydrates; therefore they are used at higher concentration without causing
stomach irritation.
Hydroxyethyl starches with specific molecular weights are commonly found
in formulations of plasma expanders, typically required after an accident or
surgery involving a large loss of blood. They can be used as a temporary
measure to restore blood volume, water and salts while the patient’s condition
is stabilized.

Acarbose Precursor
In 1990 the first drug of a new class of oral antidiabetic was commercialized
under the name of Acarbose (Glucobays)11 and used to treat type-2 diabetes
mellitus (Figure 9.2.7). Acarbose is an a-glucosidase inhibitor that acts by
competitive and reversible inhibition of a-amylase from the pancreas and a-
glucosidase. The inhibition of these enzymes results in a delayed absorption of
glucose from the gut and a reduced post-prandial increase in plasma glucose
and insulin.12
248 Chapter 9.2

HOCH2

HO
HO HO2HC
OH O
N
H HO HOCH2
OH O
O
HO
HOCH2
OH O
O
HO
OH
OH

Figure 9.2.7 Acarbose structure.

The structure of this drug is built on a maltotriose skeleton that is further

elaborated into the active product via a bioprocess. A special glucose syrup rich
in maltotriose is the ideal substrate for this process.

Sorbitol as a Humectant
Sorbitol offers a broad range of functional properties including: humectancy,
plasticizing ability, sweet taste, non-cariogenicity and good chemical stability in
harsh conditions such as alkaline pH and heat. Furthermore, it is a Generally
Recognized as Safe (GRAS) product by the United States Food and Drug
Administration (FDA).
Toothpaste production is the second largest application of sorbitol,
accounting for 50,000 mto a year in Western Europe alone. In the past,
toothpaste formulations were glycerine-based but almost every producer went
through a reformulation process to use sorbitol when the latter became avail-
able on an industrial scale.
With the recent drop in glycerine prices, the choice between sorbitol and
glycerin is now primarily determined by their price.
Other important uses of sorbitol as a humectant include formulation of
cough syrups, multivitamin preparations, emulsions and suspensions. Because
of its humectancy properties, sorbitol reduces the tendency of liquid formula-
tions to crystallize.

Glucose Syrups as Carbon Source for Fermentation Processes

Fermentation processes can be a valuable alternative to the conventional
chemical synthesis, particularly when the finished product contains specific and
complex stereochemistry.
Fermentation technology in the industrial synthesis of chemicals started to be
used in the first decades of the twentieth century. Industrial production of citric
Starch: A Versatile Product from Renewable Resources for Industrial Applications 249

Figure 9.2.8 Main products produced by fermentation.

acid by fermentation, achieved by Pfizer in 1923, was an early success in this

field. However, it was only with the production of penicillin during the Second
World War that the whole sector took off. Today, the range of products that
are produced by fermentation includes antibiotics, organic acids, aminoacids,
polysaccharides, vitamins, enzymes and, more recently, ethanol for biofuel use
(see Figure 9.2.8).
All the micro-organisms working in fermentation processes require the
fundamental building blocks for their synthesis: a source of carbon, a source of
nitrogen, salts and co-factors.
Saccharides and polysaccharides are the most common carbon sources used
as feedstock; glycerol and oils can be used to a lesser extent.
The fermentation sector is one of the largest consumers of glucose syrup,
accounting for some 600,000 tons of hydrolysate in Western Europe alone.
Over the last decade, mounting pressure on crude oil prices together with
a desire to move to more sustainable processes pushed many companies
to use the fermentation technology even for the synthesis of bulk chemicals.
The large-scale productions of lactic acid for polymers and of ethanol as biofuel
are two recent examples of this trend.

Biodegradable Plastics
Research efforts spanning eight decades have led to extensive improvements on
the performances of conventional plastics such as polypropylene, polyethylene
and polystyrene. On the other side, use of renewable materials in plastic
250 Chapter 9.2
production is still in an early stage, compared to traditional plastics, and still
suffers from some performance limitations and high costs.
Starch has been one of the first materials extensively studied for its potential
as polymer for biodegradable plastics. Impetus in this direction has come from
shortage of municipal landfills and pressure to reduce the visual pollution
caused by plastic residues abandoned in the landscape. Despite considerable
interest from both the academic and industrial sectors, production of com-
mercially viable materials has been delayed for technical and economic reasons.
The former are inherent to the chemical structure of starch itself: the vast
quantity of internal hydrogen bonds hampers thermoplastic behaviour, and the
hydrophilic nature of the polysaccharide translates into sensitivity to the
environmental humidity that, in its turn, may affect the mechanical properties
of the material.
With extensive efforts, these technical challenges have now been effec-
tively solved. Starch, in the presence of a suitable plasticizer, can be conver-
ted into a thermoplastic starch (TPS) that is suitable for conventional
plastic processing technologies, such as extrusion, film blowing, injection
moulding, etc. In addition, incorporation of polycapromolactone, poly-
vinylalcohol or other biodegradable and relatively hydrophobic polymers has
made it possible to effectively reduce the strong hydrophilic character of the
finished material.
The second factor hindering the development of starch-based material for
plastics has been the high cost of the technology required to solve the technical
issues, ultimately reflected in the cost of the finished products.
Today, there are products that satisfy the technical requirements and have
an acceptable market price. One commercial success story is represented by
Mater-bis,13 a plastic material based on TPS and other polymers that is very
versatile and suitable for applications such as composting bags, mulch film,
disposable cutlery, etc.14 However, due to the complexity of its production,
its cost is higher than conventional polyethylene or polypropylene, and it is
generally sold for applications where biodegradability is mandatory.
As legislation in several European countries is poised to limit the use of
shopping bags made of conventional polyethylene, it is likely that starch-based
materials will at least partially replace that type of plastic.
Expanded polystyrene (EPS) has been the sole packaging material for many
years and its extensive use has led to environmental concerns, partly because
of its visibility in landfills and partly because of the use of a chlorofluoro-
carbon, allegedly responsible for destroying the ozone layer, as blowing agent
during its production. Today, starch-based foam materials are commonly
produced and sold at a competitive price compared to EPS. They are biode-
gradable, have a very low density and, because of their better static electricity
insulating properties, are considered even superior to EPS for use in electronic
applications.
In 2007, about 73,640 metric tons of loose-fills made from starch were pro-
duced and consumed worldwide15 (Table 9.2.3).
Starch: A Versatile Product from Renewable Resources for Industrial Applications 251
Table 9.2.3 Global biodegradable polymer market (mto) – adapted from
Schlechter.15
Application 2006 2007 2012

Compost Bags 78,636 110,000 266,363

Loose-Fill Packaging 69,091 73,636 97,273
Other Packaginga 23,182 36,818 105,454
Miscellaneousb 15,000 25,455 77,727
Total 185,909 245,909 546,818
a
Includes medical/hygiene products, agricultural, paper coating, etc.
b
Unidentified biodegradable polymers.

Plasticizers
In general, polyols have good plasticizing properties, especially when it comes
to plasticizing carbohydrate-based products such as TPS. They have a dual
action: as primary plasticizers, altering the interaction between adjacent poly-
saccharide chains, and secondary plasticizers ensuring the presence of water –
the most efficient plasticizer for carbohydrates.
All starch-based plastics on the market contain polyols such as sorbitol,
glycerol or mixtures thereof ensuring flexibility and mechanical properties
stability of the finished product.

Formaldehyde-based Resins
The presence of numerous hydroxyl groups able to react with formaldehyde
makes starch-derived products suitable chemicals for formaldehyde-based
resins. Research on this subject started many years ago and showed that
in a number of applications it is possible to partially replace or ‘‘extend’’
urea formaldehyde, phenol formaldehyde and melamine formaldehyde resins
without significantly affecting the finished product’s performance.16 In many
applications, adhesive systems based on formaldehyde resins incorporate a
polysaccharide component. More than 4.5 Mio mto of formaldehyde-
based resins have been produced in Western Europe alone.17 The use of car-
bohydrates allows lower consumption of oil-based resins and, consequently,
reduced release of formaldehyde in the environment.

Chemical Synthesis
L-Ascorbic acid, known as vitamin C, occurs naturally in a number of sources
such as citrus fruit, berries, kiwi fruit and green vegetables. Because of its
pharmaceutical and nutritional value, ever since its discovery there has been a
strong interest in obtaining it by chemical synthesis. In 1934 Haworth was
awarded the Nobel Prize for establishing the first industrial process for the
synthesis of vitamin C, but the process is named after the Polish chemist Tadeus
252 Chapter 9.2

Reichstein process 2 Fermentation steps Single fermentation step

OH

OH
O
O

OH OH

L-Ascorbic acid
Vitamin C

Figure 9.2.9 Processes for the synthesis of vitamin C.

Reichstein, who arrived independently at the same process somewhat earlier

than Haworth.
Today, the bulk of vitamin C is produced via a ‘‘2 fermentation steps’’
reaction sequence in which L-sorbose is converted into 2-keto-L-gulonic acid
(KGA) by fermentation (Figure 9.2.9).
The production of vitamin C without isolation of KGA has remained elusive,
at least on an industrial scale, but studies in that direction are ongoing.
The current world production of vitamin C can be estimated to be as much as
80,000 tons per year consuming more than 140,000 tons of Sorbitol (100% dry
substance).
The development of surfactants based on carbohydrates and oils is an
interesting expression of ‘‘green chemistry’’ that led, among others, to two new
classes of surfactants: the alkyl polyglycosides and the sorbitan esters.
After 10 years of development work, Rohm & Haas introduced on the market
the first alkyl polyglycosides in the late 1970s. These were based on short
hydrophobic chains (C8–C10) and had poor colour quality. Their application
was limited to a few market segments such as the industrial and institutional
sectors. In the 1980s other companies, among them Henkel KGaA, developed
new APGs surfactants with different alkyl chains and with an improved colour
quality that allowed the penetration of these products in very demanding market
segments such as the cosmetic and the detergents industries.
Starch: A Versatile Product from Renewable Resources for Industrial Applications 253

CH2OH H O CH2 R = C10 - C22

n= 0-5
O O
OH R OH OH O CH2
H+
OH O
OH OH
OH O R
OH OH
n OH

OH

Figure 9.2.10 APGs synthesis scheme.

Despite many possible alternatives, the industrial production is still based on

the ‘‘Fischer glycosidation’’ process that relies on the acid-catalyzed reaction of
dextrose with fatty alcohols (see Figure 9.2.10). Dextrose monohydrate under the
form of fine particle solids is suspended in a fatty alcohol acting as solvent and as
reagent at the same time. The heterogeneous mixture is heated to evaporate
immediately the crystallization water of dextrose firstly and the water coming
from the condensation reaction as long as it is formed to drive the equilibrium
towards the finished product. After cooling, separation of the by-products and a
purification process, alkyl polyglycosides are isolated as a mixture of dextrose
oligomers condensated with the fatty alcohols.18 In general, commercial APGs
surfactants contain different derivatized dextrose oligomers with an average
degree of polymerization of 1.4 moles of glucose per mole of fatty alcohol.
Alkyl polyglycosides are known as very efficient wetting and dispersing
agents that are readily biodegradable and have very low toxicity. They are
stable in neutral and alkaline conditions; they tolerate a high salt concentra-
tion, and are compatible with many other surfactants.
Today alkyl polyglycosides are a typical ingredient in many cosmetics and in
lightweight dishwashing formulations. Cognis (formerly Henkel) is the largest
European producer with 25,000 tons capacity installed followed by Lamberti,
SEPPIC and Akzo Nobel.
The esterification of a liquid solution of sorbitol with fatty acids leads
to a variety of mild tensioactive agents commonly known as sorbitan esters.
Under esterification conditions and high temperature (42001C), sorbitol
undergoes an internal dehydration reaction to give a tetrahydrofuran structure
(sorbitan) that is esterified by the fatty acid mainly on the primary hydroxyl
group (see Figure 9.2.11). When an excess of fatty acid is used, di-esters and tri-
esters are obtained. These sorbitan esters are commonly referred to as Spans.
They have low water solubility but are soluble in most cosmetic oils. They are
typically used as water-in-oil (O/W) emulsifiers.
Sorbitan esters can be further reacted with ethylene oxide to introduce poly-
oxyalkylene chains that result in a significant increase of the surfactant’s water
solubility. These products are commonly referred to as Tweens or polysorbates.
254 Chapter 9.2
R = Alkyl
x, y, z = 4 -20 H2 H2
CH2OH OH O C C OH
x
H OH H2 H2
HC C O R O HC C O R
HO H O O
R-COOH
H OH H+ O OH− O

H OH H2 H2 H2 H2
OH OH HO C C O O C C OH
y z
CH2OH

S o r b ita n e s te r Ethoxylated sorbitan ester

Polysorbate

Figure 9.2.11 Sorbitan esters and polysorbates synthesis scheme.

Sorbitan esters are often used in the food industry, especially in chocolate
and margarine production, where a high affinity for fats is desired.
Polysorbates are also commonly used as (O/W) emulsifiers in the food
industry (salad dressing, ice cream), and in cosmetics, pharmaceuticals, deter-
gents, and in a myriad of other industrial applications. Current Western Eur-
ope consumption of sorbitol for surfactants manufacture can be estimated at
around 15,000 tons per year.
To produce polyether polyols (PEP), sorbitol is reacted in the presence of a
catalyst with propylene or ethylene oxide (see Figure 9.2.12). The reaction is
aimed at achieving polyols with a hydroxyl numberii of between 350 and 550.
Sorbitol-based PEPs are then used to manufacture rigid or semi-rigid poly-
urethane foams by reaction with a suitable polyisocyanate. These foams are
typically used in the construction industry and in packaging, industrial insu-
lation, appliances and transport applications.
Sorbitol, sucrose, pentaerythritol and other polyalcohols or polyamines are
used for the preparation of PEP for rigid foams where structures with high
cross-linking density are required, while glycerol is mainly used for flexible
foam production. Some PEP producers modulate the rigidity of the foam by
using blends of sorbitol and glycerol in different ratios.
Simple carbohydrates and polyols have mild metal-complexing properties
that are generally not good enough for industrial applications. However, it is
sufficient to introduce a carboxylic group to significantly enhance this func-
tionality. Today, two chemicals derived from glucose are used as sequestrant:
gluconic acid and glucoheptonic acid.
Gluconic acid is commonly obtained by fermentation while glucoheptonic
acid is synthesized from the cyanohydrin of glucose (see Figure 9.2.13).
These organic acids and their derivatives are mainly used as additives for
concrete admixtures, in industrial cleaning formulations, metal finishing and
agricultural applications. The functionality of gluconic and glucoheptonic acids
in these applications, except for concrete, is based on their complexing ability
towards polyvalent metal ions such as calcium, magnesium, iron, zinc, etc.

ii
Hydroxyl number is defined as the number of milligrams of KOH that is chemically equivalent to
the activity of one gram of the polyol.
Starch: A Versatile Product from Renewable Resources for Industrial Applications 255
OH
H2
O C C CH3
OH H2 H
H H2C OH H2 H H2C O C C CH3
H3C C C O H OH
H H2 H2
HO H H3C C C O H O C C CH3
H H H H2 H
OH OH- O C CH CH3
H H2 H2
OH O O C CH CH3
HO H3C C C O
H H2 H2 H
H H3C C C O H O C C CH3
H2C H2C
OH OH
OH O
H
H2C C CH3
H2 H
O C C CH3

OH
Sorbitol Polyether polyol

Figure 9.2.12 Polyether polyols synthesis scheme.

O OH

H OH

HO H gluconic acid
Aspergillus niger H OH
O H
H OH

CH2OH
H OH

HO H
O OH
H OH

H OH CHOH
1. CN-
CH2OH H OH

glucoheptonic acid
2. Saponification HO H

H OH

H OH

CH2OH

Figure 9.2.13 Gluconic and glucoheptonic acids from D-glucose.

256 Chapter 9.2

OH

O O

HO OH

OH

Figure 9.2.14 Glucono delta-lactone.

Differently from citrates and EDTA, they effectively chelate ions in strongly
alkaline solutions and they are biodegradable.
Sodium gluconate is also the precursor of Glucono-delta-lactone (Figure
9.2.14), its cyclic internal ether, a product used in the food industry to control pH.
Calcium and ferrous gluconates are used in the treatment of calcium and iron
deficiencies as well.

9.2.5 Industrial Binder Applications

One of the most widely known functionalities of starch is its capacity to bind
materials together. Its polymeric structure combined with a strong tendency to
form hydrogen bonds make starch an excellent adhesive, capable of binding
many different materials, such as paper, wood, coal, etc.
Starch has been used as a natural adhesive for centuries, and even now in the
presence of synthetic alternatives, it holds a significant market share in this
application.

Coal Briquettes
During the production of coal briquettes, coal dust is mixed with starch and
water before heating and compression into an ovoidal shape. Once gelatinized,
starch provides structural support to the briquette shape and ensures that the
structure is maintained during transport of the briquette to the oven on the
conveyor belt. Once the briquette is dry, starch provides another interesting
functionality that can be appreciated during the actual use of the briquette.
When starch is exposed to high temperatures (as during combustion) a
decomposition process starts. Among the possible decomposition pathways,
one leads to the formation of a carbon skeleton that no longer burns but acts as
a supporting structure for the briquette, increasing exposure of the coal to the
air flow. This results in a better combustion and glowing of the briquette.
Starch: A Versatile Product from Renewable Resources for Industrial Applications 257
plaster (gypsum) mix
water
card board
(back side) cutter
turn over machine
foamer
hydration belt

conveyor belt length 200 - 400 m

conveyor belt speed 40 - 120 m/min

card board drying oven

(view side) region 4 region 3 region 2 region 1
cooling area < 100°C ~180°C ~230°C air temperature

finishing
store e.g. edge polish

drying oven length 100 - 150 m

Figure 9.2.15 Gyspum board production process.

Gypsum Boards
Gypsum boards or plasterboards are typical materials used to build light walls.
The production process is based on gypsum hydration technology. At the very
beginning of the process de-hydrated calcium sulphate (gypsum) is converted
into CaSO4
0.5H2O by heating. Once dehydrated, gypsum is mixed with
starch, a foaming agent and other additives. Gypsum foam is then obtained
and spread onto cardboard running on a conveyor belt (see Figure 9.2.15).
CaSO4
0.5H2O starts the hydration and the crystallization process immedi-
ately after coming into contact with water to form CaSO4
2H2O. The new
crystals have a needle-like structure and interlock with each other creating a
solid, firm structure. The crystallization of CaSO4
2H2O generates heat that
helps starch gelatinize and migrate towards the cardboard.
During the drying phase, starch completes the gelatinization process and
concentrates in the interface between gypsum and paper, where it functions as
adhesive between the two materials.

9.2.6 Paper and Board Applications

The use of starch in papermaking is probably one of its oldest non-food
applications. An old Egyptian paper document dating from 3500 BC shows that
starch was already used for sizing. Starch as a sizing agent was also used in
China, as documented by a paper document dating from AD 312 that was sized
with starch.
258 Chapter 9.2

Wet-end, Surface Sizing and Coating

After fibres and fillers, starch is still the third most important raw material for
paper making. Various types of modified starches are applied throughout the
papermaking process from the wet-end via the size- or film-press to coating and
paper converting.
The papermaking process (Figure 9.2.16) consists essentially in continuously
forming, dewatering, pressing and drying a web of cellulose fibres.
At the beginning of the process, a dilute (99% water) pulp slurry containing
fibres, fillers, optical brightening agents and other additives is laid down to a
wire screen to form a very loose bed of fibres. This is the wet-end part of the
process in which cationic starch is used to impart the necessary strength
properties for the paper web to be formed by associating with the anionic
i.e. negatively charged cellulose fibres and inorganic fillers.
The next phase consists of the removal of the water by hydrodynamic and
suction devices. When non-cationic starches were still used during this process,
the majority of it (70% according to some authors) would be lost to the was-
tewater. On the other side, when a suitable cationic starch is used, then over
90% of it stays with the paper web.
The remaining water is then removed in a mechanical press device (press
section) working like a mangle. After that step the paper has a water content of
approximately 50%. This water cannot be mechanically removed but has to be
evaporated by a system of steam-heated rolls (first drying section) to achieve a
water content of 1–7%. At this point some paper grades are ready e.g. news-
print. Other grades of paper that need a further strengthening are impregnated
with a solution of starch alone or in combination with other functional che-
micals in a size- or film-press. As a result the surface of the paper becomes
better suited for printing and the paper strength is increased. A variety of

Machine
Chest Headbox Fourdrinier Presses Drying Film Coating Reeling
(Wire Section) Section Press
After
Dryers IR Dryer

Wet-End Surface Sizing Coating

Unthinned, cooked cationic A solution of thinned, A highly concentrated solution of
starch is added to the fibre cooked starch is applied thinned, cooked starch is used
as a dilute solution to the paper web. The as single or cobinder for the
(normally far before the viscosity and pigments.
headbox). concentration are The choice of starch amount and
increase paper strength adjusted to produce type depends on the type of
optimal penetration and coating unit, machine speed and
runnability. paper grade.

increase strength and Improve printability

improve printability

Figure 9.2.16 Papermaking process scheme.

Starch: A Versatile Product from Renewable Resources for Industrial Applications 259
starches can be used for this part of the process, the common denominator
being the continuous film-forming ability to avoid cracks, a low viscosity to be
able to operate at relatively high dry substance, and the whiteness of the pro-
duct. Commonly used products here are: oxidized starches, hydroxypropylated
starches and other stabilized starches.
After the surface-sizing section, the paper is dried again by an array of steam-
heated rolls (after-drying section) to a moisture content of 6–8%. After an
additional smoothing step calendar grades like e.g. office papers and packaging
papers are ready for use.
For higher demands with respect to gloss and printability an additional
finishing step is performed in which a coating colour consisting of inorganic
pigments like calcium carbonates and clays together with binders and further
functional additives is applied to the paper surface. This step can be performed
only once on one or both sides of the paper or repeated several times in a
sequence. After each application of a coating colour a drying step is necessary
that mostly is done by a sequence of infrared, hot air and contact drying. At
the end these papers are calendered to develop the desired gloss level. In coating
formulations starch may be used alone or in combination with synthetic lattices
to bind the pigments to each other and to the surface of the paper. The starches
used for coating applications must fulfil more stringent requirements with
respect to rheology, stability and paste solids than surface sizing starches.

Corrugated Board
A corrugated board is composed by a fluting medium (the wavy part of cor-
rugated board) glued between two layers of linerboard to achieve a very strong
structure. Very often, the paper used for the boards is recycled paper that has
been surface sized with starch to reach a good strength. The glue used to bind
the tips of the flutes to the linerboards is made of starches, caustic soda and
borax. Special equipment is used to automatically prepare glues with the right
viscosity and gel point for the variety of corrugated board qualities to be
produced. This glue is applied to the tips of the flutes that are then contacted
with the liner which is subsequently taken over a heated plate. Upon heating,
the starch gelatinizes and forms a strong bond between the flutes and the
linerboard. These steps are repeated on the other side of the fluting to create the
known sandwich structure of corrugated board.

9.2.7 Outlook
Starch and its derivatives have proven to be very versatile materials for several
different applications in many sectors. With relatively simple carbohydrate
chemistry it has been possible to have access to carbohydrates with superior
functionalities. There is still considerable potential to generate innovative
solutions based on starch but this requires a better understanding of the starch
chemistry and a strong cooperation between the agro-industry and the chemical
260 Chapter 9.2
industry. This cooperation is necessary for the starch industry to overcome the
challenges associated with the complex nature of starch and is beneficial also to
the chemical industry in its search for new and sustainable products to exploit.
Ambitious projects are already taking place and are expected to be successful
in a few years. A few of them are mentioned below.

Isosorbide and Isosorbide Derivatives

Cyclization of sorbitol in suitable conditions results in the formation of the
4,8-dihydroxy-cis-2,6-dioxa-bicyclo[3.3.0]octane, also known as 1,4:3,6-
dianhydro-D-sorbitol or Isosorbide (Figure 9.2.17).
This product is relatively expensive and is currently used in modest quantities
mainly for pharmaceutical applications as a chemical intermediate.
However, Isosorbide has significant potential in the plastics sector as
a new monomer for polymerization. For example, a modified poly-
ethyleneterephthalate (PET) can be synthesized when Isosorbide is incorpo-
rated during polymerization.19 Isosorbide’s structural rigidity increases the
stiffness of the PET chains and raises the glass transition temperature of this
plastic giving better performances than conventional PET and requiring less
material to produce an equivalent article.
In the field of plasticizers for PVC, some isosorbide esters give functional
performance equivalent to some of the most widely criticized phthalates, such
as DEHP.20 As phthalates are used in a wide number of applications (PVC
plasticizer, cosmetics, inks, lubricants, etc.) there is significant potential for
isosorbide derivatives as an alternative to phthalates.
Dimethyl isosorbide (DMI) is a colourless liquid with excellent solvent
properties. DMI has extremely low toxicity and facilitates the penetration of
active ingredients through the epidermis. It has shown interesting properties
in the delivery of substances like lactic acid, hydrocortisone, vitamin C and
hyaluronic acid. It is a solvent with clear potential for cosmetic and pharma-
ceutical applications.
The challenge that is common to all these projects is the establishment of an
industrial process that give access to a cost-competitive Isosorbide.

H
O
H O H
H

H H
H H
O

H OH

Figure 9.2.17 Isosorbide structure.

Starch: A Versatile Product from Renewable Resources for Industrial Applications 261

Figure 9.2.18 Starch-based product family tree.

New Molecules by Fermentation

Fast increasing crude oil prices and projected dwindling output mean that
fermentation processes become more and more attractive. There are indeed a
number of industrial projects aimed at producing relatively simple chemicals by
fermentation, notably methionine, acrylic acid and succinic acid.
262 Chapter 9.2
As these molecules do not require a complex chemical synthesis, one of the
main challenges will consist in achieving fermentation processes that are eco-
nomically sound. In addition to the economics, those processes may be pre-
ferable when they lead to substantial reductions in the production of CO2 and
the use of non-renewable raw materials, in line with the fundamental tenets of a
‘‘sustainable economy’’.

Starch as Part of the Biorefinery Concept

Renewable raw materials and their derivatives have been integrated in the
industrial world for a long time. With a relatively small chemical effort, it has
been possible to modify their structures and their functionalities in such a way
that they became accepted even in the chemical industry as building blocks.
Nevertheless, the volume of starch-derived products used for the technical
industry is still very low when compared to the oil-based products.
In the last decade, the increasing cost of oil-based products has stimu-
lated many efforts in finding sustainable alternatives. In that perspective, starch
is a very promising material because it can be used as a source for several
chemicals (see Figure 9.2.18). However, significant progress has still to be made
in many disciplines including chemistry, biotechnology and microbiology,
before we can handle the complexity of renewable raw material with the same
efficiency that has been set as standard by the petrochemical industry.

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15. M. Schlechter, BCC Research Report: PLS025C, 2007, Wellesley, Massa-
chussets, USA.
16. H. Koch, F. Krause, R. Steffan and H. U. Woelk, Die Stärke – Starch,
1983, 35(9), 304–313.
17. S. N. Bizzari, ed., SRI Consulting, CEH Marketing Research Report
‘‘Formaldehyde’’, 2004.
18. R. Eskuchen and M. Nitsche, in Alkyl Polyglycosides: Technology, Prop-
erties, and Applications, ed. K. Hill, W. Rybinski and G. Stoll, VCH,
Weinheim, 1996, pp. 9–22.
19. D. J. Adelman, L. F. Charbonneau and S. Ung, WO 2003106531, 2003
(Du Pont de Nemours).
20. H. Luitjes and J. C. Jansen, WO9945060, 1998 (ATO-DLO).
CHAPTER 9.3

Industrial Sucrose
STEFAN FRENZEL, SIEGFRIED PETERS, THOMAS
ROSE AND MARKWART KUNZ

Südzucker AG, Marktbreiter Straße 74, D-97199, Ochsenfurt, Germany

Sucrose, also called saccharose, or in general sugar, is produced on the

industrial scale from sugar beet or sugar cane with a present annual production
of 161 Mio mto (centrifugal sugar 2006/2007).1 Thereby about a quarter of the
total sugar produced is derived from sugar beet, three-quarters from sugar
cane (Figure 9.3.1). Whilst the beet sugar amount has been quite constant
during the last decades, the sugar production from cane has increased distinctly
from the 1960s onwards.
Though the total amount of sugar produced increased dramatically during
the past decades, today’s world market price of sugar is comparable to that 20
years ago. Nevertheless, the price has been fluctuating dramatically (Figure
9.3.2) between 100 and 400 US$ mto1 (raw sugar) and 160–500 US$ mto1
(white sugar).
Sucrose is the most available low-molecular-weight carbohydrate but until
now was mainly used for nutrition purposes and for the fermentation industry –
above all for the production of bioethanol, citric acid and lactic acid – and only
to a smaller extent as chemical feedstock.2 Though the use of renewable
resources in biotechnological processes has increased in the last years,3,4 there is
a strong price-driven competition between sucrose and starch as raw materials
for fermentative processes being influenced by regional differences.
Due to the predicted shortage of fossil resources within the next few decades,
a move from fossil resources towards renewables appears to become more and

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

264
Industrial Sucrose 265

World production of beet and cane sugar (Including noncentrifugal sugar)

200,0
180,0 Beet sugar
160,0 Cane sugar
Total
Amount [mill tons]

140,0
120,0
100,0
80,0
60,0
40,0
20,0
0,0
1900 1920 1940 1960 1980 2000 2020

Figure 9.3.1 World production of beet and cane sugar since 1900.1

Price Development of Raw and White Sugar since 1988

520
500
480
460
440
420
NY n°11 LIFFE n°5
400
380
360
340
320
300
USD/T

280
260
240
220
200
180
160
140
120
100
80
60
40
20
8

/0 88

7
08
98

05 198

27 199

17 199

04 199

26 199

24 199

25 199

21 199

11 199

02 199

05 199

02 199

28 199

22 200

14 200

11 200

03 200

26 200

11 200

30 200

20 200

16 200

06 200
9

20
/1

/1
8/

6/

3/

1/

1/

8/

6/

4/

2/

2/

0/

8/

6/

3/

1/

1/

9/

7/

4/

2/

1/

9/

7/

5/
1

0
/0

/1

/0

/0

/0

/1

/0

/0

/0

/0

/1

/1

/0

/0

/0

/0

/1

/0

/0

/0

/0

/1

/0

/0

/0
04

20

11

Figure 9.3.2 Price development of raw sugar and white sugar during the last two
decades.

more imperative.5 Thus, sucrose is depicted to be predestined, on renewable

sources based organic compounds, for becoming an alternative feedstock for
many up to now still petrochemically derived products or product applications.
Many approaches to utilize sucrose as raw material for different organic che-
micals have been attempted within the last decades but only a few are successful
today (Section 9.3.2).2
266 Chapter 9.3
6–9
9.3.1 Industrial Production of Sucrose
The technology applied to extract, purify and crystallize sucrose and thus
finally the overall economy of the process is governed to a large extent by
the sucrose companion compounds and the physical texture of the plant
material.
The differences in technology for processing sugar beet and sugar cane
follow essentially the differences in the monosaccharides content, in the high
fibre content of the cane and the physical characteristics (texture) of beet
and cane (Table 9.3.1). Sucrose as an acetal is sensitive to acids and increasingly
hydrolyzes into glucose and fructose with decreasing pH value. Therefore,
for conservation of sucrose it is an advantage to apply alkaline processing
conditions, whereas the monosaccharides (glucose and fructose) are stable
under acidic conditions but react under alkaline conditions to form acids and
colours.
Continuous efforts are made in the breeding and cultivation of sugar beet in
order to reduce the non-sugar compounds in the crop, increasing the sugar
yield and decreasing the environmental impact. Figure 9.3.3 shows the con-
tinuous reduction of the specific mineral fertilizer consumption in the last
decades for the sugar beet cultivation.
The application of herbicides for the cultivation of sugar beet could also be
reduced very significantly (2.0 kg t1 sugar in 1975–1980 to 0.7 kg t1 sugar in
2007). Further improvements – e.g. reduction of the application of chemicals and
primary energy – will be achieved by using new beet varieties including the
potential of green biotechnology.
The residues from cane extraction (bagasse) are mainly used to fire steam-
generators because their commercial energy value is higher than their feed value
and thus a cane-sugar factory is operated independently from an external
power supply. This means that certain process design principles, mainly
regarding energy-saving technologies, applied in the beet sugar industry are
even today less important for cane sugar processing.

Table 9.3.1 Contents relevant to the process engineering and properties of

sugar beet and cane.
Content Beet Cane

Water content [g/100 g] 75–77 73–76

Dry mass (DM) content [g/100 g] 23–25 24–27
Non-water-soluble compounds [g/100 g] Marc 4.5–5 Fibre 12–14
Sugar content [g/100 g] 14–20 12–14
Monosaccharides [g/100 g DM] 0.5–1 4–8
Raffinose [g/100 g DM] 0.2–0.5
Amide content [g/100 g DM] 0.5 0.9
Oxalic acid [g/100 g DM] 0.2 0.1
Aconitic acid [g/100 g DM] 1.5
Other technologically-relevant compounds Pectin Dextran
Industrial Sucrose 267

kg fertilizer / t sugar / ha
30
N
25 P2O5
K2O
20

15

10

0
80

82

84

86

88

90

92

94

96

98

00

02

04

06
19

19

19

19

19

19

19

19

19

19

20

20

20

20
Figure 9.3.3 Trend of the consumption of mineral fertilizer for sugar beet cultivation
in southern Germany.

Sugar Manufacture in the Beet Sugar Industry

In Central Europe, harvesting of the sugar beet and thus its processing nor-
mally begins in mid to end September and continues until December or Jan-
uary. The dissimilation of the sucrose in stored beets starts directly after
harvesting. Therefore, to reach the best possible sugar yield, every effort is
made to process the beets as soon as possible after harvesting.
After being washed (for total process overview cf. Figure 9.3.5) the beets are
sliced into strips (cossettes), which afterwards are fed into the so-called diffusers
where about 98% of the sucrose is extracted. High temperatures (65–70 1C) in
the diffusion apparatus denature the plant cells and open the cell membranes
for improved sucrose transfer. The entire extraction of the sucrose is carried out
via a counter current flow of the extraction medium, i.e. water and the dena-
tured cossettes.
The cossettes leave the diffusion plant after about 70 minutes residence time
and are pressed by screw presses to a dry matter content of about 30% followed
by a thermal drying in revolving drum driers. The dried cossettes compressed to
pellets represent a valuable and storable animal feed.
The extract contains, in addition to the sucrose, further solved or colloidally
dispersed components, which in the juice purification stage must be – as far as
possible – precipitated or destroyed under alkaline conditions by adding calcium
oxide. This is carried out by a multi-stage, continuous treatment with, first,
calcium oxide and, second, carbon dioxide. Both processing aids are produced in
a separate calcining process in parallel. The excess calcium oxide is precipitated
in so-called carbonation vessels with carbon dioxide from the calcining process.
All precipitates and deposits are separated in a multi-step filtration. The sludge
268 Chapter 9.3
produced contains lime, phosphate and other valuable compounds and is sold as
fertilizer (carbonation lime). For technological, ecological or economic reasons
the use of limited amounts of other processing aids, like anti-scalants or floc-
culants, may be necessary. They are used in accordance with good manu-
facturing practice and applicable food law regulations.
The clarified raw juice is called ‘‘thin juice’’ and contains between 14 and
16% of sucrose. Before crystallization, the sucrose content is enriched close to
its solubility limit by evaporation of water in an energy efficient (6–7 effect)
multi-stage evaporator station. Steam and thin juice run through a series of
apparatus, each part of which is at a gradually lower pressure, until finally an
intermediate but storable product, the so-called ‘‘thick juice’’, with 65 to 70%
of dry matter content is produced. The beet sugar industry has improved the
overall energy efficiency for white sugar production within the last decades
significantly (Figure 9.3.4).
The thick juice is fed into evaporator crystallizers in which a further gentle
concentrating under vacuum (0.2 bar abs.) is carried out to supersaturate the
solution. After adding seed crystals, crystal growth proceeds via parallel further
evaporation and reduction of progressing supersaturation through crystal-
lization. For mechanical reasons, the crystallization is finished at about 50%
crystal content.
The crystal magma is fed into a centrifuge in which syrup (mother liquor) is
separated from the sucrose crystals by centrifugation. The resulting white sugar

7.000

trend of the specific energy demand

6.000
for the production of white sugar
in the beet industry
5.000
kWh / t white sugar

4.000

3.000

2.000

1.000

0
19 /51
19 /54
19 /57
19 /60
19 /63
19 /66
19 /69
19 /72
19 /75
19 /78
19 /81
19 /84
19 /87
19 /90

19 93
19 /96
20 /99
20 /02
20 /05

8
/0
/
50
53
56
59
62
65
68
71
74
77
80
83
86
89
92

95
98
01
04
07
19

year

Figure 9.3.4 Specific energy demand for the production of white sugar in the beet
industry.
Industrial Sucrose 269
Cane Beet

Washing Washing

Cutting/
Slicing
Crushing

Fuel for Pellets

Bagasse Milling Diffusion Pulp Drying
Boiler House Animal Feed

Raw Juice

Removed Juice Purification

Nonsugar Liming & Carbonatation CaO Calcining
Fertilizer CaCO3
Carbonation Sulfitation CO2 Process
Sludge Phosphatation

Thin Juice

Evaporation

Thick Juice

Crystallisation
Run off to be
recrystallised
Molasses Centrifugation

Sugar Drying & Storage

Figure 9.3.5 Process for cane and beet sugar production.

with a residual moisture content of about 0.5% is dried and cooled for the
subsequent storage.
The syrup (mother liquor) separated in the centrifuge still contains sucrose
which has to be recovered in further crystallization steps. In this way, there is a
multi-stage process of crystallization yielding a final mother liquor (known as
molasses) from which the sucrose cannot be economically further crystallized.
Depending on the economy – i.e. price of sugar crystallized vs. price of sugar
in the molasses – in some regions of the world further extraction of sucrose
using chromatography is applied.

Sugar Production in the Cane Sugar Industry

Storage of sugar cane is associated with a more intense hydrolysis of sucrose
than in sugar beet. The cane must be processed with a minimum of delay after
harvesting. The sucrose is stored in the innermost pith of the sugar cane and
must be made accessible to extraction by destruction of the highly resistant
outer skin. The cane is cut into short pieces by rotating knives and further
crushed in so-called shredders (usually five). After shredding, the cane passes a
multi-stage pressing and extracting – by adding water – process to separate the
sucrose containing extract from the bagasse. The bagasse (25–30 kg per 100 kg
cane) produced is normally adequately used to satisfy the energy demand of a
cane sugar mill with bagasse-fired boilers.
270 Chapter 9.3
With approximately 105–110% of the initial weight of the sugar cane, the
extract is a slightly acidic raw juice which is characterized by a high content of
invert sugar (some ten times higher than in sugar beet extracts) and high
molecular companion compounds (e.g. dextran and starch). Unlike the classic
juice purification process in the beet sugar industry, the invert sugar cannot be
destroyed using strong alkaline conditions because high by-product and colour
formation would be the consequence prohibiting commercial white sugar
production. Thus high pH values and high temperatures have to be avoided in
the following processing steps.
For producing raw cane sugar precipitating of non-sucrose juice constituents
by the addition of calcium hydroxide while heating is widely practised. Various
versions of this method are applied (cold and hot liming, fractionated liming
with double heating). Phosphate content of the juices plays a significant role.
The dehydrated and flocculated hydrocolloids in the raw juice are well wrapped
by calcium phosphate, which improves their sedimentation ability as well as the
filterability.
The production of juices for the direct manufacture of white sugar requires a
more thorough elimination of non-sucrose compounds. This is achieved in the
sulphitation process by the addition of milk of lime and sulphur dioxide and
removal of calcium sulphite.
The purified juice (thin juice) with a dry mass content of some 15% is con-
centrated in a multi-stage evaporator station to 60–70% (thick juice).
Crystallization of the sucrose in the thick juice is carried out in the same
way as in the beet sugar industry (see above). The high proportion of invert
sugar has a marked effect on the residual sugar content in the cane molasses:
the purity of the cane molasses, at about 40% (true purity), is distinctly
lower than in the beet molasses, because the invert sugar content (up to 20%)
reduces the solubility of sucrose and thus facilitates the crystallization of the
sucrose.
Usually in sugar cane processing factories white commercial sugar – so-called
plantation white – is only produced for domestic consumption; most often, raw
sugar is produced. Raw sugar is traded on the world market and loaded and
transported in bulk to refineries overseas. Raw sugar, because of its often
critical hygienic status, is generally unfit for direct human consumption and
therefore requires further processing into commercial sugar.
Today, raw sugar and bioethanol production using the mother liquors of
sugar crystallization are executed very often in parallel.

9.3.2 Chemistry of the Sucrose Molecule

Sucrose (b-D-fructofuranosyl a-D-glucopyranoside, Figure 9.3.6) is a dis-
accharide of anomerically linked D-glucose and D-fructose, thus being a non-
reducing sugar. Under acidic conditions hydrolysis of sucrose into these two
building blocks occurs.
Industrial Sucrose 271

OH
6

HO 4
O
5
2
HO 3
1

HO
α
HO 6'
O
O
5' HO 2' β
4'
3' 1' OH
OH

Figure 9.3.6 Sucrose (b-D-fructofuranosyl a-D-glucopyranoside).

Sucrose could be valorized to promising organic chemicals by three main

material transformation pathways.

1. Degradation of the sucrose framework: Reactions or reaction cascades,

including dehydration/rehydration, ring opening/closure, bond scission/
formation lead to structures being of known value from petrochemically
derived compounds, but are based on the renewable feedstock sucrose, the
most prominent representatives being bioethanol and 5-hydroxymethyl
furfural (HMF).
2. Derivatization by maintaining the sucrose skeleton: The eight OH groups of
sucrose could be utilized for chemical reactions, thereby preserving the
original sucrose structure as such. Three of those OH groups are primary
(6, 1 0 , 6 0 ) and five of them secondary ones. Nevertheless, their chemical
differentiation and selectivity is not that simple like the different reactivity
order of primary and secondary OH groups in other polyhydroxy com-
pounds. In aqueous solutions hydrogen bond connections between OH-2
and OH-1 0 /OH-3 0 clearly influence these OH groups by electron with-
drawing effects. The OH-2 group is thereby the most acidic one. The type
of reaction and the applied conditions – like the solvents – have a con-
siderable impact on the selectivity, the degree of substitution and the
regiochemistry.2,10
3. Rearrangements/Reactions maintaining carbohydrate structure: Inversion
of sucrose to D-glucose and D-fructose is the simplest example, others –
more complicated ones – are the enzymatic rearrangements of the
sucrose building blocks (D-glucose and D-fructose) into more complex
carbohydrates.

The following examples give an overview about possible material transforma-

tions of sucrose leading to valuable chemical intermediates for industrial bulk-
scale production, some of them being industrially implemented today. The three
272 Chapter 9.3
mentioned reaction pathways, with and without retention of the sucrose skeleton
and reactions leading to new carbohydrate structures, are thereby addressed.

9.3.2.1 Basic Organic Chemicals by Sucrose Degradation

Degradation of sucrose under elevated temperature and pressure conditions
leads to a variety of chemical compounds either being known from petro-
chemicals or resembling petrochemicals in their structure having the potential
of replacing non-renewables.11 Also, fermentation of sucrose leads to ‘‘degra-
dation’’ products. The most important example is bioethanol.

9.3.2.1.1 Bio-ethylene
One example for a successful effort to utilize sucrose as feedstock for the
manufacture of bulk organic chemicals is the production of ‘‘green’’ ethylene
from sugar via bio-ethanol. In Brazil, the company Braskem has announced
‘‘the first certified linear polyethylene in the world made from 100% renewable
raw material’’ and planned its production on a 200,000 mto scale for 2010.12 In
a joint venture between SantelisaVale/Crystalsev and Dow Chemical the pro-
duction of 350,000 mto of polyethylene is planned to start in 2011.13
Solvay Indupa announced the expansion of their manufacturing plant of
polyvinyl chloride (PVC) in Santo Andre (Brazil) to a total amount of 360,000
mto per year. Thereby for this capacity extension the required monomer
feedstock vinyl chloride should also be based on bio-ethylene (based on bio-
ethanol sourced from Copersucar) and thus finally on sucrose and salt.14
The capacity of sugar-derived bio-ethylene seems low compared to the total
annual ethylene production of 100 Mio mto (2000) but enough to show the
capability of utilizing sucrose as feedstock for organic chemicals thereby opening
the door for the whole ethylene-derived C2-chemistry. Bio-ethylene is particularly
interesting for ‘‘decentralized’’ biorefinery concepts with good access to sucrose or
other carbohydrate feedstock where crude oil-based integrated production facil-
ities are not on-hand. There are far more syntheses possible for ‘‘petrochemicals’’
based on renewables. The long-term development of naphtha vs. sugars will
decide the industrial implementation. Well-known examples are e.g. acrylic acid
and its derivatives. A very promising new synthesis of methacrylic acid based on
sucrose or other carbohydrates is the recently developed fermentation of sugars to
3-hydroxyisobutyric acid followed by catalytic dehydration.207

9.3.2.1.2 Access to 5-(Hydroxymethyl)furfural (HMF) and its

Derivatives
HMF is an example for a potential bulk chemical obtainable from sucrose. The
chemical structure of HMF, at first glance, does not immediately allow the
Industrial Sucrose 273

CH3 O H3 C O
Sugar Cat.
Ferm.
Lactose H C C C C Polymers
Glycerol -H2O
HO CH2 OH H2C OH

3-Hydroxyisobutyric acid Methacrylic acid

Scheme 9.3.1 Synthesis of methacrylic acid via 3-hydroxyisobutyric acid by

fermentation.

recognition of its carbohydrate origin. Due to being a furanic compound

implemented with an alcoholic and an aldehyde-functionality, a petrochemical
root seems to be much more feasible. But at least its sources are hexoses. At
elevated temperature and under acidic catalysis, hexoses tend to eliminate three
moles of water, thereby forming HMF (Scheme 9.3.1). In aqueous solution the
dehydration reaction is subsequently followed by a re-hydration step leading to
levulinic and formic acid. In addition, more intermediates, side products and
the formation of coloured soluble or insoluble polymeric compounds accom-
pany the dehydration reaction.15,16
The chemical structure of HMF places it into a unique position between pet-
rochemical and carbohydrate chemistry.17 Being regarded as a ‘‘secondary’’ base
chemical derived from renewable recources,18 HMF is evaluated widely as a
potential replacer of existing petrochemically derived organic compounds. Many
attempts for a successful HMF synthesis have been made in the last decades.
Thereby, D-fructose has proven to be the feed of choice. In order to overcome the
by-product formation and thus to optimize the HMF yield, many condition
variations (catalyst, temperature, time, concentration and solvent) have been
investigated and carefully balanced out for the D-fructose dehydration to
HMF.15–16,18 Higher, almost quantitative yields have been achieved by use of the
solvent DMSO.15,16,19–21 But DMSO is ecologically unfavourable and further-
more difficult to separate from HMF. The sub- and supercritical solvent system of
acetone/water (9/1) proved to be advantageous over water as a sole solvent and
was especially successful, reaching high HMF selectivity up to 77%; water/ace-
tone is volatile, and therefore easy to separate from HMF.22–25 Ionic liquids
under acid or metal chloride catalysis allow HMF-yields higher than 80% –
almost without any formation of by-products like levulinic acid26 (Scheme 9.3.2).
When using chromium(II) chloride as catalyst even D-glucose could be used as
feedstock since this catalyst is effective for the in situ isomerization of D-glucose to
D-fructose before dehydration takes place to yield HMF in 70%.26
The upscaling of HMF synthesis was successfully executed in pilot plants.27
However, due to dehydration the mass balance of this reaction appears quite
unfavourable. Even when considering a favourable average molar yield of 70%,
only 490 g of HMF could be obtained from 1 kg of fructose.
274 Chapter 9.3
By basic chemical operations HMF could easily be transformed into organic
chemicals with large industrial potential.5,28 Especially the bi-functionalized
derivatives, the 1,6-diol, the 1,6-diamin and the 2,5-dicarboxilic acid (FDCA)
(Scheme 9.3.3) resemble petrochemically derived compounds like alkyldiols,
hexamethylene diamine, adipic and terephtalic acid and have the potential to
replace them for producing polyesters and polyamides.10,29
Despite the tremendous efforts in the elaboration of pathways for an opti-
mized HMF production and the broad variety of already gained potential
HMF-based chemical derivatives, HMF is not industrially manufactured
until now. This seems to be driven by economic reasons since the costs for
HMF production even at large scale are estimated at minimum 2 h kg1 and
thus still much more expensive than the production of petrochemical bulk
chemicals.3–4,23
Besides HMF, the rehydration product levulinic acid is also regarded as a
potential biomass-derived organic compound.28,31,32 Large volume chemicals can
be prepared from levulinic acid by chemical conversion, among them methylte-
trahydrofuran and levulinate esters (fuel additives), delta-amino-levulinic acid

O O
HO
H+ O
Hexoses HO H OH + O
- 3H2O +2 H2O H
O
HMF Levulinic acid Formic acid

Scheme 9.3.2 Formation of HMF levulinic acid from hexoses.

O
O O
H2N NH2 HO NH2 O
HO OH

2,5-Bis(aminomethyl)furan 2-Aminomethyl- 5-Hydroxymethylfuroic acid,

5-hydroxymethylfuran HFCA
O O O O
O
O HO OH O
H H HO OH

2,5-Furandicarbaldehyde, 2,5-Bis(hydroxymethyl)furan, 2,5-Furandicarboxylic acid,

FDC BHMF FDCA
O O
O O
H O H

Bis(5-methylfurfuryl) ether

Scheme 9.3.3 HMF-derived building blocks.5,28,30

Industrial Sucrose 275

O O
O
H2N
OR OH
O O
2-Methyl-tetrahydrofuran Levulinate esters δ-Aminolevulinic acid
(MTHF)
O

OH
O O O O

OH OH

Diphenylic acid α-Angelicalactone γ-Valerolactone

O
O
OH
OH
OH OH
O

Acrylic acid 1,4-Pentanediol β-Acetylacrylic acid

Scheme 9.3.4 Levulinic acid derivatives of industrial potential.28,31,32

(herbicide) and diphenolic acid (replacer for bisphenol A, polycarbonates). For

these and other chemical compounds levulinic acid is suggested as potential
starting material (Scheme 9.3.4). Like HMF, furfural is accessible by dehydration
of pentosans. An important source therefore is the pentosan-rich bagasse of cane.
Current world production for furfural is about 250,000 t a1. It is processed to
important derivatives such as furfuryl alcohol, furoic acid and tetrahydrofuran.33

9.3.2.1.3 1,2 Propylene Glycol and Other Polyhydric Alcohols

Ethylene glycol, 1,2-propylene glycol, glycerol and other higher alcohols are
accessible from sucrose either chemically by partial hydrogenation or by bio-
catalysis.18,34–36 Especially 1,2-propylene glycol is appreciated for the manu-
facture of unsaturated polyesters de-icers, antifreeze and brake fluids as well as
in cosmetics and pharmaceutical products.37
A process claimed by BASF describes the use of a cobalt/copper/manganese
catalyst for the hydrogenation of an aqueous sucrose solution thereby showing
the opportunity of influencing the composition of the product mixture by
properly maintaining the reaction temperature (230–280 1C) and the hydrogen
pressure (250 to 300 bar).38,39 Under optimal conditions the reaction favours
essentially the formation of 1,2-propylene glycol (50 to 65 weight%) and
ethylene glycol (20 to 25 weight%) accompanied by lesser amounts of 1,2-
butylene glycol (5 to 7 weight%) and hexane-1,2,5,6-tetraol (3 to 10 weight%)
(Scheme 9.3.5).
276 Chapter 9.3

50 - 65 %
H2 / Co-Cu-Mn cat. HO OH minor components:
Sucrose 1, 2-Butylen glycol
230 - 280°C,
Hexan 1, 2, 5, 6-tetraol
250 - 300 bar
20 - 25 %
HO OH

Scheme 9.3.5 Conversion of sucrose to 1,2-propylene glycol and other di- and
polyhydric alcohols.38,39

On depletion of the petrochemical feedstock, the mentioned manufacturing

process based on the renewable feedstock sucrose might become an interesting
alternative to the petrochemical pathway via hydration of propylene oxide.
In a subsequent reaction 1,2-propylene glycol and other polyols containing
vicinal OH-groups could be reacted to aldehydes, respectively ketones, by acid-
catalyzed dehydration and subsequent intramolecular rearrangement according
to the pinacol-pinacolon-rearrangement (conc. sulphuric acid) or preferably
under improved mild conditions using catalytic amounts of acetic acid in water
by applying high temperature and pressure.18

9.3.2.2 Sucrose-derived Products of Industrial Relevance

Maintaining the Sugar Skeleton
Chemical modifications of sucrose under preservation of the sugar skeleton
fortunately have succeeded in several products with important food and non-
food applications – among them the following examples:

9.3.2.2.1 Sucralose
Studies on the selective replacement of hydroxyl groups in the sucrose molecule
by halogens led to a variety of halogenated sucrose derivatives which partly
showed a remarkably enhanced sweetness compared to sucrose itself.40–43
From these compounds finally sucralose (4,1 0 ,6 0 -Trichloro-4,1 0 ,6 0 -trideoxy-
galactosucrose) was evaluated to show the most convenient physico-chemical
properties concerning the quality and intensity of sweet taste, good solubility in
water (for use in beverages) and attractive stability of the glycosidic linkage
under acidic conditions. Dependant on the field of application, sucralose is
about 400 to 800 times sweeter than sucrose and has been commercialized by
Tate & Lyle under the Splendas brand name44 up to a scale nowadays of more
than 1000 tons per year used in the food industry.
Since its first synthesis, optimizations of the detailed reaction sequence have
been carried out during the past decades finally leading to a bundle of patents
covering different possibilities to execute this reaction cascade.45–64 Out of these
patents a rather straightforward sucralose synthesis could be assembled
(Scheme 9.3.6), the first step of which is a dibutyltin-oxide-supported selective
Industrial Sucrose 277

OH OAc
selective 6
O OH O OH
HO acetylation HO
HO O HO O
HO HO HO HO
O O
OH OH
OH OH
Sucrose Sucrose-6-acetate

regioselective
chlorination

Cl OH Cl OAc
4 O 4 6
Cl O Cl
1' deacetylation
HO O 1' O
HO
HO HO HO HO
O O
6' Cl Cl
OH 6'
OH
4,1',6'-Trichloro-4,1',6'-trideoxy- 6-O-Acetyl-4,1',6'-trichloro-
galactosucrose 4,1',6'-trideoxy-galactosucrose
Sucralose

Scheme 9.3.6 Short and efficient reaction pathway from sucrose to sucralose.

acetylation of the 6-OH-group in the glucose part.45–50 Other selective

approaches are reported, like acetylation at low temperature,51 using orthoester
formation52 or enzymatic techniques.53–56 Secondly, the chlorination reaction
performs with high efficiency and regioselectivity at the desired positions (4-
OH, 1 0 -OH and 6 0 -OH) when using acid chlorides like SOCl2, POCl3, SO2Cl2 or
PCl5 in DMF according to a Vilsmeier reaction type.57–59 The chlorination step
takes place under inversion of configuration at C-4 leading to a chlorinated
galactosucrose. In a third step, after removal of the solvent DMF, deacetyla-
tion is conducted under basic conditions to yield sucralose, which is purified by
crystallization.60–64 Using this reaction sequence sucralose could be obtained in
overall yields of about 40%.

9.3.2.2.2 Sucrose Esters for Food and Non-food Application

Sucrose esters are non-ionic surface-active materials which could be utilized as
emulsifiers and fat replacers.65,66 They are synthesized by esterification linking
lipophilic fatty acids to the hydrophilic sucrose. Especially the three primary
OH groups of sucrose are more easily substituted through fatty acids compared
to the secondary ones, thus leading preferably to mono-, di- and tri-esters.
These lower-substituted sucrose esters are well suited for application as food
emulsifiers especially in dressings and sauces, confectionery, icings and bakery
fillings. Cosmetics are another important field of application.
278 Chapter 9.3

OH OR
6
O O
HO 4 5 RO
2
HO 3 1 RO
HO RO
HO 6' O RO O O
O
5' HO 2' RO
4'
3' 1' OH OR
OH OR

R= n = 1-7
n
prefered esterification O
at primary OH-groups (Sucrose polyesters)

R = acetate or isobutyrate (SAIB)

Scheme 9.3.7 Preferred substitution positions for sucrose fatty esters and fully
esterificated sucrose esters.

Sucrose polyesters (Scheme 9.3.7) have characteristic properties like fats and
oils but are only partly or even totally non-digestible by the body’s lipases and
not absorbed by the human digestive system. In 1996, the US Food and Drug
Administration (FDA) approved sucrose polyesters with 6 to 8 acyl moieties
for certain uses as fat replacers67 known under the brand names Olestras and
Oleans. They are used in food application e.g. in the preparation of dietary
fried snacks.
Sucrose fatty esters could be prepared by reacting sucrose with fatty acid
esters (interesterification) in a solvent (DMF, DMSO) or emulsion process
(propylene glycol).65–66,68–70 Most interesting – because it avoids hazardous
solvents – is the melt process where sucrose and the fatty acid ester (e.g. methyl)
are reacted together without any solvent.65
By these esterification reactions preferably the three primary OH groups of
sucrose could be addressed, though the reactivity of the OH groups in sucrose
decreases in the order 6-OH, 6 0 OH, 1 0 -OH and secondary-OH (Scheme 9.3.7)
mixtures of different substitution patterns are obtained. Enzymatic esterifica-
tions became attractive due to the more specific reactions and thus better
defined products.65–66,71
Sucrose acetate isobutyrate (SAIB, Scheme 9.3.7) is a mixed sucrose polye-
ster prepared by reaction of sucrose with acetic and isobutyric anhydrides.70
It is by far the largest industrially utilized sucrose ester and covers food
(weighting agent in beverages) as well as non-food applications (gloss and
adhesion improvement in lipstick and nail polish, pigment dispersion).72,202

9.3.2.2.3 Polyurethanes
Polyurethanes are formed by polyaddition of diisocyanates with dihydroxy
compounds. The use of polyhydric alcohols instead of diols leads to cross-
Industrial Sucrose 279
linked polyurethanes which proved to be more rigid: the higher the number of
OH functionalities the bigger the impact on the rigidity of the polyurethane.
Therefore, sucrose with its eight hydroxyl groups is of great importance in the
preparation of rigid polyurethane foams.73–76 Physico-chemical properties
of the polyurethane foam are improved when sucrose is first alkoxylated
with alkylene oxide (ethylene or propylene oxide) and the resulting polyether
polyols are used as polyhydric components for the polyurethane formation
reaction.73–77
A number of studies used partially protected sucrose esters to obtain well-
defined polymers.78 Investigations into the regioselectivity of the carbamoyla-
tion reaction of sucrose in DMF showed in the case of alkylisocyanates a clear
preference for the reaction position at the 2-OH and that for phenylisocyanate
the 6-OH group in the glucose-part is the favoured position.79,80 These
regioselectivities could also be proved in the reaction of the respective diiso-
cyanates with sucrose.80
Besides sucrose itself, also short chain di- and polyols derived from partial
hydrogenolysis of sucrose could be used for the formation of polyurethanes.

9.3.2.3 Sugar Derivatives While Maintaining Carbohydrate

Structure
Based on the universally available renewable resource sucrose, a few technically
interesting substances maintaining the carbohydrate structure can be produced.
Thereby, the bound glucose and fructose units of the sucrose molecule are
either split or rearranged (Figure 9.3.7).
The driving force of all these enzymatic reactions is the comparatively high
free standard enthalpy of the glycosidic linkage between the glucose and the
fructose unit (DG1¼27 kJ mol1). This enthalpy is nearly in the same order as
that of the phospho-anhydride bond within adenosine triphosphate (ATP,
DG1¼31 kJ mol1). ATP acts as an energy source in nearly all biological
systems.149 Thus, for these types of rearrangements sucrose is not only the
material educt but also the energetic driving force that means no additional
energy is required for the synthesis. This is completely different from most of
the common chemical reactions.
Compared to classical chemistry, there are some great advantages of bio-
transformations especially concerning ecology: enzymatic reactions are nor-
mally carried out in water at ambient temperature and pH, without the need for
high pressure and extreme conditions.160 As a general rule, these reactions are
very efficient without costly organic solvents and without producing many by-
products. Many chemical reactions providing complex molecules require multi-
step organic synthesis in different organic solvents often under the use of
protecting groups. These groups are introduced into the molecule by chemical
modification of a functional group in order to obtain chemoselectivity in a
subsequent chemical reaction. Enzymes provide this chemoselectivity innately.
This fact plays a key role in waste prevention.86 The often-discussed
280 Chapter 9.3
disadvantage of low product concentrations for enzymatic reactions is not
relevant here, because all enzymes mentioned in Figure 9.3.7 are active
even at sucrose concentrations up to 50% (w/w). The low water activity of
highly concentrated sucrose solutions also reduces the risk of microbial
contamination.

9.3.2.3.1 D-Glucose and D-Fructose

D-glucose and D-fructose are the most easily obtainable carbohydrates from
sucrose. Simple hydrolysis of the sucrose glycosidic linkage leads to these two
building blocks. The reaction could be performed either under acidic conditions
(homogeneous or heterogeneous) or enzymatically.200 The resulting invert
sugar syrup (the optical rotation changes [‘‘inverts’’] during the hydrolysis
from+to –) contains, depending on the inversion degree, D-glucose, D-fruc-
tose and still remaining sucrose and is produced e.g. for the German market in
an annual 350,000 to 400,000 tons scale. These syrups are mainly used in food,
e.g. beverages and dairy products.
The heterogeneous acid-catalyzed process by an acidic ion exchange resin in
a fixed bed column is established as the state-of-the-art process for the sucrose
inversion. A sucrose solution (50–60 weight%) can be completely hydrolyzed
continuously at a temperature of 30–45 1C. The inversion product, a mixture of
D-glucose and D-fructose, could then be separated chromatographically.
Thereby, the batch-wise process is replaced by semi-continuous or continuous
simulated moving bed (SMB) technology yielding D-glucose and D-fructose
fractions with a purity of minimum 95%.
By use of invertase from Saccharomyces cerevisiae (b-D-fructofuranosidase),
a highly specific hydrolysis of sucrose could be achieved. However, high enzyme
costs and the batch-wise operation mode proved economically disadvantageous
over the ion exchange process.

9.3.2.3.2 Isomaltulose (Palatinoset) and Trehalulose

There are five other natural isomers of sucrose (a-D-glucopyranosyl-(1-2)-
b-D-fructofuranoside, IUPAC name (2R,3R,4S,5R,6R)-2-[(2S,3S,4R,5R)-3,
4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]oxy-6-(hydroxymethyl)oxane-
3,4,5-triol, CAS-No. 92004-84-7, Table 9.3.2), which, for example, are found in
honey in small amounts.91,130,151,153 These isomers are enzymatically provided
by diverse bacteria using sucrose isomerases, also called a-D-glucosyl-
transferases (EC 5.4.99.11).
Sucrose formally acts as a-D-glucose donor in the related enzymatic reaction.
Because sucrose is an inexpensive and commonly available a-D-glucose donor,
there is a high industrial potential for the enzymatic synthesis of the sucrose
isomers and their follow-up products. The production of these follow-up pro-
ducts via functionalization of sucrose isomers by chemical modification can
avoid the problem of the weak a-1,2-linkage of the glycosidic bond and the eight
chemically very similar hydroxy groups of the sucrose molecule.85,118,123,141
 OH OH

Industrial Sucrose
O O
HO HO
α + HO
HO 1 2
HO OH
OH OH

glucose fructose

cleavage H+
hydrolysis ion exchange resin
inversion β-D-invertase (EC 3.2.1.26)

OH
OH
OH transglucosylation O OH transglucosylation
HO
HO O
O HO 1 O glucosyltransferase
HO glucosyltransferase
HO α HO EC 5.4.99.11 HO 1'
HO EC 5.4.99.11
1 O
β
2
HO α
HO α 6
OH O
1
O O OH OH O
HO sucrose HO

OH
α-D-glucopyranosyl-(1→2)-β-D-fructofuranoside HO OH
OH OH
isomaltulose (palatinoseTM) trehalulose
α-D-glucopyranosyl-(1→6)-β-D-fructofuranose polymerisation α-D-glucopyranosyl-(1→1)-β-D-fructofuranose
GOS FOS OH OH
glucans fructans O O
OH + fructose + glucose HO HO
HO 1
dextran HO
O
glucosyl- fructosyl-
HO 1
α α
HO HO
α-(1→6)-linked glucose HO α
1 transferase
O OH O
HO O O
O HO O O O O
HO HO HO HO
OH CH2
6 OH
O OH OH
O HO
HO OH OH OH OH CH2
1 HO 1
α
HO α OH
HO
n n
HO 4
O O
n levan OH O
O
HO 1 OH CH2 β-(2→6)-linked fructose O
HO 4 6 O
O HO HO
inulin
O n HO 1
HO α β-(2→1)-linked fructose OH
amylose (neo-amyloseTM) HO HO OH
OH OH
α-(1→4)-linked glucose

281
Figure 9.3.7 Reactions of sucrose maintaining the carbohydrate structure.
282 Chapter 9.3
Table 9.3.2 Natural isomers of sucrose (a-D-glucopyranosyl-(1-x)-b-D-
fructofuranose).
a-D-glu-(1-x)-b-D-fru Isomer CAS No.

1 Trehalulose 51411-23-5
2 Sucrose 92004-84-7
3 Turanose 5349-40-6
4 Maltulose 17606-72-3
5 Leucrose 7158-70-5
6 Isomaltulose (palatinoset) 13718-94-0, 15132-06-6

Up to now isomaltulose (Palatinoset) and the related trehalulose have

obtained commercial relevance, whereas isomaltulose (Palatinoset) is pro-
duced on a large industrial scale.84,112,113,124,137,142,146,154,157 Most of the iso-
maltulose (Palatinoset) produced is applied as a sugar replacer or used as a
precursor for the production of the sugar replacer isomaltt at present (see
below). An additional advantage for ‘‘syntheses based on sucrose’’ is reached
using isomaltulose (Palatinoset) as intermediate. In contrast to the hydroxyl
groups of sucrose, the reactive carbonyl group of isomaltulose (Palatinoset)
can selectively be functionalized. An example is the reductive amination of
isomaltulose (Palatinoset) with hydrogen in the presence of n-dodecylamine,
which leads to biodegradable surfactants.88–89,196
In addition to the particular main product the different sucrose isomerases
also produce the other isomer as a by-product (Table 9.3.2). The ratio of the
products obtained from the sucrose isomerase varies with the bacterial strain
and the reaction conditions, particularly the temperature and pH. Furthermore
small quantities of other products, such as isomaltose (glu-a-1,6-Glu, CAS No.
499-40-1), the trisaccharide isomelezitose (a-D-glucopyranosyl-(1-2)-b-D-
fructofuranosyl-(6-1)-a-D-glucopyranoside), and the cleavage products glu-
cose and fructose may be formed.140,161,167–169
It was shown for the sucrose isomerases of more than one strain that the
enzyme catalyzes the reaction to both products, whereas isomaltulose (Palati-
noset) is the kinetically and trehalulose the thermodynamically preferred
product.110–111,134,157,169 The difference in the reaction mechanism between the
isomaltulose (Palatinoset) and trehalulose formation is an additional tauto-
merization step of the fructose from the fructofuranose to the fructopyranose
form in the catalytic pocket of the enzyme, which finally results in the treha-
lulose formation.169
After clarifying the structure and the reaction mechanism of the sucrose
isomerase specifically changes of relevant amino acid residues in the sequence,
it seems to be possible to increase the product specificity and reaction
rate.81–82,140,167 These actual efforts and current classical optimization of the
fermentation parameters, the strains and the related technical process
partly including statistical methods like the response surface metho-
dology110,101–107,111,115–117,121,132–135 may further decrease the price of the bulk
chemicals isomaltulose (Palatinoset) and trehalulose in future.
Industrial Sucrose 283
Isomaltulose, also known as Palatinoset (IUPAC name (2R,3R,4S,5R,6S)-
2-(hydroxymethyl)-6-[[(2R,3R,4S)-3,4,5-trihydroxy-5-(hydroxymethyl)oxolan-
2-yl]methoxy] oxane-3,4,5-triol), and sucrose have similar physical and
organoleptic properties. Isomaltulose (Palatinoset) is a reducing, free-flowing,
non-hygroscopic crystalline compound which can be crystallized easily from
aqueous solutions with one mole crystal water. Crystalline isomaltulose
(Palatinoset) melts at 123–124 1C.112,145,146,154 The crystal structure197 and
C13-NMR spectrum97,150 were identified. The water solubility at 20 1C is about
one-quarter compared to that of sucrose. The viscosity of aqueous isomaltulose
(Palatinoset) solutions is in the same range as that of sucrose.145,146
Isomaltulose (Palatinoset) shows a neutral sweetness like sucrose without any
aftertaste, but it is only 42% as sweet as sucrose.90,96,112,146 Apart from lower
sweetness, isomaltulose (Palatinoset) is non-cariogenic.87,112,131,138,139,143,155,
156,158
Isomaltulose (Palatinoset) has a low glycaemic index therefore the
insulin release is correspondingly reduced compared to other sugars.108,109,112
In humans, isomaltulose (Palatinoset) is hydrolyzed by isomaltase and
absorbed as glucose and fructose, thus its energetic value is 4 kcal g1 as in
sucrose.112,146,156 It is suggested that isomaltulose (Palatinoset) has favourable
effects on fat metabolism and mental performance in humans.100 Because iso-
maltulose (Palatinoset) is less hygroscopic and more stable and acid resistant
than sucrose, it is used more and more as a sweetener not only for diabetics
but also for sports food and drinks.112,115,156,166 After comprehensive verifi-
cation of its safety, isomaltulose (Palatinoset) is approved as food for human
nutrition.83–84,98,125,126,166
Most characteristics of trehalulose (IUPAC name (3S,4R,5R)-3,4,5,6-tetra-
hydroxy-1-[(2S,3R,4S,5R,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-
hexan-2-one) are similar compared to those of isomaltulose (Palatinoset).
Trehalulose is almost as sweet as isomaltulose (Palatinoset), but its solubility in
water is quite different. Trehalulose is a non-crystalline sugar which makes other
applications possible.112,134 But isomaltulose (Palatinoset) and trehalulose are
not only used in the food and beverage industry. Isomaltulose (Palatinoset) and
trehalulose are technically used as mild reducing agents because of their reducing
properties. With isomaltulose (Palatinoset), trehalulose or mixtures thereof
sulphur and vat dyes can be gently reduced in aqueous alkaline medium for
example.95,112
Up to now, many other micro-organisms have been reported to be capable of
transforming sucrose into isomaltulose (Palatinoset) but only the strain
of Protaminobacter rubrum den Dooren de Jong (ATCC-No. 8457 and CBS
574.77, respectively) – which Lorenz et al.128,129 originally isolated in 1957
from sugar beet raw juice – has been suitable for industrial scale use so far.99,124–
129,136,142,163–165
The molecular weight of P. rubrum’s a-D-glucosyltransferase is
69,000–70,000 and the isoelectric point is 9.9 (Figure 9.3.8).137,198
Technical processes using viable, free micro-organisms have the disadvantage
of higher product purification costs and lower yield but techniques using
immobilized non-viable whole cells119 proved to be more cost effec-
tive.92,93,120,142,146–148,159 The industrial process based on immobilized cells starts
284 Chapter 9.3

Figure 9.3.8 Enzymatic conversion of sucrose into its isomer isomaltulose

(Palatinoset).

Table 9.3.3 Product pattern of the glycosyltransferase of P. rubrum.

Product % on total solids

isomaltulose (Palatinoset) 79.0–84.5

trehalulose 9.0–11.0
fructose 2.5–3.5
glucose 2.0–2.5
isomaltose 0.8–1.5
sucrose 0.5–1.0
isomelezitose 0.5
others 0.7–1.5

with the propagation of the cells. Because there is no need for isolation of
the enzyme effecting the conversion of sucrose to isomaltulose (Palatinoset), the
whole cells are immobilized. Almost all immobilization methods described in the
literature are suitable for P. rubrum. The best technique so far is the immobili-
zation in classical calcium alginate beads according to the method of Lim and
Sun (1980).142,146,147,152 The biocatalyst is transferred to a packed bed reactor.
The sucrose used for conversion to isomaltulose (Palatinoset) is dissolved and
the pH is adjusted to 6.0 before it is sterilized and pumped into the reactors.
Downflow operation has been found to be advantageous. Flow rate is adjusted
individually for each reactor to convert almost all sucrose being supplied. The
product pattern of the solution leaving the reactors is shown in Table 9.3.3.146,147
Long-time stability of the immobilized enzyme is remarkably high even if
high concentrations of sucrose up to 550 g L1 are used. A half-life of more
than 5,000 hours is very common.199
The by-products can be easily removed from the product solution leaving the
column reactors by multi-step crystallization. After evaporation and crystal-
lization isomaltulose (Palatinoset) is separated by centrifugation and dried. The
process yields isomaltulose (Palatinoset) as a free-flowing, non-hygroscopic
crystalline substance with one mole crystal water. The mother liquor of the
isomaltulose (Palatinoset) crystallization is the only by-product of the process.
Because this liquid is used e.g. as feed stuff, the whole isomaltulose (Palatinoset)
production process is free of waste products.112,124,142,146,147
Industrial Sucrose 285
Production of isomalt. Although isomaltulose (Palatinoset) is a sugar replacer
itself, most of the product is currently used as a precursor for the production of
the sugar replacer isomalt. If isomaltulose (Palatinoset) is processed to isomalt
by hydrogenation wet crystals from crystallization are directly used.
Hydrogenation of isomaltulose (Palatinoset) solution can easily be done
under moderate temperature and pressure conditions and at neutral pH or under
mildly alkaline conditions using, for example, Raney-Nickel or supported
e.g. noble metals in pelletized form in a fixed bed reactor. The reduction of
isomaltulose (Palatinoset) is expected to yield an equimolar mixture of
1-O-a-D-glucopyranosyl-D-mannitol (1,1 GPM, CAS No. 20942-99-8 or 64519-
82-0) and 6-O-a-D-glucopyranosyl-D-sorbitol (1,6 GPS) but depending on the
conditions of hydrogenation the rate of each component can vary between 43
and 57% (Figure 9.3.9). The other sucrose isomers and saccharides can be
hydrogenated in the same way leading to the corresponding sugar alcohols
(Table 9.3.4).114,142,146,147 After filtration and ion exchange (to remove traces
of nickel) the isomalt solution is evaporated to appropriate concentration.
The isomalt solution is either sold as such or evaporated to super saturation
followed by crystallization.114,142,146,147 The GPM part of isomalt crystallizes
with two moles of crystal water,127 whereas GPS crystals are anhydrous.122,134
This results in an overall water content of about 5% in crystalline
isomalt.114,142,146,147
Properties and applications of isomalt. Isomalt is an odourless, white, crys-
talline substance containing about 5% (w/w) water of crystallization. It tastes
just as natural as sugar, is not sticky, is tooth-friendly (it helps to prevent
cavities and plaque formation), is suitable for diabetics and has only half the

OH
H2
O
HO
HO 1' OH O catalyst
HO α OH
O 6

OH OH
isomaltulose (palatinose™)

OH OH

O HO O
HO
1' OH OH HO 1' OH OH
HO
HO α HO α OH
OH O 6
O 1
OH OH
OH OH
6-O-α-D-glucopyranosyl-D-sorbitol
1-O-α-D-glucopyranosyl-D-mannitol (1,6-GPS)
(1,1-GPM)
isomalt (palatinit™)

Figure 9.3.9 Hydrogenation of isomaltulose (Palatinoset) to isomalt.

286 Chapter 9.3
Table 9.3.4 Different saccharides and their corresponding saccharide alcohol
provided by hydrogenation.
Saccharide Corresponding saccharide alcohol
trehalulose (1-O-glucosyl-fructose) 1-O-a-D-glucosyl-D-sorbitol (1,1 GPS)
1-O-a-D-glucosyl-D-mannitol (1,1 GPM)
isomaltulose (6-O-glucosyl-fructose) 6-O-a-D-glucosyl-D-sorbitol (1,6 GPS)
1-O-a-D-glucosyl-D-mannitol (1,1 GPM)
isomaltose (6-O-glucosyl-glucose) 6-O-a-D-glucosyl-D-sorbitol (1,6 GPS)
glucose sorbitol
fructose sorbitol
mannitol
(glucosyl)2-fructose (glucosyl)2-sorbitol
(glucosyl)2-mannitol
leucrose others, e.g. 5-O-a-D-glucosyl-D-sorbitol
(1,5 GPS)

calories of sugar because it cannot be completely metabolized. Isomalt is a bulk

sweetener and can substitute sugar in a 1 : 1 mass ratio. It should not be mixed
up with so-called intense sweeteners, which have much higher sweetening power
(between a hundred and a thousand times as high) but no bulking properties.
For this reason, these intense sweeteners are only applied in minute quantities.
Because isomalt is similar to sucrose, it is particularly suitable for making
products such as candies, chewing gum, chocolate, compressed tablets or
lozenges, baked goods, baking mixtures and pharmaceutical products using
conventional equipment. Isomalt’s nutritional and physiological benefits are ideal
for use in sugar-free, low-calorie and diabetic products. It is particularly suitable
for food and pharmaceutical applications (trade name galenIQt). Isomalt also
offers many advantages for technical uses.114,142,146,166 Because the polyol isomalt
is relatively thermally stable, it is used in the plastics industry for polymer sta-
bilization in PVC.162 In coatings based on melamine resins isomalt is used as
polymer plasticizer.114 The electrical industry uses isomalt as glue for temporary
fixing of semi-conductor plates. The glue is washed out later.144 In the production
of ceramics isomalt can act as binder in the ceramic raw mixture. Later in the
processing, isomalt causes no residues of combustion in the ceramics.94

9.3.2.3.3 Oligofructose, Inulin and Levan, Amylose

(Neo-Amyloset) and Dextran
All these oligo- and polysaccharides in nature are synthesized (in vivo) via
sucrose. Technical synthesis (in vitro) found industrial practices mainly for
oligofructose, Neo-amyloset and dextran following the reaction pathways as
outlined in Figure 9.3.7.
Inulin. Fructans are natural polymers of fructose. In nature, there are two
different types of fructans. One is named levan with a backbone of b-(2-6)
Industrial Sucrose 287
linked fructose monomers which is a generally high molecular weight
polysaccharide of micro-organisms. In contrast, inulin is characterized by a
b-(2-1) linked backbone structure. Inulin is generally found in plants such as
chicory (up to 20%), Jerusalem artichoke and onions as reserve carbohydrate,
but also in some bacteria. The degree of polymerization (DP) of plant inulin is
rather low (up to 200 maximum) compared to the DP of bacterial inulin which
has a very high DP, ranging from 10,000 to over 100,000. Bacterial inulin is
highly branched (Z 15%) which results in low intrinsic viscosity in spite of its
high molecular weight. It has a compact, globular shape. In the case of plant
inulin, the DP varies with plant species and with the life-cycle of the plant. The
DP and the presence of branches are important properties since they influence
the functionality of the molecule. For many possible applications it would be
advantageous to produce high molecular weight inulin like the bacterial inulin,
but without branches similar to plant inulin.
Both levan and inulin mostly have a glucose molecule at one terminus.
A unique specific structural feature within the family of polysaccharides is
that no bond of the fructose furanose ring is part of the macromolecular
backbone. That means e.g. the linear polyfructan inulin has a comb-like
structure with a ‘‘polyethylene’’-like backbone and the furan ring being lat-
erally fixed whereas in the analogue polyglucan amylase the pyran rings form
the backbone. There are only a few natural polymers where the carbohydrate
exists in the furanose form. Compared to the pyranose ring the furanose ring is
less rigid which brings additional flexibility to the whole molecule as such.
Inulin is produced from chicory in large scale for food applications including
functional food. Oligofructose is produced semi-synthetically via sucrose
(Figure 9.3.7) or via endo-inulinases from inulin. Oligofructose is used as
prebiotic functional ingredient mainly in dairy products. Long-chain inulin (dp
ca. 25) provides food with a fat-like structure and taste. The blend of oligo-
fructose and long-chain inulin improves mineral, e.g. calcium, absorption.
Fructans can also be used for the manufacturing of furan-based and other
chemicals.187,189,190,193,194, 203–206
Bacterial and plant inulin are different not only in molecular weight and in
the degree of branching but also in the synthesis and the enzymes applied. Both
inulins are synthesized via sucrose. Glucose is generated as by-product.
The synthesis of plant inulin in vivo follows a two-step reaction, starting
with a sucrose-1-fructosyltransferase (1-SST). One sucrose molecule acts as
donor and another sucrose molecule as acceptor of a fructosyl unit. This
leads to the formation of the trisaccharide 1-kestose. Catalyzed by a fructan-
fructan-1-fructosyltransferase (1-FFT) fructosyl units are shuffled between
the 1-kestose and higher polymeric b-(2-1) linked fructan molecules in the
second step. Repetition of this step results in inulin with b-(2-1) linkages
only.186,187,190,191
For the production of bacterial inulin only the enzyme fructosyltransferase
(FTF, EC 2.4.1.9) is required, which shuffles fructosyl units from the
sucrose donor to another sucrose molecule or 1-kestose or higher polymeric
b-(2-1) linked fructan molecules acting as acceptor. The enzyme partly leads
288 Chapter 9.3
to b-(2-6) linkages, which results in branches within the inulin molecule.187,195
This fructosyltransferase and the related fructan is interesting for many pos-
sible applications. Only based on sucrose as raw material high molecular weight
inulin, preferably without branches similar to plant inulin, can be produced in
aqueous solution. Scale-up is the same as the production design for dextran or
neo-amylose. The utilization of the simultaneously formed glucose as food, feed
or fermentation medium should be no problem.
Levan. Like dextran, microbial levan is often an undesirable by-product
in the sugar industry. It was first reported by Lippmann in 1881 as a
product which increases the viscosity of the processing sugar liquor.192 In 1901,
Greig-Smith found that a strain of Bacillus grown on sucrose produces a
fructose polymer which was named levan by analogy to dextran.188
Levan is produced from sucrose under action of the enzyme levansucrase
(sucrose 6-fructosyltransferase (FTF), EC 2.4.1.10) in a step-by-step addition
of single fructofuranosyl units at the C-6 hydroxyl group of the non-reducing
fructose terminal unit of the growing levan chain. It is possible to obtain levan
either from the culture broth of bacterial strains like Bacillus or Zymomonas or
from the enzymatic reaction of the cell-free supernatant with sucrose. Pre-
cipitation with alcohol and drying results in amorphous or microcrystalline
levan. Levan has a varying solubility in cold water, is very soluble in hot water
and is almost insoluble in ethyl alcohol. The solubility of levan is generally
better than that of inulin. Levan can easily be hydrolyzed by acid. Molecular
weight and viscosity of levan respectively vary with the strain and the reac-
tion conditions used.189,190 Even though levan has interesting properties, it has
never had extensive industrial use up to now.189
Neo-amyloset. Neo-amyloset is a biopolymer analogous to amylase, which
can be synthesized via biocatalytical polymerization of sucrose to form a water-
insoluble, unbranched poly-1,4-a-D-glucan with a chain length of up to 35–100
glucose units. As crystalline Neo-amyloset cannot be hydrolyzed by human
digestive enzymes, it can be claimed as resistant starch. The biocatalyst used for
the synthesis of the glucan is the enzyme amylosucrase (AmSu; sucrose-glucan
Glycosyltransferase/EC 2.4.1.4) derived from the non-pathogenic bacterium
Neisseria polysaccharea, originally isolated from the throat of a healthy child.170
Amylosucrase splits sucrose into glucose and fructose and adds subsequently the
glucose moiety to the non-reducing end of an a-1,4-D-glucan. Fructose is the
by-product of the enzymatic reaction. The advantage of the process is that no
activated a-D-glycosyl nucleosid diphosphate substrate is needed.

Amylosucrase
Sucrose þ ða-1; 4-GlucanÞn ! ða-1; 4-GlucanÞnþ1 þ Fructose

The enzyme amylosucrase can either be expressed in Neisseria itself or

overexpressed in non-pathogenic Escherichia coli strains.171 In 1999, the gene
encoding the amylosucrase was sequenced and characterized in detail.172
Briefly, the synthesis of the a-1,4-glucan is performed by fermenting the
micro-organisms and extracting the amylosucrase from the biomass. After-
wards, the enzyme is brought into contact with a highly concentrated sucrose
Industrial Sucrose 289
solution. As the chain of the glucan grows in length during biotransformation
it crystallizes with other molecules and co-precipitates from the solution.
Therefore, it can easily be isolated and dried.
The pure polymer powder derived from biotransformation can be processed
via heat-moisture treatment to form a type-3 amylase resistant starch with a
degree of resistance of 490% (RS3).
Applications. Neo-amyloset can be used for both food as well as non-food
applications. As already mentioned at the beginning of this chapter, crystalline
Neo-amyloset cannot be hydrolyzed by human pancreatic a-amylases.173
After consumption by human beings, as much as 90% of the heat-moisture
treated polymer is transferred into the large bowel and is fermented by colonic
bacteria to form short-chain fatty acids such as acetate, propionate and
butyrate.
Besides the application as dietary fibre, Neo-amyloset can be used for the
production of smooth particles with a size of 10–100 mm by re-crystallization in
dimethyl sulfoxide (DMSO). The application of these particles as a supplement
to cosmetics such as creams, lotions or as UV-reflector has been described in
WO 0038623.174 Further hard or soft films can be produced from Neo-amy-
loset in order to generate gelatine-free capsules for encapsulation purposes.175
Dextran. Dextran is a linear homopolysaccharide of glucose composed of
a-(1-6)-linked a-D-glucose units with only occasional branches via O-2
(a-(1-2)), O-3 (a-(1-3)) or O-4 (a-(1-4)). The exact structure of each type
of dextran depends on the producing dextransucrase and the microbial strain,
respectively; several strains can produce more than one type of dextran.178,179
Because dextran is formed from sucrose it has been known for a long time as
a source of trouble with slimy contaminations in food and especially in the
sugar industry.180 The corresponding enzyme dextransucrase (EC 2.4.1.5) is an
extracellular glucosyltranferase (GTF), which catalyzes the cleavage of the
sucrose molecule and the transfer of the D-glucopyranosyl residue to dextran
while fructose is released. Commercial dextran is mainly produced by growing
cultures of Leuconostoc mesenteroides. In addition to the sucrose (usually initial
sucrose concentration is 2% (w/w)) the medium also contains an organic
source of nitrogen such as peptone, growth factors, certain trace minerals and
phosphate. After 24–48 h fermentation at 25 1C without aeration the cells
are removed by centrifugation. The dextran is harvested from the cell-free
supernatant by alcohol precipitation and purified by further precipitation after
redissolution in water.
An alternative process uses the cell-free supernatant from fermentation for
enzymatic synthesis of the dextran. This process allows fermentation and
synthesis under different sets of conditions. The resulting product is more
uniform and easier to purify. The elongation and branching of the dextran can
moderately be influenced by the reaction conditions, especially by temperature
and concentration.176,178,179,182,183
The biopolymer dextran produced on the basis of the renewable resource
sucrose is a very interesting raw material for many applications. It was used
first as a blood-plasma volume expander in the 1940s. Up to now, there are
290 Chapter 9.3
many other applications based on native dextran, partially degraded dextran
and its derivatives such as esters or ethers.176–179,182,185
The reaction of dextran with epichlorohydrin results in a cross-linked
gelatinous product that is used as a molecular sieve for separation and
purification of biochemically important macromolecules like proteins, poly-
saccharides or nucleic acids. Its commercial name Sephadexs is derived
from SEparation PHArmacia DEXtran and stands for many different
successful products including further derivatized materials such as carboxy-
methyl, diethylaminoethyl, diethyl(2-hydroxypropyl)-aminoethyl, and sulfo-
propyl Sephadexs.182
Dextran and its derivates have found some applications in the medical field.
Dextran sulphate has anticoagulant properties similar to those of heparin.176
Recent studies show antiviral properties of the sulphate esters of dextran,
particularly in the treatment of the human immunodeficiency virus.181 Oral
dextran sulphate has been used in Japan against arteriosclerosis for 20 years
without harmful side-effects.184,201 Mercaptodextran is discussed for therapy of
acute heavy-metal poisoning because it has a higher affinity for heavy metal
ions such as silver, mercuric, cupric and auric ions than most other thiols and
chelating agents. The properties of mercaptodextran are of interest regarding
environmental clean-up of heavy metal contaminations.182
By incorporating dextran into X-ray and other photographic emulsions,
photographic companies could reduce silver usage without loss of grain
fineness.176
Due to its excellent biocompatibility, moisturizing properties and proven
stability under several conditions dextran can be found in several cosmetic
formulations for the eye- and skin-care market. Furthermore, dextran improves
the softness, crumb texture and loaf volume of bakery products and it is also
known to be used in clinical nutrition and as an additive in products such as
candies and ice-cream.178,179

9.3.3 Outlook
At first sight, the consumer’s choice for products mostly depends on reasonable
prices and convenience. But times have changed and the consumer’s awareness
focuses – besides price and application profiles – more and more on ecological
aspects like greenhouse-gas emissions. There are far more products on the basis
of sucrose developed in the past being able to replace ecologically unfavourable
petrochemically based products of today.
Just to mention only two examples:

 Acetylated oxidized sucroses could replace nitrogen-containing ecologi-

cally unfavourable surfactant boosters in washing formulas both as
booster and as sequestering agent.
 Alkyl amine derivatives of isomaltulose (Palatinoset) have very low cri-
tical micel concentrations (cmc) far better than today’s petrochemically
Industrial Sucrose 291
based ones. They are very synergistic with classical anionic surfactants like
sodium dodecyl sulphates and are easily biodegradable.

Both examples demonstrate that excellent application profiles combined with

high ecological performance are today not sufficient to introduce products into
the market. There are far more hurdles to overcome:

 Until today, petrochemicals often are very cheap products because they
are produced on the basis of cheap by-products of oil refineries in a very
integrated processing on large scales.
 Newly developed ecologically more favourable products based on renew-
ables have to start on small scales but cannot compete price-wise with
the cheap mass products based on non-renewables. Their production is
not possible in the same integrated steam-cracker-based facilities of the
chemical industry but very often in stand-alone production sites.

To conclude: even today – being faced with increasingly high oil prices – if
society wants to have more ecologically favourable products it remains a
political task to support the introduction of these products. But – bearing in
mind regulations like ‘‘REACH’’ – the reality is exactly the contrary.

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Industrial Sucrose 299
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CHAPTER 9.4

Wood
ELISABETH WINDEISEN AND GERD WEGENER

Holzforschung München, Technische Universität München, Winzererstr. 45,

D-80797 München, Germany

9.4.1 Introduction
The twenty-first century is expected to become the century of bio-based materials
and biorefining processes,1–5 which are now on the horizon to replace fossil-
based materials gradually but continuously. Comparable developments are
taking place in the energy sector where a multitude of renewable energy resources
are complementing and substituting fossil-based energy and nuclear power.6
Driving forces are primarily the fact of dwindling fossil resources, along with
uncertainties concerning availability and prices as well as the globally accepted
certainty of society and politicians about climate change and the resulting
effects on quality of life and living space for man, animals and plants. Keeping
these aspects in mind, including all basics of sustainability, it is no exaggeration
to say that forests and wood utilization play an important role in meeting
global demands for materials and energy on the one hand and on the other
hand contributing effectively to quality of life and climate protection.
In the context of ‘‘Green Chemistry’’ and against the background of sus-
tainability wood utilization is demonstrated on the basis of the chemistry of
wood in four sectors:

 Pulp and paper;

 Wood-based composite materials;
 Modified solid wood products;
 Wood as building material.

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

300
Wood 301

Wood and biomass are raw materials (Figure 9.4.1) for traditional building
products like sawn timber, prefabricated timber elements and systems as well as
wood-based materials in the form of boards (e.g. particle- and fibreboards), but
also as construction elements from glued products like laminated beams, ply-
wood, oriented structural boards or laminated veneer lumber.7
New developments give options in the form of hybrid materials combining
wood with conventional plastics (e.g. Wood Plastic Composites, WPC) (Section
9.4.4) or as solid wood improved by heat treatment or chemical modification,
e.g. acetylation, oil treatment etc. (Section 9.4.5).
Additionally, wood and biomass represent traditional and new energy pro-
ducts (such as pellets or briquettes) to be used both in small private heating
systems and also in large biomass heat processing units, also producing elec-
trical power by power-heat-coupling systems. In this sector wood and biomass
compete with typical fossil energies such as oil, gas and coal but also with
additional renewable energy sources like wind, water, geothermal heat and
waste, besides the most promising natural energy coming from the sun and
used by different techniques like sun collectors, photovoltaic systems, etc. For
electricity, nuclear power is still an important factor for many countries
worldwide. In the field of fuels for stationary and mobile systems biofuels based
on forest and agricultural biomass (biodiesel, ethanol, etc.) are the option as
alternatives to fossil fuels like petrol and diesel but also to future hydrogen
power systems, etc. In the wide field of chemistry wood- and biomass-based and
derived green chemicals compete with established oil-based chemicals and
plastics as described in other chapters.
In the context of chemical utilization of wood, other parts of the tree, the
so-called Non-Timber-Forest-Products (NTFP), have always been closely related

Figure 9.4.1 Wood utilization in competitive markets.

302 Chapter 9.4
to the cultural development of mankind. The Egyptians already used myrrh for
embalming mummies and for the preparation of salves in 2000 BC; the hand-
written books from the High Middle Ages could not have been written without
ink from oak galls and gum arabic. Besides the utilization as foods (fruits, nuts,
spices like cinnamon), raw materials (exudates, e.g. maple syrup, caoutchouc,
chicle for the production of chewing gum), odorous substances for perfumes and
cosmetics (e.g. eucalyptus oil), dyestuffs, tanning agents and many others have
been used. The progress in organic chemistry at the beginning of the twentieth
century changed the market for NTFP. More and more, it was possible to
produce these products synthetically. Nevertheless a few products, such as nat-
ural caoutchouc, still remain indispensable due to their excellent properties.

9.4.1.1 Perspectives of Sustainability

Sustainability intrinsically means planning ahead for the future. Apart from
economic action, ecological criteria as well as social aspects and responsibility
need to characterize the life and economic activities of a continually growing
world population. Only then will the planet be able to provide a humane foun-
dation for life on Earth. Today, there are 6.5 billion people living on Earth, in 15
years there will be 1.5 billion more. Especially in industrial countries this presents
increasing pressure on politics, economy and society to rapidly and effectively
review economic processes and consumer behaviour. At global, regional and
local levels, suitable strategies will have to be developed or made use of. This will
not be possible by way of a more efficient technology alone, but can only succeed
if economic, social and cultural rethinking result in joint efforts of redirected
acting. Sustainability in its sense of planning for the future is multi-faceted: thus
the climate is to be protected, resources are to be conserved, energy should be
employed efficiently, renewable resources and renewable energies are to be uti-
lized and at the same time biodiversity needs to be sustained and, on a global
scale, fair trade is to be safeguarded. Not least, individuals find themselves in a
position where there is a need to change their hitherto existing concept of
prosperity from living standard to quality of life. While living standard describes
personal materialistic prosperity in terms of gross national income or per-capita
income, quality of life comprises much more. The latter also implies other ele-
ments and values such as education, health, social status, occupational career,
working environment quality and availability of nature.
Apart from long-term changes to be aimed for, measures that swiftly take
effect and setting courses is required in order to fulfil the climatic objectives of
the European Union by 2020: carbon dioxide emissions are to be reduced by
20%, renewable energies are to be part of the energy mix and energy is to be
employed more efficiently by 20%. In this context, the former director of the
UN Environmental Programme, Klaus Töpfer, recently wrote on the topic of
‘‘Sustainable Construction and Reconstruction’’ ‘‘that it would be out of all
reason, even inexcusable, not to pay regard to the contribution of the forests
and the usage of wood to its full extent’’.8
Wood 303
9.4.1.2 Forests as Ecosystem and Resource
The forests of Earth are multi-faceted and constitute vital ecosystems. With
their 39 Mio km2 they cover about one-quarter of the land area worldwide.
About half of the global forest area is shared by five countries – Russia, Brazil,
Canada, USA and China. This ought to be considered with regard to forestry
and timber strategies, when it comes to third-party certification with respect to
sustainable management. Per annum, still 130,000 km2 of forests are cleared –
which is more than the entire forest area of Germany. This contrasts with an
increase in the forest area in other regions by 57,000 km2. However, this mostly
does not concern real forest, but plantations, mainly in the southern
hemisphere.
In many cultures forests play an important role. They fulfil many tasks for
water sources, soil and air. They are habitats for plants, animals and humans
alike. Via photosynthesis, they produce wood, the quantitatively most impor-
tant raw material throughout the world. The forest industry supplies industry
with wood, which in turn processes it into products like pulp and paper,
composite materials, construction material and energy. A very large part of
humanity is dependent on firewood as energy source. With 52%, more than
half of the globally utilized 3.4 billion m3 (¼ solid cubic metre) wood is used as
fuel wood.9
Since forests serve as wildlife habitat, biotope and recreation refuge, and
supply wood as raw material and a source of energy, their cultivation and
afforestation effectively contribute to the objectives of sustainability and cli-
mate-protection: since forests take up and store carbon dioxide, they help to
attenuate climate change, especially generated by the usage of fossil fuels like
carbon, crude oil and natural gas. Wood products retain this carbon even after
the felling of a tree. At the end of their life span they can be burnt, still pro-
viding similar amounts of energy as direct burning of wood does. Presently,
forests in Germany take up and store temporarily about 8% of the around 900
Mill. t carbon dioxide annually emitted in Germany. Subsequently, this carbon
is retained in the forests themselves or in wood products. Moreover, wood
products replace products that, like plastics, are made from crude oil as well as
products like steel, concrete or aluminium, which have to be produced and
disposed of in energy-intensive processes. In order to meet the growing world
population’s increasing demands for products and energy without continuing
to endanger the climate, not only does energy need to be saved as well as energy
and resources to be employed more efficiently, but also biomass and thus
especially forests need to be utilized in sustainable ways.

9.4.1.3 From Wood Resources to Wood Products

The fact that not only forests but also wood products retain carbon is an
important strategic element concerning climate protection politics. From the
nearly 1.7 billion m3 industrial roundwood harvested annually, 420 Mio m3
304 Chapter 9.4

Figure 9.4.2 Global annually harvested amount of round wood and its utilization.

timber, 220 Mio m3 wood-based materials and 370 Mio mto paper are pro-
duced (Figure 9.4.2).9
Even though Europe only has 5% of the global forest area, it produces nearly
30% of all wood products worldwide due to its large stocks of wood, efficient
manufacturing technologies and a high rate in net product.
Today, in a global comparison, Germany, ahead of Sweden (2.9 billion m3),
holds the largest stocks of wood in its forests (3.4 billion m3). Eight percent of
the entire European net product is contributed by the forest, wood and paper
industry. Europe also holds the globally leading market for wood and wood-
based products. 60% of all exports and nearly 50% of all imports are trans-
acted in the European market.
In view of economy, and from the viewpoint of ecology, forest, wood and
paper constitute ‘‘heavyweights’’. According to the European definition also
downstream economic sectors like the printing and publishing industry are
assigned to the forest and wood domain. Ecological advantages arise already as
wood is being produced in the forest. In addition wood products replace fossil
and other non-renewable resources and their subsequently manufactured
products.
Since the residues accruing during wood processing make good raw material
for further products, the wood industry hardly produces any refuse. When
wood products like paper are no longer wanted, they can either be recycled or
burnt, subsequently supplying new products or utilizable energy. Therefore,
already today, the forest and wood domain contribute substantially to meeting
important environmental demands. Thus, a renewable resource is employed
snatching greenhouse gas from the air; its production processes use up little
energy and generate few pollutants. Not only does the bioproduct wood supply
sustainable energy, but it also facilitates building sustainability.
Wood 305
For climate protection construction material too needs to be selected
according to ecological criteria. This is particularly important, because con-
struction represents an essential economic element, also reflecting the intellec-
tual and cultural value benchmark of a society.
In Germany, for example, more than two-thirds of the wood utilized ‘‘ends
up’’ in buildings as construction material, insulating material or furniture.
Therefore, the forest and wood industry plays an important part where envir-
onmental objectives are concerned. Its task is to offer suitable wood species
characterized by the required properties like density, strength, stability, hardness,
durability, surface shape and colour. From glulam (glue-laminated timber) to
ultra-light structural particle board, high-capacity raw material and suitable
building parts as well as structural systems need to be supplied, fulfilling all the
technological, aesthetic and hygienic requirements of future construction.
Building has always been of significant importance for mankind’s culture and
development. It determines the appearance of our villages and cities, reveals the
social structures of the society and is an important economic factor itself.
Architecture and construction are essential characteristics of all types
of buildings in general. Under ecological and environmental aspects, however,
the choice of the building materials is additionally gaining more and more
importance. Taking these aspects into account a renaissance of wood as a
building material is taking place. There are good reasons for that, e.g.:

 Mankind was always familiar with the utilization of wood;

 Wood is produced in an extraordinary factory under exceptional envir-
onmentally friendly conditions; forests additionally fulfil a multitude of
environmental beneficial functions;
 Wood is produced by the basic process for all life on Earth:
photosynthesis;
 Photosynthesis implies capturing CO2 from the atmosphere and fixation of
carbon in the material, thus acting as a carbon sink. Any use of wood as
building material therefore represents an important contribution to one
of the biggest challenges of mankind today: climate change as a result of an
exaggerated release of CO2 resulting from the use of fossil resources;
 Photosynthesis generates a material for multiple use and a wide range of
products due to its chemical composition and structure (- green chem-
istry, pulp and paper) and anatomical and morphological structures and
properties as well;
 This makes wood the most important and extremely variable renewable
raw material and a universal construction material with many unique
characteristics and properties such as:

J high strength and stiffness and low mass at the same time;
J it can be processed easily and with low energy input;
J it has excellent heat and sound insulation properties;
J it provides a healthy living climate in houses due to the ability of
absorbing and releasing moisture;
306 Chapter 9.4
J it reveals important fire safety characteristics;
J thousands of different wood species with different properties and
appearance offer a wide range of options for the use of wood as con-
struction, equipment and decoration material;
J wood and wood products keep their energy content over the whole
lifetime of a building and the energy can be used at the end of the life
span.

Wood for building purposes can be used in the form of roundwood, but
mostly as sawn timber such as beams, planks, boards or slats as traditional
components of building elements such as floors, walls, ceilings, roofs, etc.
Mostly softwoods, preferably spruce or pine wood, but also hardwoods such as
oak, are used e.g. for windows, doors or parquet.
The solid wood products are supplemented by a large number of wood-based
composites (see Section 9.4.4).

9.4.2 Chemistry of Wood

9.4.2.1 Survey
Wood is a material with very differing properties: different wood species, the
site, the tree age, stemwood or knotwood, heartwood or sapwood offer an
extremely broad range of biological, chemical, technological and appearance
properties.
The vast diversity of nature can be a disadvantage for industrial purposes as
all the various wood properties must be taken into account during processing.
On the other hand, many advantages emerge as well. There is always at least
one wood species fitting for the intended use.
Out of about 30,000 woody plant species worldwide some 500 are regarded as
timber available in a significant amount and are being traded internationally.
20–30 commercial wood species are commonly and typically used in Europe.
The most important softwood species are spruce, pine, larch, fir and Douglas
fir, and the most important hardwood species are beech, oak, aspen, birch,
poplar, maple, lime, locust along with lesser available species, such as cherry or
walnut.10,11
It is a matter of common knowledge that from a chemical point of view,
wood is composed of mainly organic compounds, which include, on the one
hand, macromolecular components which are important for pulp production
particularly the polysaccharides cellulose and polyoses (hemicelluloses) as well
as lignin, and on the other hand the low molecular components of wood. In the
case of the latter being of organic origin they are referred to as accessory
components or more frequently as extractives according to their isolation
method while the inorganic components are usually identified as ash (see Figure
9.4.3).12
In nearly all wood species of the temperate zones 90–99% of the wood
substance is made up from polysaccharides (cellulose, polyoses) and lignin
Wood 307

Figure 9.4.3 Chemical composition of wood.12

Table 9.4.1 General chemical composition of wood.

Constituent Hardwoods [%] Softwoods [%]

Cellulose 40–50 40–50

Polyoses (hemicelluloses) 25–35 20–30
Lignin 20–30 25–35
Extractives 0.5–10 0.5–10
Inorganics (ash) 0.1–1 0.1–1

forming the cell wall; the extractives can often be found in comparatively low
percentages (Tables 9.4.1 and 9.4.2).
Even if, in the first instance, it might seem that this material does not vary a
lot, the different amounts and differing chemical composition of the polyoses
(see Section 9.4.2.3) and the lignins (see Section 9.4.2.4) in hardwood and
softwood strongly affect the manufacturing processes. This applies for the
extractives too, which due to their large chemical diversity influence some of
the properties of wood and behave respectively different with regard to the
chemical utilization of the wood.
As previously mentioned the chemical diversity of the wood species devel-
oped by nature most often is a utilization benefit; however, with regard to the
chemical utilization, methods and processes must often be optimized for each
wood species separately, as due to the specific chemistry of the wood species it is
not always possible to transfer them.
In the following, the chemical components cellulose, polyoses, lignin,
extractives and ash are briefly described. Further information can be found in
various books and literature cited therein.12–17

9.4.2.2 Cellulose
With an estimated vegetable production of 1011 mto per annum, cellulose is on
a quantity basis the most important organic natural material worldwide.12
Since cellulose is a homopolymer it is composed of a single component, namely
the D-glucopyranose, which is linked by ß-1-4-glycosidic bonds. The cellulose
308 Chapter 9.4
Table 9.4.2 Comparison of the chemistry of various wood species excluding
inorganic components18 (with permission of Wiley-VCH Verlag
GmbH & Co. KGaA).
Cellulose Polyoses Lignin Extrac-
Wood species Common name [%] [%] [%] tives [%]

Softwood
Abies Balsam fir 38.8 28.5 29.1 2.7
balsamea
Pseudotsuga Douglas fir 38.8 26.3 29.3 5.3
menziesii
Tsuga Eastern hemlock 37.7 27.9 30.5 3.4
canadensis
Juniperus Common juniper 33.0 30.3 32.1 3.2
communis
Pinus radiata Monterey pine 37.4 33.2 27.2 1.8
Pinus sylvestris Scots pine 40.0 28.5 27.7 3.5
Picea abies Norway spruce 41.7 28.3 27.4 1.7
Picea glauca White spruce 39.5 30.6 27.5 2.1
Larix sibirica Siberian larch 41.4 29.6 26.8 1.8
Hardwood
Acer rubrum Red maple 42.0 28.9 25.4 3.2
Fagus sylvatica Common beech 39.4 33.3 24.8 1.2
Betula Silver birch 41.0 32.4 22.0 3.2
verrucosa
Betula Paper birch 39.4 34.5 21.4 2.6
papyrifera
Alnus incana Gray alder 38.3 30.9 24.8 4.6
Eucalyptus Blue gum 51.0 25.2 21.9 1.3
globulus
Acacia Black wattle 42.9 33.6 20.8 1.8
mollissima

content in wood varies between 40 and 50%. The mean degree of poly-
merization of native cellulose ranges on average between 8000 and 10,000.
Cellulose forms linear, unbranched chains. Intramolecular hydrogen bridges,
which may predominately occur in native cellulose (cellulose I) between the
hydroxyl groups on C2 and C6 and the hydroxyl groups on C3 and the C5
oxygen (Scheme 9.4.1), prevent free rotability and account for the relatively
high stiffness of the straight-chained molecular chains. Due to the formation of
intermolecular hydrogen bridges further degrees of order are formed. Thus, in
solid state, crystalline regions alternate with the ones of a lower degree of order
(amorphous regions).
Thirty to one hundred strands of cellulose aggregate into so-called elemental
fibrils (cross section approximately 2–4 nm) via H-bridges, which in turn
aggregate into microfibrils (cross section approximately 10–30 nm) and these
into macrofibrils (cross section approximately 500 nm). The orientation of the
cellulose fibrils in the wood cell wall differs. The strongest cell wall layer, for
example, shows a constitution parallel to the axis which accounts for the high
tensile strength of wood.12
Wood 309

Scheme 9.4.1 Structure and molecular chain constitution of cellulose I (native

cellulose) with hydrogen bonds.

Due to its structure, cellulose does not dissolve in common solvents nor in
water or in dilute acids, even though non-crystalline structural regions can swell
in water and in doing so adsorb 8–14% of its volume to water. In alkaline
solutions, cellulose strongly swells at first and the short-chained parts with
DPo200 are dissolved (e.g. a-cellulose can be obtained after treatment with
17.5% NaOH or 24% KOH). Only strong acids cause a hydrolytic degradation.
In addition to several solvent systems containing heavy metal salts and ammonia
or aliphatic di- or triamines (Schweizers reagent respectively cuoxam (Cu/NH3),
cuen (Cu/ethylene diamine), nitren (Ni/diethylene triamine), 4-methylmorpho-
line-4-oxide (NMMO), dimethylsulfoxide blends and ionic liquids (ILs), besides
others, are employed as organic solvents for cellulose.12,18–23
The chemical reactivity of cellulose generally depends on the percentage of
accessible hydroxyl groups, which are not occupied by hydrogen bonds. At
first, chemical reactions occur in amorphous regions of a lower degree of order
until crystalline regions take part. A further decisive factor for the succession
and the extent of the interaction is the molecular size and character of the
interacting agent in relation to the capillaries and interstices allowing its
penetration into the cellulose substrate.24
The possible uses of cellulose of various forms is manifold (fibres, cellulose
derivatives as well as new products such as cellulose aero gels), however a che-
mical synthesis of cellulose, as demonstrated by nature, has not yet been rea-
lized.20,25,26 In order to meet the high requirements for products made of
cellulose, it is usually necessary to obtain cellulose from plant material by selective
removal of non-cellulose components. In the case of wood, mechanical, mainly
mechanical-chemical, as well as chemical pulping is employed (see Section 9.4.3).

9.4.2.3 Polyoses (Hemicelluloses)

Polyoses (hemicelluloses) are irregular, amorphous polymers, which, in con-
trast to cellulose, are composed of various sugar components like hexoses
310 Chapter 9.4
(glucose, mannose, galactose, rhamnose) and pentoses (xylose, arabinose) as
well as uronic acids. The molecular chains are significantly shorter than cel-
lulose and have a significantly lower DP of 50–250. Furthermore, polyoses have
side groups (e.g. parts of the OH groups are substituted for acetyl groups) as
well as side chains. Due to their structure and chemical composition polyoses
can serve as bonding components between lignin and cellulose in the cell wall.
As already mentioned, there are differences in the content and the compo-
sition of polyoses in hardwood and softwood. While xylans (pentosans) are
dominant in hardwood, mannans (hexosans) predominate in softwood. The
xylans are so-called homopolymers, as the main chain consists of xylose only
(Scheme 9.4.2), whereas the mannans present a heteropolymer consisting of
glucose and mannose (Scheme 9.4.3). Furthermore, softwood has a higher
content of polyoses as well as acetyl groups compared to softwood. The
higher content of acetyl groups in hardwood can cause elimination of acetic
acid in certain procedures (e.g. steaming of beech or thermal modification,
Section 9.4.5).
In contrast to cellulose, polyoses are alkaline-soluble and partly water-
soluble (e.g. arabinogalactan of larch).
At present, only a few polyoses from wood are chemically used. An example
is the utilization of xylose (Figure 9.4.4), which can be obtained as a by-product
in the pulping process of beech or birch wood and which is used in the form of
the sugar alcohol xylitol as a sugar substitute (E 967) as well as arabinogalactan
as a thickening agent (E 414) in the food industry.

Scheme 9.4.2 Hardwood xylan.

Scheme 9.4.3 Softwood glucomannan.

Wood 311

Figure 9.4.4 Example of mass balance of a beech sulphite pulping.

9.4.2.4 Lignin
Lignin (lat. lignum ¼ wood) is the second most common organic natural
material and the real lignification substance. By integration of lignin in the cell
wall and by association with the cellulose fibrils via the polyoses, high material
strength develops, whereby the tree can stand upright and absorb static and
dynamic forces. Hence, the presence of lignin in the cell wall of the plant is a
pre-condition for the strength of the wood.
The aromatic lignin is formed by way of the so-called Shikimate biosynthesis
from glucose. Lignin components form phenylpropan units with differing
amounts of methoxy groups (Scheme 9.4.4). Depending on the plant group, the
percentage of the basic units of coumaryl- (H), coniferyl- (G-) and sinapyl
alcohol (S-) varies. Thus, softwood mainly contains G-lignin, whereas hard-
wood is composed of G- and S-units. The lignin of softwood lignin is more
strongly condensed than the lignin of hardwood; it features a higher carbon
content due to the lower amount of methoxy groups as well as less acid-soluble
parts.12
Lignin is an amorphous, three-dimensional heteropolymer without any
defined chemical structure (Scheme 9.4.5). According to present knowledge, the
polymerization not only takes place by reaction of monomers with polymer
stages but also by reaction of already existing aggregates (di-, tri-, etc. lignans).
The described molar masses, e.g. approximately 10,000 in the case of spruce
MWL (milled-wood-lignin) produced in the laboratory, of isolated lignins are
not uniform or representative, as they depend on the isolation method.
Lignin shows thermoplastic properties at approximately 160 1C (glass
transition), which are used for the manufacture of certain composites
(Section 9.4.4).
Regarding lignin, it always has to be considered that it is not a uniform and
defined product, but it can vary a lot depending on the origin and the isolation
312 Chapter 9.4

Scheme 9.4.4 Basic units of lignin.

method.12,27 This is one of the reasons why lignin is materially utilized only in
specific cases, although it is, along with the fossil resources, the only natural
resource for aromatic compounds.
Most of the 70 Mio mto of lignin annually accruing as a by-product in
pulping is used for energy generation in the course of sulphate pulping (Kraft
pulping). Only about 1.5% of lignin and its by-products are materially utilized.
In particular sulphurous lignin variations like lignin sulphonate obtained from
the sulphite pulping are commercially utilized in quantities of 1,000,000 mto
a1 or Kraft lignins (alkali lignin) obtained from Kraft pulping in quantities of
100,000 mto a1.28–30
The existing markets of lignin are either for low-value products as lig-
nosulphonates mainly in dispersing and binding applications or limited to
very narrow market segments as high-quality dispersants from chemically
modified Kraft lignin as well as speciality chemicals like vanillin or agro-
chemicals.31 Nevertheless, numerous potential applications have been studied,
e.g. as tanning agent, resin component for wood-based boards, dispersing
agent, antioxidants and binder for different purposes.12,29,32 Lignin has a
relatively high application potential in the sector of wood-based products,
where wood adhesives, phenol and epoxy resins or carbon fibres can be
made from lignin. Approximately 300,000 mto a1 of lignin are required for
the resin market. Lignin with a high degree of purity is employed as a UV-
stabilizer for the polyolefin production or as a filler for the production of
polyurethane.31,33
In the form of thermoplastically processed products (e.g. ARBOFORMs
and FASALs), lignin is used as a composite material for various applications
(see Section 9.4.4). However, these are mainly niche products shown by the
production volume of ARBOFORMs of approximately 300 mto a1.34 A
significantly higher material utilization of lignin would, on the one hand,
increase the added value of wood and on the other hand, crude oil-based
substances like plastics could partly be replaced.
Wood 313

Scheme 9.4.5 Section of softwood lignin.

9.4.2.5 Extractives
Table 9.4.3 and Scheme 9.4.6 show that contents as well as structure of the
extractives can vary greatly between the wood species. Furthermore, there are
large differences between wood parts of, for example, sapwood and heartwood
(see below) or between wood and bark. Therefore, it is very difficult to briefly
describe extractives and the reader is referred to the literature.12,14,15,16,17
Since the name of the extractives refers to their isolation method, it follows
that the term extractives includes non-specifically all substances which can be
extracted from the wood using solvents with most different polarities. Hence
the term extractives must be considered in a much differentiated manner, as
314 Chapter 9.4
35
Table 9.4.3 Typical extractive contents in wood.
Solvent Cyclohexane/Ethanol [%] Water [%]

Softwood
Spruce 1–2 0.5–2
Pine 4–7 0.5–2
Larch 3–6 8–10
Douglas fir 3–6 3–6
Hardwood
Beech 0.5–1.5 o1
Oak 3–8 6–10
Tropical wood
Teak 5–7 2–3
Quebracho up to 40 20–25

most probably only part of the low molecular organic compounds of a number
of wood species have yet been described.
The classification of extractives is rarely made strictly according to substance
classes. Therefore it can usually be divided into lipophilic and hydrophilic
extractives due to the polarity (Table 9.4.4) or into primary and secondary
extractives due to their biological function (Table 9.4.5).
The first differentiation is used in various sectors of the wood-processing
industry like the pulp and paper industry, as its chemical behaviour is
defined by the polarity. Depending on the chemical pulping, certain extractives
can show negative effects on the production, e.g. pinosylvin and its mono-
methyl ether during acid sulphite pulping.13 In contrast, other pine extractives
(resin acids, terpenes, etc.) are useful by-products in Kraft pulping (see
Section 9.4.3).
Looking at the biological function, the primary extractives are necessary for
maintaining the metabolism and supply of the components for the biosynthesis
of the secondary substances. Typical primary substances include carbohydrates
(sugars), which can be found for example as monosaccharides, disaccharides
and as starch as well as fats and proteins. As sapwood is responsible for the
constant water and nutrient supply of the whole tree, mainly primary extrac-
tives are involved, which are also used by various micro-organisms as a source
of food.
Heartwood contains very few or no primary extractives, but usually sig-
nificantly more secondary extractives than sapwood. The secondary substances
include almost all the other extractive classes, hence they have enormous
structural variety including most different substance classes like alkaloids,
quinones, fats, oils, saponins, terpenes, tropolones, waxes and a number of
aromatic or phenolic compounds (stilbenes, lignans, flavonoids, tannins, etc.).
The secondary substances play an essential role in the use of wood, for example
the heartwood of most of the wood species is more durable than the sapwood.
Whether and to what extent the chemical, biological, physical and optical
properties of the wood species are influenced by the extractives depends gen-
erally on the quantity and the substance class, which is in turn specific to the
Wood 315

Scheme 9.4.6 Examples of extractives.

wood species. In Table 9.4.5, the effects on properties as well as the processa-
bility are summarized.35
A very important criterion determined by the extractives is the natural
durability of wood. Furthermore, colour, odour and taste are mainly caused by
316 Chapter 9.4
14
Table 9.4.4 Solubility of wood extractives.
Glycosides,
Resin acids, Fats, fatty sugars,
Major compound monoterpenoids, acids, steryl Phenolic starch,
classes other terpenoids esters, sterols substances proteins Inorganics

Solubility in
Alkanes +++ +++ 0 0 0
Diethyl ether or +++ +++ ++ 0 0
dichloromethane
Acetone +++ +++ +++ ++ +
Ethanol ++ ++ +++ + +
Water 0 0 + +++ ++
+++: easily soluble, ++: soluble, +: slightly soluble, 0: insoluble

Table 9.4.5 Extractives in wood: functions, effect on properties and

processability.
Function Primary extractives: substances for maintaining the metabolism;
formation of components for the biosynthesis of secondary
substances;
Secondary extractives: substances for the protection against biologi-
cal decay etc.
Effect on Colour, Odour, Taste,
properties pH value,
Natural durability,
Light resistance,
Dimensional stability,
Calorific value, Combustibility etc.
Effect on Reactions with additives or metals (adhesion properties, staining,
processability corrosion etc.);
Surface treatment;
Reactions during pulping (e.g., pitch problem);
Toxic or allergic effects;
Volatile organic compounds (VOC)

the extractives present. In addition to the decorative aspects in various areas of

wood utilization, extractives are distinguished, for example, for the production
of wine, whiskey and cognac, where mainly white oak and chestnut wood is
used for barrels. The colourless distillates absorb the phenolic compounds of
the wood as well as wood dye, where the typical more or less golden colour of,
for example, cognac comes from. Concurrent oxidation and esterification
processes improve the aroma and the taste.36
Furthermore, extractives determine the pH value due to their solubility,
which can often play a role in wood processing. Certain extractives, which can
be found for example in larch, oak or various tropical woods, can cause
staining or even corrosion when in contact with ferrous materials. In the same
way, light resistance or swelling and dimensional stability of the wood can
be affected by lipophilic extractives. Furthermore, a relation between certain
extractives and the calorific value or even combustion has been reported.15
Wood 317
In general, reactions with additives might occur in such a way that adhesion
properties or coatings and surface treatment processes are affected or staining is
caused. Furthermore, pitch problems in pulping as well as toxic or allergic
reactions might be induced by components of certain wood species during
processing.14,37 In recent years, parts of the lightly volatile extractives have been
discussed with regard to the problem of volatile organic compounds (VOCs),
which concerns mainly softwood or products thereof.38
Since time immemorial, humans have used nature as a pharmacy and plant
parts of the tree other than wood have also been used. Hippocrates recommended
using the bark of poplar and willow trees against rheumatic pains. Although the
willow bark does not contain salicylic acid but only salicylic alcohol derivatives,
it was not only an eponym (Latin salix ¼ willow), but also a paradigm of one
of the most famous drugs namely Aspirins. Furthermore, in a Chinese book
concerning agriculture and medicinal plants, probably composed between 300 BC
and AD 200, the use of extracts of the foliage of Gingko biloba as medicament is
described, which is still traded as a natural remedy for the purpose of increased
mental efficiency by presumed improved blood circulation of the brain.20
Even today, researchers are looking for new and highly efficient substances in
plants and animals. In recent years, the so-called phytomedicine showed an
increasing interest in biologically active substances.
Although wood and barks still play an inferior role, there might be a large
potential.39,40 The need for further research is demonstrated on a number of
native wood species where there is still little known about the biological activity
of their substances.41 Another aspect is that the secondary products of pulp
production are insufficiently used from an economic point of view. Some well-
known as well as new and promising aspects are presented below.
A few years ago, a Finnish research group at Abo Academy discovered a new
potential for the utilization of knotwood extractives.42 It was found that
knotwood contains a very high percentage of bioactive phenolic extractives,
mainly lignans, which are on their way to being technically utilized. Thereby,
knotwood, which usually is not desired in pulp production, has turned out to
be an interesting raw material for the pharmaceutical industry. Knotwood
contains up to 24% lignans of which 0–85% is 7-hydroxymatairesinol
(Scheme 9.4.7), which is already in possession of the Investigational New Drug

Scheme 9.4.7 Chemical structures of betulin, hydroxymatairesinol and aesculin.

318 Chapter 9.4
Approval by the FDA, as it seems to be effective against previously incurable
cancer diseases. In Finland, a process was developed to separate and extract
knotwood during the production of wood chips.42–45
Phytopharmaca have been developed, for example, due to the cytostatically
effective (-)-taxol of the bark of the yew tree, even if today it is predominantly
obtained from plant cell cultures or partially synthetic from taxanes existing in
the needles of yew trees.20 Further examples for biologically active substances
include the analgetic salicin of various willow species as well as avicine from
the Australian acacia or Argan oil from the Moroccan argan tree, which can
be used in cosmetics (see Chapter 9.7).46,47 Pycnogenols, a water extract of the
bark of lodgepole pine (Pinus maritima), which consists of 490% flavonoids,
shows a high antioxidant effect.48
Furthermore, betulin, which is found in birch bark at up to 25–35%, is the
subject matter of many investigations. The pharmacological spectrum efficacy
of betulin (Scheme 9.4.7) is very broad. In the treatment of skin diseases and
skin disorders, betulin proved to be anti-inflammatory, anti-bacterial and
beneficial to wound healing. In recent research, further potential and very
interesting properties of the medicine emerged. Antiviral, hepatoprotective
and antitumorigenic effects were found. This is currently the subject matter of
worldwide betulin research.17,49
The reason why the horse chestnut was voted medicinal plant of the year
2008 in Germany is the fact that modern medicine ascribes medically valuable
aspects with regard to humans to the awarded tree. In addition to the abate-
ment of diarrhoea or itching, the ingredients of the horse chestnut are especially
efficient against venous diseases, in particular vein weakness. The bark of
the horse chestnut is rich in tanning agents, which can abate diarrhoea and
haemorrhoidal disorders like weeping and itching. Furthermore, it contains an
especially high amount of aesculin (Scheme 9.4.7), which is isolated from the
plant and then included in sunscreens. It also contributes to the abatement of
chronic venous insufficiency.50
There is certainly still potential regarding the material utilization of extrac-
tives including in particular other parts of the tree like the bark which have been
barely used or not used at all industrially up to now.

9.4.2.6 Inorganic Components (Ash)

The term ash reflects the determination method. Herewith all inorganic sub-
stances are described that can be quantitatively detected after incineration. The
ash is composed of important nutritional elements (e.g. potassium, calcium,
magnesium, manganese, sodium, phosphorus) and trace elements (iron, zinc
and many more). While the ash content of wood species in temperate zones
ranges between 0.2 and 0.5%, it can be significantly higher in tropical wood
species (41%) due to silicon incorporation.12 This also applies to the bark,
which often contains ten times more than the wood. Usually, inorganic com-
ponents are irrelevant in the processing of wood. However, during energetic
utilization, certain elements influence the processes (see Chapter 7),
Wood 319
e.g. potassium together with an acidic pH value may cause corrosive effects.6
Silica compounds influence tools used in mechanical machining processes
(saw blades, knives, etc.).

9.4.3 Pulp and Paper

9.4.3.1 Production and Environmental Aspects
Currently applied processes for the chemical utilization of wood are almost
exclusively geared towards chemical pulping. Although, to some extent, the
utilization of by-products like vanillin, xylose, furfural, acetic acid or resins (tall
oil, rosin and products thereof (e.g. sitosterol); see Chapter 9.7) is also included,
very often not more than 50% of material utilization is obtained (e.g. sulphite
mass balance in Figure 9.4.4).
Pulping of lignocellulosic materials results in fibres termed pulps. Pulping of
wood can generally be divided into mechanical and chemical pulping or mix-
tures of both types. In chemical pulping, nowadays the alkaline Kraft sulphate
pulp process is predominant compared to the sulphite process.
In principle, all pulps are intermediates in paper production obtained by
different treatments of wood or other non-wood fibrous raw materials such as
different grasses, bagasse (sugar cane, stalks after sugar removal) or cotton
fibres and secondary or recovered fibres from used paper.
About three thousand paper assortments and grades are finally composed of
different portions of selected specific pulps and varying additives to yield the
final paper properties with respect to strength, surface quality, printability,
colour, etc.
The treatment may exclusively be a mechanical treatment by grinding or
refining the raw materials in the presence of hot water or vapour in specialized
processes, yielding pulp products like groundwood or thermo mechanical pulps
(TMP). Both types of mechanical pulping can be improved and supplemented
by addition of small amounts of chemicals to the aqueous systems, or working
under pressure, etc. Since in these types of processes lignin is not removed the
yields are high with values between 90 and 98%.
Another group of pulps is produced by a large number of so-called semi-
chemical or high-yield processes in which mechanical and chemical treatments
are combined. Since, in this case, part of the lignin is removed the yields differ
between 60 and 90%.
The most important pulps are chemical pulps produced by a cooking treat-
ment with selective lignin dissolving chemicals in a wide pH range from strong
acidic to strong alkaline conditions. The prominent and important pulping
process applied worldwide is the sulphate or Kraft process (Table 9.4.7) using
Na2S, NaOH and Na2CO3 as leading chemicals for the removal of most of the
lignin. Thus, the typical yields for chemical pulps drop to about 50% of
the starting material as most of the polyoses and part of the cellulose is also
dissolved along with lignin and extractive components.
320 Chapter 9.4
While mechanical pulps are used mostly in low-quality paper grades and
assortments, e.g. for newsprint or packing papers, Kraft pulps are the strongest
pulps used in all-quality papers and paperboards where high strength proper-
ties are required.12,18,21,51,52
To attack residual portions of lignin which were not dissolved during the
cooking process in chemical pulping a series of different bleaching sequences
are applied. In principle there are two types of bleaching concepts: reductive
bleaching and oxidative bleaching. Reductive bleaching with reducing chemi-
cals (e.g. NaHSO3, Na2S2O4 or formamidinesulfinic acid [FAS]) does
not remove lignin but only converts chromophoric groups in more oxygen and
light stable functionalities. To prevent the paper from yellowing, oxidative
chemicals used in bleaching, today mostly oxygen, ozone, hydrogen peroxide,
etc., remove residual lignin portions to yield pulps with high brightness and
brightness stability.
In all cases in modern pulp bleaching, elemental chlorine is excluded and only
chlorine dioxide is applied to yield elemental chlorine-free pulps (ECF pulps).
If any chlorine-containing compound is avoided totally chlorine-free pulps
(TCF pulps) are achieved. Concerning the bleaching, Kraft pulp mills have
been converted predominantly to elemental chlorine-free (ECF) bleaching.
Totally chlorine-free (TCF) bleaching is the method of choice for sulphite mills.
Therefore, the extent of TCF bleaching remains at around 5% of the pulp
production.
Many efforts regarding the research on alternative pulping processes have
not yet been realized on an industrial scale. This is true for organosolv pulping,
using organic solvents to support the removal of lignin from wood or acid-
catalyzed organosolv pulping processes such as Formacell and Milox or ASAM
(alkaline sulphite with anthraquinone and methanol) pulping.
Although the operation of a pulping process requires energy, modern mills
do not require fossil fuel as the source, because all the energy comes from
combustion of the compounds (mainly lignin) dissolved during the pulping
process.18
Recovery of the pulping chemicals has been increased significantly and
substantially contributes to the economy of pulp manufacture.
The pulp and paper industry has been regarded as a ‘‘dirty’’ industry,
neglecting environmental aspects and matters of sustainability up until
the 1980s and 1990s due to huge amounts of required energy and water,
and the release of volatile and solid emissions and contaminants to the atmo-
sphere, to the aquatic environment and to the ground. In addition, the
industry was claimed to be partly responsible for diminishing valuable
forests by the use of ever-increasing amounts of suitable wood species and
assortments.53
In contrast, most of the modern pulp mills nowadays have reduced their
environmental impacts applying ‘‘accepted modern technology’’ (AMT) or
‘‘best available technology’’ (BAT). Improvements in technology are supple-
mented by the use of wood which is certified by means of internationally
accepted and applied forest certification standards e.g. FSC and PEFC.
Wood 321
The essential steps towards clean technologies in pulping were achieved by
preferring Kraft pulping to sulphite pulping (see Table 9.4.6), which reduced
the negative environmental impacts by better recoveries of involved chemicals
and dissolved organic wood components. In bleaching, the removal of ele-
mental chlorine and the extended use of oxygen and oxygen-based chemicals in
bleaching sequences as well as high standards in the sewage plants, including
sophisticated cleaning and biodegradation technologies also contribute to
environmental improvements.18,53 Overall, modern and up-to-date pulp and
paper production can be characterized as an extremely complex and difficult
conversion technology and business which succeeded over the last 20 years in
reducing the negative impacts of pollution, effluents, solid wastes, odour, water,
energy consumption and CO2 emissions. In addition, the ecological standards
of raw materials and final products on an international level are fulfilled by the
pulp and paper industry. An example for the reduction of energy in the German
pulp and paper industry is given in Figure 9.4.5.
An overview of the worldwide pulp production, divided into the respective
categories, is presented in Table 9.4.6. Figure 9.4.6 shows the countries with
more than 1 Mio mto annual production.9 Figure 9.4.7 reflects the major trade
flow of wood pulp worldwide. The percentage of mechanical pulp is approxi-
mately 10% and that of chemical pulp is approximately 40%. Thus, it can be
clearly seen that, by now, approximately 44% of the pulping raw materials is
composed of recycled fibres. The use of waste paper strongly depends on the
pulp percentage produced inland. Thus, in Central Europe, for example in
Germany (58%), significantly more waste paper fibres are used than in Scan-
dinavia. Moreover, 5% of the total pulp production is made from non-wood
plant fibres, including stalk, bast, leaf and seed fibres.

Figure 9.4.5 Energy input per ton of pulp and paper production in Germany.54
322 Chapter 9.4
18
Table 9.4.6 Global pulp production by category (2000) (with permission of
Wiley-VCH Verlag GmbH & Co. KGaA).
Pulp production
Pulp category [Mio mto]

Chemical 131.2
Kraft 117.0
Sulfite 7.0
Semichemical 7.2
Mechanical 37.8
Nonwood 18.0
Total fibres 334.0
Total virgin fiber 187.0
Recovered fiber 147.0

Figure 9.4.6 Worldwide production of total (mechanical and chemical) pulp;

countries with more than 1 Mio mto annual production.

The pulp and paper industry is a branch where large, multinational com-
panies dominate pulp production on a global scale, often combined with mass
paper production. On the other hand, medium-sized and small companies are
producing a large number and variety of speciality papers. In Germany, for
example, four to five international companies (‘‘global players’’) produce
pulp and paper in big tonnages, while about 160 paper mills act in the field of
speciality papers.
Pulp represents the major raw material basis for the two main applications: a)
about 95% for paper and board production, where the pulp fibres are addi-
tionally modified to give a coherent paper sheet and b) about 5% for chemical
Wood 323

Figure 9.4.7 Major trade flow of wood pulp worldwide (2004). (Thickness of arrows
corresponds to trade volume.)

conversion to products such as regenerated fibres and cellulose derivatives. The

former is denoted as paper grade pulp, the latter as dissolving grade pulp.18,21
The paper grades produced by the paper industry are multitudinous and run
into thousands. However, the paper grades can be summarized into groups, like
graphic paper including printing paper and writing paper, as well as packaging
paper and board, sanitary paper and technical speciality paper, as can be seen
in Figure 9.4.8.21
Dissolving pulps are high-quality, intensely bleached pulps. As they are used
as chemical intermediate product or source material for viscose rayon and

Figure 9.4.8 Applications of chemical pulping.

324 Chapter 9.4
besides cotton linters for cellulose derivatives (e.g. cellulose ether and ester),
they feature a significantly higher degree of purity when compared to paper
pulp. Thus, the contents of polyoses (0.5–10%), lignin and extractives (o0.2%)
are much lower depending on the application.55

9.4.3.2 Products
There are manifold applications for dissolved pulp, as can be seen in
Table 9.4.7. Today, regenerated cellulose fibres are of utmost importance. They
are produced either through the viscose process by derivatization with CS2 or
according to the lyocell process through direct solution in 4-methylmorpholine-
4-oxide (NMMO). In addition, there are a number of cellulose derivatives
with very specific properties. Thus, cellulose ethers and esters like methyl cel-
lulose (MC), methyl hydroxypropyl cellulose (MHPC), carboxymethyl cellu-
lose (CMC) and hydroxyethyl cellulose (HEC) are used, for example, as glue
for wall paper (MC), as protective colloids in suspension polymerization of
vinyl chloride (MC, MHPC) and in emulsion polymerization of vinyl acetate
(HEC) as entire deposition agent for laundry detergents (CMC) or as thick-
ening agents in aqueous paints, cosmetics and food (e.g. E 461–E 466) due to
their ability to influence the rheology of liquid systems. Cellulose esters such as
acetates are used for cigarette filters due to their specific filtration and
adsorption properties and they are also used as raw material in photographic
films due to their excellent optical properties. Properties like surface activity,
impact strength, transparency and brilliancy present an advantage when
nitrocellulose is used as a coating raw material.56
As already mentioned, 95% of the pulp is used for the production of paper.
In Figure 9.4.9 it can be seen that, despite the development of electronic media,
the worldwide production of paper is still increasing. Thus, the paper demand
in developing countries is especially increasing.54
In Table 9.4.8 the largest paper and paperboard producing countries
worldwide and their share in the world production are presented.

Table 9.4.7 World production of dissolving pulp by end-use (2003)18 (with

permission of Wiley-VCH Verlag GmbH & Co. KGaA).
Cellulose product Examples of end-use [Mio mto]

Regenerated fibres Staple, filaments 2.20

Cellophane Sponges, casings 0.10
Cellulose acetate Tow, filament, plastic 0.53
Cellulose ether Protective colloids, wall paper 0.47
glue thickening agents
Microcrystalline cellulose Moulding powder 0.09
Others (e.g. nitrocellulose) Varnishes, speciality papers, 0.26
explosives
Total 3.65
Wood 325

Figure 9.4.9 Development of paper production worldwide.

Table 9.4.8 Top Ten of worldwide paper manufacturing countries (2006).

Country [Mio mto] [%]

USA 84.0 22
China 65.0 17
Japan 31.1 8
Germany 22.6 6
Canada 18.1 5
Finland 14.1 4
Sweden 12.0 3
South Korea 10.7 3
France 10.0 3
Italy 10.0 3
Total of top ten 277.6 73
World 382.6 100

9.4.4 Wood-based Composites

9.4.4.1 Conventional Concepts and Products
The concept of wood-based products is to glue together wood parts or particles
in a specific way. The wooden part may be boards, veneers, strands, particles or
fibres thus yielding e.g. laminated beams, plywood, oriented strand boards
(OSB), particle boards, fibreboards (e.g. medium-density fibreboards, MDF)
in a multitude of specifications. The gluing components are predominantly
oil-based glues, but can also be inorganic adhesives like gypsum or cement.
326 Chapter 9.4
The advantageous characteristics of wood-based products in comparison with
solid wood products are e.g.:

 Wood-based products overcome the limited dimensions determined by

height and diameter of the tree;
 Wood-based products are exclusively processed in industrial plants
yielding reproducible characteristics and quality;
 Parts of wood-based products, e.g. particle boards, can afford the use of
low quality and mixtures from different raw materials and assortments
(e.g. residues containing bark and branches, used timber and used
products);
 Wood-based products are much more homogenous compared with solid
wood. Therefore, dimensional stability, surface quality, individual strength,
properties, etc. can be perfectly made for special applications and needs.

9.4.4.2 New Concepts and Products

The materials referred to as Wood-Plastic-Composites (WPC) mainly consist of
the renewable raw material wood, synthetic resins, recycled and conditioned
plastic chips and additives. The composites are mixed and processed according
to established plastics-processing technologies. For lack of suitable standards,
the terminology for WPCs is quite vague. Synthetic resins impart bonding;
additives like UV absorbers, heat stabilizers or plasticizers and lubricants
improve processing and performance properties, pigments are added for col-
ouring. WPCs can be processed by thermal-forming technologies like extrusion,
injection moulding or moulding techniques.57,58
Suitable plastics for the production of WPCs are relatively cheap and can be
processed at temperatures below 200 1C. Further increase in temperature would
cause damage of the wood components (lignin, wood polyoses). Suitable
plastics are, for example, polyethylene, polypropylene or polyvinyl chloride.57
The wood components are mainly obtained from the by-products of the saw
mill industry. The subsequent mechanical properties of WPCs are mainly
influenced by the fineness and the slenderness ratio. It depends on the slen-
derness ratio whether the wood is used as filler or product reinforcement.57
Bonding agents like maleic anhydride are used for improved bonding
between wood, the plastic, calcium carbonate, talcum or mica. The strength
and the heat resistance are increased; creeping is compensated. Additional
additives will be added depending on the application of the WPC in order to
reduce combustibility or to improve the resistance and the durability.57
Compared to wood-based products, WPCs are freely mouldable, moisture
resistant and fairly resistant to rot. After-treatment of the products is not
required.
Furthermore, they show higher strength, stiffness and a significantly lower
coefficient of expansion compared to purely used plastics. An increase in the
wood percentage leads to efficient cost savings. Since, however, WPC is mainly
Wood 327
57
for exterior use, resistance of the product against fungi is important. There-
fore, the addition of fungicidal acting additives is required.
WPCs are mainly used for interior and exterior floor covering, but also for
the construction of patios, stairs and terraces (Figure 9.4.10). Furthermore,
WPCs are used for promenades, noise barriers, docks, fences, railings, window
frames and doors.59,60 Future markets could be found in the furniture and
automobile industry.60
In the United States, approximately 75% of the WPCs are used in the
building sector and approximately 50% of the entire market volume is used
for terraces and patios.60,61 In the year 2003, the market share of WPC products
for exterior use was 14%, comprising a financial volume of approximately
3.5 billion US$. These so-called deckings consist of polyethylene with a wood
percentage of 50–70%.
The annual growth of the markets is considerable. Worldwide, over 1 Mio
mto of WPC are produced per year. While it is just under 1 Mio mto in
Northern America, Europe has, with an estimated 105,000 mto (2006), still
quite low values, followed by Asia with approximately 100,000 mto.60
The mechanical properties of Wood-Plastic-Composites substantially depend
on the quality of the raw material, the composite and the manufacturing
process. The density of WPC lies between 0.9 and 1.4 g cm3 and is higher than
that of one of the two components, plastic and wood, alone. The porous wood
structure is densified during the production process and plastics and additives
partly penetrate into the cavities. Thus, water absorption is made harder, and
the material swells less and more slowly.57
In general, the stiffness of a WPC increases linearly with increasing wood
percentage. The stiffness of WPCs with a wood percentage of 50% is five times

Figure 9.4.10 WPC for exterior use.

328 Chapter 9.4
62
higher than the one of pure polyproylene. Mean bending strengths of up to
40 N mm2 are common for WPC.57
In principle, WPC products are recyclable. They are melted down and pro-
cessed into granules. A second extrusion or injection moulding is technically
feasible. However, the quality of recycled WPCs and the reaction of the wood
component is still unclear.57 Furthermore, the blending of various plastic
components often makes the recycling even more complex.63
ARBOFORMs and FASALs are examples for the development of com-
posites made of wood and other materials corresponding to the idea of ‘‘green
chemistry’’.
ARBOFORMs consists of the three basic components, lignin, plant fibres and
additives on the basis of renewable raw materials. For the first time, this mixture
was successfully developed as a material capable of injection moulding at the
Fraunhofer-Institute for Chemical Technology Pfinztal, Germany, in 1996.
Further development of the material was carried out by TECNARO, a company
founded by the Fraunhofer-Institute in 1998.64 The product name is derived from
the Latin term for tree (arbor).34 At present, ARBOFORMs is successfully used
for the manufacture of marketable products like precision parts, toy figures or
loudspeaker housings by means of extrusion and injection moulding.34 Ongoing
research projects deal with the development of circuit boards, the manufacture of
bipolar panels in batteries and building boards (Figure 9.4.11).60,64–66
Qualitative and quantitative modification of the raw materials significantly
influences the product properties. The properties of the lignin are influenced by
the origin, since the proportion of the elements (p-hydroxyphenyl-, guaiacyl-,
syringyl units) in softwood, hardwood or annual plants varies and, hence,

Figure 9.4.11 Boards made of ARBOFORMs.

Wood 329
differences in the chemical reaction behaviour result. Particularly, the kind of
the technical lignin (from either the Kraft or the sulphite process) influences the
material properties of the lignin.
Resource and manufacturing processes affect the chemical composition and
reactivity as well as the geometry of the fibres in plant fibres. Lignin, reactive
substances like tannins, resins and tanning agents as well as reactive wood
polyoses or smooth surfaces of the elements significantly influence the quality
of the bonding and, hence, the later product properties. Furthermore, particle
size and slenderness ratio play a role.
The additives have different functions within the product. They afford the
bonding of the lignin on the plant fibres or particles and improve the rheology.
Other additives act as flame retardants or as fungicides.
Similarities between FASALs and ARBOFORMs can be found. The fibre
components of FASALs are wood particles, rice husks or coconut fibres.
Natural starch, such as for example from maize, and partly proteins are used as
binders. Resins or pigments from natural raw materials are used as additives.
Processing is done by processing techniques used in the plastics industry, e.g. by
extrusion. The application is comparable to the one of injection moulded
ARBOFORMs.67
Since the two products consist of renewable raw materials, they can be
recycled or energetically used after their service life.

9.4.5 Modified Solid Wood Products

Although wood is used for many applications because of its excellent material
properties, it can show disadvantages with undesirable effects in specific
application areas too. Prominent examples are the variation in dimensional
stability as a result of altering atmospheric conditions or the low natural
durability of many domestic wood species. Wood modification has also become
a topic of renewed interest because of increasing environmental considerations,
e.g. some modified woods can substitute tropical hardwoods due to their darker
colours and higher durability. Wood modification represents a process that is
used to improve the material properties of wood, but produces a material that
does not show at the end of a product life-cycle a higher environmental hazard
than the unmodified wood during the disposal.
Driving forces for wood modification are:

 Improvement of important application properties (higher dimensional

stability, higher durability);
 Increasing demand for outdoor applications of wood (higher durability);
 Substitution of tropical wood species (higher durability and/or darker
colours);
 Alternatives for chemically preserved wood (durable and low-maintenance
assortments of domestic wood).
330 Chapter 9.4
This chapter can give only a short insight into some important aspects. A
comprehensive overview with further and detailed information can be found in
the literature.68,69

9.4.5.1 Chemical Modification

‘‘Chemical modification of wood is defined as the reaction of a chemical reagent

with the wood polymeric constituents, resulting in the formation of a covalent
bond between the reagent and the wood substrate.’’69
’’Impregnation modification of wood is defined as any method that results in the
filling of the wood substance with an inert material (impregnant) in order to bring
about a desired performance change.’’69

In this chapter no distinction is made between a real chemical modification

(acetylation), where covalent bonds between the reagent and the chemical
constituents of wood are formed, and the impregnation modification, where
monomers diffuse into the wooden cell wall and become polymerized there, like
Hill suggested in his definitions (see above), because it was shown that
DMDHEU and furfuryl alcohol not only swell the cell wall and polymerize
there but also have the potential to form some covalent bonds.70,71
This chapter deals mainly with commercially used processes, which are at the
moment:

 Acetylation with acetic anhydride (e.g. Accoyas of TITAN WOOD);

 DMDHEU ¼ Dimethylol dihydroxy ethylene urea (Belmadurs of BASF);
 Furfurylation with furfuryl alcohol (e.g. Kebonys, VisorWoods).

During the chemical modification of wood with acetic anhydride

(Scheme 9.4.8), the reaction takes place with the cell wall polymeric hydroxyl
groups to form ester bonds. Acetic acid is produced as by-product.
A commercial plant (Titan Wood) has started to produce acetylated wood
and has given the acetylated wood the name of a ‘‘new wood species’’:
Accoyas. Improved properties are high durability, high dimensional stability
and high UV-resistance.68
Dimethylol dihydroxy ethylene urea (DMDHEU), a resin primarily devel-
oped for the textile industry, was used on wood (Scheme 9.4.9), e.g. beech

Scheme 9.4.8 Reaction of acetic anhydride with wood.

Wood 331

Scheme 9.4.9 Reaction of DMDHEU with wood.

Scheme 9.4.10 Reactions of furfuryl alcohol.

veneers. After impregnating the wood with DMDHEU solution, drying at a

temperature of more than 100 1C causes cross-linking and polycondensation
reactions.
A commercial product is Belmadurs from BASF, which is harder, more
durable and more dimensionally stable than the respective untreated wood.72
The principles of forming furan polymers from the condensation of furfuryl
alcohol have become attractive for modifying wood, when ways of controlling
the polymerization in dilute systems were discovered. There are several com-
peting reactions: condensation and cross-linking reactions of furfuryl alcohol
with itself and also the reaction between furfuryl alcohol and lignin units is
supposed (Scheme 9.4.10).70,71
Sweden is the largest producer with nearly 1,000,000 m3 impregnated wood
in 2003. Finland and Norway were treating approximately 360,000 m3 each,
while Denmark treated 151,000 m3 in 2003.
VisorWoods is furfurylated Scots pine (sapwood and heartwood) and is
used for outdoor applications like cladding and decking roof boards, where
durability is required.68
Kebonys is sapwood of various pines or temperate hardwoods like beech
and ash and is marketed as an alternative for tropical hardwoods and is suited
for floors, interior panels and other applications where tropical appearance,
hardness and dimensional stability are important criteria.68

9.4.5.2 Thermal Modification

‘‘The thermal modification of wood is defined as the application of heat to wood in
order to bring about a desired improvement in the performance of the material.’’69
The thermal modification of wood has become a topic of great interest
since the first heat-treatment plant was built in Finland in the early 1990s.
The production volume of thermally modified wood in Europe increased from
332 Chapter 9.4
3 3 73
about 100 m in 1995 to about 130,800 m in 2007 (Figure 9.4.12). However,
also in North America there are some developments concerning the thermal
modification of wood.
One consequence of increased market relevance is that in November 2007 the
European Committee for Standardization (CEN) drew up the first technical
specification (TS) about thermally treated wood (TMT).
Without application of chemicals as wood preservative, the thermal treat-
ment can be seen as a contribution to the increasing environmental protection,
even though an energy input is necessary for the production of TMT.69 There
are different types of thermal modifications (Table 9.4.9).
Of greatest importance still is the classical thermal modification in an
atmosphere of water vapour and volatiles from wood without additional
pressure. Most of the existing plants are based on this process, which has been
optimized in different ways regarding the chamber system or the process
sequence. The technical details in which the processes and accordingly the
plants differ are company secrets.
The other processes apply partly different atmospheres. In the oil-heat-
treatment (OHT) vegetable oil is used; in the French systems e.g. nitrogen is
used (RetifiedsWood [bois rétifié], NOW [new option wood]). The multi-stage
PLATO (Providing Lasting Advanced Timber Option) process uses in the first

Figure 9.4.12 European production of TMT.

Table 9.4.9 Thermal treatment processes.73

Process Process conditions
s s
ThermoWood , Stellac Wood, Water vapour and volatiles from
Thermoholz, Perdure etc. wood without additional pressure
PLATO Thermo hydrolysis (autoclav) and high
temperature treatment
Retifications (Baladur, NOW), Nitrogen
OHT Vegetable oil
Wood 333
step water vapour under pressure, which is named hydro thermolysis followed
by drying, curing and conditioning.
Typical applications of thermally treated wood are e.g. garden furniture
(Figure 9.4.13), deckings for balconies, terraces or swimming pool borders and
for wet areas.
The application of heat to wood results in chemical changes in the material.69
The properties of the modified products depend on the one hand on the specific
chemical composition of the different wood species, but, most notably between
hardwoods and softwoods, on the other hand on the process conditions.
Maximum temperatures, atmosphere and the duration of the thermal load
are among the main parameters. Further influencing factors are the sample
dimensions and whether the system is open or closed.
The results of several published chemical investigations of thermally treated
wood are not comparable in each case, because the changes and their extent are
due to treatment conditions, such as temperature and atmosphere during the
treatment or duration of the treatment.69,74–77
In general, properties such as colour, natural durability and dimensional
stability of thermal treated wood differ from those of untreated wood.
Depending on the duration and the power of the process, thermally treated
wood shows improved rot-resistance properties and also demonstrates
increased resistance to both fungi and climatic influences.69,74 To warrant the
natural durability it must be ensured, however, that the TMT products have
no contact to the ground.78 Furthermore, its dimensional stability can be
improved as well as its adhesion property against hydrophobic materials.79,80

Figure 9.4.13 Furniture at the German Horticultural Show in München 2005

334 Chapter 9.4
Moreover, darker tints, which are normally characteristic only for tropical
wood species, can be achieved.79,81
It is well known that the chemical changes are caused by autocatalytic
reactions and that changes starting with hydrolysis of polyoses mainly depend
on the applied temperature. Afterwards amorphous cellulose and lignin are
affected by the treatment as reported in numerous papers.12,69,75–77 Due to the
various chemical natures of wood species it is nevertheless difficult to make
prevailing predictions of the treatment results in detail. In general, there are still
several deficits. Above all, there are varying properties due to the multiplicity
of different thermally modified assortments. Missing standardization and
quality control for market products leads sometimes to a lack of confidence
of potential customers. Furthermore, there is still a lack of knowledge on the
mechanisms of modification and application restrictions due to varying
strength properties.

9.4.6 Outlook
The principles of green chemistry may be summarized in the simple statement
‘‘applying fundamental knowledge of chemical processes and products to
achieve elegant solutions with the ultimate goal of hazard-free, waste free,
energy-efficient synthesis of non-toxic products without sacrificing efficacy of
function’’.82
As the worldwide shortage of exhaustible resources can be predicted quite
reliably and is accompanied by an increase in price of crude-oil-based products,
this will in turn promote the marketability of substitution products on the basis
of renewable raw materials, which is more sustainable than the production of
oil-based materials and products.
The trees and the forests as well as any other biomass are a renewable resource,
the potential of which has not yet been exploited. Hence, different compounds
like flavonoids, lignans, terpenes, phenols, alkaloids, sterols, waxes, fats, tannins,
sugar, gum, suberins and resins from different woods and plant components can
be extracted and converted to useful market products. The utilization of wood as
a provider of components for niche and premium products is certainly able to
grow. In this regard, various research fields have been opened and extended,
focused on raw materials, products, processes and development of methods as
well. This needs efforts and contributions by politics, industry and research. Even
if science will not eventually invent or detect another acetylsalicylic acid, there are
a number of open questions like identification of unknown, biologically active
compounds or the regulation of the biosynthesis of various extractives. Fur-
thermore, a large added value could be achieved by the production of pharma-
ceutically active or health beneficial ingredients, which include for example
phytohormones, polyphenols or triterpenes.
In future, by using wood, or one of its components, as a renewable resource,
the entire process chain or an entire reaction system can be regarded under
‘‘green’’ aspects including energy efficiency.
Wood 335
An established instrument for ecological evaluation of processes or products
is life-cycle-assessment, which is particularly useful for ecological comparison
and optimization of processes and products. A consequent realization of the
mentioned aspects and challenges will lead to a better and more sustainable
situation on our planet for both nature and mankind.

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49. http://www.betulin.de/ (retrieved 23.01.2008).
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51. J. Gullichsen and C.-J. Fogetholm, (Ed.), Chemical Pulping 6A, 6B, Fapet
Oy, Helsinki, 1999.
52. M. Ek, G. Gellerstedt and G. Henriksson, ed., Ljungberg Textbook,
Pulping Chemistry and Technology, Stockholm, 2006.
53. W. Sandermann, Papier. Eine Kulturgeschichte, Springer, Berlin, 3.
Auflage, 1997.
54. Verband Deutscher Papierfabriken e.V. (VDP), ed., Papier: Ein Leis-
tungsbericht, 2008.
55. R. Janzon, B. Saake and J. Puls, http://www.bfafh.de/iud/projekte/3-2006/
5-1.pdf (retrieved 23.01.2008).
56. H. Harms, in Lignovisionen, High-Performance Materials from Nature,
University of Natural Resources and Applied Life Sciences, Vienna, 2006,
pp. 27–34.
57. Anonymous, http://www.nova-institut.de/pdf/06-01_WPC-Studie.pdf (ret-
rieved 13.04.2006).
58. A. Teischinger, U. Müller and H. Korte, Holztechnologie, 2005, 46, 30–34.
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sites in structural applications (retrieved 28.05.2004).
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Kunststoffe, 2008, p. 29.
61. P. Schwarzbauer and A. Eder, in 4. Internationales Seminar für die
Holzindustrie in der Schweiz, Wien, 2003.
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ceedings, Wien, 2006, pp. 126–129.
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der 25. Holzschutz-Tagung der DGfH, Biberach 20–21 September, 2007,
pp. 143–161.
79. D. Johansson, Thesis, Lulea University of Technology, 2005.
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(retrieved 04.07.08).
CHAPTER 9.5

Natural Rubber
LAURENT VAYSSE,a FRÉDÉRIC BONFILS,b PHILIPPE
THALER,c AND JÉRÔME SAINTE-BEUVEb
a
CIRAD, UMR 1208, Joint Research Unit ‘‘Agropolymers Engineering and
Emerging Technologies’’ CIRAD, Montpellier SupAgro, INRA, Université
de Montpellier 2; Rubber Technology Laboratory Agro-Industry Building 3,
8th floor Kasetsart University, Bangkok 10900, Thailand; b CIRAD, UMR
1208, Joint Research Unit ‘‘Agropolymers Engineering and Emerging
Technologies’’, CIRAD, INRA, Montpellier SupAgro, Université de
Montpellier 2, 73 rue JF Breton, F-34398 Montpellier Cedex 5, France;
c
CIRAD, UPR80, Functioning and management of tree based cropping
systems, Campus international de Baillarguet, F-34398, Montpellier Cedex 5,
France

9.5.1 Introduction
Natural rubber, India rubber and caoutchouc are all names for the solid elastic
material isolated, one way or another, from the ‘milk’ or latex of Hevea bra-
siliensis, and various other tropical plants like Castilloa elastica. Natural rubber
and natural rubber products have been known to the ancient cultures of
Amazonia and Mesoamerica since time immemorial. According to the Spanish
historian Antonio de Herrera Tordesillas, Christopher Columbus returned
from his second voyage, bringing back the first rubber balls from the West
Indies to Europe. The term cahuchu or caoutchouc was used by the Maninas
Indians according to the French explorer Charles de la Condamine. It is gen-
erally taken to be based on the Indian cao ochu, which could be translated as

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

339
340 Chapter 9.5
teardrops of the weeping tree, an interpretation which was publicized by Vicki
Baum’s eponymous novel The Weeping Wood.124
Rubber is one of the most important products to come out of the rainforest.
The history of natural rubber since the beginning of the industrial age is a
fascinating sequence of inventions (vulcanization, Charles Goodyear and
Thomas Hancock, 1843/1844; pneumatic automobile rubber tyres, Robert
William Thomson, 1846; synthetic rubbers: polyisoprene, Fritz Hofmann,
1909; polydimethylbutadiene, IG Farben 1910; BUNA, IG Farben, 1910;
SBR emulsion polymerization, Walter Bock, 1929) as well as a trade
embargo (the Brazilian export embargo for Hevea seeds enforced by the death
penalty and broken by Henry Wickham’s ‘‘rubber theft’’, which laid the ground
for the Southeast Asian rubber plantations), the opulence of social life and the
brutality of the rubber barons in Manaus (e.g. Alberto Vazquez-Figueroa’s
novel, Manaos and Werner Herzog’s epic movie Fitzcarraldo, starring Klaus
Kinski).
Rubber is one of the few examples where chemical synthesis succeeded in a
nearly identical performance copy of a natural polymer (polyisoprene) – albeit
with a completely different chemical composition (styrene-butadiene-rubber,
SBR). Regarding sustainable development, the complete imbalance of the early
rubber history has emanated during recent years into equilibrium between
natural and synthetic rubber.
Natural rubber from Hevea brasiliensis is a natural polymer composed of an
association of poly(cis-1,4-isoprene) [poly(2-methyl-1,3-butadiene)] and biolo-
gical elements,1 giving it highly specific properties. Originating from the
Amazon Basin, Hevea was already booming in Asia at the turn of the twentieth
century.

9.5.2 Challenges Facing the Supply Chain

Natural rubber (NR) production – 9.7 Mio mto in 20072 – is mainly provided
by estates (usually 440 ha) and smallholdings (of around 2 ha) primarily
located in Asia between the Tropics; Thailand and Indonesia are the two main
producers. Some tens of millions of people earn a living from this crop, making
it a very important development factor in the region. Among the other stake-
holders operating in the production system, agro-industry is present but does
not hold the place that it occupies in the palm oil supply chain, which might
explain the difference in behaviour between these two supply chains in terms of
responsiveness (weaker in the case of NR, both economically and envir-
onmentally). In terms of consumption, the scheme is different, with an oligo-
poly-type situation where three tyre manufacturers3 share 50% of the market.
Both NR and SR are traded in a dry and in a liquid form. The elastomer
market (Table 9.5.1) is divided into three major zones (USA, Europe and
Southeast Asia) each of which has its own dynamics very closely linked to its
internal growth. In the years 2006–2007 China increased its synthetic rubber
consumption (+19.3%) more quickly than its natural rubber consumption
Natural Rubber 341
Table 9.5.1 Elastomer market (1000 mto) – Source: International Rubber
Study Group (IRSG); NR ¼ natural rubber; SR ¼ synthetic
rubber.
NR production SR production NR consump- SR consump-
2007 2007 tion 2007 tion 2007

North America 0 2790 1157 2129

Latin America 228 684 565 861
Africa 454 71 117 105
Europe 0 2811 1377 2623
Russia and others 0 1267 273 1057
Thailand 3056 156 374 217
Indonesia 2755 48 391 133
Malaysia 1200 67 446 123
China 600 2215 2550 3435
India 811 103 851 290
Japan 0 1655 887 1162
Others, Asia 622 1671 896 1129
Total 9726 13538 9884 13264

(+6.3%), whilst over the same period North America reduced its synthetic
rubber consumption (–3.4%) and stabilized its natural rubber consumption
(+0.8%). The effect of globalization has been to relocate the means of tyre
production to Southeast Asia, particularly to China. The rising price of energy
is likely to modify that situation profoundly as transport costs escalate. In
addition, the impending arrival of new stakeholders – especially in the Middle
East – in the synthetic rubber production sector risks destabilizing the elasto-
mer market.
Newly planted rubber trees take 5 to 7 years before they can be tapped and
reach their peak production in 10 to 20 years. Of the major global challenges,
the environment occupies a dominant place for rubber trees and natural rub-
ber, even on smallholdings where Hevea is usually intercropped with other tree
crops or food crops, thereby constituting agro-forests, which nowadays have
important secondary functions (maintaining biodiversity, environmental con-
servation, rehabilitation of degraded zones, etc.).4
As a tree, Hevea plays a role in carbon sequestration and may therefore be
eligible for the Clean Development Mechanism (CDM).5
Lastly, Hevea produces wood, which is effectively exploited today6 and
produces natural rubber in its laticifer rings, which man has learned perfectly to
use to his advantage. The car industry exerted such demand that supplies fell
short, opening up the way for synthetic rubbers, which have become the ideal
substitute capable of satisfying all the requirements of the industry. Substitu-
tion of natural rubber by synthetic rubber peaked in 1979 (29.5% of elastomers
consumed worldwide were made from natural rubber). Since then, the trend has
reversed, mainly due to industrial development in producing countries, which
favoured their own national production of natural rubber; in 2006 43% of
elastomers consumed worldwide were made from natural rubber. Since 2001,
342 Chapter 9.5

SMR20
3 100

Brent 90
2.5 80
70

US$ barrel-1
US$ kg-1

2 60
50
1.5 40
30
1 20
10
0.5 0
2000 2000 2001 2001 2002 2002 2003 2003 2004 2004 2005 2005 2006 2006 2007 2007 2008

Date

Figure 9.5.1 Natural rubber prices – TSR 20 – FOB Kuala Lumpur. SMR ¼
Standard Malaysian Rubber, SMR 20 is a medium grade

China has amplified the phenomenon, creating a supply/demand imbalance

fuelling a spectacular rise in natural rubber prices (+540% in 6 years between
2002 and 2007 – FOB price Kuala Lumpur in US$ – TSR 20) – Figure 9.5.1 –
further amplified by speculation. The price of natural rubber currently exceeds
that of most synthetic rubbers (around 20% higher). Might that inversion risk
encouraging further substitution by synthetic rubbers produced from fossil
carbon? In some areas of industry, a readjustment is likely to occur, but it will
not clearly alter the share of natural rubber insofar as the global context has
evolved, especially as regards energy, the existence of greenhouse gases and
European regulations (REACH):

 in the coming years, the new energy context – permanently expensive

petroleum oil and climate change – will modify transport, but also the cost
of producing synthetic rubbers; oil consumption will therefore have to be
reduced;7 it takes 0.4 mto of oil equivalent (TOE) to produce one tonne of
natural rubber, whereas 3.7 to 5 TOE are required to make one tonne
of synthetic rubber.8 Natural rubber consumption therefore allows savings
of 36 million TOE, amounting to 40% of total primary energy con-
sumption in France;9
 it will be necessary to store or use greenhouse gases. Recycling greenhouse
gases into natural polymers through the green factory – Hevea – is a tre-
mendous opportunity; using polluting and toxic products during elastomer
processing will be profoundly modified in the next 10 years, in order to
achieve the REACH standard. Substitution by preferably natural non-toxic
products will be necessary; better knowledge of products – apart from iso-
prene – existing naturally in latex and remaining unexploited for the
moment should provide some initial solutions (particularly antioxidants).
Natural Rubber 343

9.5.3 Water and Carbon Budget of the Rubber Tree

9.5.3.1 Carbon and Water in Plants
Like any plant, the rubber tree relies on photosynthesis for carbon acquisition
and on root uptake for water and nutrient acquisition. Through photosynth-
esis, solar energy is intercepted and converted to synthesize energy-producing
carbohydrates (CH2O)n, which is the basis for all subsequent metabolic
pathways in plants. These carbohydrates are monosaccharides (glucose, fruc-
tose, ribose), oligosaccharides (sucrose, maltose, raffinose) and polysaccharides
(starch). Following synthesis in leaves (sources), carbohydrates are partitioned
among the different sinks (leaves, shoots, trunk, flowers, fruits, roots) through
phloem vessels. The major form of carbohydrate transported is sucrose,
whereas the major non-structural reserve form is starch, mainly stored in the
parenchyma. Cellulose, hemi cellulose and pectin constitute structural carbo-
hydrates. In sink organs, carbohydrates are catabolized to provide energy for
cell functions, releasing CO2 and consuming O2 (respiration). Consequently,
the respiration rate of any organ is directly related to its activity, be it growth,
maintenance or specific functions.
Water taken up together with mineral nutrients by roots is transported via
the xylem towards the leaves, where it is transpired through stomata.
According to the cohesion theory of sap ascent in plants, transpiration creates a
tension (negative pressure) in xylem conduits, driving water from soil to root
and throughout the shoot. Atmospheric water vapour pressure deficit (VPD) is
therefore the main climatic factor determining water demand in plants, whereas
soil water availability limits actual uptake. However, transpiration is not a
passive process; it is regulated by plants by controlling stomatal opening.
Under water stress, stomatal conduction drops, in order to limit water loss. On
the other hand, as CO2 uptake takes place in stomata too, stomatal closure also
limits photosynthesis. Water use efficiency (WUE) for carbon, the amount of
absorbed carbon to the amount of transpired water, is a major parameter in
plant ecophysiology.

9.5.3.2 Photosynthesis and Water in the Rubber Tree

Rubber clones differ in their photosynthetic activity, not only in terms of
maximum net photosynthesis, Pmax, or the light response curve,10 but also in
their ability to cope with changing light conditions.11 In a rubber plantation, a
large proportion of the leaves in the canopy are found under limiting light
conditions; however, in leaves exposed to sunlight, stomatal conductance
declines rapidly in the afternoon, limiting photosynthesis activity. Thus,
shaded leaves in rubber plantations may contribute significantly to total
photosynthesis.12
Photosynthesis in rubber is highly temperature-dependent. It decreases
sharply below 20 1C and above 36 1C.13 The response of photosynthesis to
temperature is a key area concerning both global climate change14 and adap-
tation of crops to new planting areas. Temperature may directly affect the
344 Chapter 9.5
properties of key enzymes such as ribulose-1,5-bisphosphate carboxylase
oxygenase (Rubisco) and the regeneration of ribulose-1,5-bisphosphate
(RuBP).15 Moreover, photosynthesis rates can be affected by temperature not
only through biochemical processes but also by impact on stomatal con-
ductance for CO2.16
As rubber plantations are currently expanding to new areas under drier cli-
matic conditions than traditional ones (north-eastern Thailand, Mato-Grosso
in Brazil, north-western India), the performance of rubber trees under water
stress has become a major issue. Two main traits are to be considered: per-
formance (the ability to transfer water and grow under water stress) and
resistance (the ability to avoid damage and survive under water stress). Per-
formance mainly relies on the conductivity of the hydraulic system from root to
leaf,17 whereas resistance mainly relies on susceptibility to cavitation, leading
to embolism, within xylem vessels.18 Stomatal closure occurs to avoid severe
cavitation. Hence, differences in susceptibility to cavitation among rubber
clones19 are likely to induce differences in resistance to severe water stress.

9.5.3.3 Tapping, Latex Yield and Carbon Budget of the

Rubber Tree
Tapping brings about major changes in rubber tree functioning. Both rubber
production and growth require assimilates from photosynthesis, mainly in the
form of sucrose. Sucrose is both the source of metabolic energy and the basic
molecule for metabolic pathways to isoprene biosynthesis (see Section 9.5.4).
A fundamental feature is that an untapped rubber tree synthesizes very little
rubber, as latex is not naturally exuded by the tree. However, in response to
tapping (cutting a thin slice of trunk bark each day to every five days) the
laticifer vessels included in soft bark tissue are severed and latex flows out. A
secondary metabolism is artificially induced for regeneration of exported latex,
which uses assimilates derived from the other sinks,20–22 particularly from
trunk growth. The negative relation between latex production and wood bio-
mass creation is well documented.21–23 Silpi et al.24 showed an 80% growth
deficit for tapped trees as compared to untapped trees, over a period of
5 months of tapping. Preserving a balance between these two sinks is a key to
high and sustainable productivity in rubber plantations21,25 particularly when
wood production is considered, too. However, the amount of carbon stored in
the wood biomass of untapped rubber trees is always higher than the amount of
carbon in the wood biomass of tapped trees, plus the equivalent in carbon
exported by latex exploitation (taking into account the higher carbon cost of
latex than wood). It therefore looks as though some carbon is missing in tapped
trees. This may be partly explained by increased respiration activity in trunk
bark following repeated wounding by tapping.26
Inside laticifer vessels, the sucrose content drops sharply following tapping.27
Latex sucrose content indicates the balance between sugar uptake and utili-
zation (catabolism to rubber). Crossing sucrose laticifer content with inorganic
phosphorus content (Pi, indicator of latex metabolic activity) is the basis of
Natural Rubber 345
28
Latex Diagnosis (LD) methods used to evaluate tapping systems and char-
acterize rubber clones. Rubber clonal typology is mainly based on sucrose and
Pi content under low intensity tapping and changes in these parameters fol-
lowing an increase in tapping intensity.29 Some clones are considered ‘‘quick
starters’’ as they exhibit high latex yield together with high Pi and low sucrose
under low tapping intensity. On the other hand, some clones are ‘‘slow starters’’
but exhibit high potential for intensification as their metabolic activity is able to
increase and their sucrose resources are high.
However, the range in yield-related sucrose changes is clone-dependent. For
a given amount of exported latex, hence a given amount of sucrose consumed,
some clones, such as PB 217, are able to maintain a higher sucrose balance than
others.30 As isoprene biosynthesis pathways are not likely to differ among
clones, this shows that clones differ in their ability to upload sucrose into
laticifer cells. Regulation of active sucrose transport from phloem and par-
enchyma to laticifer vessels through medullar rays may explain such differences
that could also be related to differences in carbohydrate reserves in the vicinity
of the tapping cut. Despite increased competition for carbohydrate induced by
tapping, there is more reserve accumulation in the trunk wood of tapped trees
than of untapped trees.31 Moreover starch accumulation is positively correlated
to yield when different tapping systems are compared.32 Such surprising find-
ings show that trees tend to adapt their level of carbohydrate reserves to
metabolic demand, at the possible expense of radial growth. The trunk area
affected by tapping is not limited to the vicinity of the cut, but covers almost all
the trunk area up to at least 2 m high.26 Latex metabolic activity, latex sucrose
content, wood and bark starch content, as well as radial growth, is affected
throughout both sides of the trunk, even in areas which are too far from the cut
to be directly involved in latex regeneration following tapping. Latex diagnosis
mapping is used to determine the latex regeneration area (high Pi, low sucrose).
Latex yield per tapping day is positively correlated to the size of that area.33

9.5.3.4 Tapping and Water Budget of the Rubber Tree

Latex contains approximately 65% water. Consequently, human activity arti-
ficially removes water from the tree by tapping. However, the volumes of water
flowing out of the trunk following tapping (a few dl per tapping) are negligible
when compared to the amount ascending along the xylem and transpired
through leaves (between 60 and 200 l per day in 12-year-old trees).34 However,
tapping may locally and temporarily disrupt bark water status.35 In the first
minutes after tapping, latex flow – driven by turgor pressure – is high and water
has to flow from the parenchyma surrounding the laticifer tissues to compen-
sate for water loss from latex. Radial contraction of trunk bark was measured
after tapping, indicating interference between water mobilization towards
laticifer tissues and normal changes in the water content of parenchyma
throughout the day.36 A transient imbalance between latex flow and water
recharge may be a triggering factor in bark necrosis symptoms under unsuitable
soil and climatic conditions.37
346 Chapter 9.5
As turgor pressure is responsible for latex flow, water availability for laticifer
tissues is a major factor determining flow duration and consequently rubber
yield. It determines the more or less rapid blocking or ‘‘plugging’’ of the open
ends of latex vessels. A plugging index has been defined and is widely used to
characterize the decrease in latex flow dynamics.38 Seasonality of this index is
well related to rainfall or soil water content. Moreover, very early observations
showed that tapping at different times of the day influenced latex yield. This is
related to a marked drop in turgor pressure at the tapping site during the day,
when tension within the xylem increases following the onset of transpiration.
Tapping is therefore carried out early in the morning in most places and even at
night in Thailand.
Carbon, assimilated through photosynthesis into carbohydrates, is parti-
tioned among the main sinks: vertical growth, radial growth, respiration and
reserves (Figure 9.5.2). When trees are tapped, some of the carbohydrates are
diverted to regenerate the exported latex, a sink that is artificially created and
maintained by the exploitation process.

CO
CO22

Vertical
growth

Photosyntesi
Photosyntesis s

Carbohydrate
Carbohydrates s

R
Respiration (growth e
and maintenance) s Radial
e growth
r
v
e
s

Latex regeneration

Figure 9.5.2 Effect of tapping on carbohydrate partitioning in the rubber tree.

Natural Rubber 347
9.5.4 Biosynthesis of poly(cis-1,4-isoprene)
Poly(cis-1,4-isoprene) is the polymer that gives natural rubber a very compe-
titive share of the elastomer market. In Hevea brasiliensis latex, this polymer is
stored in so-called ‘‘rubber particles’’, which make up 20 to 45% of the latex
volume. Much work has been undertaken to understand the biosynthesis
pathway of this very-long-chain polymer, which stands out through having
almost 100% cis double bonds.

9.5.4.1 Polyisoprenoids
Poly(cis-1,4-isoprene) belongs to the family of polyisoprenoids, which are the
most structurally diverse and abundant natural products known, with more
than 23,000 primary and secondary metabolites. This huge family comprises,
for example, sterols which display not only structural functions (control of
biological membrane fluidity) but also hormonal functions (steroid hormones).
Key phyto-hormones, such as abscisic acid, gibberellins and cytokinins, are
isoprenoids too. Moreover, isoprenoids are used in protein prenylation, which
is a key step in the activation and the localization of metabolic enzymes in many
organisms. The first common step of all isoprenoid biosynthesis pathways is the
formation of isopentenyl diphosphate (IPP).39

9.5.4.2 Biosynthetic Pathway

The biosynthetic pathway of linear isoprenoids can be divided into three steps:
initiation, elongation, and termination.39–42 A synthetic pathway is presented in
Figure 9.5.3.

9.5.4.2.1 Initiation
The initiation step consists in the formation of IPP (12), and its isomer DMAPP
(13). The conventional metabolic pathway to form these two molecules is called
the acetate/mevalonate pathway (MVA pathway) in which three molecules of
acetyl-CoA (3) condense successively to form 3-hydroxy-3-methylglutaryl-CoA
(HMG-CoA) (5), which leads to a key intermediate molecule, namely meva-
lonic acid (MVA) (6). The latter is further phosphorylated and decarboxylated
to form the IPP molecule (12). In Hevea brasiliensis, this cytosolic pathway was
described by Lynen43 and Lebras44 in the early 1960s and reviewed more
recently by Kekwick45 and Ohya.46 Most experimental validations were
obtained by observing the incorporation of radioactive tracers, such as [2-14C]
MVA and [3-14C]HMG-CoA. The incorporation of [14C]IPP into rubber was
found to be much faster than that of [2-14C] MVA. This was assumed to be due
to slow conversion of MVA into IPP.43–44,46 Another explanation might be that
the MVA pathway was not exclusive for IPP biosynthesis. Indeed less than 10
years ago, a new, mevalonate-independent, IPP biosynthesis pathway was
discovered by Rohmer.47 This plastidic DXP-MEP pathway initiates with a
348 Chapter 9.5

Figure 9.5.3 Pathway of poly(cis-1,4-isoprene) biosynthesis.

condensation of pyruvate (2) and D-glyceraldehyde 3-phosphate (8) to form

1-deoxy-D-xylulose 5-phosphate (DXP) (9) catalyzed by DXP-synthase.
DXP is converted to 2-C-methyl-D-erythritol 4-phosphate (MEP) (10) by the
DXP reducto-isomerase. The last step of this pathway is the reduction of
Natural Rubber 349
4-hydroxy-3-methyl-2-butenyl-4-diphosphate (HMBPP) (11) catalyzed by
HMBPP reductase, whose structure and reaction mechanisms are still
unknown.48 This new pathway has been found in bacteria, algae and higher
plants.47 Concerning Hevea brasiliensis, the expression of DXP synthase has
been shown in latex and leaves.49 The IPP derived from this second pathway
may diffuse from the plastids and join the cytosolic pool.40
Given that acetylCoA (3) is produced from pyruvate (2) by the pyruvate
dehydrogenase complex, both pathways (MVA or DXP-MEP) leading to the
formation of IPP start with a pyruvate which is a product of glucose (1) cat-
abolism by glycolysis.
In addition to the formation of IPP (12), initiation includes as well the for-
mation of dimethylallyl diphosphate (DMAPP) (13) by isomerization of IPP,
catalyzed by IPP isomerase.

9.5.4.2.2 Elongation
Elongation consists of the sequential condensation of IPP and allylic diphos-
phate through the action of the prenyl chain elongating enzyme, commonly
called prenyl transferase. The reactions catalyzed by prenyltransferases start
with the formation of allylic cations after the elimination of pyrophosphate
ions, to form allylic prenyl diphosphate. This is followed by addition of an IPP
with stereo-specific removal of the proton at the 2-position. This is the key
reaction which determines cis- or trans-configuration of the double bonds
contained in the linear isoprenoid chain. Cis-trans isomerism is dependent on
the nature of the prenyltransferase involved in elongation catalysis. A com-
prehensive review of cis- and trans-prenyltransferases was recently undertaken
by Takahashi and Koyama.39 Cis-prenyltransferases are much less well known
than their trans-homologues.
For linear isoprenoid biosynthesis, elongation of the polymer chain can be
described in two main phases as shown in Figure 9.5.3:

 Phase 1: the formation of short-chain allylic diphosphates where geranyl-

PP (14), farnesyl-PP (15) and geranylgeranyl-PP (16) are formed by the
action of trans-prenyltransferases.
 Phase 2: the trans-short-chain allylic diphosphates obtained are then
employed as allylic primer substrates for additional IPP condensation with
trans- or cis-configuration.39

In the case of natural rubber from Hevea brasiliensis, which is almost entirely
made of cis-isoprene units, it could be assumed that cis-prenyltransferase is
exclusively involved in phase 2. Unfortunately it is more complex. Authors agree
on phase 1, which is trans-condensation catalyzed by a cytosolic soluble trans-
prenyl transferase40,50–52 Farnesyl diphosphate synthase has been cloned from
rubber latex.53 The most probable prenyldiphosphate used as a primer for phase 2
is farnesyl-PP (15) or geranylgeranyl-PP (16).46,54,55 Phase 2 is catalyzed by a still
not clearly identified ‘‘rubber transferase’’ system. Different proteins have been
350 Chapter 9.5
described as being involved in cis-condensation of IPP by acting as prenyltrans-
ferase itself, or as co-factors. A dimeric protein with a monomeric molecular mass
of 38 kD was purified by Light56 and showed prenyltransferase activity leading to
chain elongation. Nevertheless, in the presence of DMAPP, that enzyme only
catalyzed trans-condensation of IPP leading to FPP and GGPP.46 Many authors
have stated that this reaction is catalyzed by the association of a prenyltransferase
with several co-factors. The two most cited are Rubber Elongation Factor (REF),
which is a 14 kD protein tightly bound with large rubber particle membrane, and
Small Rubber Particle Protein (SRPP), which is a 22 kD protein.50,57,58 More
recently, two Hevea brasiliensis genes encoding Hevea rubber transferases (HRT1
and HRT2) were isolated by homology with other cis-prenyltransferases cloned in
other organisms.52 The expressed protein HRT2 had a molecular mass of 33 kD
and showed cis-prenyltransferase activity in the presence of washed bottom
fraction particles (WBFP). It is interesting to note that in most of the reported in
vitro studies, the addition of some part of initial latex, such as washed rubber
particles or WBFP, is required to achieve cis-prenyltransferase activity. This
shows that the rubber synthesis machinery is complex and probably involves the
participation of several proteins. In addition to proteins, the presence of metal
divalent cations such as magnesium or manganese ions is required as a co-factor
of rubber transferase activity.54

9.5.4.2.3 Termination
Very little is known about the final biochemical termination event. Different
alpha end groups have been identified by NMR indicating the presence of
phosphate and fatty acid. These could be attributed to the presence of a
phospholipid molecule.
Although it is not part of the biosynthesis pathway, stricto sensu, it is worth
mentioning that after termination the linear isoprene chain may undergo fur-
ther chemical modifications. Indeed, abnormal groups such as aldehyde, epoxy
or lactone have been detected on the polymer chain.59

9.5.4.2.4 Polyisoprene Chain Length Control

The control of polyisoprene chain length and therefore molecular weight has
been attributed to several factors:

 The concentration of substrates such as IPP and FPP. High IPP con-
centration leading to higher molecular weight, while a contrary phenom-
enon occurs with FPP concentration;
 The magnesium ion, which is a necessary co-factor for Hevea brasiliensis
prenyltransferase, has also been described as a molecular weight
regulator;54
 Tangpakdee60 also assumed that molecular weight could be regulated by
the activity of IPP isomerase, which is necessary to produce DMAPP, and
Natural Rubber 351
then to initiate rubber biosynthesis. A lower IPP isomerase activity would
lead to a higher molecular weight.

9.5.4.3 Localization of Rubber Biosynthesis

The synthesis site for allylic diphosphate primers and cis-polyisoprene is largely
assumed to occur on the surface of pre-existing rubber particles,51,61,62
but rubber biosynthesis activity has also been localized in the membrane of
non-rubber particles from the bottom fraction after ultracentrifugation of
latex.52,63,64 The latter authors64 presumed that previous localization of rubber
biosynthesis on rubber particles was due to an artefact resulting from the rapid
deterioration of bottom fraction (BF) particles after tapping, which led to the
migration of rubber synthesis machinery from BF particles to rubber particles.

9.5.4.4 Conclusion
The details and understanding of rubber biosynthesis are still ambiguous and
clear evidence has not yet been convincingly presented. Modern proteomic
techniques should provide a clearer understanding of reaction mechanisms,
especially the cis-condensation of IPP, as well as the biosynthesis location. This
knowledge would be very useful for considering genetic improvement of the
biosynthesis machinery. This work should be done in close collaboration with
rubber tree physiologists who are working on sugar availability in laticiferous
cells: indeed, it is pointless optimizing engine power if there is a lack of fuel.

9.5.5 Natural Rubber Structure

9.5.5.1 Introduction
As for all materials, a study of natural rubber and of the relations existing
between its structure and properties calls for different structural levels to be
defined. We have opted to define them in terms of microstructure, mesos-
tructure and macrostructure. The macrostructure of natural rubber concerns
the raw material in its entirety, which is assumed to be homogeneous with little
or no destructuring. We shall not be looking at this structural level in detail
here as it primarily involves rheological characterizations. For a polymer,
definition of the microstructure varies depending on the authors. Koenig65 and
Sperling66 consider the microstructure to involve the (chemical) composition,
configuration and conformation of the chain. Mirau et al.67 propose: the precise
way in which monomers are linked to each other to form a polymer (chemical
structure). For natural rubber, the microstructure concerns the chemical
structure of the poly(cis-1,4-isoprene) macromolecules, but also the composi-
tion of non-isoprene constituents (lipids, proteins, etc.), their chemical structure
and their interactions with poly(cis-1,4-isoprene) macromolecules. These
352 Chapter 9.5
interactions play a paramount role in the mesostructure of natural rubber and
its specific properties. For natural rubber, the mesostructure corresponds to the
macromolecular structure and to the aggregates formed by the association of
poly(cis-1,4-isoprene) molecules (gel).

9.5.5.2 Microstructure
For synthetic rubbers, analysis problems boil down to two determinations:
identification of the constitutive groups and determination of spatial arrange-
ment. For natural rubber, those two determinations have undergone a great
deal of research already mentioned.68 The poly(cis-1,4-isoprene) chain in the
plants studied comprises three parts (Figure 9.5.4): a (o) end group containing
1 dimethylallyl group and 2 or 3 trans groups, a long chain of cis configuration
and an (a) end group (Figure 9.5.4a). For natural rubber from Hevea, the
chemical structure of the two end groups has yet to be completely identified.
Neither the hydroxyl group nor the dimethylallyl group have been revealed.
Studies on deproteinized natural rubber from which lipids had been removed
by methanolysis led Tanaka et al. 69,70 to suggest the existence of a protein
(or polypeptide) on the (o) group and a phospholipid (or fatty acid) on the
(a) end group (Figure 9.5.4b). Those two non-isoprene compounds attached by
covalent bonds to the polyisoprene chain would seem to lie behind the inter-
actions responsible for the associative structure of natural rubber.
Non-isoprene compounds (lipids, proteins and sugars) will be covered in
Section 9.5.6.

9.5.5.3 Mesostructure
The mesostructure covers both the macromolecular scale (dimension, con-
formation and architecture of the macromolecules) and also the supramole-
cular scale (complex aggregates between macromolecules). It is this last point
that is the key to the specific properties of natural rubber. This associative

CH3

C CHCH2 CH2 (a) CH3

CH3 CH3
C CH C CH
CH3 CH2 CH2 CH2 CH2C CHCH2 OH
m n

(b)
CH2
Protein CH2 CH2 CH3
CH3
C CH C CH
CH3 CH2 CH2 CH2 CH2C CHCH2 Lipid
m n

Figure 9.5.4 Microstructure of poly(cis-1,4-isoprene) (a) for latex plants other than
Hevea and (b) for Hevea.
Natural Rubber 353
mesostructure is gradually and partly destroyed when dissolved in a conven-
tional solvent of polyisoprene (cyclohexane, tetrahydrofuran). However, in
many cases, a proportion of natural rubber remains insoluble in those solvents,
a fraction commonly referred to as the gel phase or macro gel. The soluble
fraction contains polyisoprene macromolecules and a variable quantity of
micro-aggregates making up the micro gel.

9.5.5.3.1 Macromolecular Structure

In 1972, Subramaniam71 investigated inherent molar mass distribution
(MMD0) in natural rubber. MMD0 is the MMD of natural rubber on leaving
the tree without undergoing any modification linked to post-harvest processing
(coagulation, maturation, drying, etc.). The MMD0 of natural rubber is an
important criterion for forecasting a certain number of natural rubber prop-
erties that will be obtained after processing.72 Depending on the clone, MMD0
will lie between two extreme types: bimodal or unimodal with a shoulder
(Figure 9.5.5). MMD evolves after processing depending on the process used.72
Natural rubber from Hevea is characterized by polyisoprene chains of very
variable size ranging from a few thousand to some tens of millions of g mol1.
It is therefore characterized by a very wide molar mass distribution, with a
polymolecularity index (I) sometimes exceeding 8, and a very high average
number molar mass (150,000oMno300,000 g mol1). Among around twenty

VM515
GT1 or PB312
RRIC121
PB330

1.E+03 1.E+04 1.E+05 1.E+06 1.E+07

Molar mass (g/mol)

Figure 9.5.5 Examples of inherent molar mass distribution for several Hevea clones
(Size Exclusion Chromatography in cyclohexane according to Bonfils
et al.80).
354 Chapter 9.5
73
latex-bearing plants studied by Swanson et al. only rubber from guayule
contained such long macromolecules.

9.5.5.3.2 Gel
Non-isoprene mechanisms and compounds responsible for gel formation have
been intensely studied. Prior to the recent proposals made by Tanaka et al.,69
so-called abnormal compounds were incriminated in the interactions respon-
sible for gel. Those compounds (aldehydes,74 epoxy,75 esters76) were linked to
the polyisoprene chain and reacted with some non-isoprene compounds (amino
acids77 or proteins,76 metal ions78).
Many methods can be used to determine the quantities of macrogel and
microgel in a polymer.79 For natural rubber, the proportion of macrogel is
determined by gravimetry after centrifugation. The quantity of microgel can be
measured by filtration, but that quite laborious method can be replaced by size
exclusion chromatography (SEC).80 Macrogel and microgel exist in both dry
rubber (TSR or RSS) and stabilized latex (field latex or concentrate) that has
matured.81,82
The proportion of macrogel can vary enormously, reaching rates of almost
60% in extreme cases depending on the authors. Allen and Bristow83 showed
that the proportion of gel depended on the solvent used, and the dissolution
time and temperature. It is therefore unlikely that difficulties in dissolving dry
rubber are solely linked to chemical cross-linking problems.
In many studies, the authors settled for measuring the amount of macrogel
whilst microgel is clearly preponderant in many cases.84 Bloomfield85 defined
the microgel found in latex harvested from Hevea left to rest for several months
as: internally cross-linked molecules similar in size to latex particles. The
quantity of microgel, determined by filtration, in a natural rubber sample (5 to
30%) would seem to vary and greatly depend on clonal origin.86 Larger
quantities can be found depending on the technique used.87 Campbell and
Fuller88 associated the same definition with the term microgel to describe the
cloudy solutions obtained when dissolving a sample of SMR L in dichlor-
omethane. Allen and Bristow83 presumed that microgel is due to chemical
bridges generated inside latex particles. Those bridges would seem to form
between leaving the tree and coagulation, maybe even inside the tree. Voz-
nyakovskii et al.89 used dynamic light scattering (DLS) to study natural rubber
solutions (RSS and DPNR,i [NR]E1 to 3 mg ml1). They showed that
microgel displayed two populations, one centred on 1.1 mm (P1, 0.9odo5 mm)
and the other around 10 mm (P2, 5odo12 mm). The deproteinized sample
(DPNR) only contained small-sized micro-aggregates (P1), whereas for smoked
sheet (RSS1) they were mostly around 10 mm (P2). Steam treatment, which
eliminates a proportion of the proteins, reduced the quantity of large micro-
aggregates (P2) to the benefit of small micro-aggregates and the soluble por-
tion. Although protein removal did not eliminate all the microgel,
i
RSS: Ribbed Smoked Sheet; DPNR: Deproteinized Natural Rubber.
Natural Rubber 355
population P1 persisted. They concluded that the interactions lying behind
micro-aggregate formation were linked to the existence of proteins. They also
discovered the thermo-reversibility of the interactions leading to microgels.
Heating solutions (20 to 80 1C) did not eliminate microgels but reduced
the average size (dE10 mm at 20 1C, dE5 mm at 60 1C, for RSS). The con-
centration and size of micro-aggregates also depend on the concentration in
the solution.

9.5.6 Non-isoprene Components of Natural Rubber

Non-isoprene components of Hevea brasiliensis latex account for around 10%
of its dry matter while they account for about 5% of the raw dry rubber
derived from latex (Table 9.5.2). They comprise proteins, carbohydrates, lipids
and inorganic constituents and represent the main composition difference
between natural rubber (NR) and its synthetic counterpart, namely poly(cis-
1,4-isoprene) synthetic rubber (IR). They could therefore be involved in the
irreplaceable specific qualities of NR. The nature and quantity of these non-
isoprene components can vary greatly depending on the clones, the exploitation
system and environmental conditions.90 Some of these components are either
dissolved or suspended in the aqueous medium of the latex while the others are
adsorbed on the surface of rubber particles.

9.5.6.1 Non-isoprene in the Different Compartments of Hevea

brasiliensis Latex
Many hydrophilic non-isoprene components of latex are leached by the
numerous washing operations with water during the process leading to dry
rubber. Nevertheless, it is interesting to observe the initial allocation of non-
isoprene in latex compartments.

Table 9.5.2 Composition of natural rubber latex and raw dry rubber.
Latexa Dry rubberc
% w/w dry
% w/v fresh latexa matter of latexb % w/w dry matter

Rubber hydrocarbon 35.0 87.0 94.0

Proteins 1.5 3.7 2.2
Carbohydrates 1.5 3.7 0.4
Lipids 1.3 3.2 3.4
Organic solutes 0.5 1.1 0.1
Inorganic substances 0.5 1.2 0.2
Approximate values only (highly dependent on clone, season and physiological status of the tree).
a
averaged from data published by Wititsuwannakul, 2001.100
b
calculated.
c
Sainte-Beuve, 2006.115
356 Chapter 9.5

Rubber phase 25–45% v/v

Frey-Wyssling particles; 1–3% v/v

Serum C; 40–50% v/v

Bottom fraction; 15–20% v/v

Figure 9.5.6 Various fractions of centrifuged latex. From Moir.91

Fresh latex can be separated into various layers by ultracentrifugation at low

temperature (Figure 9.5.6). Four main layers are identified:91

 A white upper layer or rubber cream consisting of rubber particles

amounting to 25 to 45% of latex volume. The particles are strongly pro-
tected in suspension by a film of adsorbed proteins and phospholipids.
This protein and phospholipid layer imparts a net negative charge to the
rubber particle, contributing to colloidal stability.92,93
 An orange or yellow layer containing Frey-Wyssling particles which form
1 to 3% of latex volume. These particles are surrounded by a typical
double membrane and accumulate lipid globules, isoprenic compounds,
carotenoids, plastochromanols and plastoquinones.94
 An aqueous layer, called serum or cytosol, amounting to 40 to 50% of
latex volume. It contains carbohydrates, minerals, organic acids, amino
acids, nitrogenous bases, reducing agents and high-molecular-weight
compounds such as proteins, lipids and nucleic acids.
 A bottom layer consisting mainly of lutoid particles and also
including other particulate components with a density greater than that of
serum.95–98 Lutoid particles amount to 15 to 20% of latex volume. Their
negatively charged tonoplast membrane, rich in phosphatidic acid,
encloses a fluid serum known as B-serum. The vacuolar medium is acidic
and positively charged. It includes cations, basic amino acids and a whole
range of hydrolases.96

9.5.6.2 Non-isoprene Families

Non-isoprene can be classified into four families: proteins, carbohydrates,
lipids and inorganic compounds. Table 9.5.2 presents an approximate
composition expressed versus either fresh or dry matter. Around half of
Natural Rubber 357
non-isoprenes are leached or degraded during dry rubber processing, those
remaining being logically the most hydrophobic, i.e. lipids.

9.5.6.2.1 Proteins
Fresh latex contains roughly 1.5% of proteins of which about 25–30% are
bound to the rubber phase, another 25% being associated with the bottom
fraction (lutoid) and the remainder (45–50%) being reported as cytosolic.99,100
Two major particle surface-bound proteins of 14 kD (rubber elongation factor)
and 22 kD (small rubber particle protein) have been identified. In the bottom
fraction, the two major proteins are hevein (450%), an anionic protein, and
hevamine. The molecular weight of the proteins in this fraction is narrow,
ranging from 14 to 45 kD. In C-serum, proteins are numerous and range from
14 kD to 133 kD.94,98,100
Proteins play an important role in metabolism, in the structure of rubber
particles and in the quality of rubber products. Enzymes involved in the gly-
colysis as well as the rubber biosynthesis pathways are obviously part of
the protein pool of latex. Furthermore, rubber particle proteins confer,
with phospholipids, a negative charge to the particle surface, which
ensures colloidal stability. Proteins have been declared to influence the tech-
nological properties of rubber. For example, they are involved in the
water retention process during rubber drying101 and in the stress relaxation of
unfilled NR vulcanizate.102 Lastly, an unwanted property of latex proteins is
their allergenic character in latex-dipped goods. However, proper washing
processes can reduce allergenicity to a reasonable level. Nevertheless, this
remains an issue for a minor, overexposed population such as healthcare
workers.99

9.5.6.2.2 Carbohydrates and Inositols

Latex cytosol contains sucrose (0.3–0.4% of latex weight), which is the sugar
supply for the rubber biosynthesis pathway as the source of pyruvate (see
rubber biosynthesis section). Sucrose concentration is a key parameter in latex
diagnosis used to assess the physiological status of the rubber tree enabling
monitoring of the tapping intensity.103–105 In addition to sucrose, a smaller
amount of glucose, fructose and raffinose are present in latex.
But the most important water-soluble non-isoprene is another carbohydrate
called quebrachitol, or 2-O-methyl-L-inositol (see chemical structure in
Figure 9.5.7), which can account for more than 1.2% of fresh weight. Its phy-
siological function remains unknown.100 Quebrachitol can be used as a starting
material to synthesize chiral drugs with therapeutic effects for the treatment of
cancer, early ageing, diabetes and AIDS. An international patent for the
extraction process has therefore been filed by a Malaysian team.106
358 Chapter 9.5

O-CH3

HO OH O
O
H3C
HO OH
OH
CH3
HO

L-quebrachitol Furan fatty acid

>1% of fresh latex weight >1% of dry rubber weight (for specific clone only)

Figure 9.5.7 Two examples of potentially high value-added by-products from Hevea
latex.

9.5.6.2.3 Lipids
As mentioned before, lipids are the family of non-isoprenes that is the most
retained with the rubber during processing. Their extraction for analytical
purposes has been optimized recently by Liengprayoon.107 Depending on the
clone, lipids amount to 2.5 to 3.8% versus rubber in latex, and 1.8 to 3.3% in
dry natural rubber. Three families of lipids can be distinguished:108

 Phospholipids: these account for 18–25% of lipids in fresh latex but only
4–5% of lipids in dry rubber. The main phospholipid is phosphatidyl
choline, amounting to more than 60% of latex phospholipids. As
amphiphilic molecules they are involved in the structure and charge of
particle membranes, but could also be linked to polyisoprene chains.
 Glycolipids: these account for 25–35% of lipids in fresh latex and 10–14%
of lipids in dry rubber. Like phospholipids, they are degraded and/or
leached during dry rubber processing. The two main glycolipids are
digalactosyldiglyceride (DGDG, approximately 45% of latex glycolipids)
and steryl glucoside (SG, approximately 35%). They also have a structural
role in membranes.
 Neutral lipids: these account for 40–60% of lipids in fresh latex but
82–86% of lipids in dry rubber. This share increase is due to the leaching of
hydrophilic lipids (phospho- and glycolipids) as well as to the hydrolysis of
fatty acid moieties from those hydrophilic lipids: newly released free fatty
acids thus join the neutral lipid family. Indeed, free fatty acids account for
less than 2% of lipids in latex while they account for more than 20% of
those extracted from dry rubber. Neutral lipids can be divided into fatty
acids and unsaponifiables.

J Fatty acid composition: linoleic acid (C18:2) is generally the most

important with 40 to 50% of the fatty acids, followed by oleic acid
(C18:1), stearic acid (C18:0) and furan fatty acid. These latter fatty
acids each account for approximately 10–15% of the fatty acids. For
a specific clone, furan fatty acid (see structure in Figure 9.5.7)
Natural Rubber 359
can amount to 80% of the fatty acid pool. This uncommon fatty acid
has been reported to have a biological activity in the treatment of
cardiovascular diseases.109 As for quebrachitol, this co-product,
present in not insubstantial quantities, could be put to use. Fatty
acids have been described as having a technological role in some
properties of rubber, such as green strength110 and tack property111
and are known to be activators of vulcanization.
J Unsaponifiables: the major unsaponifiable is b-sitosterol (37–45% of
unsaponifiables) followed by g-tocotrienol (17–22%), D5-avenasterol
(16–20%), stigmasterol (6–8%), octadecanol (4–7%) and a-toco-
trienol (4–6%). Some unsaponifiables may have an antioxidant
activity, which is of great importance in protecting the double bonds
of isoprenic chains.112,113

9.5.6.2.4 Inorganic Compounds

The total concentration of inorganic ions in fresh latex is about 0.5%, the
major ions being potassium, magnesium, copper, iron, sodium, calcium and
phosphate.114 Even in small quantities they are key co-factors in metabolic
pathways, and are also involved in the technological properties of rubber, such
as susceptibility to thermal oxidation.113

9.5.6.3 Conclusion
Non-isoprenes of natural rubber are various and play important physiological
roles, especially in metabolism (carbon source and enzymes for polyisoprene
biosynthesis), and in the structural organization of latex (membranes of rubber,
lutoid or Frey-Wyssling particles, colloidal stability). They are also involved in
some technological properties of rubber, which give natural rubber its unique
properties. Finally, uncommon molecules with high value-added potential, such
as quebrachitol or furan fatty acid, are present in large quantities (41%), which
confirms that Hevea brasiliensis is a green chemical factory of great interest.

9.5.7 Specific Properties versus Synthetic Counterparts

Through its partly associative structure (molar mass, molar mass distribution,
gel and overlap density) natural rubber from Hevea brasiliensis exhibits a set
of properties unequalled by its synthetic rivals, but also certain drawbacks.
The main advantages are:

 Higher elasticity;
 Strain-induced crystallization;
 Low heat build-up at high temperature;
 Higher tack and high green strength.
360 Chapter 9.5
The main disadvantages of natural rubber still remain today its variable
processability and allergy risks for latex-based articles for uses involving
human contact.

9.5.7.1 Elasticity
Natural rubber displays elastic properties – the ability to return to its initial
shape after initial stress is halted – which are remarkable in raw rubber but also
when it is vulcanized (around 700% elongation at break) due to its ability to
crystallize under strain (100% cis- and associative structure). Its properties are
used in elastic bands but also in dipped items such as gloves.

9.5.7.2 Strain-induced Crystallization

Unlike synthetic elastomers such as polybutadiene with a high level of cis
configuration or polychloroprene, natural rubber crystallizes very slightly at
cold temperature without strain. Kawahara et al.116 suggested that the presence
of free fatty acids in natural rubber might be conducive to cold crystallization.
But under important strain (4400% of elongation) natural rubber crystal-
lizes at high temperature (4100 1C), undergoing crystallization that is partly
perpendicular to the strain depending on the specificities of the network.117
Such crystallization is reversible, with crystallites disappearing when stretching
stops.118 This property is also found in synthetic elastomers, but at lower
deformation rates.119 Strain-induced crystallization is largely due to the ste-
reochemical regularity of macromolecules (NR: 100% cis-), but for natural
rubber it is probably linked to the associative structure, which gives rise to
branching.119 Even recently, studies were conducted to elucidate the structure
and form of crystallites,120 or the influence of cross-linking density on crys-
tallization kinetics.117

9.5.7.3 Heat Build-up

Heat build-up is the temperature rise in a tyre resulting from the dissipation in
heat form of part of the energy (viscous or loss part) due to an applied strain
(rolling+weight). As rubbers have low thermal conductivity, heat is not easily
dissipated. Energy loss in the medium under strain is linked to the existence of
chain extremities that can move freely. The more chains are linked by bridges
as, for example, during vulcanization, or even by the presence of gel involving
non-isoprene compounds, the less there will be heat dissipation. Too great an
increase in tyre temperature, particularly the sidewalls, will lead to a certain
number of problems and may cause the tyre to burst under certain conditions
of use. Natural rubber is the elastomer with the lowest heat build-up, making it
unavoidable for dynamical applications with high strain and high frequencies
such as tyres subjected to heavy strains (trucks, planes, etc.).
Natural Rubber 361
9.5.7.4 Tack and Green Strength
Tack and green strength are two important properties of many ela-
stomer compounds. In manufacturing, these two properties enable the many
components of a non-vulcanized tyre to hold together until moulding and
curing. Tack is the ability of two materials to resist separation after bringing
their surfaces into contact for a short time under light pressure. The green
strength of an elastomer is its resistance to deformation and fracture before
vulcanization. Natural rubber has good tack (very mobile low molecular weight
chains) and good resistance to separation; the high molar mass chains are able
to deform without slipping before the process of crystallization under stress
starts.

9.5.7.5 Vulcanization
Vulcanization remains a prime stage in the manufacture of rubber articles. It
consists of linking (cross-linking) the polymer chains with each other with
sulphur, sometimes with peroxides. This essential stage eliminates flow phe-
nomena by adding crosslinking points. It makes it possible to reduce hysteresis
by maintaining an acceptable level in terms of elongation/break. Numerous
chemicals are involved with the sulphur to catalyze the reaction (stearic acid,
zinc oxide and vulcanization accelerators).121 Unlike its synthetic counterparts,
natural rubber withstands much higher vulcanization rates without losing its
properties and displays a shorter scorch time. This phenomenon has been
attributed to the existence of natural vulcanization activators, notably free fatty
acids (1.5 to 2.5% w/w NR). Some studies in this field have also identified the
involvement of certain amino compounds: neutral and basic amino acids122 and
the amino bases arising from the hydrolysis of certain phospholipids.123 Whilst
there is abundant literature on vulcanization chemistry121,123 very few studies
have been undertaken to understand the action mechanisms of natural acti-
vators in natural rubber.

9.5.8 Conclusion
Rubber and Hevea offer a tremendous opportunity for offering some solutions
to major global challenges. Indeed, rubber growing is relatively easy and not
very sophisticated, making it accessible to the largest number of people; it does
not require rich soils. Current prices are advantageous for smallholders, which
encourages them to plant rubber. It is a tremendous machine for recycling
atmospheric carbon, enabling the production of polymers that will become
increasingly rare in the future given the expected shortages in petroleum oil
production. Lastly, the richness of natural elements occurring in latex – apart
from isoprene – has yet to be exploited and suggests uses in some very different
fields.
362 Chapter 9.5
Acknowledgement
Thanks to Mr Philippe Schill for his shrewd advice, which enabled us to gain a
clearer understanding of the specificities of natural rubber.

References
1. P. Compagnon, Le caoutchouc naturel, ed. G. P. Maisonneuve et Larose,
Paris, France, 1986; M. J. R. Loadman, The Exploitation of Natural
Rubber, Publ. 1531, Malaysia Rubber Producer’s Res. Association,
Brickendonbury, Engl. version from U. Giersch and U. Kubisch,
Gummi – die elastische Faszination, Nicolai, Berlin, 1995.
2. H. Smit, Tire Technology International, 2007, 100–104.
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CHAPTER 9.6

Natural Fibres
MARTIN MÖLLERa AND CRISAN POPESCUb, c
a
DWI an der RWTH Aachen e.V., Pauwelsstraße 8, D-52056 Aachen,
Germany; b DWI an der RWTH Aachen e.V., Pauwelsstraße 8, D-52056
Aachen, Germany; c University ‘‘Aurel Vlaicu’’, Bd. Revolutiei 77,
RO-310130 Arad, Romania

9.6.1 Generalities
Natural fibres are raw materials directly obtainable from an animal, vegetable or
mineral source for which the diameter is negligible in comparison with the length.
Along the centuries until comparatively recently, natural fibres were the basis for
producing clothes, paper, ships’ sails and insulation and building materials.
It is not certain when people first started wearing clothes. Scientists estimate
that this happened more than 100,000 years ago, because the body louse
(pediculus humanus humanus) apparently diverged from the head louse (pedi-
culus humanus capitis) at that time. The first clothes were made from natural
materials: animal skin and furs, grasses and leaves and the first needles are
recorded about 30,000 years ago.
The use of natural fibres, both plant and animal, to meet our needs plays a
significant role throughout history. Wool, as a representative of animal fibres,
has been used since the dawn of mankind. One of the oldest recorded uses of
plant fibre for fabrics is that of hemp, already being cultivated in China in 2800
BC. The common nettle is probably the best example of how society’s interest in
natural fibres fluctuates along the years. It was used for cloth in Neolithic times,
and then became important for nets for fishing. Nettle cloth was manufactured
in Scandinavia and Scotland until the nineteenth century and shortages of

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

368
Natural Fibres 369
cotton during the First World War forced the Germans to use it again for
making fabrics. Now it has almost vanished from textile classifications.
With the industrial revolution, textile manufacturing turned into industry
and the requirements for a fibre to be used for textiles became more exactly
defined. For use in textiles a fibre should have properties which render it
spinnable and wearable, enumerated below:

 geometrical properties: minimum length of 6–7 mm, diameter to length

ratio of 1 : 2–5000
 mechanical properties: strength, extensibility and flexibility
 comfort properties: moisture management, dyeability, fast to sun and heat
 economic properties: cheap and abundant

The minimal values of the properties are very much related to those of
natural fibres, which were the only fibres when textile manufacturing emerged
as an industry.
During the last century there has been a turn away from natural fibres
towards chemically obtained materials, mostly derived from petrochemicals.
This change was a result of the technological revolution and the short-term
economic advantages of synthetics.
As a result of the developments there is a large variety of fibres available on
the market, classified into two large classes: natural and chemical fibres. Each
of them may be further developed into subclasses, as detailed in Figure 9.6.1.
Out of the group of natural fibres, those under mineral fibres (asbestos fibres)
are of diminishing interest after being related to lung cancer.1
The newly inserted group of synthetic fibres based on renewable sources is
just beginning, with poly-lactic fibres (PLA) as the prominent representative.
One may also consider that, due to the move away from petrol sources, this
group will become increasingly interesting in the coming decades.

9.6.2 Demands and Restraints for Sustainable Fibres

Sustainability is a characteristic of a process or state that can be maintained at a
certain level indefinitely. The term, in its environmental usage, refers to the
potential longevity of vital human ecological support systems, such as the
planet’s climatic system, systems of agriculture, industry, forestry and fisheries,
systems on which they depend in balance with the impacts of our unsustainable
or sustainable design.
We are now witnessing a growing movement away from petrochemical-based
fibres back to natural fibres. There are some reasons for this, e.g.:

 petrochemical-based fibre production has undergone continuing rising

costs;
 synthetic fibres rely on precious non-renewable resources and incur
environmental costs in their production;
370 Chapter 9.6

Natural fibres

Cellulosic Animal/proteinic Mineral

Duvets Liberiene Hard Keratin Silk Asbestos

Cotton Linen Sisal Wool Bombyx Mori
Kapok Hemp Alfa Fine hairs Tussah
Jute

Chemical fibres

Natural polymer Renewable Oil source Inorganic

(Artificial fibres) source (Synthetic fibres) fibres

Cellulosic Proteinic Polyaddition Polyaddition Poly- Glass,

Viscose Caseine PLA PE, PP, PVC, condensation Metallic,
Acetate Soya bean PUR PA, PET Carbon
Alginate Acrylics

Legend: PLA polylactic acid, PE polyethylene, PP polypropylene, PVC polyvinyl chloride, PUR
polyurethane, PA polyamide, PET polyethyleneterephthalat

Figure 9.6.1 Classification of fibres

 petrochemical-based products pose a health risk in most applications, both

from direct exposure and also from secondary exposure through soil,
water and air pollution.
Although environmentally and health conscious consumers have tradition-
ally favoured natural fibres over synthetic clothing, there are several factors
which pledge against their use, such as:

 due to the amount of insecticides required, cotton is one of the most

environmentally unfriendly crops grown;
 during the processing of the fibres, cotton and wool produce the largest
amount of polluted effluents per kilogram of fibre.

The new ‘‘organic’’ fibre industry that is rapidly developing across North
America and Europe aims at answering these problems. However, there is still
the need to address the steadily increasing demand of fibres by an increasing
population (now at 7.94 kg per capita for 6.3 billion inhabitants, 2006; see
Chapter 5, Figure 5.2).
Natural Fibres 371

6 Wool
Natural fibres
5 Total fibres

0
1950 1960 1970 1980 1990 2000 2002
Year

Figure 9.6.2 The world fibre production growth (1950 ¼ 1).

Cross-
section

Length-
wise view
Skin-Core Side-by-Side Fibril-Matrix

Figure 9.6.3 Schematic fibre structures.

As shown in Figure 9.6.2, the demand has been responded to, so far, by a
continuously increasing contribution of chemical fibres to the total, with nat-
ural fibres seeming to reach a plateau in production. The limits of natural fibres
are imposed by the amount of arable land required for producing them: the
total arable land available is estimated at 20 Mio km2 and for producing
the 55 Gkg fibres used in 20062 one has a maximum available of some
3.5  104 km2 per kilogram of fibre. When comparing this with the demands
of roughly 0.02 km2 for 1 kg clean wool, and 0.01 km2 land for 1000 kg cotton,
respectively, it appears that developing a sustainable chemical fibres industry is
the only solution to keeping most arable land for food production.

9.6.3 Fibre Structure

Fibres have a complex structure. A simplified view of the general types of
structure is given in Figure 9.6.3.
372 Chapter 9.6
While any of the chemical fibres is easily described by one of the structures in
Figure 9.6.3, natural fibres look more complex, with a defined arrangement at
each level of organization. This reflects, ultimately, the fact that natural fibres
are produced by living organisms (in the cells) and their apparent homogeneity
comes from the supra-organization of similar elements.

9.6.3.1 Chemistry and Structure of Cellulose Fibres

Cellulose fibres originate from the seed of the plant (cotton), its stem (bast
fibres) or its leaves (sisal, alfa), having, as a consequence, different percentages
of cellulose, lignin and hemicellulose. Basically, any plant may be used as a
source of cellulose fibres, and it is a matter of historical development, avail-
ability and abundance that cotton, hemp and linen (flax) are today the most
used cellulosic fibres.
Cellulose, the base of all cellulosic fibres, is a complex composite material
which structurally comprises three hierarchical levels:

(i) the molecular level of the single molecule;

(ii) the super-molecular level concerning the packing and aggregation of
the molecules in crystals called micro-fibrils; and
(iii) the morphological level, i.e. the arrangement of micro-fibrils and
interstitial voids in relation to the cell wall.

On the molecular level, cellulose is a linear polymer of b-(1-4)-D-gluco-

pyranose units in 4C1 conformation. The fully equatorial conformation of
b-linked glucopyranose residues stabilizes the chair structure, minimizing its
flexibility.

The chains consist of 2000–14,000 residues which form crystals (cellulose Ia)
where intra-molecular (O3-H-O5 0 and O6-H-O2 0 ) and intra-strand (O6-
H-O3 0 ) hydrogen bonds hold the network flat allowing the more hydrophobic
ribbon faces to stack. Each residue is oriented 1801 to the next with the chain
synthesized two residues at a time. This tendency to form crystals utilizing
extensive intra- and intermolecular hydrogen bonding makes it completely
insoluble in normal aqueous solutions (although it is soluble in special solvents
such as aqueous N-methylmorpholine-N-oxide, NMNO). It is thought that
water molecules catalyze the formation of the natural cellulose crystals by
helping to align the chains through hydrogen-bonded bridging, as shown
subsequently.
Natural Fibres 373

The cellulose molecules in cotton are organized into parallel arrangements

called crystallites, and subsequently into larger aggregates called fibrils. The
elementary fibril is made up of 36 cellulose chains3 and is widely regarded as the
basic crystalline unit of cotton cellulose.4 In nature, elementary fibrils associate
into aggregates to form micro-fibrils and larger aggregates called macro-fibrils.
Different papers report slightly different dimensions for these fibrils, but typi-
cally the elementary fibrils measure 3.5–10 nm wide, the micro-fibrils 10–40 nm
and the macro-fibrils 60–300 nm.5
The spatial arrangement of elementary fibrils and larger aggregates deter-
mines the morphology and properties of a fibre and in maturing cotton the
arrangement of these structural units differs, depending on the state of fibre
development.
There are six polymorphs of cellulose (I, II, III1, III11, IV1 and IV11), which
can be inter-converted, as shown in Figure 9.6.4.6,7 More recently, evidence
for two polymorphs of cellulose I has been offered;8 that is to say what was
previously thought to be one polymorph (I) has now been found to be a mixture
of two polymorphs (Ia and Ib). Proof of the polymorphy of cellulose comes
from nuclear magnetic resonance (NMR), infrared and atomic force

Figure 9.6.4 Inter-conversion of the polymorphs of cellulose.

374 Chapter 9.6
9
microscopy (AFM) studies. Cellulose I, or native cellulose, is the form found
in nature. Cellulose II, the second most extensively studied form, may be
obtained from cellulose I by either of two processes: a) regeneration, which is
the solubilization of cellulose I in a solvent followed by re-precipitation by
dilution in water to give cellulose II, or b) mercerization, which is the process of
swelling native fibres in concentrated sodium hydroxide, to yield cellulose II on
removal of the swelling agent. Celluloses III1 and III1110 are formed, in a
reversible process, from celluloses I and II, respectively, by treatment with
liquid ammonia or some amines, and the subsequent evaporation of excess
ammonia.11 Polymorphs IV1 and IV1112 may be prepared by heating celluloses
III1 and III11, respectively, to 206 1C, in glycerol.
The natural crystal is made up from meta-stable Cellulose I with all the
cellulose strands parallel and no inter-sheet hydrogen bonding. The reason for
this meta-stable crystalline form is that the conversion of glucose into cellulose
takes place on the surface of an enzyme having about 30 active sites.13 As a
consequence polymer molecules grow together in the same direction, producing
a parallel faces crystal.
Cellulose I (natural cellulose) contains two allomorphs, namely cellulose Ia
(triclinic) and cellulose Ib (monoclinic). They are found in varying proportions
dependent on its origin, cellulose Ia being found more in algae and bacteria,
whilst cellulose Ib is the major form in plants.
Cellulose Ia and cellulose Ib have the same fibre repeat distance (1.043 nm for
the repeat dimer interior to the crystal, 1.029 nm on the surface14) but different
displacements of the sheets relative to one another. The neighbouring sheets of
cellulose Ia (consisting of identical chains with two alternating glucose con-
formers) are regularly displaced from each other in the same direction whereas
sheets of cellulose Ib (consisting of two conformationally distinct alternating
sheets) are staggered.
It has been found that cellulose Ib significantly alters the water structuring at
its surface out to about 10 Å, which may affect its enzymatic digestion.
Cellulose Ia and cellulose Ib are inter-converted by bending during micro-
fibril formation and meta-stable cellulose Ia converts to cellulose Ib on
annealing.
When re-crystallized (for example, from base or CS2), cellulose I gives the
thermodynamically more stable Cellulose II structure with an anti-
parallel arrangement of the strands and some inter-sheet hydrogen-bonding.
Cellulose II contains two different types of anhydroglucose (A and B)
with different backbone structures; the chains consisting of -A-A- or -B-B-
repeat units. Cellulose III is formed from cellulose mercerized in ammonia and
is similar to cellulose II but with the chains parallel, as in cellulose Ia and
cellulose Ib.

9.6.3.2 Chemistry and Structure of the Protein Fibres

Protein fibres are grouped into animal fibres (wool and other animal hairs,
known also as a-keratin fibres) and insect fibres (silk, a fibroin fibre). Both
Natural Fibres 375
a-keratin and fibroin are fibrous proteins. Their elemental analysis shows
carbon, hydrogen, oxygen, nitrogen and sulphur. The high sulphur percentage
(around 5 wt.%) found in wool and other animal hairs results from the high
cystine content of these fibres and distinguishes them from silk.
Total hydrolysis of the peptide bonds in proteins yields the 20 common
natural a-amino acids given in Table 9.6.1 (cystine, thiocysteine and cysteine
are considered to be faces of the same amino acid).15 More than 100 amino-
acids bind to each other to form the protein chains, schematically shown
subsequently.

Table 9.6.1 The 20 common natural a-amino acids found in protein fibres.
Group Name Side chain

‘‘Acidic’’ amino acids and their o-amides

Aspartic acid –CH2–COOH
Glutamic acid –(CH2)2–COOH
Asparagine –CH2–CONH2
Glutamine –(CH2)2–CONH2
‘‘Basic’’ amino acids and tryptophan
Arginine –(CH2)3–NH–C(NH2)¼NH
Lysine –(CH2)4–NH2
Histidine H
N CH2

N
Tryptophan CH2

NH
Amino acids with hydroxyl groups in the side chain
Serine –CH2–OH
Threonine –CH(CH2)–OH
Tyrosine –CH2–C6H4–OH
Sulphur-containing amino acids
Cysteine –CH2–SH
Thiocysteine –CH2–S–SH
Cystine –CH2–S–S–CH2–
Methionine –(CH2)2–S–CH3
Amino acids without reactive groups in the side chain
Glycine –H
Alanine –CH3
Valine –CH(CH3)2
Proline CH2
CH2
CH2
Leucine –CH2–CH(CH2)2
Isoleucine –CH(CH2)–CH2–CH3
Phenylalanine –CH2–C6H5
376 Chapter 9.6
Because they contain both cationic and anionic groups, protein fibres are
amphoteric. The cationic character is due to the protonated side groups of
arginine, lysine and histidine, and free terminal amino groups. Anionic groups
are present as dissociated side groups of aspartic and glutamic acid residues and
as carboxyl end groups.
The amino acid amounts differ in a-keratin fibres from silk, as revealed by
data in Table 9.6.2.
The peptide arrangement in protein fibre has been investigated since the first
half of the twentieth century. Astbury18,19 used X-rays to demonstrate the nature
of a crystalline phase in hair. The X-ray diffraction pattern of animal hairs shows
a meridian reflection at 0.51 nm and an equatorial reflection at 0.98 nm. Inter-
preting these results Pauling et al.20 proposed the a-helix structure to give
account of the secondary structure of the keratin fibre, shown in Figure 9.6.5.
The a-helix contains 18 amino acid residues in five turns, i.e. 3.6 amino acid
residues per turn. To obtain the distance between successive turns of the helix
that leads to the observed meridian reflection (0.51 nm), the helical chain must
itself be slightly coiled (super-helix, coiled coil21). Two super-helices combine to
form a left-handed two-stranded rope-like assembly in which the super-helices
are arranged in such a way that the hydrophobic side groups at the outside of
the helices interlink to form a stable ‘‘buttonhole’’ structure.22 These dimers are
the actual structural subunits of the micro-fibrils, and can be termed ‘‘mole-
cular twins’’. The force that keeps two a-helices together in the coiled-coil
dimer (the ‘‘brick’’ of the intermediate filament rod, IF) is given by the geo-
metry of the arrangement of amino acid residues in the polypeptide chain and
by the hydrophobic effect. The geometry requires a repeating sequence of seven

Table 9.6.2 Amino acids composition of a-keratin16 and of fibroin and

sericin.17
Amino-acid (mol %) a-Keratin (wool) Fibroin (silk) Sericin (silk)

Glycine 8.1 42.8 16.6

Alanine 5.0 30.0 4.7
Serine 10.2 12.2 31.3
Glutamine+Glutamic acid 12.1 1.4 4.1
Cystine 11.2 0.1 0.8
Proline 7.5 0.5 0.7
Arginine 7.2 0.5 3.2
Leucine 6.9 0.6 1.1
Threonine 6.5 0.9 7.9
Asparagine+Aspartic acid 6.0 1.9 19.0
Valine 5.1 2.5 3.6
Tyrosine 4.2 4.8 1.9
Isoleucine 2.8 0.6 0.7
Phenylalanine 2.5 0.7 0.6
Lysine 2.3 0.4 2.3
Tryptophan 1.2 0.2 1.2
Histidine 0.7 0.2 1.4
Methionine 0.5 0.1 0
Natural Fibres 377

Figure 9.6.5 Structure of a-helix as proposed by Pauling, Corey and Branson.20

amino acids (abcdefg), a heptade, with the residues a and d representing

hydrophobic ones, as shown in Figure 9.6.6.15
The further organization of the a-helices in proto-filaments, proto-fibrils to
micro-fibrils or intermediary filaments follows a pairing rule illustrated in
Figure 9.6.7.
Morphologically, the fibres are composed of the cortex and the cuticle. Each
of the two components is formed of various other morphological compo-
nents (Table 9.6.3). The cortex contains cortical cells and the cell membrane
complex. The cortical cell is further composed of macro-fibrils and intermacro-
fibrillar material. The macro-fibrils consist of micro-fibrils and intermicro-
fibrillar matrix. In summary, the cortex is formed of micro-fibrils (intermediate
filament, IF, or keratin proteins, KP) and keratin associated proteins
(IFAP or KAP), which compose the intermicrofibrillar matrix containing
cytoplasmatic and nuclear remnants. This ensemble is wrapped up in the
cuticle, as an external sheath which also has its own architecture, being
formed of four layers: the epicuticle, the a-layer, the exocuticle and the
endocuticle.
Thus, the a-keratin fibre is the best example of a natural composite system,
having a complex dual structure at all levels.
378 Chapter 9.6

Figure 9.6.6 The coiled-coil dimer structure. The letters may be replaced by any
amino acid residue from Table 9.6.1, with the only requirement that
amino acids a and d are hydrophobic ones.15

Figure 9.6.7 Structure of the intermediate filaments. A and B: helical domains;

L: non-helical linkers; N, C: N and C termini, respectively.16
Natural Fibres 379
Table 9.6.3 Animal fibre structure.
Composite Type Component 1 Component 2

Hair fibre Ring/core Cuticle Cortex

Cortex Filament in matrix Cortex cells (spindle shape) Cell membrane complex
Cortex cell Filament in matrix 5–8 macro-fibrils Intermacrofibrillar matrix
Macro-fibril Filament in matrix 500–800 micro-fibrils (IFs) Intermicrofibrillar matrix

Figure 9.6.8 Arrangement of hydrogen bonds in the anti-parallel chain pleated sheet
b-structure described by Pauling and Corey.23

The different production history and composition in terms of amino acid

percentages found in silk reflects into a different X-ray pattern, described by an
arrangement of the chains in what is termed as anti-parallel b-sheet and shown
in Figure 9.6.8.23 The same configuration, which is stable for silk fibroin, is also
achieved metastably by a-keratins when stretched in a wet environment.24
Fibroin contains long regions of anti-parallel b-sheets. Other parts of
fibroin are not in the form of b-sheets. These contain bulky amino acids that
interrupt the b-sheet structures and may account for the ‘‘stretchiness’’ of silk
fibres. The b-sheet regions contain, almost exclusively, multiple repetitions of
the sequence:

½Gly-Ala-Gly-Ala-Gly-Ser-Gly-Ala-Ala-Gly-ðSer-Gly-Ala-Gly-Ala-GlyÞ8 

Notice that almost every other residue is a glycine and that between them lie
either alanine or serine residues. This repeating structure results in simple,
tightly organized structures, such as the structure of silk fibroin shown in
Figure 9.6.9.
In raw form silk consists of some 75% fibroin, 20% sericin and 5% of
various salts. The former is crystalline fibrous proteins and the latter is
amorphous and soluble in hot water or dilute alkali solutions.15 The degree at
380 Chapter 9.6

Figure 9.6.9 Packing of the amino acid chains in fibroin.

which sericin is removed leads to the various qualities of silk materials, with the
highest value for the highest percentage of fibroin.
The amino acid composition of the two proteins forming the raw material
differs, as shown in the last two columns in Table 9.6.2.

9.6.4 Fibre Sourcing

9.6.4.1 Cotton
Cotton fibres are the seed hairs of the plant Gossypium hisutum. The fibre
consists typically of between 88 and 96% cellulose with the rest being protein,
hemicellulose, ash and wax. When the fibre begins growing inside the seed, it
emerges like a hollow cylinder. The hole in the middle is the lumen and, around
it, the fibrils are laid down in a helical form on the inner wall under a fairly
constant angle of 211 throughout the thickness of the fibre. The sense of the
helix reverses periodically up to 50 times along the length of the fibre and this is
supposed to provide a torsional balance.
The fully developed cotton fibre consists of a waxy cuticle that envelopes it, a
cell wall that is differentiated into primary (outer) and secondary (inner) layers
and residual protoplasm called the lumen. Although this concept of the fibre
structure persists, more recent ideas do not differentiate between the cuticle
and the primary wall, which is less than half a micrometer thick and consists
of around 50% cellulose, with pectin, waxes and proteins making up the
remainder. The secondary wall, which differs considerably in chemical com-
position and structure from the primary wall, consists of up to 95% cellulose.3
The cellulose in the secondary wall is laid down in a series of concentric
growth rings or lamellae that reflect diurnal temperature fluctuations during
fibre development.25 Lord26 reported up to 50 lamellae; other workers27 have
estimated between 25 and 40 lamellae in a ‘‘mature’’ fibre. The first rings
deposited on the inside of the primary wall are known as the transition
lamellae.
Natural Fibres 381
When a cotton boll opens, the fibres are cut off from the transpiration system
of the plant. The fibres then dehydrate and become flattened and twisted. The
cross section of the cotton fibre after dehydration is generally kidney-shaped,
although the shapes range from near circular in mature fibres to flat in
immature fibres. The kidney shape is an inherent phenomenon due to zones of
different density in the secondary wall layers.28
Cotton grows on every continent, in a strip, the Cotton Belt, between 381
north latitude and 281 south latitude.29 Cotton plants need heat (10–251C
for 150 days), a lot of sunshine and water, particularly during flowering. It is
one of the crops most severely affected by pests and diseases worldwide.
Consequently, cotton is one of the most environmentally expensive fibres to
produce. Cultivation of cotton accounts for 25% of global insecticide sales.
It has the second largest agricultural use of pesticides in the world, with five
of the nine top ‘‘nasty’’ pesticides used. Cyanide, dicofol, naled and propargite
are commonly used in cotton production and these chemicals are known
cancer-causing chemicals. This prompted research for genetically modified
(GM) plants. The best known and most widely grown GM cotton varieties
produce a protein that kills bollworms, enabling farmers to cut their chemical
insecticide use.
Cotton plantations are intrinsically tied to the history of the erstwhile
Confederate States of the USA. Cotton is a crop that, besides fibre (cotton lint),
delivers food (cottonseed oil) and feed (meal). For each 100 kg of cotton fibre
produced, the plant produces about 150 kg of cottonseed. About 50 cottonseeds
are contained in a pod, which opens when it is ripe. After removal of the cotton,
the seeds are still covered with fine hairs (linters), which are removed with
delintering machines. The linters are used as a chemical cellulose source in
personal care products, in batting for upholstered furniture and mattresses, in
high-quality paper and for celluloseether production.
The collecting of cotton fibres that surround the seeds in cotton bolls is
known as picking. The picked product, ‘‘seed cotton’’, comprises roughly 55%
seeds, 40% fibre and 5% trash and requires cleaning by machines for removing
firstly the large impurities (leaves, twigs or bolls) and for separating it from
seeds (ginning). By the end of the line, the clean cotton fibre is compacted and
compressed for being delivered to further processing.
The production of cottonseed varies directly with cotton fibre production
and cotton growers generally consider seed and oil as by-products. Cottonseed
oil is the sixth most widely consumed oil worldwide (see Chapter 9.1). It is high
quality and rich in polyunsaturated fatty acids and vitamin E (Figure 9.6.10.).

9.6.4.2 Bast Fibres (Flax, Hemp)

Bast fibres are obtained from the stems of the corresponding plants: hemp is a
variety of Cannabis sativa L (differing from marijuana by having a considerably
low content of D-9-tetrahydrocannabinol, the narcotic substance), and flax is
obtained from the plant Linium usitatissimum. The fibres contain 70–75%
cellulose, with about 4% lignin, 17% hemicellulose and 6% pectin in hemp and
382 Chapter 9.6

Cotton

Seed 40% Linters 27% Wool 33%

Kernel 28% Hull 12%

Protein 6.5%

Oil 6.5%

Fibre 5%

Other 10%

Figure 9.6.10 Composition of cottonseed.

2% lignin, 20% hemicellulose and 3% pectin in flax.30 The helical arrangement

of the fibrils found in cotton exists also here, but the angle of the helix and its
sense differ at each fibre: the helix makes 41 and follows a Z sense in hemp fibre,
and makes 101 with an S sense in flax.
Within the stem there are a number of fibre bundles, each containing indi-
vidual fibre cells or filaments. The filaments are made of cellulose and hemi-
cellulose, bonded together by a matrix of lignin or pectin.
The pectin and lignin also surrounds the bundle for holding it on to the stem.
For separating the bundles of fibres from the rest of the stem and using them
industrially the pectin and other impurities have to be removed. The first stage
for achieving this is retting, a microbial process that breaks the chemical bonds
that hold the stem together and allows separation of the bast fibres from the
woody core. The two traditional types of retting are field and water retting,
differing by the amount of water required (dew only for field and water basins
for water retting, respectively) and the obtained quality. High-quality fibre
results from water retting, but the process is very labour- and capital-intensive,
requiring knowledgeable workers and uses large volumes of clean water that
must be treated before being discharged. Research is carried out using micro-
organisms or enzymes for producing textile-quality bast fibres. Scutching is the
next step to be done. This process mechanically extracts the fibres from the
retted straw. The resultant fibres are further processed by industry.
The fibres are only part of the total plant culture; they represent 4–5% of
hemp, or 35–40% of flax plant, and 33–40% of cotton seeds (Figure 9.6.11).
The rest of the plant is also used for various other purposes, more particularly
fodder and oil (see Chapter 9.1). The fibre output per hectare of cultivated land
differs also from one plant to another: cotton reaches 1000 kg fibres ha1, hemp
may yield 1800 kg fibres ha1, and flax up to 2000 kg fibres ha1.
Natural Fibres 383

Flax, linum

Seed Stem

Preferentially low Preferentially high

growing, branched growing, unramified
flax species > 30 cm flax species up to
height 100 cm height

Breeding Linseed Flax fibre

Linola™ Protein 24%

NuLin™ Oil 40%

Other 36%

Figure 9.6.11 Composition and industrialization of flax.

Compared to cotton the cultivation of bast fibres is much more sustainable.

Although not botanically related, both plants grow well in a moderately cool,
temperate climate and can be grown in almost any country in the world. The
plants are resistant to pests and do not require pesticides.

9.6.4.3 Animal Fibres

Animal fibres have a slightly elliptic cross section and are protected by the
scales arranged on their surface as tiles on a roof.
Keratin fibres are available almost everywhere in the world. Wool, produced
by sheep, is by far the most widely used keratin fibre, while shatoosh produces
the most expensive one and is found only on the high peaks of Himalaya.
Among all keratin fibre producers, the sheep is the most important one.
Economically the sheep is a fibre factory without wastes. The by-products of the
factory are defined from the point of view of the down processing industry. For
example, the textile industry regards milk and meat (lamb) as secondary products.
Compared to other keratin producers, sheep give the largest fibre amount
from a given pasture surface. Due to the way sheep eat grass the pasture
regenerates quickly after a sheep passage – to compare with the Cashmere goat
after whose passing at least 2–3 seasons are required for regenerating the
pasture. Very roughly, a sheep produces 1 kg greasy wool (or some 0.6 kg clean
wool) annually from 1 ha of average pasture.
Sheep have several pests and there are insecticides that are used for fighting
them. For fighting flystrike, occurring notably in Australia, farmers developed a
process called mulesing. Mulesing is a surgical procedure by which the wrinkled
skin in the animal’s breech area is cut away from the perianal region down to the
384 Chapter 9.6
Table 9.6.4 Composition (%) of greasy wool. The micron limits for the three
wool types are only orientative.
Wool type Grease and suint Sand and dirt Vegetable matters Fibre

Merino (o25 mm) 15–30 5–40 0.5–10 30–60

Crossbred (25–33 mm) 15–30 5–20 1–5 40–65
Long wool (433 mm) 5–15 5–10 0–2 60–75

top of the hind limbs. This is thought to be painful for sheep and for this reason
the animal protection organization PETA (People for the Ethical Treatment of
Animals) spoke against the practice. There is research targeting the development
of an alternative for this, since by 2010 mulesing will be phased out.
The bringing of the fibres to the textile industry is a labour-intensive process.
The shearing and collecting of greasy wool are manual operations and so are
the skirting (selecting the parts of the fleece) and classing. The collected greasy
(raw) wool comprises various amounts of different impurities, as detailed in
Table 9.6.4.
To deliver clean fibres to industry the greasy wool goes through scouring.
This consists of washing the raw fibres with about 1% surfactant in a con-
tinuous 5–6 bowl line for removing the grease, suint, sand and dirt from the
fibres. The discharged waters from the first three basins from washing fibres
with more than 10% grease (usually Merino type) are further used for
extracting lanolin by an Alfa-Laval process. In spite of lanolin separation the
waste waters from wool scouring are heavily polluted with organic matter and
much effort is dedicated to cleaning and reusing them for saving water con-
sumption. The recent development of biodegradable surfactants31 helps toward
building a more environmentally friendly wool scouring process. Some 5–7
litres of water are required for obtaining 1 kg clean wool under severe control of
the parameters, but 20 litres is more common.
Vegetable matter, if more than 2–3%, has also to be removed before going to
further processing. The operation, known as ‘‘carbonization’’, makes use of the
good resistance of wool to strong acids (particularly sulphuric acid) and of the
hydrolysis of cellulose in the same environment. The fibres with vegetable
matter (grass, burrs) are soaked in a 20% sulphuric acid solution, dried and
baked and then crushed for separating the carbonized cellulosic matters from
the rest. The fibres are then neutralized and dried. The process produces acid-
polluted waters and carbon dust in air, besides weakening the wool fibres,32 for
which reason alternatives, like the use of enzymes, are sought.

9.6.4.4 Silk
Silk is produced by silkworms (caterpillars) fed with fresh mulberry leaves,
while spinning their cocoons. Liquid silk produced by spinnerets is coated in
sericin, and solidifies on contact with the air. Within 2–3 days, the caterpillar
spins about 1500 m of filament and is completely encased in a cocoon. Most
Natural Fibres 385
caterpillars are then killed by heat (boiling) and some are allowed to meta-
morphose into moths to breed the next generation of caterpillars.
Stifled cocoons are sorted, and then brushed to find filaments. Several fila-
ments are gathered together and wound onto a wheel (reeling). Each cocoon
yields approximately 1000 m of silk filament, known as raw silk, or silk-in-the
gum, fibre.
Wild silk (Tussah) production cannot be reeled, because cocoons are har-
vested after the moth has matured and left. As an average yield one may take
30 kg mulberry leaves for 1 kg cocoon. As the harvesting of the silk from the
cocoon requires the killing of the larvae, silk-culture has been criticized by
animal rights activists.

9.6.5 Summary of the Properties of Natural Fibres

The ‘‘classical’’ two-phase model assuming a composite arrangement of distinct
crystalline and extended amorphous regions to describe the superstructure of
natural fibres apparently has to be revised. Concepts like crystallinity and
amorphicity are well adapted to describe homogeneous states of matter. They
are, however, rather ill-defined when it comes to treating dense composite
materials like cellulose, or proteins, given that intermolecular correlations do
not build up or die off abruptly at some fictitious interfaces.
The mechanical characteristics of the fibres well reflect the complexity of
their structures. While wool shows a decrease of E-modulus and an increase of
elongation at a break in the wet stage compared to the dry one, cellulosic fibres
behave inversely. A summary of the mechanical properties of natural fibres is
given in Table 9.6.5.

9.6.6 Processing of Natural Fibres

The numerous chemical and mechanical processes through which the fibres are
turned into end-product can be grouped into:

 operations which transform the fibres into fabric;

 operations of cleaning the fabrics;

Table 9.6.5 Properties of glass and natural fibres.

Cotton Bast Wool Silk E-Glass
3
Density (g.cm ) 1.5–1.55 1.4–1.52 1.32 1.25 2.55
E-modulus drya (Gpa) 8–12 60–75 4–6 20–25 73
E-modulus wetb (Gpa) 3–4 20–30 2–4 5–6 73
Elongation drya (%) 6–10 1.5–4 35–50 20–30 3
Elongation wetb (%) 8–12 7–10 45–65 40–50 3
Moisture absorptiona 7–11 8–10 15–18 9–11 –
a
measured at 65% relative humidity and 22 1C.
b
measured at 100% relative humidity and 22 1C.
386 Chapter 9.6
 operations of stabilizing the dimensions of fabrics;
 operations of coating-infiltrating for colouring and finishing the fabrics;
 operations of surface treatment.

These operations are similar for both natural and chemical fibres. The details
of the operations differ with the fibre chemistry and origin, and with the way the
fabric was obtained: by weaving or by knitting, respectively. In all cases chemical
products are used for assisting, or for producing the required effect, and in all
cases pollutants are produced, either in effluents, or in the atmosphere.
Most operations make extensive use of surfactants for assisting mechanical
processes, for washing/scouring, for improving the quality of bleaching, of
dyeing, or for finishing (softening, stiffening) the materials. The surfactants are
subsequently discharged into the waste waters and pose serious problems for
cleaning. Besides, the surfactants interact with the skin/eyes of the operators in
the mills, or of those laundering at home.
The actual trend of natural surfactants based on renewable raw materials33
combine a high emulsifying power with good electrolyte stability and extremely
good skin compatibility.
The biodegradability of chemical substances depends on their chemical
structure. Branched hydrocarbon chains such as tetrapropylene alkylbenzene
sulphonates, alkylphenol polyglycol ethers on the one side and quaternary
ammonium compounds on the other show poor biodegradability, more parti-
cularly under anaerobic conditions.33,34
The nature of renewable raw materials matches the requirement for biode-
gradability under aerobic and anaerobic conditions (Table 9.6.6). The linear
hydrocarbon chains facilitate biodegradability without the formation of eco-
toxic metabolites as is the case with alkylphenol polyglycol ethers.
Textile softeners form a special group among surfactants. They should
remain on the textile in order to make the fabric ultra smooth and soft without
affecting its texture. Depending on the washing conditions (temperature, etc.)

Table 9.6.6 Anaerobic biodegradability of various surfactants.33,34

Surfactant type Biodegradability
Sulphonated anionic surfactants (LAS, SAS) biodegrades poorly
Sulphated anionic surfactants (fatty alcohol sulphates, alcohol biodegrades well
ethoxysulphates)
Fatty acids and soaps biodegrades well
Fatty alcohol ethoxylates biodegrades well
Sugar-based surfactants (alkyl polyglucosides, glucamides) biodegrades well
Alkylphenol ethoxylates partially degradable,
leaving alkylphe-
nol residues
Mono-or di-alkyl quaternary compounds (TMAC, biodegrades poorly
DTDMAC)
Esterified mono-or di-alkyl quaternary surfactants (esterquats) biodegrades well
Natural Fibres 387
the softeners will be washed off after 1–5 washing cycles at the earlist, which
also means the product stays in contact with the human skin during wear.
Besides they form the largest part of finishing agents, which share about 65% of
textile auxiliary sales.35 Because of this, potential allergenic problems are
regarded more closely. For that purpose the German Skin and Allergy Relief
Fund (DHA Deutsche Haut-und Allergiehilfe) has conducted a survey of der-
matologists, paediatricians and allergists regarding the use of consumer market
laundry softeners (Weichspüler in German). Seven out of ten of those surveyed
considered the use of fabric conditioners by people with sensitive skin as useful
and convenient, and one in four even recommended fabric conditioners expli-
citly, since the smoothened fibre surfaces reduce the potential of mechanical
friction, which is advantageous for sensitive and damaged skin.36
Textile softeners are mainly cationic or pseudo-cationic surfactants. They
attach by electrostatic forces to textile fibres with the polar (charged) end of the
cation oriented toward the fibre and the fatty tail exposed which imparts the
feeling of softness to the fabric.
The main ingredients of fabric softening formulations used by the main
manufacturers in Europe and since proliferated around the world are the so-
called Esterquats.37
Their synthesis is performed by the condensation of fatty acids and etha-
nolamines, followed by the quaternizing of the tertiary nitrogen with a methyl-
chlorine, or dimethyl-sulphate:

2RCOOH þ CH3 NðCH2 CH2 OHÞ2 ! CH3 NðCH2 CH2 OOCRÞ2 þ 2H2 O
CH3 NðCH2 CH2 OOCRÞ2 þ CH3 Cl ! ½ðCH3 Þ2 NðCH2 CH2 OOCRÞ2  þ Cl
Esterquat

Esterquats based on triethanol amine, diethanol amine or N,N-dimethyl-3-

aminopropane-1,2-diol are usually abbreviated to TEAQ (triethanol amine
quat), DEEDMAC (diethyloxyester dimethylammonium chloride) or HEQ
(Hamburg Esterquat), respectively. Esterquats as cationic surfactants were
introduced in the European market in the early 1990s when concerns were
raised about the environmental profile of the cationic surfactants used up to
then (Di-Hardened Tallow Di-Methyl Ammonium Chloride, or DHTDMAC)
and initiated their decline in use and international initiatives (e.g. PARCOM
recommendation 93/4) calling for them to be phased out. Esterquats are similar
to what was used before except that ester links have been introduced into the
head-group of the molecules, which have the quality that they are subject to
degradation by hydrolysis and greatly facilitate biodegradation. Most, if not
all, fabric conditioners marketed in Europe are now based on these three
Esterquat materials: TEAQ, DEEDMAC and HEQ. They combine good
environmental profile – especially ready and ultimate biodegradability – with
the structural features required for an effective fabric conditioner.
Also being sold are the amphoteric softeners, the betaines (general
structure: (CH3)3N1CHR1-COO). Amphoteric/betaine surfactants are generally
mild with low eye and skin irritation. They produce a good handle and greatly
388 Chapter 9.6
increase the hydrophilic properties. Their mildness makes them suitable for baby
clothing laundry detergents and their compatibility with quats and esterquats for
‘‘detergent and fabric softener in one’’ formulations. Betaines and non-ionic
products, such as ethoxylated fatty alcohols, RO(CH2CH2O)nH, ethoxy-
lated fatty acids, RCOO(CH2CH2O)nH, ethoxylated fatty amides, RCONH-
(CH2CH2O)nH, or ethoxylated fatty amines RN(CH2CH2O)nH and acetylated
sugar ethers increase hydrophilicity and have found applications as co-softeners.
Also polydimethylsiloxane (PDMS) emulsions and micro-emulsions are well
known as conditioners in textile finishing imparting softness, dimensional
stability and wrinkle and stretch recovery. When combined with quats and
esterquats they improve the water absorbency of softened cotton fabric. Long-
chain PDMS with amino- or amido-functional side groups anchor the silicone
to the fibre by way of attractive electrostatic forces. Interfibre friction is
reduced in this way, producing a distinct and substantive softener effect.38

9.6.6.1 Operations Which Transform Fibres into Fabric

This group gathers several mechanical operations which help transform the
fibres into a yarn (carding, combing and spinning) and further a yarn into a
knitted or woven fabric (knitting and weaving, respectively). The making of the
yarn requires the grouping of fibres in a roving of fairly constant density, which
is eventually spun. The fibres are kept together in the yarn by fibre–fibre friction
and the twisting movement during spinning ensures a compact packing. Pro-
viding the fibres in the yarn are parallel or randomly arranged the yarn is
known to be worsted (its formation includes a combing for parallelizing the
fibres and the yarn is fine and smooth) or woollen (carded yarns, as combing is
not used). The yarn is then used for producing the 3D structure (fabric) by
knitting or weaving.
Alternatively, non-woven fabrics are produced by directly transforming
fibres after carding (formation of the web) into a fabric, without the inter-
mediation of the yarn. Except in the production of felts, which makes use of the
felting property of wool (and other animal fibres), fibre–fibre friction plays no
role here and there are resins used for bonding.
These operations do not make a distinction between fibres, which is to say
that all fibres are processed alike.

9.6.6.2 Cleaning Operations

Washing/scouring and bleaching are the two operations of cleaning the fabrics.
Scouring aims to wash out the chemical auxiliaries used in assisting the
spinning, knitting or weaving.
While animal fibres go through a scouring process before being industrially
processed into end-products, cotton fibres meet water only as yarns or fabrics.
Consequently the scouring of cotton fabrics is more severe (boiling temperature,
enzymes for desizing and hypochlorites or chlorites for cleaning), as it is
required in eliminating the rest of the seeds and other waxes from the plant.
Natural Fibres 389
The bleaching process also has peculiarities depending on the type of fibre
which is treated. The most common and environmentally friendly bleaching agent
used for fibres is hydrogen peroxide. Cotton is also partly bleached while scouring,
under the action of sodium chlorite. Some yellow wools or bast fibres may require
a harsher bleaching, for which reason sodium dithionite or sodium formaldehyde
sulphoxylate (for wool) and sodium chlorite (for bast fibres) are also used.
Due to the fact that chemical fibres are produced under controlled para-
meters, their cleaning requires fewer chemicals and even the bleaching is,
sometimes, unnecessary.
A common bleaching agent used domestically (more particularly in Medi-
terranean countries and North America) is Javel water, which is sodium
hypochlorite in water.

9.6.6.3 Stabilizing the Dimensions

This group of operations is the most diverse depending on the nature of the
fibre.
Wool fabric requires crabbing, wet and dry decatizing for setting the
dimensions. The chemical background of wool fabric setting is the breaking
and reforming of interchain cystine bonds in the desired places by using a wet
environment, mechanical stretch and heat-cold shock. A chemical setting is also
possible by using treatment with thio-glycols under stretching, followed by
hydrogen peroxide reformation of the disulphide bonds, as in permanent
waving of hair, but it is considered too expensive for industrial purposes.
Cotton and bast fibres fabric dimensions are set by mercerizing and
sanforizing.
The mercerizing is based on the action of cold strong alkali (usually NaOH)
solution and concomitant application of a stretching force, followed by neu-
tralization. As is shown in Figure 9.6.4, this allows cellulose fibre to pass from
the meta-stable natural crystalline structure I to the stable cellulose II form.
The mercerization produces effluents with very high pH, requiring further
acidic treatment for discarding.
Sanforizing, a complementary operation for stabilizing the dimensions of
cellulose fabrics, is an induced shrinkage of cotton fabric achieved by con-
trolled dampening and drying of the relaxed fabric to remove any tensions and
distortions which have appeared as a result of other processing. It does not
produce pollutants.
The stabilizing of fabrics made of chemical fibres requires a thermosetting
operation, performed in the stenter. The pollutants produced are volatile
organic compounds (VOCs) arisen from the oligomers volatilizing at 180–
200 1C required by thermosetting.

9.6.6.4 Coating and Infiltrating

The coating and infiltrating operations cover most of the dyeing and wet fin-
ishing processes.
390 Chapter 9.6
The colouring process renders most of the commercial value of a fabric. It is
achieved either by coating (pigment printing) or by infiltrating (printing and
dyeing) the fibres. While pigment printing binds by a coating resin colouring
pigments which have no affinity for the macromolecules of the fibre, the other
printing systems and the dyeing makes use of molecules which diffuse and
eventually bind on active sites inside the fibre, or aggregate to form difficult to
removable clusters. The dyes used for the natural fibres belong to practically
any dyeing classes; it is only the disperse dyes which are of low interest, due to
their poor affinity, and this class remains dedicated exclusively to polyester
fibres. Historical textile dyeing handicraft operations, because of the multi-
colour aspect, are highly attractive for tourism on one side, but on the other the
colouring operations, either dyeing or printing, produce polluted (coloured)
waters because the process yield is usually only up to 80%.39
The pigment printing issues also volatile organic compounds (VOCs) and
fumes from resin curing.
The wet finishing operations comprise flame-proofing treatment, softening
or easy-care. Among them the easy-care finish is probably the most important
one.
Easy-care finishing reduces the tendency of the fabric to crease in wear and
makes it much easier to iron after laundering. It may also prevent shrinkage
during washing. These types of finish have greatly reduced the maintenance
which cotton and wool in everyday use require, and have increased their suit-
ability for apparel of all types. However, there is a price for these advantages:
pollution.
The easy-care treatment of wool fabrics has to handle the felting property,
which affects also the dimensional stability of wool fabrics. The felting process
makes use of the particular surface of wool fibre, whose scales enable the
directional frictional effect. Consequently, any mechanic action in a wet
environment on a wool fabric translates to a shrinking of dimensions by
increasing the compactness. The felt-proofing treatment aims at shaving the
scales on fibre surface and/or at fixing the fibre-to-fibre by chemical resins. The
cleaning of the scales is achieved by Alwörden’s reaction,40 which involves a
controlled cold chlorination followed by neutralization and a resin application.
The process produces large amounts of halogenated organic compounds
(AOX) in the effluent, besides gaseous chlorine in the atmosphere, for which
reasons new methods are under investigation. Treatments with enzymes,41 with
ozone42 or with plasma,43 followed by resin application, are some of the
available alternatives.
The easy-care treatment of cellulose fabrics uses padding with methylol-urea
resins and curing them to cross-link inside the fibres. Consequently for-
maldehyde is the most important pollutant accompanying the easy-care finish.
Alternatives were developed with resins without formaldehyde (reactive elas-
tomere silicones, or dicarboxylic acids able to react with the OH groups of
cellulose) but the results need still to be improved. Ammonia may also be used
for improving the easy-care treatment in a mercerization-like process. This
produces, on the other side, ammonia pollutants.
Natural Fibres 391
The mechanics of the chemical fibres make easy-care treatments unnecessary
for fabrics made out of these fibres. The blends of natural fibres with chemical
fibres are based on this feature for producing easy-maintainable fabrics for
apparels at low cost of pollution.

9.6.6.5 Surface Treatments

Surface treatments are, generally, mechanical operations giving the final aspect
to fabric surface. Pressing (ironing), raising, suing and shearing are, probably,
the most important ones.
These operations, particularly raising, suing and shearing, produce certain
amounts of dust and fuzzy fibres as pollutants.

9.6.7 Conclusions
While artificial fibres came onto the market with the 1889 invention of rayon by
Hilaire de Chardonnet, and synthetic fibres emerged with the 1931 DuPont
patent for Nylon, natural fibres have been around since the dawn of mankind,
flax having a documented history (burial shrouds for the Egyptian pharaohs) of
more than 7000 years. No matter in which climatic zone humans settled, they
were able to find and utilize the fibres of native species to make products such as
clothes, cloths, buildings and cordage.
The first composite material known was made with clay and straw to
build ziggurats in the ancient world. About 3000 years later there is a strong
belief that the field of natural fibre composites is set to expand enormously in
the near future. The environmental and health problems associated with syn-
thetic fibres mean that they should be replaced by natural alternatives in a vast
number of different applications. Their moderate mechanical properties
restrain the natural fibres from being used in high-tech applications, but for
many reasons they can compete with glass fibres. The natural fibres are light-
weight, which makes them particularly attractive to the automotive industry.
Statistics show that already in 2002 Germany and Austria together used
around 17,000 mto of natural fibres in the automotive industry, out of which
about 9,000 mto are flax and 2,500 mto are hemp fibres, and the yearly growing
rate is 22%.
The modern composite materials, which merge the advantages of
natural fibres with synthetic matrices and environmental goals, aim to go
beyond the fibre competition during the last 100 years and to answer the new
challenges.

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CHAPTER 9.7

Plant-based Biologically Active

Ingredients for Cosmetics
CHARLOTTE D’ERCEVILLE, FLORENCE HENRY,
PATRICE LAGO AND ANDREAS RATHJENS

Laboratoires Sérobiologiques, Division of Cognis France, 3 rue de

Seichamps, CS 71040 Pulnoy, 54272 Essey Les Nancy Cedex, France

9.7.1 Introduction
Plant-based biologically active ingredients are used in different kinds of
industries and have achieved a particularly high importance in the development
of cosmetic actives with a proven biological effect. However, what about other
aspects of modern economies? Is it sufficient that the products are just derived
from plant origin? The simple answer is no. In today’s world, we have to find
the right balance between economic interests and the ecological limits imposed
by the capacity of the biosphere to provide society with all of its resources for
present and future generations. This is not a contradiction at all; instead,
society and industry are forced to respect nature, to set up and follow clear
rules on what sustainable development should look like and to accept their
Corporate Social Responsibility (CSR). These aspects are discussed using a
concrete example, cosmetic active ingredients from the Argan tree.

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

394
Plant-based Biologically Active Ingredients for Cosmetics 395
9.7.2 Active Ingredients and their Functionality in
Cosmetic Applications
One definition of active ingredients comes from the pharmaceutical area.1 An
active ingredient, also active pharmaceutical ingredient or API, is a drug that is
pharmaceutically active. The traditional word for API is pharmacon, adopted
from the Greek ‘‘pharmacos’’, which originally denoted a magical substance.
However, the term ‘‘active ingredient’’ is now also common and applied in other
areas, for example nutrition and personal care, especially in the field of cosmetics.
In all cases, we speak about a component that is considered to fulfil the intended
activity of a final product, described by its claim, and gives the desired physio-
logical effect. The main distinction lies in the delivery mode, which is oral intake
for nutritional application and topical application for cosmetic formulations.
Going a step deeper into the cosmetic domain and focusing on skin care appli-
cations, we can therefore describe an active ingredient as a substance or a group of
molecules with the ability to improve the structure and appearance of skin when
applied topically. To give some examples, knowing that the list of claims is much
longer, we might speak about skin moisturization, reduction of wrinkles and
protection against environmental stress, such as sun light or pollution or the wish
to change one’s skin colour either by whitening or by tanning. Figure 9.7.1 gives a
representative overview of biological targets for skin care active ingredients.
Cosmetics in general are more than simple externally applied formulations to
change or enhance the beauty of skin, hair, nails, lips and eyes. The key issues
of today are related to well-being and convenience. Consumers are looking for
solutions that reduce the complexity of their daily life, support their demand of

Figure 9.7.1 Biological targets for skin care active ingredients.

396 Chapter 9.7
excellent performance and are in line with their ‘‘green’’ consciousness. As a
result, cosmetic products are intended to deliver not only the functional benefits
they promise, such as an anti-aging effect or protection against harmful
environmental influences etc. (see Figure 9.7.1), but also to give the user a sense
of well-being. Thus, consumers are looking more and more for a holistic pro-
duct experience that appeals to all their senses.

9.7.3 Plant-based Raw Materials

Plant-based raw materials are important for the development of active ingre-
dients. It is not mandatory that the source for a cosmetic active substance is a
plant; mineral and animal materials or synthetic molecules are also widely used in
the industry in order to achieve or improve performance and benefits of a cos-
metic formulation. Although the limited fossil resources are still the main basis
for the chemical industry, they are more and more regulated, have the dis-
advantage of not being ‘‘renewable’’ and, in addition, prices are continuously
increasing due to the growing worldwide demand, predominantly for energy
generation. Animal-based raw materials have received negative reports since the
1990s, regarding bovine spongiform encephalopathy, which have left a feeling of
discomfort with consumers when coming into contact with them. The request for
plant extracts has continuously increased since that time in order to replace
animal-derived ingredients.2,3 Moreover, taking into account the modern con-
sumer demand for ‘‘green’’ and environmentally friendly products, supporting
the wellness and sustainability trend, natural renewable sources are the raw
material of choice for extraction and chemical synthesis. Thanks to the huge
potential and diversity of the plant kingdom with more than 287,000 species
described on Earth, plant-based active ingredients are today the driver of inno-
vation and most probably their importance will increase in the coming years.4
Aside from flora biodiversity, plants contain a high variety of phytochemical
compounds with performance on a wide range of cosmetics functionalities. For
instance, proteins and polysaccharides act as film formers and tightening active
ingredients. Seed oils, rich in fatty acids and triglycerides, are used for their
emollient and moisturizing properties and, finally, secondary metabolites are
increasingly applied in cosmetics to reduce the effects of different environ-
mental stress, e.g. flavonoids for UV photo-protection.2
The use of plant-based biologically active ingredients in all branches of
industry and in different applications is the subject of intensive discussions in
the media and in the wider public. Historically, natural products from plants
have provided an endless source of medicine and remain an undiminished
starting point for the development of new pharmaceuticals.5
The conservation of biological diversity, the sustainable use of its compo-
nents, and the fair and equitable sharing of benefits arising out of the utilization
of genetic resources is promoted by the Convention of Biological Diversity
(CBD), a legally-binding instrument with 191 parties to date, which was
negotiated under the auspices of the United Nations Environment Program
Plant-based Biologically Active Ingredients for Cosmetics 397
(UNEP) at the Earth Summit in Rio de Janeiro and entered into force in 1993.7
The 9th Conference of the Parties (COP) recently held in Bonn has specifically
discussed the economic importance of genetic resources and the direct and
indirect relationship of companies with biodiversity, as well as potential
pathways for integrating biodiversity into their strategies and daily activities
(‘‘Business & Biodiversity Initiative’’). It was mentioned that 35,000 plant
species worldwide are used and 2000 species are marketed in Europe for
medicinal and aromatic purposes. Finally, 70% of modern pharmaceuticals are
based on plants.
The worldwide market size for medicinal plants, exotic fruits and seeds has
been estimated to be 18,000 Mio US$. In parallel, it seems clear that there is an
increasing number of consumer goods using plant derived raw materials, such
as phytopharmaceuticals, cosmetics and dietary products.6
From here, we would like to focus on the cosmetic industry and explain in
more detail the modern principles of sustainability and Corporate Social
Responsibility with a concrete example: the Argan tree story.

9.7.4 Sustainability Concept and Corporate Social

Responsibility (CSR)
Behind the term ‘‘sustainability’’ lies the quest for future-viable solutions for
the environment, technology, business and our social structures. The drivers of
the sustainability trend are society’s changing values. According to a study
published in 2005 by the Natural Marketing Institute (NMI), a new group of
consumers is emerging all across the world. It is referred to as LOHAS (Life-
style Of Health And Sustainability), and already one-third of US consumers
belong to this group.8 They are not searching for a compromise in terms of
excellent product performance, but want the complete package including high
efficacy, environmentally friendly manufacturing processes and no risk on
product safety.
According to the European Commission, CSR is ‘‘a concept whereby com-
panies integrate social and environmental concerns in their business operations
and in their interactions with their stakeholders on a voluntary basis’’.9
Stakeholders exist both within and outside a firm. CSR is concerned with
treating the stakeholders of the firm ethically and in a socially responsible
manner. The aim of social responsibility is to create higher and higher stan-
dards of living, while preserving the profitability of the corporation for all its
stakeholders.10
A company operates sustainably when its actions do not impair the planet’s
ability to provide the necessary resources in both the present and the future and
when it integrates, on a voluntary basis, social and environmental concerns in
its business operations and its interactions with its stakeholders. This is a
commitment to find a healthy balance between financial, environmental and
social imperatives, without compromising the development opportunities of
398 Chapter 9.7

Figure 9.7.2 Four dimensions of sustainability.

future generations. Based on the principles of Agenda 21,11 we are focusing on

four key aspects (Figure 9.7.2):

 People: the business is built around people; we aim to be a responsible and

attractive employer, develop and improve continuously the skills and
expertise of our employees, and to be a good neighbour.
 Environment: the use of natural renewable raw materials is a key. At the
same time, we offer to manufacturing industries and consumers solutions
that are both cost-effective and environmentally friendly.
 Company: strict quality, environmental, health and safety standards are
part of our integrated management system. Working in partnership with
the communities, either in industrialized regions or developing countries, is
essential to our philosophy.
 Products: to develop innovative performance products that meet the
highest standards in terms of occupational and consumer health, safety
and environmental protection.

9.7.5 From the Botanical Raw Material towards the

Final Product
The development of a novel plant-based biologically active ingredient generally
follows well-defined steps correlated to a logic process flow, which is less
dependent on the part of the plant used, e.g. fruits, flowers, leaves, by-products
such as oilcakes, or the intended final performance. All work starts with the
identification of a suitable raw material and corresponding suppliers. The
aforementioned principles of sustainability have to be applied already at this
stage, and all available information must be analyzed in a critical manner. Key
Plant-based Biologically Active Ingredients for Cosmetics 399
elements of our sourcing process take into account a responsible and envir-
onmentally friendly approach by evaluating:

 Bioavailability of the natural resource;

 Plant status, e.g. protected, vulnerable, threatened or endangered species,
etc.;
 Preference for value creation of by-products, e.g. oilcakes or fruit hull
from other industrial applications;
 Social impact of controlled collection and farming;
 Cultivation and collection following organic principles;
 Traceability, GMO (genetically modified organisms) risk, pesticide level, etc.;
 Implementation of environmental impact studies;
 Intellectual property rights of third parties;
 Toxicological profile of the plant or its extracts based on literature
information.

Concerning the natural raw material supplier, it is fundamental to have

reliable partners. This is in practice only possible not by multiplying the
number of suppliers, but by capitalizing on long-term partnerships with
selected ones, who share the same targets on social and environmental com-
mitment. They are responsible for a more extensive group of raw materials and
have therefore the critical mass to build up a network for cultivation and
harvesting. Moreover, the implementation of local added value in the form of
technical or operational empowerment is easier for a larger organization.
Once the source and potential supplier are selected, the product development
phase begins. A number of extracts are prepared, by using a different solvent
system, preferably water, and purifying protocols. These prototypes are
extensively tested in vitro in order to evaluate their efficacy and to identify the
one performing best with regard to the desired claim. The final version can then
be focused upon. Product safety must be assessed by performing a series of
toxicological tests, the product stability itself and in the final application form,
for instance cosmetic frame formulations, has to be confirmed. Finally, the
biological activity is validated by a clinical study involving healthy human
volunteers. The transfer to industrial manufacturing is then prepared. Ques-
tions of the environmental impact of industrial production are taken into
consideration, and the most appropriate processes using novel technologies to
reduce waste, energy and water consumption are selected.

9.7.6 Sustainable Development and CSR for the

Supply of Natural Products Derived from the
Argan Tree
The Argan tree (Argania spinosa), Figure 9.7.3, is an endemic tree of South
Morocco, growing in a region that runs from Safi in the north to the edge of the
Sahara in the south. The main zone extends south-east from Essaouira to the
400 Chapter 9.7

Figure 9.7.3 Environmental impact study: experimental area, localization of Argan

forest, Argan.

Souss plain, covers about 800,000 ha containing more than 2 million trees and
acts as a green belt against desert advancement. Argan is the second most
common species in Morocco, behind the evergreen oak (Quercus ilex) and ahead
of the thuya (Tetraclinis articulata). The tree is particularly resistant to the dry
and arid conditions of this region, can tolerate temperatures ranging from 3 to
501C and grows at altitudes of up to 1500 metres. Its roots, which extend over a
large area and are very deep, can search out water at more than 30 metres under
the ground, which helps it to survive the dry periods that can last for several
months each year. The tree reaches heights of 8 to 10 metres and has a shape
similar to an olive tree. Its life is quite long and it is not uncommon for it to reach
ages of 150 to 200 years; even some 250-year-old trees have been recorded.12
Argan leaves are small, dark green and grow on branches that can be spiky at
their ends. It is usually an evergreen plant but may lose its leaves in a persistent
dry period. The tree has small oval greenish yellow fruits that become brown
when they ripen and contain a very hard shell enclosing one to three almond-
like kernels. The ripening period is quite long taking 2 years.13
The Argan forest plays a crucial social and economical role as it ensures the
subsidence of over 3 million people of the rural Moroccan population.
Unfortunately, due to the demographic pressure, Argan woodland suffers from
continuous degradation. Over-exploitation, soil erosion and advancing deser-
tification are amongst the threats to this unique heritage. The natural growth of
the population leads to an increase in wood collection, which is used both for
construction and as firewood. Excessive grazing makes it more difficult for the
Argan trees to recover. The climate, which is always hard in these regions, is
accompanied by erosion that makes the soil even more arid.14
Plant-based Biologically Active Ingredients for Cosmetics 401
UNESCO, under the program ‘‘Man and the Biosphere’’ (MAB), took this
up and classed the Moroccan Argan forest as a Biosphere Reserve (RBA) in
1998.15 Biosphere Reserves are delimited regions in land-based ecosystems
where one tries to reconcile economic development with conserving the bio-
diversity. Biosphere Reserves serve in some ways as ‘‘living laboratories’’ for
testing out and demonstrating integrated management of land, water and
biodiversity, which is the principle of the ecosystem approach that has resulted
from the biological diversity convention (UNESCO 1996).16 Biosphere
Reserves have to fulfil three main tasks that are complementary and synergistic:

 Conservation role: to contribute to the conservation of the whole range of

biodiversity elements especially the landscapes, the ecosystems, the species
and the genetic variation;
 Development role: to foster economic and human development, which is
socio-culturally and ecologically sustainable;
 Logistic role: to provide support for research, monitoring, education and
information exchange related to local, national and global issues of con-
servation and development.

9.7.6.1 Targanine Network

In this context, the Targanine network was founded in 1996 by Professor
Zoubida Charrouf with the support of Mohamed V University in Rabat and
the association Ibn Al Baytar with the aim to:

 educate stakeholders of the Argan forest to protect their ecological

patrimony;
 enhance economic valorization of Argan fruits;
 improve the social status of women: increase their incomes and access to
literacy programs.

Today, 15 cooperatives for crushing and 6 cooperatives for pressing, invol-

ving more than 2000 women, are involved in the production of organic Argan
oil used in food and cosmetics. The EIG Targanine (Economic Interest Group)
was established in 2003 in Agadir with the goal of assisting cooperatives in
marketing, promotion and value creation at the national and international
level.17 Figure 9.7.4 illustrates the principles of sustainability applied by the
cooperatives of EIG Targanine.

9.7.6.2 Partnership Between EIG Targanine and Cognis

For nearly six years, the Targanine network of cooperatives and Cognis have
been working together in a close partnership. Initialized and supported by
Professor Zoubida Charrouf, this collaboration focuses on new products
derived from the Argan tree with the condition that these activities must
402 Chapter 9.7

Figure 9.7.4 Sustainable approach of EIG Targanine.

Table 9.7.1 Composition of Argan oil according to literature18,19

Benzaria et al. Khallouki et al.

Fatty acid (%)

Myristic acid (C14:0) 0.42  0.01
Palmitic acid (C16:0) 13.49  0.05 16.5
Stearic acid (C18:0) 5.40  0.08 3.7
Oleic acid (C18:1 o-9) 41.19  0.15 45
Linoleic acid (C18:2 o-6) 38.9  0.22
Eicosadienoic acid (C20:2 o-6) 0.4  0.02
Dihomo-g-linoleic acid (C20:3 o-6) 0.21  0.01
Saturated fatty acid 19.31  0.11
Polyunsaturated fatty acid 39.5  0.22
Tocopherols 629  28
Squalene 311  2
Sterols 272  10

support and encourage the protection of the Moroccan Argan forest and in
parallel add local value. The following points were defined as main targets:

 Identification of specific parts of the Argan tree (leaves and oil cake) that
could be valuable in cosmetic applications and provide additional incomes
to the Targanine members;
 Evaluation of the environmental impact of harvesting Argan leaves and
definition of the most appropriate and respectful way to do this;
 Involvement of local populations in the protection of the Argan forest by,
for example, creation of a tree nursery.

What is the situation now after a couple of years? Whilst the Argan is mainly
known for its seed kernel oil (see Table 9.7.1), the joint research program
Plant-based Biologically Active Ingredients for Cosmetics 403
focused on adding value to its by-product, the oil cake rich in proteins, and as a
second target on the leaves. After intensive phytochemical studies and a com-
prehensive performance-testing program including in vitro as well as clinical
assays, we were able to finalize two new active ingredients for application in
cosmetic products. The first, Argatensylt is a high-molecular-weight protein
complex extracted from the oil cake, which possesses skin-tightening properties
and a biological effect on existing wrinkles. The second one, Arganylt, is
derived from the leaves and contains valuable polyphenols that protect the skin
from premature aging and strengthens the cutaneous structure.
Furthermore, we decided together also to commercialize a cosmetic grade of
the precious oil Lipofructylt Argan, rich in polyunsaturated fatty acids
(including linoleic acid (omega-6) and oleic acid) and natural tocopherol, for its
nourishing and protective properties. Figure 9.7.5 gives an overview on the
development activities and the outcome.
Since 2004, Targanine supplies Cognis directly via its local cooperative net-
work with the Argan oil, the oil cake and the dried leaves. The principles of
sustainable trade, direct with the cooperative, paying fair prices with prepay-
ment conditions (50% payment at the time of order of the goods), are all part of
this business. These guarantee Targanine an additional and diversified income
for the network’s members and ensures a sustainable activity.

Figure 9.7.5 Argan-based products.

404 Chapter 9.7
The environmental effect of collecting Argan leaves for cosmetic applica-
tions, target 2, depends on the tree’s ecology, the dynamics of the ecosystems
and the socio-economic circumstances. An impact study looked at these dif-
ferent factors during a three-month mission to Morocco in 2004 by monitoring
an experimental area in the village of Amelne, Tiznit province, in the South of
Agadir. The experimental area, established on a plot of the Argan forest,
involved the follow-up of growth, flowering and fruit production of trees,
which were subject to a range of sampling protocols. This work was done
after having received approval from the provincial governor and the local
authorities.
There are several options for collecting leaves:

 Collection of yellowing leaves on the ground, or on the trees;

 Picking green leaves on the trees;
 Recovering leaves from sylvicultural operations (maintenance) on the
Argan forest: coppicing.

After evaluating several possibilities, the practice of coppicing was selected.

This operation consists of thinning the tree in order to rationalize its growth
and enhance fruiting. The procedure is recommended by the Water and Forest
Government Agency and supports the perpetual improvement of the Argan
tree in the forest. Thanks to the cosmetic value of Argan leaves, an incentive for
the local population to perform this often neglected, but important, main-
tenance task was established.
Finally, a technology transfer program to extend the existing tree nursery
was implemented in the Targanine network cooperatives. The project has been
submitted to the provincial governor, the Water and Forest Government
Agency and local authorities who have given their approval and offered their
support. Cognis has financed this project with the aim to extend and increase
reforestation of the Argan forest, and it has developed a protocol for germi-
nating Argan seeds and planting new trees. A forestry engineer has trained the
staff to manage and monitor the nursery, and each woman in the cooperatives
is involved in this reforestation program.20,21
The cooperation between IEG Targanine and Cognis is based on a sus-
tainable partnership including all elements mentioned before and by sharing
the same principles of CSR, although translated to their specific environment
(see Figure 9.7.6).

9.7.7 Conclusion
The use of natural renewable sources for the development of active ingredients
is only one of many alternatives for modern economies. Taking up the trends of
modern consumer demand and their growing environmental consciousness
forces society and industry to search for solutions, and plant-based raw
materials fit perfectly. There is an increasing need to facilitate, demonstrate and
Plant-based Biologically Active Ingredients for Cosmetics 405

Figure 9.7.6 Shared CSR approach of IEG Targanine and Cognis.

promote Corporate Social Responsibility to enhance long-term sustainable

economic developments. The example of products from the Argan tree shows
that economic interests can be in alignment with environmentally friendly
sourcing which helps to preserve our ecosystem, in this case the fragile Argan
forest. All stakeholders have to be involved in this process (authorities, local
partners, manufacturers, etc.) and their commitment is necessary to ensure a
sustainable social impact and to support the local economical development.
Looking to the future, we speak about an ongoing process, and further
improvements must be generated proactively from within, driven by individuals
as well as by corporate conscience.

References
1. Food and Drug Administration guidance, http://www.fda.gov/cder/
guidance/index.htm.
2. T. Aburjai and F. M. Natshem, Phytother. Res., 2003, 17, 987.
3. P. Hövelmann, Perspektiven nachwachsender Rohstoffe in chemischen
Anwendungen in 7. Symposium Nachwachsende Rohstoffe für die Chemie,
Schriftenreihe Nachwachsende Rohstoffe, Bd. 18 Landwirtschaftsverlag,
Münster (2001).
4. International Union for the Conservation of Nature and Natural
Resources (IUCN), Table 1: Numbers of threatened species by major
groups of organisms (1996–2004), http://www.iucnredlist.org/info/tables/
table1.
5. B. M. Schmidt, D. M. Ribnicky, P. E. Lipsky and I. Raskin, Nat. Chem.
Biol., 2007, 7, 360.
406 Chapter 9.7
6. A. Drews, The requirements in the convention on Biological Diversity
to Using Genetic Resources, International Conference ‘‘Business & Biodi-
versity’’, Bonn, 2008.
7. Convention on biological diversity, http://www.cbd.int (retrieved
12.07.2008).
8. LOHAS Market Research Review: Marketplace Opportunities Abound,
S. French and G. Rogers, 2005, The Natural Marketing Institute, http://
www.lohas.com/journal/trends.html.
9. Commission of the European Communities, COM (2001), 366 final, Green
Paper: Promoting a European framework for Corporate Social Respon-
sibility, Brussels, 18.7.2001.
10. M. Hopkins, Working Paper No. 27, Policy Integration Department,
World Commission on the Social Dimension of Globalization, Interna-
tional Labour Office, Geneva, May 2004.
11. United Nations – Division for Sustainable Development, http://www.
un.org/esa/sustdev/publications/publications.htm.
12. J. F. Morton and G. L. Voss, Econ. Bot., 1987, 41, 221.
13. O. M’Hirit, M. Benzyane, F. Benchekroun, S. M. El Yousfi and
M. Bendeenoun, in L’arganier : une espe`ce fruitie`re-forestie`re à usages
multiples, ed. Mardaga, Belgique, 1998, p. 150.
14. Z. Charrouf and D. Guillaume, J. Ethnopharmacol., 1999, 67, 7.
15. Biosphere Reserve Information – Morocco – Arganeraie, http://www.unesco.
org/mabdb/br/brdir/directory/biores.asp?code¼MOR+01&mode¼all.
16. UNESCO, Réserve de Biosphère : la stratégie de Séville et le cadre statuaire
du réseau mondial, Paris, UNESCO, 1996.
17. 20 ans de recherche-action pour le développement durable de l’Arganier –
Association Ibn Al Baytar, Professeur Z. Charrouf, 2007.
18. A. Benzaria, N. Meskini, M. Dubois, M. Croset, G. Nemoz, M. Lagarde
and A. F. Prigent, Nutrition, 2006, 22, 628.
19. F. Khallouki, C. Younos, R. Soulimani, T. Oster, Z. Charrouf, B. Spie-
gelhalder, H. Bartsch and R. W. Owen, Eur. J. Canc. Prev., 2003, 12, 67.
20. L. Pumadera, F. Henry, Z. Charrouf and G. Pauly, Environmental impact
of the cosmetic valorization of the leaves of Argania spinosa (L.) Skeels,
Morocco, Beyond wood, Cornwall, 2004.
21. L. Pumadera, F. Henry, Z. Charrouf, G. Pauly and G. Falconnet, Bois &
Foreˆts des Tropiques, 2006, 287, 35.
CHAPTER 10

Sustainable Solutions – Green

Solvents for Chemistry
CARLES ESTÉVEZ

IUCT, Alvarez de Castro, 63, E-08100 Mollet del Valles, Barcelona, Spain

10.1 Introduction
Solvents as a class of chemicals appear late in the history of mankind. Indeed,
Nature does not need any solvents apart from water. Ancient caveman paint-
ings, the Chinese and Japanese art of lacquering (based on urushiol, the latex of
the Chinese lacquer tree),1 the Mediterranean fresco painting and medieval oil
paintings did not use solvents (except eventually spirit of turpentine obtained
by the distillation of resin from terebinth or pine trees).The notion of solvents
appeared (in the tradition of the Arabian al-kimiya) with the European
alchemists who believed in the possibility of ‘‘transmuting’’ inferior metals,
more particularly lead and mercury, into gold. The English friar and alchemist
Roger Bacon believed that gold dissolved in aqua regia was the elixir of life. The
Swiss alchemist Philippus Paracelsus believed in the existence of one undis-
covered element common to all, of which the four elements (Fire, Earth, Air,
Water) posited by Empedokles (c. 430 BC) were merely derivative forms.
Linking alchemy with medicine, Paracelsus maintained that this prime element
of creation termed alkahest, if it were found, would prove to be the philoso-
pher’s stone, the universal medicine and the irresistible solvent.2 When in the
twelfth century alembics with efficient cooling were invented, distillation of
wine yielding concentrated alcohol, aqua vitae, was possible.3 Extraction of
aromatic substances (essential oils, from Latin quinta essentia, quintessence)

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

407
408 Chapter 10
with alcohol followed by distillation would eventually become the oldest
application of a solvent as such.
The ability of non-water-based solvents to remove soil and stains from fabrics
was accidentally discovered in 1825 by French dye-works owner Jean Baptiste
Jolly after his maid knocked over a lamp, spilling spirits of turpentine. Jolly had
noticed that when the oil evaporated the area of the cloth was cleaner and he
developed a service for cleaning people’s clothes in this manner, which he termed
nettoyage à sec (dry cleaning in English). In the early days, garment scourers and
dryers found several fluids that could be used as dry-cleaning solvents, including
camphene, benzene, kerosene and gasoline. These fluids are all dangerously
flammable, so dry cleaning was a hazardous business until the introduction of
carbon tetrachloride in 1910, and perchloroethylene in the 1930s.
The history of industrial chemistry cannot be dissociated from the develop-
ment of organic solvents. On the contrary, both went hand in hand. Between
1826 and 1845 August Wilhelm Hofmann’s research on coal tar led to the
development of synthetic coal tar dyes as well as to the synthesis of aromatic
solvents like benzene, xylene and toluene based on coal tar.
Solvents play vital roles in modern economies.4 Oxygenated, hydrocarbon
and chlorinated solvents, to mention only a few examples of the existing che-
mical families, make possible the formulation and manufacture of adhesives,
paints, household products, active pharmaceutical ingredients, agrochemical
compositions and edible oils. These and many other important products and
processes demand a massive solvent usage. According to a study by the Free-
donia Group5 the overall world demand for solvents, including hydrocarbon
and chlorinated types, is on the order of 20 Mio mto annually (2007), the lion’s
share of 58% being used in the coatings, inks and adhesives industries. Demand
for hydrocarbon and chlorinated solvents, though, will continue its downward
trend as a result of environmental regulations, with oxygenated and green
solvents replacing them and growing at an average of 6–7%.
Because of the solvent properties of existing solvents and the engineering
design of process technologies, a significant fraction of the solvents used in
processes or formulations is released to the environment or has to be managed
as a liquid organic waste and ultimately incinerated. Only in the fine chemicals
sector, solvents contribute to as much as 50% of the total mass of waste.6 The
impact on small and medium enterprises (SMEs) is higher because SMEs often
lack efficient means to develop environmentally benign second generation
processes. In 2006, the European Commission alerted that SMEs are respon-
sible for 60–70% of all industrial pollution in the European Union.7

10.2 The Design of Safer Chemicals and Solvent

Innovation
Historically, solvents have been designed to maximize technical performance
and minimize cost. To achieve a high efficacy of function, molecular properties
of solvents (e.g. polarity, solubility, viscosity, vapour pressure, density and
Sustainable Solutions – Green Solvents for Chemistry 409
surface tension) and, hence, their molecular structures have been tailored to fit
in the very narrow windows of specifications characteristic of each particular
industrial application. Therefore, the characterization of physico-chemical
properties and the discovery of the chemical laws governing solvent effects in
chemical systems has been a major research goal over the past decades.8
Unfortunately, a major characteristic of many traditional solvents is their
potential to pose health and environmental risks due to their intrinsic (eco)-
toxicity and potential for environmental damage. Note that both characteristics
are also manifestations of molecular structure. Table 10.1 indicates the health
hazard categories used to characterize chemical substances. Figure 10.1 pro-
vides evidence of the health hazard categories of the 64 most used traditional
solvents. A large portion falls into the toxic and very toxic classes and only 3%
can be considered completely safe for human health.

Table 10.1 Health hazard categories and their corresponding health effects.
Hazard
Level description Health effects

0 Negligible None
1 Low Irritation
2 Moderate Serious damage if in contact with skin, eyes or respiratory
tract. Accumulation in breast milk. Toxic to reproduction
(Cat. 3). Impaired fertility.
3 High Toxic if in contact with skin, eyes or respiratory tract. Toxic
to reproduction (Cat. 1 or 2). Carcinogenic and mutagenic
(Cat. 3). Cumulative effects.
4 Very high Very toxic by inhalation, in contact with skin and if swallowed.
Carcinogenic and mutagenic (Cat. 1 or 2). Cancer and heri-
table genetic damage.

Negligible
Very High 3.1%
7.8%
Low
High 28.1%
23.4%

Moderate
37.5%

Figure 10.1 Distribution of the 64 most used traditional solvents in 5 health hazard
categories ranging from negligible hazard to very high hazard.
410 Chapter 10
Table 10.2 Hazardous chemicals, their Environment Health & Safety effects
and major protocols, regulations and programmes.
Protocols, Regulations
Chemical EHS Effects and Programmes Year

CFCs, CCl4, CH3Cl,  Stratospheric  Montreal Protocol 1987

CH3Br, Halons, ozone depletion
HBFCs
Fossil fuels  Greenhouse  Kyoto Protocol 1997
effect (CO2)
 Global Earth
warming

Dangerous/toxic  Water  Framework Direc- 2000

substances contamination tive: 2000/60/CE
 Related directives:
80/68/CE, 76/464/CE

Persistent Organic Pol-  Bioaccumulation  UNEP Chemicals 1997

lutants (POPs)  Toxicity Programme
 Persistent  Rotterdam
Convention
 Stockholm
Convention

Solvents  VOCs emission  Directives: 99/13/CE, 1999

 Tropospheric 2001/81/CE
ozone  CAFE Programme
formation  Occupational Health
 Occupational
health

Commercial chemicals  Health hazard  REACH 2003

Table 10.2 summarizes the different regulations affecting most of the cur-
rently used solvents.
Basically, there are two principal approaches available to delineate the risk
profile and address the concerns created by the usage of solvents. First, control
of exposure minimizes the exposure to the hazardous solvent by using engi-
neering designs such as closed systems with 100% recovery and zero emissions.
An obvious disadvantage of these systems is that they do not eliminate the
intrinsic hazard of the chemical substance. The second approach is based on
control of hazard. It implies the substitution of the hazardous solvent by safer
alternatives which may in certain cases involve process modifications to
accommodate the new solvent. Replacement of hazardous solvents by bulk or
full solids technologies without the need of solvents, water-based systems or the
use of green solvents are examples of hazard control strategies.
Since the identification by Anastas and Warner of the replacement of
undesired hazardous substances by safer alternatives as a key green chemistry
research area,9 many researchers in industry and academy have united in what
Sustainable Solutions – Green Solvents for Chemistry 411

Green Solvents

Ester Solvents Speciality Supercritical Fusible solids

Solvents gases

volatile non-volatile waxes ionic liquids

• carrier oils
• plasticizers
• coalescents

• isopropyllaurate • glycerolcarbonate • SCCO2 • hydrogenated • tricaprylmethyl

• rapeseed methyl castor oil ammonium
ester (biodiesel) • capryldimethylamide chloride
• oleic acid • stearyl
propylenglycol • dioctylether stearate • 1-butyl-3-methyl
monoester imidazolium
• TOFA ethyleneglycol- • dimerdiolcarbonate methylsulphate
monoester
• butylepoxystearate • ethyl lactate • 1-butyl-3-methyl
• glyceroltriacetate imidazolium
• dibasic esters • 2-ethylhexyl lactate octylsulphate

TM

Figure 10.2 Examples of commercially available green solvents (proprietary design;

reproduction with the permission of Cognis GmbH, Monheim/D; ref. R.
Höfer, J. Bigorra, Comunicaciones, Jorn. Com. Esp. Deterg., 2006, 36,
43–64).

we envision as an incipient global effort to systematically design safer chemi-

cals.10 Solvents are no exception. Over the past decade, supercritical fluids,11
ionic liquids,12 fluorous phases13 and switchable or expanded solvents14 have
been proposed by the academic research community as alternative solvents and
reaction media. The growing experimental evidence suggests that these inno-
vative solvents can not only replace traditional solvents in performing a wide
variety of chemical processes and transformations but also have led to the
discovery of new applications. Figure 10.2 shows examples of existing green
solvents commercially available in industrial quantities.15
Despite these promising advances, many solvents with undesirable health
and environmental profiles are still being used in commercial processes and
formulations because satisfactory safer replacements have yet to be developed.

10.3 SOLVSAFE: A Roadmap for the Design and

Application of Safer Functional Organic Solvents
10.3.1 Background and Sustainability Goals
The general lack of knowledge and strategies to reconcile functional perfor-
mance with environmentally benign properties, reduced human risk and
412 Chapter 10
Table 10.3 SOLVSAFE EHS objectives.
1 Reduction in the number and quantity of hazardous solvents utilized.
2 Reduction of Volatile Organic Compounds (VOC) emissions to the atmosphere.
3 Reduction of CO2 emissions.
4 Increase in the quantity of renewable materials utilized.
5 Reduction of health risks on production sites by decreasing the Occupational
Exposure Level (OEL) due to hazardous solvents.

economic viability prompted IUCT chemists to develop new methodologies to

discover safer and functional replacements of existing solvents with undesired
properties. In January 2003, the research team felt that a useful way to test the
discovery tools was to create a research consortium where molecular designers
and industrial researchers could collaboratively design effective green solvents.
A primary focus of the project was to achieve simultaneously both a maximum
efficacy of function for each specialized technical application and a benign
environmental, health and safety profile. The projected research activities
encompassed design, synthesis, physico-chemical characterization, perfor-
mance tests, toxicology characterization and economic viability calculation.
The project, SOLVSAFE, was sent to the EU FP6 NMP Programme for
evaluation and was granted by the European Commission. In 2005 the Con-
sortium started R&D activities with 19 partners from 6 different European
countries.16
Sustainability being a central concept in SOLVSAFE, the project was
designed to fulfil five environment, health and safety (EHS) working objectives
aimed at reducing human health hazard, eco-toxicity, fossil carbon utilization
and waste generation (Table 10.3).

10.3.2 Design Strategy

Molecular control over EHS as well as performance properties were attained
through a design strategy that started with the creation of a chemical library
composed of 239 potential solvent candidates. Relevant platform molecules
were selected in order to fulfil a diversity of design criteria including a high
renewable atom index, moderate to low vapour pressure and a cost-effective
synthetic accessibility (see Table 10.4).
The ensemble was composed of 11 chemical families:

 A: Carboxylic acid dialkylamides

 B: Carboxylic acid esters
 C: Monopropyleneglycol esters
 D: Glycerol acetals and ketals
 E: Glycerol esters
 F: Glycerol diethers
 G: Glycerol triethers
 H: Fluorinated glycerol diethers
Sustainable Solutions – Green Solvents for Chemistry 413
Table 10.4 Design criteria for platform molecules used as sources of SOLV-
SAFE solvents.
Design criteria Category Parameter

1 Molecular structure derived from Environmental Renewable Atom

renewable platform molecules Index
(e.g. glycerol, carboxylic acids
and derivatives thereof).
2 Low VOC emission. Environmental Vapour pressure
& Safety
3 Low flammability. Safety flash point
4 Efficient and green synthetic route. Technical Number of synthetic
steps
Environmental CO2 utilization
5 Functional group compatibility. Technical Reactivity

 I: Fluorinated glycerol triethers

 J: Organic carbonates
 K: Hydrocarbons

Figure 10.3 compares the distributions of a dataset containing the 108 most
used existing solvents and a dataset of 239 SOLVSAFE solvent candidates in
two principal components which account for the structural diversity of both
datasets. One of the defining features of chemical spaces is that molecular
structures can be represented as points whose coordinates depend on the values
of relevant descriptors or variables. To characterize each molecular structure,
SOLVSAFE used 52 structural descriptors. The principal component statistical
analysis projects the data contained in the 52-dimensional chemical space into a
two-dimensional space (plot in Figure 10.3). This approximation provides an
overview of the systematic variation and distribution of the structural infor-
mation and reveals how significant is the dissimilarity of the SOLVSAFE
dataset when compared with the traditional solvents dataset.
In a second design stage, the chemical library was evaluated with in silico
health hazard estimation methods developed by IUCT and state of the art eco-
tox expert systems. Prediction of the health hazard and eco-toxicological
profiles and physico-chemical properties with a sufficient degree of confidence
allowed selection of those molecular structures exhibiting lower levels of
intrinsic hazard. Figure 10.4 shows the calculated health hazard distribution of
the SOLVSAFE dataset.
Note that the distribution of traditional solvents is peaked on health hazard
level 2 (Figure 10.1 and Table 10.1) while the SOLVSAFE virtual library dis-
tribution is peaked on hazard level 0 (Figure 10.4). Furthermore, the fraction of
SOLVSAFE solvents in the lowest hazard levels 0 and 1 is 77%, which is sig-
nificantly higher than the corresponding fraction of traditional solvents which
amounts to 31%. In addition, no solvent candidate was predicted in the higher
hazard level 4 in the SOLVSAFE dataset. Figure 10.5 shows the percentage of
solvents in the low or negligible hazard levels according to their effects in five
414 Chapter 10

14

7
pc1

0
-10 -5 0 5 10

-7

-14
pc2

Figure 10.3 Principal components analysis of the structural characteristics of

SOLVSAFE (filled circles) and traditional (circles) solvents.

environmental, health and safety categories, namely health hazard, aquatic

toxicity, volatile organic compound emission, fire hazard and occupational
exposure potential. The fraction of safer solvents is higher than 70% in all
cases.
Most of the SOLVSAFE solvent candidates are characterized by a relatively
low aquatic toxicity for the three trophic levels. This is a key property in those
applications where the environmental impact should be minimized. The vapour
pressures of SOLVSAFE solvents ranged from 0.001 to 200 hPa. The average
vapour pressure of 1.35 hPa was significantly lower than the average value of
the 64 most used solvents, 87 hPa. Interestingly, the dataset was composed of
70% non VOC solvents, an invaluable feature for those applications in open
systems. The solvents in the dataset exhibit high flashpoints (87% of the sol-
vents have flash points higher than 55 1C) assuring a safer alternative for those
uses in which fire hazard needs to be minimized. The occupational exposure
hazard of the SOLVSAFE dataset is negligible according to current risk eva-
luation procedures.17 The average renewable mass index, a measure of the
renewable mass content, exceeds 60%. The average CO2 emission potential, a
Sustainable Solutions – Green Solvents for Chemistry 415

High
3.5%
Moderate
20.3%

Negligible
50.3%

Low
25.9%

Figure 10.4 Distribution of 143 SOLVSAFE solvent candidates according to their

calculated health hazard.

100

80

60
%

40

20

0
Health Aquatic VOC Flammability Occupational
toxicity Emission Exposure

Low or Negligible Hazard Moderate to High Hazard

Figure 10.5 Classification of SOLVSAFE solvent candidates according to their

effects in five environmental, health and safety categories. Health adverse
effects according to Table 10.1. Toxicity for aquatic organisms based on
LC50 96 h (fish) and ready biodegradability. VOC emission potential is
considered when the vapour pressure at normal temperature is higher
than 0.1 hPa. Low fire hazard is assigned whenever the flashpoint is
higher than 55 1C. A low exposure potential in workplaces is considered
when the vapour pressure is less than 10 hPa.

parameter that quantifies the CO2 emission upon complete oxidation, is 47%
lower than the average value of 68 traditional solvents. Note that the high
renewable mass index of SOLVSAFE solvents may contribute to greenhouse
gas savings provided that sustainable practices are used in the manufacture of
the platform molecules.
Once a subset of potentially safer solvents is available, the next step involves
the synthesis of the actual solvents. Green synthetic methodologies are selected
in order to provide economically viable manufacturing processes leading to
high quality solvents with the lowest cost per kilogram. In a subsequent stage,
technical performance in different industrial applications follows a two-stage
evaluation. First, efficacy of function for a specific industrial application is
416 Chapter 10
estimated using a predictive model developed by IUCT. Subsequently, an
experimental investigation of the relevant solvents is carried out and the results
compared with the predicted values. In the final step, the best performing
solvents are subjected to experimental toxicological evaluation using protocols
that minimize the use of laboratory animals.
We use the term safer functional organic solvent (SFOS) to refer generically to
the green solvents designed under the SOLVSAFE design strategy. For the
purpose of our investigation, we defined an SFOS as an organic solvent dis-
playing such molecular properties that enables it to achieve maximum functional
performance for a particular application while minimizing its intrinsic potential
for environmental or human health hazard. It is worth clarifying our under-
standing of the term green solvent in view of the different contributions to this
subject.18 If we consider a green solvent as an evolutionary product of chemical
innovation, then a green solvent has to bear a number of environment, health
and safety (EHS) characteristics that differentiate it from existing hazardous
solvents. Toxicologists, environmental scientists and industrial safety experts
have identified quantifiable EHS parameters, metrics (e.g. LD50, LC50,
flammability, ozone depleting potential, global warming potential, etc.) and
threshold values above which the property poses a serious hazard to human
health or the environment. Therefore, each parameter can be in the safe or
unsafe domain depending ultimately on the specific molecular structure which
determines this property. Any chemical substance with efficient solvency
characteristics displaying a higher number of green traits (EHS parameters in
the safe domain) when compared to a reference substance, typically the current
industrial standard, can be considered a green or safer solvent. Alternatively,
we could define a green solvent in absolute terms imposing the more restrictive
condition that it possesses the maximum number of green traits (i.e. all of the
EHS parameters in the safe domain). In the absence of consensus, each author
will choose the relative or absolute definition according to specific circum-
stances. In any case, a full specification of the EHS parameters is necessary to
describe and evaluate the ‘‘green solvent’’ under consideration.
SOLVSAFE is aimed at developing SFOS for their innovative application in
key products and processes within six different sectors ranging from metal
degreasing, paints and varnishes, crop protection formulations to fine chemi-
cals manufacture and extraction of vegetable oils.

10.4 Industrial Application of SOLVSAFE Solvents:

Results and Perspectives
10.4.1 Fine Chemicals
The manufacture of fine chemicals is one of the greatest challenges in synthetic
chemistry. With a variety of commercial products ranging from organic pig-
ments, explosives and surfactants to more sophisticated molecules such as
pharmaceutical active ingredients, the sector is committed to delivering high
Sustainable Solutions – Green Solvents for Chemistry 417
purity substances to a market that is highly regulated in terms of product
quality and safety and process environmental performance. Solvents are of
extraordinary importance to the sector since their role is to achieve the max-
imum amount of synthetic construction in the shortest amount of time, with the
highest isolated yield for the lowest cost per kilogram. Their impact actually
goes beyond the product quality, affecting the safety of operators during pro-
cessing and during transportation as well as the environmental burden of the
process (spills, emissions to the atmosphere, waste water streams and disposal
of wastes).19 Following the design strategy, a subset of 22 SOLVSAFE solvent
candidates were investigated for the replacement of methyl isobutyl ketone in
the synthesis of Pimozide, an antipsychotic drug for the treatment of schizo-
phrenia, chronic psychosis, the Gilles de la Tourette syndrome and resistant
tics. The synthetic route to Pimozide has five steps (Scheme 10.1). In the final
step, the one leading to the active principle, an alkyl chloride (1) reacts with a
secondary amine (2) in methyl isobutyl ketone at 120 1C to yield Pimozide (3).
Methyl isobutyl ketone has a boiling point of 117 1C, a vapour pressure of
15 mmHg and a TLV-TWA exposure limit of 50 ppm. Glycerol formal and
glycerol isobutyral were selected because of their expected superior technical
performance. The comparison of relevant EHS properties for the two candi-
dates is summarized in Table 10.5. The lower CO2 emission potential and
higher renewable mass index of glycerol formal prompted us to select this
candidate. Glycerol formal is a non toxic glycerol acetal, less flammable than
MEK and exhibits superior technical performance as evidenced by the

O F
NH
Cl N O
HN HN
N N
Na2CO3, KI, MIBC
F F

F
(1) (2) (3)

Scheme 10.1

Table 10.5 Comparison of solvent properties and EHS data of two solvent
candidates for methyl isobutyl replacement in an SN2 reaction.
Properties Glycerol formal Glycerol isobutyral

Melting point 59 1C 49 1C

Boiling point 191 1C 195 1C
CO2 emission potential 0.42 Tm CO2/Tm 0.90 Tm CO2/Tm
Renewable mass index 86% 60%
Health Hazard Level 0 Under evaluation
418 Chapter 10
Table 10.6 Comparison of selected reaction parameters between traditional
synthesis using methyl isobutyl ketone and the new glycerol for-
mal route.
Reaction parameters MEK Glycerol formal

Molar ratio (1)/(2) 1.2 1.1

Temperature 120 1C 90 1C
Time 6h 6h
Yield 80% 97%

improved stoichiometric and volumetric yields and reduced temperature

regime20 (see Table 10.6).
The new process was scaled-up successfully. The yield obtained was similar
to that of the classical route and the new process proved to be cost effective.
Only considering raw materials is the classical route less economic. The 15%
reduction in the overall process cost is due to a higher efficiency of the glycerol
formal route and a smaller waste stream generated during the manufacture.

10.4.2 Metal Degreasing

Over the past few years, one of the major challenges in the area of metal
degreasing has been the transition from fully emissive open-top systems based
on the use of chlorinated solvents to closed-loop metal-degreasing systems
based on low-VOC-emission, low-toxicity solvents. Alternative chlorinated
solvents such as trichloroethanol, chloroform, methyl chloride, CFC-113,
HFCs, HCFCs, CO2 jets, scCO2, semi-aqueous solvents, alkaline cleaning
agents, emulsifying detergent-based cleaners, aliphatic-hydrocarbon-based
solvents and azeotropic mixtures have been proposed to replace tri-
chloroethylene, one of the most widely used metal degreasers. However, none
of the proposed alternatives fully satisfy the key industrial needs of the metal
finishing sector. The ideal process would allow the carrying out of metal
degreasing operations in highly variable settings, with metal parts of different
sizes and shapes, while minimizing diffuse emission, release of contaminated air
during loading and unloading, and solvent release from cleaned metal parts.
The process would not generate large waste streams, allowing an easy and cost
effective recycling of solvent and rinsing water, and ultimately deliver ade-
quately conditioned parts for immediate use in subsequent steps of the metal
finishing process. The SOLVSAFE metal degreasing procedure involves a two-
step process in which the metal parts protected with grease are put in contact
with a solvent of low volatility and toxicity at room temperature. In a second
phase, the solvent is removed by rinsing the metal parts with water. Both sol-
vent and water can be separated and reutilized in the process (Figure 10.6).
Functional efficacy prediction led to the discovery of two solvent candidates
with excellent technical performance. Laboratory tests confirmed the
in silico estimation and found an excellent efficiency when metal parts were
degreased by immersion and subsequently rinsed with water.
Sustainable Solutions – Green Solvents for Chemistry 419

STEP 1
STEP 2
Metal parts DEGREASING Cleaned
RINSING WITH
TREATMENT WITH metal parts
WATER
SOLVENT

SOLVENT WATER+SOLVENT
RECOVERY RECOVERY

Figure 10.6 Metal degreasing process with SOLVSAFE solvents.

Table 10.7 Degreasing efficacies and EHS parameters for three fatty acid
dimethylamides as compared with the current industrial standard
trichloroethylene.
CO2 emission
Vapour pres- potential Renewable
Degreasing Degreasing Health Aquatic sure at 20 1C (Tm CO2/ mass index
solvent efficacy (%) hazard a hazard a (hPa) Tm) (%)

CO-01 100 2b 0 0.13 0.61 69.2

CO-02 98 2b 0 0.06 0.51 74.3
CO-03 81 0 0 0.02 0.44 77.9
Trichloro- 100 4 4 78 0.67 0
ethylene
Average value – – – 87 1.96 0
(68 traditional
solvents)
a
Level 0 corresponds to negligible hazard. Level 4 indicates maximum hazard.
b
Predicted values. Health properties under evaluation.

Table 10.7 compares the degreasing efficacy and various EHS properties of
three dimethylamides of natural fatty acids with different chain lengths, tri-
chloroethylene, and the average value for traditional solvents. Because of the
low vapour pressure, the VOC emission potential is very low and the occupa-
tional exposure and flash point reach safer values. As they are based on natural
vegetable oils, the alternative solvents exhibit a high renewable mass index.21

10.4.3 Paints and Varnishes

The paints and varnishes sector still consumes large volumes of industrial
solvents despite the enormous progress made over the past decade to reduce the
solvent content in formulations. The SOLVSAFE goal is to evaluate and find
new medium- and high-boiling-point solvents or film forming agents (coales-
cents), with very low environmental impact and very high solvent or coales-
cence efficiency, for high solid 2-pack PUR coating systems (based on high solid
polyols and high solid aliphatic isocyanates) on the one hand, and for water-
borne coatings (e.g. 2-pack waterborne PUR systems) on the other. The
420 Chapter 10
ultimate goal is to replace existing solvents and coalescents and obtain for-
mulations with higher solid content at application viscosity (high solid coat-
ings), and with less coalescent content (waterborne coatings), in such a way as
to maintain or even enhance their efficacy of function while improving their
environmental profile.
A new series of SOLVSAFE solvents with reduced VOC potential have been
obtained and tested in paint formulations. Coalescent products are employed in
aqueous paints in order to improve film formation and levelling. There are well-
established products on the market that are mainly based on non-renewable
feedstock. Any greener alternative should contribute to impart the desired
properties of the final decorative paint quality, for example the hiding power,
gloss, drying, durability and cost. Laboratory research has found that certain
dialkyl carbonates display excellent viscosity and coalescence properties when
compared with the current industrial standard butyl glycol. Propyleneglycol
monoleate22 and glycerol acetals and, more particularly, glycerol isobutyral
have been evaluated as greener alternatives to existing coalescent products with
good results. Glycerol isobutyral exhibits similar film-forming properties when
compared with existing well-established industrial solvents and coalescents
such as butyl glycol and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate
(TMB).23

10.4.4 Crop Protection Formulations

The ideal composition of an agrochemical formulation would enable full
exploitation of the biological potential of each active ingredient as a crop
protection or nutrition agent (i.e. improving uptake and leaf coverage), with
full respect to the environment, users (mainly farmers) and consumers of
treated crops or processed food obtained from treated crops. The design of
safer organic solvents (SFOS) having the potential to increase plant protection,
bioavailability and reduce environmental impact of existing crop protection
formulations is a primary focus of the SOLVSAFE project. A significant
number of emulsifiable concentrate (EC) formulations have been investigated
using greener alternatives to existing hazardous solvents. Emulsifiable con-
centrates are liquid compositions containing an agricultural active ingredient in
a liquid form. They usually consist of a single phase. ECs are to be diluted in
water, in order to form a direct emulsion in which a liquid hydrophobic phase
containing the active ingredient is dispersed throughout the water. For exam-
ple, a farmer would dilute an emulsifiable concentrate comprising a hydro-
phobic agricultural active ingredient in water, and readily obtain an emulsion
to be applied on a field. This procedure, where the farmer prepares from a
concentrated composition the final product to be applied on a field, is usually
referred to as a ‘‘tank mix’’ procedure. An emulsifiable concentrate is also
referred to as a ‘‘tank mix’’ composition. One of the main advantages of EC
formulations is that the solubilized active ingredient can display a higher
bioavailability which results in an increased efficacy. Insecticides are generally
activated using this kind of formulation. The active ingredients delthametrin,
Sustainable Solutions – Green Solvents for Chemistry 421

Scheme 10.2

dimethoate and novaluron (Scheme 10.2) are, respectively, representative

examples of three important insecticidal chemical classes: pyrethroids, orga-
nophosphates and benzoylureas.
Esters, dialkylamides and carbonates were investigated as components of
agrochemical EC formulations, obtaining promising preliminary data. Proto-
types with acceptable stability were evaluated for their biological efficacy and
selectivity under field conditions.
In addition, EC formulations were prepared using a few proprietary
experimental herbicides, belonging to the protoporphyrinogen oxidase (PPO)
inhibitors (Figure 10.7). Several safer solvents were tested and most formula-
tions resulted in a generally increased efficacy, but only a select number of long-
chained lactic acid esters were found to provide a significantly increased
selectivity toward crops.24
The SOLVSAFE strategy also incorporated the research of innovative water-
based micro-emulsions containing green solvents as the lipophilic component.
Micro-emulsions are environmentally friendly formulations as water is the
main component. The addition of lipophilic substances such as long-chain
alkanes (i.e. mineral oil), lipophilic esters (preferably, SFOS) or their compo-
sitions was shown to increase the magnitude of the expected biological effects.
The functional performance of SFOS was tested when micro-emulsions were
successfully applied to a number of triazole and strobilurin fungicides.25 The
422 Chapter 10

treated

untreated

Figure 10.7 Post-emergence control of Gallium aparine treated with PPO inhibitors.

bioavailability of each active ingredient was magnified when compared to a

traditional formulation, as demonstrated in greenhouse tests and field trials.
The novel micro-emulsion technology is expected to benefit fungicides, herbi-
cides and insecticides.

10.5 Conclusions
The development of less hazardous and commercially viable solvents, the
shift away from inefficient, solvent-consuming chemical routes towards bio-
based synthesis and the replacement of oil-based feedstock by renewable
starting materials are only a few examples of necessary strategic goals for the
twenty-first-century chemical industry. Research efforts over the past decades
have evidenced the formidable complexity of designing commercially viable and
benign solvents and other functional products. Reconciling non-toxicity with
efficacy of function, or environmental performance with industrial operability, to
mention just two examples of simultaneously desired and often conflicting
properties, are major challenges that need to be addressed in the upfront design
stage.
SOLVSAFE, an industrial research consortium under the EU Sixth Fra-
mework Programme, is a first attempt at collaborative research between
industry, specialized research centres, and academia towards a common
research agenda for the development of safer organic industrial solvents.
Sustainable Solutions – Green Solvents for Chemistry 423
The innovative SOLVSAFE design strategy, based on novel basic science
linking molecular structure with environment, health hazard and chemical
functionality, has been very successful in surmounting current barriers to
bringing greener solvents to commercial manufacturing facilities and industrial
research laboratories. The new solvents display not only good functional
characteristics but also fundamental sustainability traits, making them highly
competitive in the marketplace.

References
1. M. Kopplin in Museum für Lackkunst, BASF Lacke + Farben AG, ed.,
Münster, s.a.
2. R. Höfer, P. Birnbrich, S. Busch and J. Bigorra, Chimica & L’Industria,,
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4. H. Kittel, Lehrbuch der Lacke und Beschichtungen, 2. völlig neu bearb.
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Verl, Stuttgart, 2007; E. W. Flick, ed., Industrial Solvents Handbook,
William Andrew Publishing/Noyes, Westwood, 5th edn, 1998; D. Stoye
and W. Freitag, Paints, Coatings and Solvents, Wiley-VCH, Weinheim,
1998; H. Gnamm and W. Sommer, Die Lösungsmittel und Weichma-
chungsmittel, Wissenschaftl, Verlagsges, Stuttgart, 1958.
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1%20-%20Andrea%20Vettori.ppt (retrieved 25.11.2008).
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Handbook of Green Chemistry - Green Solvents, Wiley-VCH, Weinheim
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(Green Chemistry Series), OUP, Oxford, New York, 2003; C. Capello,
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25. Patent application pending.
CHAPTER 11

Sustainable Solutions for

Adhesives and Sealants1,2
JÜRGEN O. WEGNER

The ChemQuest Group Inc., Bilker Strasse 27, D-40213 Düsseldorf, Germany

11.1 Introduction
‘‘Sustainability is changing the way products are being designed, produced, and
discarded. It will certainly change the way we think about the raw materials that
go into these products, and it will certainly have a major effect on the adhesives
and sealants industry.’’3

Traditionally adhesives and sealants are typical cross-sectional technologies

with myriad applications across all industries. In daily life they play an
important active role to enable sustainable solutions in the first place. Passively,
through intelligent formulations, they also contribute to minimizing any
negative kind of footprints, and maximizing material, energy and process
efficiency. This chapter will concentrate on the sustainable formulation of
adhesives and sealants themselves, and will only briefly touch on the enormous
impact the bonding technology as such has on many sustainability improve-
ments in construction, woodworking, paper and packaging, transportation,
aerospace, in labelling, electronics and medical applications. Often enough the
adhesive bonding in itself is from a sustainability point of view advantageous
over other bonding techniques, be it welding and soldering, be it ‘‘classic’’
mechanical assembly like bolting, screwing, nailing, the impact, however,
depends on actual conditions. Energy generation from renewable sources like

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

425
426 Chapter 11
wind and sun radiation would simply be impossible without appropriate
adhesives, adhesive resins and sealants, as are any desired weight reductions of
airplanes and cars for gaining better fuel efficiencies, as is triple glazing and
building insulation in construction for reducing energy transfer in residential
living – just to give a few illustrative examples.
The use of adhesives and sealants is almost as old as mankind. For many
millennia adhesives have been natural, based on rubbers, plant and animal
glues, and in Mesopotamia 2500 years ago even some boat sealants were
already in use based on naturally occurring crude oil tars – an early example of
the petrochemical base of today’s modern chemistry in general, and the for-
mulation of state-of-the-art adhesives and sealants in particular. Before the
invention of macromolecular or polymer chemistry in the 1920s and 1930s all
adhesives came from nature, and returned back to it through decomposition at
the end of service life. Definitely polymer chemistry disrupted the circle of
natural recycling. The use and performance of today’s adhesives and sealants
would even be unthinkable without the latest insights in polymer science and
technology. Progress in macromolecular science and advancements in adhesives
and sealants depend upon each other – adhesives are applied polymers. The
more demanding a bonding is to take place, the more precise the chemistry at
given physical frame conditions has to be adjusted for achieving a decent and
reliable job. The adhesives industry constantly strives to lowering the envir-
onmental impact of its products. Often sustainability and natural base of
materials are used interchangeably, and this chapter will shed some light on the
question to what extent, based on current knowledge, modern design of
adhesives and sealants can be achieved with technologies from renewable
sources. How dependent are adhesive and sealant formulators upon petro-
chemical raw materials? What prospects and limitations are to be seen in this
field? What do we learn from Mother Nature with its abundant examples of
bonding techniques? Do we see those techniques one day replacing petro-
chemical-based, depletable and thus non-sustainable adhesive and sealant
alternatives?

11.2 Features and Requirements of Adhesives and

Sealants
Adhesives are designed to bond different or similar materials with each other.
Adhesives function through well-understood adhesion and cohesion phenom-
ena. They all interact with the surface to be bonded (adhesion), and need to
develop sufficient internal strength for bearing the load applied onto bonded
parts (cohesion).4 Adhesives must be liquid at the stage of application for
perfectly wetting the surface to be bonded. They must solidify for bearing the
load no matter if through chemical reaction and/or through physical means.
The only exemption is pressure sensitive adhesives (PSA), which are highly
viscous liquids usually spread on a carrier substrate, i.e. an adhesive tape or an
adhesive label. Despite often-heard marketing claims there is no such thing as a
Sustainable Solutions for Adhesives and Sealants 427
universal adhesive. The contrary is true: the more demanding an adhesive
bond relative to dissimilarity of materials, force to be applied onto the bond,
chemical and physical compatibility with surrounding conditions during
assembly and bond life, assembly speed, initial tack required, the more likely
the ultimate formulation requires a very specific adhesive for meeting all
requirements. Structural adhesives are one of the fastest growing global market
segments.5 On top of all the other requirements they have to meet very specific
norms, safety codes and/or customer specifications that call for a narrow and
consistent quality. Fine-tuned precision is paramount, as is specialization.
Today two- and multi-component adhesives with well-defined curing char-
acteristics dominate in structural adhesion, as does light, radiation, induction
and/or microwave curing that constantly moves the chemical prerequisites to
new frontiers.
The development of sealants takes a similar direction from a linseed-oil-based
caulk of yesterday to a hi-tech, silicone-based structural sealant of today to a
molecular designed, silane-terminated technology of tomorrow. Sealants by
definition form a permanently flexible joint between moving parts, they adhere
well to the flanks of both parts and fill the ever changing gap dimension at any
time during service life. The deformation can be plastic or elastic in nature, with
the percentage of elastic recovery in most cases directly correlating to sealant
quality. It is an everyday experience that a rubber band perfectly resembles the
performance of a sealant: when pulled only slightly, the band fully recovers its
shape upon release. However, the more stress is applied, the more the shape
changes irreversibly until at a certain point a final rupture occurs, a phenomenon
which also depends on age, exposure and temperature. Sealants in construction,
transportation and aerospace are permanently exposed to thermal expansion and
shrinkage, to vibration, UV and other radiation, to chemicals, oils, greases and
cleaning agents, but nevertheless have to endure the lifetime of its host product,
or at least a full service period. Preferably, without primering sealants should
perfectly adhere to all materials to be sealed. This may be glass, metals, con-
struction elements, wooden planks, tiles and sanitary elements. These materials
play an important role in automotive assembly, in marine and aerospace
applications. As with adhesives, the quality requirements for sealants are rapidly
increasing. They have to meet very high quality hurdles defined by norms and
specifications, and in fact we even see a tendency of gradually blurring bound-
aries between adhesives and sealants caused by an increasing overlap of func-
tionalities. Insulating glazing and photovoltaic elements are just two examples
where huge amounts of edge sealants have to assure proper functioning for at
least 15 years of guaranteed service life despite heavy exposure to UV radiation
and atmospherics plus permanent temperature changes.
As a consequence adhesives and sealants of today and tomorrow truly are
hi-tech products designed and optimized for the very specific and narrow area
of their use. Their chemical composition must be well defined to meet all
technical requirements, and must on top of that fulfil very strict safety, health
and environmental prerequisites as usually set forth by local and government
authorities.
428 Chapter 11
11.3 Chemical Composition of Adhesives and Sealants
Over Time
Until about 1910 all adhesives and sealants were based on ‘‘natural’’ compo-
nents, most of them resulting from renewable animal and plant sources, the rest
representing early usage of chemical by-products like hemicelluloses from
paper and cellulose manufacturing, coal tars from gas production, plus natu-
rally occurring bitumen. This picture dramatically changed in the 1920s with
the then booming rubber industry, new discoveries in macromolecular science
and technology, dramatic progress in the chemical industry as a whole and
finally the intensive use of crude oil, natural gas and coal as a rising feedstock
for a vast variety of petrochemical technologies. Figure 11.1 shows the relative
share of adhesives and sealants based on renewable resources over the past 80
years including a projection into 2020.6 It shows that especially in the 1950s and
1960s a sharp decline occurred coupled with a steep rise in adhesives and
sealants tonnage: whereas the absolute volume of ‘‘natural’’-based renewable
adhesives remained fairly constant over most of the time, it was almost all
growth in tonnage (and even more dominant in value) clearly associated with
petrochemical-based raw materials.
Today all formulated adhesives and sealants combined represent a global
tonnage of 8.5 Mio mto (dry, annually), and are projected to grow to 10.2 Mio
mto by 2010.7 These figures do not include typical binders for paper manu-
facture and for use in the woodworking industry. From this tonnage a mere
15.5% (2006), respectively 15.0% (2010), represent adhesives and sealants
based on natural origin with or without additional chemical modification.
With the volume ratio of adhesives and sealants remaining fairly constant
over time in the 80-85 : 15–20% range2,8 the amount of crude-oil-based

18
16 Petrochemical base
Natural base
14
Volume (1000 kt dry)

12
10
8
6
4
2
0
1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 2010f 2020f
Year

Figure 11.1 Total worldwide production of adhesive and sealants including share of
natural-based components.
Sustainable Solutions for Adhesives and Sealants 429
formulations may look quite immense with 7.2 Mio mto in 2006 and 8.5 Mio
mto in 2010.
However, this represents just 0.006% of all oil consumed per annum even if
this amount has been doubled by factoring in the material and energy needs for
processing the base ingredients for adhesives and sealants, and also taking into
account the difference between ‘‘dry’’ and ‘‘wet’’ adhesives as representing on
average a factor of 3.
Considering a global plastic production of 245 Mio mto (2006),9 petro-
chemical-based adhesives and sealants represent just 3% of this. ‘‘Dry’’ adhe-
sive in this sense is the solid portion of an adhesive governing its overall
performance properties, whereas ‘‘wet’’ adhesives describe the ready-to-use
product in its average proportion of solid (34%) and liquid (66%) ingredients.
The liquid phase commonly and increasingly is water, but 0.71 Mio dry mto
(2006), respectively 0.78 Mio dry mto (2010), remain solvent- and thus crude-
oil-based,10 a sizable factor that has to be regarded as well.
The following graphs (Figures 11.2 to 11.5) inform about the global usage of
adhesives relative to area of use, base chemistry, regional spread and adhesives
technology.

11.4 Ongoing Sustainability Evolution

Considerations of safety, health and environmental impact always played a
governing role in formulating adhesives and sealants, and one of the greatest
challenges was and remains to be the replacement of questionable ingredients
against those with a proven record without sacrifice in technical performance,
or even by improving both simultaneously, the sustainability and technical
profile as well. Adhesive formulators invest heavily in R&D to prove that
benign sustainability does not equal inferior performance. In fact proactive
anticipation and compliance with ever more demanding regulations is one of

7000
6000 2006
dry mt x 1000

5000 2010 F
4000
3000
2000
1000
0
n

er

ng

n
pe
io

tio
um

di

di
ct

ag

Ta

rta
n

n
ru

bo

ck

bo
on

po
st

Pa
on

id

id
C

s
an
rig

ig
C

Tr
-
on
N

Figure 11.2 Global adhesive volume per use area.

430 Chapter 11

3500
2006
3000
2010 F
dry mt x 1000

2500
2000
1500
1000
500
0
s

Ac

s
d
be
ic

ie

er

er

er
en

EV

VA
PU

se
PV
l

ox

m
ry

b
pr

ba
ru
ly

ly

ly
Ac

Ep

eo

po

po

po
tic

al
N

co

co

ur
he

er
at

th
nt
k

ln
oc

S/

lo
Sy

Al
Bl

Al
Figure 11.3 Global adhesive volume per base chemistry.

6000
2006
5000
2010 F
dry mt x 1000

4000

3000

2000

1000

0
na

pe

LA

e
pa

op
N

A/

O
hi

ro

Ja

ur
R
C

n.
Eu

-E
ai
E-

em

W
R

Figure 11.4 Adhesive usage per region.

the most important sources for innovations in this industry, and ranks second
next to solving or improving so far unmet customer needs.
The replacement of solvent-based adhesives by either water-based or full
solid systems is just one of those examples. Solvent-based adhesives usually are
proven technologies with a robust usage profile, whereas their rather sophis-
ticated, water-based counterparts are sensitive to low-temperature and high-
humidity applications, require film-forming (often VOC-based) agents them-
selves, and are usually 20–30% more expensive per adhesive bond. In any case
the switch from solvent to water requires drastic usage changes at higher costs,
one of the reasons why solvent-based adhesives show negative growth in
Western Europe and North America, but nevertheless grow globally with 2.2%
relative to 4.2% for adhesives in general11 due to local production in emerging
Sustainable Solutions for Adhesives and Sealants 431

Solvent-based

Water-based

Hotmelts

Radiation cure
1-c reactive

2-c reactive

Calandred

Figure 11.5 Volume spread per adhesives technology (in 2006).

economies. No doubt this is an area where the enforcement of government-

imposed restrictions could help to drastically reduce the use of solvents in
adhesives on a global scale, and thus to cut back the relevant environmental
footprint. The aim of the adhesives and sealants industry should be to limit the
use of solvents to the utmost necessary, i.e. where in weld bonding of plastic
pipes the solvent plays the role of the adhesive.
Hand in hand with the replacement of solvents goes the development of full-
solid adhesives and sealants, and so called hotmelt adhesives are just one of
those technologies progressing well over the last two decades. Usually hotmelts
are completely emission-free, and represent an almost ideal sustainability
profile. They are applied above melting temperature, and develop their bonding
strength immediately with cooling. Thermoplastic by nature they de-bond with
elevated temperature which might be desirable or disadvantageous. Reactive
hotmelts overcome those difficulties as they eventually after application become
thermoset through cross-linking reactions, and represent one of the fastest
growing adhesive specialities with numerous fields of usage in woodworking
and packaging, in electronics, bookbinding and transportation.
In general the quality evolution of adhesives and sealants over the past
decades is characterized by numerous examples of technological steps that all
have in common the relative reduction of ecological footprint coupled with
meeting ever higher safety standards at affordable costs. Be it the drastic
reduction of monomers, the ban of heavy metal catalysts and tin-organic
compounds, the replacement of formaldehyde-containing binders against other
polymer systems, the substitution of solvents as described above, the respon-
sible use of plastification technologies or the drastic reduction of VOC, all these
examples prove full commitment of the adhesives industry towards a sustain-
ability level as high as possible.
432 Chapter 11
11.5 Quality Features and Gaps with Natural-based
Adhesives and Sealants
Adhesives and sealants based on renewable sources show a number of
advantages, but also major disadvantages that effectively limit their broader use
at present. On the positive side they usually show an excellent bio-compatibility
given that their chemical modification did not completely alter this. Natural-
based products in general show a positive Greenhouse Gas (GHG) balance,
and thus do not directly contribute to climate change. They show a fairly good
price/performance ratio, usually are available in sufficient quantity and show
no or low toxicity.
However, natural-based materials like starches and soybean oils are used in
direct competition to animal or human food consumption. Technically, they are
not at all suitable for high modulus adhesive and sealant joints. They usually are
sensitive to hydrolysis and oxidization. Exposure to atmospheric conditions or
chemical attack can drastically limit their service life expectancy. They are sen-
sitive to elevated temperatures and need to be protected against microbiological
decay with more or less toxic preservatives. In light of those features and based
on today’s knowledge some important conclusions can be drawn:

 For the time being and in the foreseeable future high performance and so-
called reactive adhesives and sealants will rely on petrochemical key
components;
 There is on the other hand room for stopping the downturn trend or a
further decline of adhesives and sealants based on renewable resources;
 Structural adhesion and structural sealants are important growth markets
in themselves and through increasing replacement of physical joining
techniques like bolting, welding and soldering, they often require chemical
or physical means for the desired curing, and can by no means be for-
mulated based on natural key components except functional moieties like
polyurethanes based on oleochemical polyols, dimer acid based polyesters
or blends of natural and synthetic rubber in the tyre industry, but the
cross-linking reaction in all these cases is all but ‘‘natural’’;
 In low to medium modulus applications of sealant caulks and adhesives,
however, where curing takes place through physical solidification, i.e. due
to cooling and/or drying, the use of raw materials based on renewable
sources is quite common, and can certainly be expanded with focused
research for overcoming inherit shortcomings.

11.6 Current Use of Renewable Raw Materials in

Adhesives and Sealants
Table 11.1 shows an overview reflecting the actual state-of-the art.11 We see
that ‘‘natural’’-based key components often have a direct impact on product
and quality performance criteria.
Sustainable Solutions for Adhesives and Sealants 433
Table 11.1 Typical quality features when using natural-based components in
adhesives, foams and sealants.
Base material Typical use area Special technical feature

Starches & Dextrines Paper & packaging, labelling, Remoistenable, low-to-no

wallpaper toxicity, bonding speed
Cellulose ethers Tiling, construction, wallpaper Quick hydration, long open
time, flow, workability
Tall resins & colopho- Hotmelts, flooring adhesives Extender, tackifier
nium derivatives
Caseines Labelling, levelling compounds Cold water resistance, flow
Oleochemical PU foams Homogene & uniform foam
lamelles
Dimeric fatty acids PE and PA-based hotmelts, Flexibilizing extenders
epoxies
Source: The ChemQuest Group Inc.; own market survey.

Table 11.2 Global status for use of natural-based adhesives (wet mto, average
solids 50%).
Natural resin base 2006 2010 AGR (%)

Natural rubber 455 502 2.5

Starches/dextrins 1668 1892 3.2
Natural tree resins 17 16 –0.1
Resin emulsions 15 15 1.1
Cellulose ethers 40 44 2.4
Total natural based adhesives 2195 2469 3.0
Total wet adhesives natural and petrochemical based 14120 16608 4.1
Total share of natural-based adhesives 15.50% 15%
Source: The ChemQuest Group Inc.; proprietary database.

11.7 Major Use Areas for Adhesives Based on Natural

Resources
Table 11.2 gives a survey about major use areas for adhesives based on
renewable sources. The share of renewable raw materials in the sealants market
is well below 5%. Numbers in Table 11.2 do not include polyurethanes con-
taining oleochemical-based polyols, vegetable oil-based polyesters and poly-
amides based on dimer fatty acids in total estimated at 35 mto in 2006, 42 mto
in 2010. Projection into 2010 shows that without disruptive innovations the
share of natural-based adhesives will further decline to a mere 15% in total.

11.8 Outlook and Conclusion

Research teams around the world are currently studying adhesive strategies and
bonding techniques developed in the biosphere by plants and animals. The way
434 Chapter 11
molluscs attach themselves to the hull of a ship, the way geckos and spiders
walk through bonding and de-bonding on-command, even upside down against
gravity on low-energy surfaces, are striking examples where in nature very
sophisticated bonding techniques have emerged through evolution. Although
quite fascinating from a scientific point of view, the practical value of biological
insight translated into everyday adhesives and sealants is very limited so far.
We are particularly optimistic about new discoveries in protein chemistries, and
also believe in new technological routes of producing adhesive raw materials via
bio-engineering techniques. This will help to produce them by using ‘‘green’’
chemistries for better efficiency with a lower carbon footprint at a much
improved sustainability profile.
But undoubtedly the major sustainability impact of adhesives and
sealants lies today and in the future in their direct usage as an enabling bonding
technology. Relative to their indirect impact, estimates range from 100 to
several 1000 times. Adhesives and sealants contribute through their sheer
existence to sustainable solutions in all walks of life, ranging from medical to
transportation to construction, electrical and electronic, packaging and
woodworking applications. Through higher performance the specific
amount of an adhesive to form a reliable bond consistently declines and this
also has to do with ever more precise dosing of application machinery.
Adhesives are made to adhere, and sealants to seal, with no compromise
whatsoever in their expected reliability. At present bio-based or natural-based
adhesives in their specific performance are at best second class especially under
demanding or critical conditions, and clearly are outperformed by petro-
chemical-based alternatives. One day this may change, however, but for
the foreseeable future we will have to live with them, and benefit from the
much larger sustainability impact they indirectly offer through their almost
limitless usage.

References
1. Contains part of a presentation titled Adhesives Based on Renewable
Sources, held by the author at the World Adhesives Conference in Miami,
April 2008.
2. Daniel S. Murad, Adhesives & Sealants Industry, July 1, 2008.
3. E. M. Petrie, Adhesives and Sealants, Editorial, Oct 1, 2008.
4. G. Gierenz and W. Karmann, Adhesives and Adhesive Tapes, Wiley-VCH,
Weinheim, 2001.
5. World Adhesives Database of The ChemQuest Group Inc., partly accessible
via www.chemquest.com.
6. ASC, FEICA, IVK data, compiled by The ChemQuest Group Inc.
7. Global Market Forecast conducted by The ChemQuest Group Inc.,
Cincinnati.
8. Estimation of the author.
Sustainable Solutions for Adhesives and Sealants 435
9. S. Marcinowski, Renewable Raw Materials – a Novel Approach in
Polymers, Bio & Polymers, Biannual Meeting of the GdCh-Division of
‘‘Macromolecular Chemistry’’, Aachen, 2008, http://www.gdch.de/vas/
tagungen/tg/5325__e.htm; Anonymous, . . . .
10. ChemQuest Survey.
11. From a presentation the author held at the European Coatings Show 2007,
Nuremberg/Germany titled Drivers of growth for the worldwide adhesives
business, partly published in Adhäsion, 2007, 718, 14–19 and in European
Coatings Journal, 2007, 6, 34–46.
CHAPTER 12

White Biotechnology
THOMAS HAAS,a MANFRED KIRCHER,a TIM
KÖHLER,b GÜNTER WICH, c ULRICH SCHÖRKENd AND
RAINER HAGENe
a
Evonik Degussa GmbH, Creavis Technologies & Innovation,
Paul-Baumann-Straße 1, D-45772 Marl, Germany; b Evonik Goldschmidt
GmbH, Goldschmidtstraße 100, D-45127 Essen, Germany; c Wacker Chemie
AG, Consortium für elektrochemische Industrie, Zielstattstraße 20, D-81378
München, Germany; d Cognis GmbH, Henkelstraße 67, D-40589 Düsseldorf,
Germany; e Uhde Inventa-Fischer GmbH, Holzhauser Straße 157–159,
D-13509 Berlin, Germany

12.1 The Status of White or Industrial Biotechnology

12.1.1 Introduction
White Biotechnology and industrial biotechnology are synonymous. According
to EuropaBio – the European Association for Bioindustries – ‘‘industrial bio-
technology is the application of biotechnology for processing and production
of chemicals, materials and energy. It uses enzymes and micro-organisms to
make products in sectors such as chemicals, food and feed, paper and pulp,
textiles and energy. By using biotech processes, all these sectors can make
significant contributions to mitigate climate change. Industrial biotechnology
can help prevent pollution and offers new ways to produce goods and services.
Environmental benefits are often combined with increased economic efficiency,
leading to cost savings in the production process while the production
output and quality remains the same or increases. In summary, industrial

RSC Green Chemistry No. 4

Sustainable Solutions for Modern Economies
Edited by Rainer Höfer
r The Royal Society of Chemistry 2009
Published by the Royal Society of Chemistry, www.rsc.org

436
White Biotechnology 437
biotechnology often delivers environmental and economic benefits at the
same time.’’
The relevance of White Biotechnology is well documented. OECD, the Royal
Belgian Academy Council of Applied Science, Dechema as well as US-NREL
and US-DOE, outlined White Biotechnology’s innovative power and future
potential.1–6 The worldwide volume of white biotech production sums up to
an estimated h50 billion – close to biotech’s pharma product volume of $55
billion.7
All biotechnological processes depend on enzymes – either in whole-cell
living systems or isolated out of their biological context. In fact, purified
enzymes are established in processing food and textiles and are supplements in
feed and detergents – all products of everybody’s daily life. Whole-cell systems
particularly in the field of specialty chemicals provide a broad range of methods
and processes. For many years, enantiomerically pure amino acids for food,
feed and pharma industries have been produced by microbial fermentation.
Ambitious R&D resulted in enzymes especially modified and optimized for
a desired chemical reaction such as biocatalysis of optically active amines,
alcohols, epoxides and more.8

12.1.2 Relevant Market Segments

12.1.2.1 Enzymes in Food, Feed and Households
The most powerful driver of White Biotechnology is its ability to perform
specific biochemical reactions synthetic chemistry is not able to provide. An
example is White Biotechnology’s first product – a protease – which was
launched in 1909 by Röhm & Haas in Darmstadt. Its application is digesting
tissue residues from animal skin when starting the tanning process. Still today
enzymes are an inevitable tool in the tanning industry. Enzymes captured more
and more industrial fields – either as a processing tool like this example from
tanning or as the active agent itself. Processing of food today depends strongly
on enzymes: 8 Mio mto of liquid sugar are produced annually mainly for the
beverage industry by splitting corn starch by amylases. Pectinases clear fruit
juices and the production of cheese depends on chymosin and more enzymes.
In detergents a mix of especially selected and optimized proteases, lipases and
amylases not only remove protein, fat and starch stains but also allow for
washing laundry effectively at a temperature of only 30 1C. Current R&D
efforts target even room temperature by further lowering the laundry enzyme
mix’s optimum temperature while keeping its activity. This example demon-
strates how biotechnological processes deliver products of high functional
quality and at the same time save energy significantly. Like this one, many
biotechnological processes and products help in minimizing the ecological
footprint.
Another example from a significant but often overlooked market is the feed
additive industry. Phytase is an enzyme added to feed enabling swine and
poultry to utilize the typical plant phosphate storage compound phytic acid
438 Chapter 12
because these animals do not express the digestive means of splitting phytic
acid. Therefore providing phytase with feed has an economical and especially
an ecological impact: The farmer saves adding phosphate to the feed and – even
more important – the phosphate burden of liquid manure from undigested
phytic acid is significantly reduced. More applications of enzymes in different
markets are shown in Table 12.1.

Table 12.1 Use of technical enzymes in diverse applications.

Products from Enzymatic Catalysis
Annual Price
Production EUR/
Product/Process mto a1 kg Application Producer

Chemicals
Acrylamid 100,000 1,4 Polymers Mitsubishi Rayon
Amino Acids
L-asparaginic acid 13,000 Aspartam Tanabe Seiyaku,
DSM
L-methionine 400 20 Pharma
L-Dopa 300 Pharma Ajinomoto
L-alanine 500 Pharma Tanabe Seiyaku
D-, L-valine 50 Pharma DSM
L-tert. Leucine 10 500 Pharma Evonik Industries
L-Carnitin 200 Lonza
ß-phenylalanine 1 Dow Pharma, Evonik
Industries
Food
Glucose 20,000,000 0,3 Liquid sugar
Isoglucose 8,000,000 0,8 Liquid sugar
L-malic acid 100 20 Acidification Tanabe Seiyaku
Isomalt 70,000 Sweetener Südzucker, Cerestar
Aspartam 10,000 Sweetener HSC
Fructooligosaccharides 10,500 2,5 Prebiotic Beghin Meji, Orafti,
Sensus, Cosucra
Antibiotic-derivatives
6-APA 10,000 Kaneka, DSM,
Novartis
7-ACA 4,000 Novo, Novartis
D-4-Hydroxyphenylglycin 7,000 Kaneka, Recordati
Intermediates, chiral
products
(S)-2-cloropropionic acid 2,000 Herbicides, Avecia
D-pantolacton 2,000 Pharma, Fuji Pharma
(S)-Methoxyisopropylamin 1,000 Herbicides, BASF
Mandelic acid 200 20 Pharma Mitsubishi Rayon,
BASF
Ethyl (S)-4-clor-3-hydro- 150 Pharma Daicel Chemical
xibutyric acid Industries, Rütgers
Ephedrin 1,500 90 Pharma BASF
Source: Dechema Positionspapier, Frankfurt, 2004; personal communication3
White Biotechnology 439
12.1.2.2 Cosmetic Ingredients
Also in the field of cosmetics White Biotechnology unfolds its ecological and
economical benefits. A successful example is Evonik Industry’s enzymatic
process to emollients. Emollients are functional esters in skin care products
giving skin a soft and comfortable feeling. Conventionally they are produced by
chemical synthesis through a multi-step process which needs a lot of energy
input and produces volatile, aqueous and solid waste. In contrast the new
enzymatic catalysis based on lipase needs only one step. It saves energy, avoids
waste and leads to superior product quality (Figure 12.1).
Obviously the enzymatic process is beneficial concerning the ecological bal-
ance. Energy input, side products and emissions are reduced or avoided com-
pletely. By simplifying the production plant to only a few steps fixed and
variable costs drop down.
More cosmetic ingredients or precursors thereof are produced by fermenta-
tion. The example of sphingolipids is discussed in more detail in Chapter 12.2.1.

12.1.2.3 Fine and Specialty Chemistry: Amino Acids

Another innovation was added to White Biotechnology when in 1956 Kyowa
Hakko selected Corynebacterium glutamicum for large-scale fermention of

Conventional Enzymatic

raw mat. raw mat.

volatile
reaction catalyst reaction
comp.

aqueous
desodor. steam
waste catalyst
recycled

bleaching bleach

aqueous temperature
waste drying
> 180°C
140°C
100°C
solid 60°C
waste filtration 20°C

packing packing

Figure 12.1 Conventional and enzymatic production of emollient esters.

440 Chapter 12
–1
L-glutamic acid. Today 1.5 Mio mto a of this amino acid are produced
worldwide and predominantly used in food as a flavour-enhancing additive.
The essential amino acids L-lysine, L-threonine and L-tryptophan are pro-
duced by fermentation for the feed additive market. In 2004 worldwide 770,000
mto a1 L-lysin and 65,000 mto a–1 L-threonine were produced by bacterial
fermentation. According to Ajinomoto sales of feed additive amino acids grow
up to 9% per year. Today Evonik Industries produces feed grade L-lysine, L-
threonine and L-tryptophan by large-scale fermentation9 and produces
pharma-grade L-alanine, L-aspartic acid, L-isoleucine, L-proline, L-valine and
L-tryptophan for applications in the pharma markets. More products from
fermentation are shown in Table 12.2.
Amino acid fermentation is predominantly based on Corynebacterium glu-
tamicum and Escherichia coli. Corynebacterium’s decisive advantage is the
relatively easy to manipulate anabolic network. E.g. the metabolic regulation
of Corynebacterium’s lysine biosynthesis is in contrast to other species
quite simple. By manipulating only a few key steps the precursor flow is
directed to lysine (Figure 12.2). Aspartate kinase is the key enzyme to enhance
and deregulate the intermediate flow towards lysine and threonine. Further-
more reducing homoserine dehydrogenase pushes the carbon flow towards
lysine. However, developing competitive high-performance strains requires
optimizing the whole complex metabolic network and de-bottlenecking of
lysine biosynthesis itself including all precursors starting from the carbon
source uptake.
Corynebacterium actively excretes amino acids through its cell wall mem-
brane and does not degrade L-lysine due to the lack of lysine-decarboxylase.
For 60 years all these characteristics have made this microbe the species of
choice in L-lysine production. In addition it demonstrates the potential of
natural biosynthesis pathways for commercial purposes. In contrast Escher-
ichia coli entered the field of industrial amino acid fermentation not because
of comparable advantages provided by nature but because of the availability of
effective tools for genetic engineering. In the early 1980s such methods
were state of the art for Escherichia coli but were only on an infant level for
Corynebacterium. Developing industrial strains based on Escherichia coli,
which at that time was not broadly covered by intellectual property (IP),
provided room to build new IP in the field of amino acid fermentation.
This example of amino acid fermentation demonstrates that the establish-
ment of a species as an industrial production system depends on three factors:
(i) suitability given by nature, (ii) availability of R&D tools and (iii) freedom to
operate.
As already described for phytic acid, also adding amino acids to feed has an
economical as well as an ecological impact. The most relevant feed plants are
soy and corn. Their profile of essential amino acids – and that of other plant
materials as well – does not meet exactly the livestock’s essential amino acid
demand profile. Since the animals eat feed-protein until the demand of the most
limited amino acid is filled the remaining overflow of other amino acids cannot
be transformed into body mass. It is excreted. Consequently liquid manure of
White Biotechnology 441
Table 12.2 Products produced by fermentation.
Fermentative Products
Annual
Production Price
Product/Process mto a1 EUR/kg Application Producer

Amino Acids
L-glutamate 1,500,000 1,2 Flavor Enhancer Ajinomoto
L-lysine 700,000 2 Feed Evonik Industries,
Ajinomoto, ADM
L-threonine 30,000 6 Feed Evonik Industries,
ADM
L-phenylalanine 10,000 10 Sweetener, DSM
Pharma
L-tryptophane 1,200 20 Feed-, Food Ajinomoto
L-arginine 1,000 20 Pharma, Kyowa Hakko
Cosmetic
L-Cystein 500 20 Food, Pharma Wacker
Acids
Lactic acid 150,000 1,8 Food, Leather,
Textiles
Gluconic acid 100,000 1,5 Food, Textiles, Jungblunzlauer
Metall,
Construction
Citric acid 1,000,000 0,8 Pharma, Food,
Metal, Laudry
Acetic acid 190,000 0,5 Food
Itaconic acid 4,000 Comonomer Cargill
Enzymes
Total 3,000,000 Novozymes, Genencor
Laundry Novozymes, Genencor,
Henkel
Food processing Novozymes, Genencor
Textile-, leather- Novozymes, Genencor
processing
Feed additive Novozymes, Genencor,
BASF
Antibiotics
Bacitracin A 4 3.000,00 Organ
transplatation
Cyclosporin 3 5.200,00 Pharma, Feed
additive
Penicilline 45,000 300
Biopolymers
Polylactid 140,000 2,25 Food, Nature Works
Oilproduction
Xanthan 40,000 8,4 Blood substitute Evonik Industries
Dextrane 2,600 200 Novozymes
Hyaluronic acid 500
Vitamins Feed
Riboflavin (B2) 30,000 Feed BASF, DSM
Cyanocobalamine 20 25.500,00 Feed
(B12)
Vitamin C 80,000 8
Lipids
Phytosphingosine Cosmetics Evonik Industries
Energy
Ethanol 39,000,000 0,35 Energy ADM, Brazil Sugar
Refineries
Source: Dechema Positionspapier, Frankfurt, 2004; personal communication3
442 Chapter 12

Figure 12.2 Metabolic scheme and key steps in lysine biosynthesis.

cattle bred on pure plant feed carries a high burden of nitrogen. Adapting the
feed’s amino acid profile to the animal’s need by adding essential amino acids
therefore reduces the manure’s nitrogen burden significantly.
L-Cysteine – another amino acid produced by fermentation will be described
in more detail in Chapter 12.2.2.
More essential amino acids are produced by fermentation for the pharma-
ceutical markets – as ingredients in infusion solutions or as a precursor for
pharmaceutical amino acid derivatives. The latter requires extremely ambitious
bio-catalytic processes including co-factor regeneration. Evonik Industries
developed a process to the pharma-building block L-tert.leucine based on
formate-dehydrogenase and NAD+-regeneration (Figure 12.3). Today this
process runs on a tons scale.

12.1.2.4 Monomers

12.1.2.4.1 Diamines and Diacids. In addition to the diverse applications of

amino acids even products of their degradation are also of industrial interest.
1,5-diaminpentane or cadaverine results from decarboxylation of L-lysine.
White Biotechnology 443

O
+
CO2 NAD(P)H + H R CO2H

α-keto acid

FDH amino acid

formatede hydrogenase dehydrogenase

CO2H
HCO2NH4 NAD+ R NH2

L-amino acid

Production of L-tert.-leucine on a tons scale (ee >> 99%)

Figure 12.3 1-Step bio-catalysis including co-factor regeneration.

Cadaverine is only a representative example of diamines and related diacids

which are the building blocks of polyamides – polymers currently produced
synthetically from fossil carbon sources. Based on industrial lysine producing
strains of Corynebacterium glutamicum a fermentative process to cadaverine
starting from sugar has been developed.10 A comparable biotechnological
alternative might become reality for dicarboxylic acids providing the possibility
to produce polyamides completely from renewable feedstock.
Lactic acid is, besides cadaverine, another example of easily accessible
microbial intermediates which provide the potential for monomers leading to
polymers and plastic materials. It is also an example of biotechnology’s dis-
ruptive power penetrating and modifying traditional chemical processes: in
contrast to pure biotechnological production of amino acids described earlier
these new processes combine biotechnological and chemical steps. The mono-
mer or its precursor is produced by fermentation followed by chemical synth-
esis and polymerization. Poly-lactic acid (PLA) is a prototypical example of
such type of new polymers based on sugar. In 2001 Cargill (NatureWorks) set a
140,000 mto a1 PLA plant on stream. Today PLA is applied in quite different
markets from packaging, benches and clothing. It will be discussed in more
detail in Chapter 12.2.4.
More bio-based polymers are in the chemical industry’s pipeline for all
performance specifications from commodities and engineering up to high-
performance polymers. Biotechnology restarted the innovation cycle which
stopped for petrochemical polymers 15 years ago (Figure 12.4).
444 Chapter 12

Number of New Polymers per Year BioRenewable

Petrochemical
C-Sources C-Sources
15
Ethylene Propandiol
PPS Pipeline
POM BioPolymers Succinic acid
Propylene
PED PAR
10 PUR PTFE
Butadiene PIB PDM PHA Lactic acid
PET EPDM PBS
PA isoPP NOP Vegetable oils
Benzene
SBB HOPE PA
LDPE ABS LLDPE APC
Toluene UPR Hydroxy alkonoates
5 PMMA PAN PEEK
BR Epoxy PES PTT
Xylene UF PS PBT PI PLA Epoxy Xylene
PF PVC Silicone PEI LCP
Methanol Isosorbid
0
00

10

30

40

50

60

70

80

90

00

10

20
19

19

19

19

19

19

19

19

19

20

20

20
Source: DSM

Figure 12.4 Innovation in monomers and polymers.

12.1.2.4.2 1,3-Propanediol, PDO. Whereas all examples mentioned so far

are based on natural biochemical pathways, biotechnology really enters a
new level in industrial application when synthetic pathways engineered
towards a specific product are tolerated and expressed by living systems.
In White Biotechnology recently the first successful example in microbial
production of 1,3 PDO has been reported. 1,3 PDO is the bio-based building
block for producing DuPont’s polymers Soronas (Figure 12.5) and Cere-
nols (Figure 12.6), both new polymers with a promising market potential.
DuPont claims a broad range of applications for PDO-formulations and its
PDO-based polymer Soronas and PDO-based polyols Cerenols in auto-
motive refinishing, inkjet inks, personal care, lube and greases, elastic fibres
and a variety of articles for automotive and sporting end uses (Figure 12.7).
The future market success depends decisively on the polymers’ performance
where e.g. Cerenols is superior to PLA and starch-based polymers concerning
the strength versus stiffness index (Figure 12.8).
Also according to DuPont Cerenols shows value-adding characteristics
which give it a competitive advantage in comparison to conventional

Figure 12.5 Soronas.

White Biotechnology 445

Figure 12.6 Cerenols.

Figure 12.7 Applications for PDO-formulations and its PDO-based polymer

Soronas.
446 Chapter 12

Figure 12.8 Performance profile of Soronas.11

OH OH
Cell mass,
by-products
(e.g. acetate, NADH)
OH

Glycerol dehydratase (dhaB1-3)

H2O
OH O

H
NADH
1,3-Propanediol oxidoreductase (dhaT)
NAD+
OH OH

Figure 12.9 Biosynthesis of 1,3 PDO from glycerol.

polyols in low volatility, non-flammability, high flash-point, less reactivity, low

toxicity, high oxidative stability and overall easier handling, processing and
transporting.12
The new synthetic pathway to produce 1,3-PDO from glucose is based on
intracellularly formed glycerol. This glycerol is converted to the product
(Figure 12.9).
Citrobacter, Chlostridium, Enterobacter, Klebsiella and Lactobacillus spe-
cies use this pathway when growing anaerobically on glycerol. However, it runs
with low yield and does not allow producing 1,3-PDO when growing aero-
bically on D-glucose. To overcome these limitations pathways from several
species have been combined in one host strain. In a first step in Escherichia coli
glyceraldeyde 3-phosphate dehydrogenase (gap) has been down-regulated
White Biotechnology 447
resulting in an increased flow of precursors towards 1,3-PDO. Furthermore
D-glucose uptake was increased by manipulating the phosphotransferase sys-
tem (PTS).13 However, the link between the aerobic glucose metabolism and
the PDO pathway starting from glycerol was still missing. Therefore the genetic
pathway to glycerol from yeast was introduced. Finally a strain combining
the benefits of three different species has been constructed which directs 60%
of its carbon uptake towards 1,3-PDO and only 11% into biomass whereas
the original E. coli uses 63% of its uptake for building biomass.11 In this strain
the procaryote Escherichia coli is the host providing a biological system well
established in industrial processes and delivering an efficient sugar uptake
system, the eukaryote Saccharomyces cerevisiae contributes the pathway genes
to glycerol and the genes for the final catalytic steps to 1,3-PDO originate from
the eukaryote klebsiella pneumoniae (Figure 12.10).11
1,3-PDO is the first example of a trend-setting scientific and technical
breakthrough in engineering a synthetic pathway targeting a biotechnological
intermediate well known to chemists but new to the engineered organism. The
chemical industry turns out to be the driver in biotechnological innovation.

12.1.3 The Drivers of White Biotechnology

The products mentioned above are just examples for the most relevant market
segments of the chemical industry: monomers and polymers, fine and specialty
chemistry, pharmaceuticals as well as detergents and body care. With a sales
volume of h98 bn in 2007 these market segments represent 75% of the German
chemical industry. In addition these markets are those with the highest annual
growth. In 2007 inorganics and petrochemicals grew by only 1% whereas the
annual growth rate of polymers has been 3% and fine- and specialty chemistry,
pharmaceuticals as well as detergents and body care even reported growth rates
between 5 and 9% (Figure 12.11).
White Biotechnology is generally well established especially in those fields
where it is the only option. There is no economical alternative to biotechno-
logical production of functional proteins such as enzymes or enantiomerically
pure amino acids. However, new ecological and economical drivers move the
chemical industry’s focus on products so far produced by chemistry starting
from fossil carbon sources. The highly visible climate change and unpredictable
economics of fossil oil have pushed the chemical industry towards bio-
renewable feedstocks for many years. However, bio-renewable carbon
sources come with a significant burden. In contrast to fossil carbon sources
50% of their molecular weight is oxygen. Comparing fossil and bio-renewable
carbon sources therefore needs to standardize on the cost of carbon
(Figure 12.12).
On this basis bio-renewables have become quite competitive in the last few
years (Figure 12.13).
In summary, changing feedstock markets in combination with the enormous
progress in biotechnologies are the boosters of White Biotechnology.
 H OH

448
O HO OH
HO
HO H OH

H H
OH H Escherichia coli

HO OH

Klebsiella
pneumoniae
HO O~ P HO OH O OH

OH OH
Saccharomyces
cerevisiae

HO OH

Chapter 12
Figure 12.10 Genetic pathways to industrial production of 1,3 PDO.
White Biotechnology 449

Sales of the German Chemical Industry AGR %

Fine &- Special Chemistry 5–9%

Polymers 3%

Pharmaceuticals 5–9%

Petrochemicals & Derivatives 1%

Detergents & Bodycare

5–9%

Anorg. Basic Chemicals

1%

0 5 1 1 2 2 3 3

Annual Sales of the German Chemical Industry (bn €: 2006)

Figure 12.11 Sales volume in the market segments of the German chemical industry
(VCI). In the grey segments industrial biotechnology is already
established or is starting (monomers and polymers).

Biotechnological plants of industrial scale have been announced all over the
world (Figure 12.14).
Consequently chemical industries are in urgent need of clean technologies,
processes and products. Targeting on alternative biotech processes leading to
well-established compounds is just the beginning not the end. With growing
familiarity with biotechnological processes the chemical industry more and
more realizes the potential of modern biotechnology to deliver new high-per-
formance products available by pure biotechnology or combined with
chemistry.

12.2 Recent Examples

12.2.1 Sphingolipids
12.2.1.1 Sphingolipid Functions and Applications
Sphingolipids along with sterols and glycerophospholipids are the most
abundant class of lipids constituting eukaryotic cellular membranes.
Their functions have been best studied in the model yeast Saccharomyces
cerevisiae. Here, apart from structural functions, they play important roles as
second messengers in signal transduction pathways, regulating diverse cellular
processes like growth, nutrient uptake, heat stress response, cell wall synthesis
450 Chapter 12

Petrochemicals

Production Price C H O Carbon

Ethylene C2H4 110 mio mto a-1 1228 €/mto 86% 14% 1428 €/mto C

Propylene C3H6 75 mio mto a-1 1015 €/mto 86% 14% 1180 €/mto C

Benzene C6H6 45 mio mto a-1 871 €/mto 92% 8% 947 €/mto C

Naphtha CnH2n 605 €/mto 86% 14% 703 €/mto C

BioRenewables
Production Price C H O Carbon

Sucrose C12H22O11 172 mio mto a-1 180 €/mto 42% 6% 52% 429 €/mto C

Bio-Ethanol C2H6O 39 mio mto a-1 357 €/mto 52% 13% 35% 687 €/mto C

Corn-Glucose C6H12O6 330 mio mto a-1 223 €/mto 40% 7% 53% 558 €/mto C

Prices as of September, 2008, 1€ = 1.48 US$,

Sources: Naphtha Europe - CMAI; Propylene Europe Contract–CMAI; Benzene Europe –ICIS;
Sugar No. 11® – ICE; Ethanol (Hydrous) Brazil – Cepea; Glucose in Corn (65%) - CBOT.

Figure 12.12 Cost of carbon from fossil and biorenewable feedstocks.

and repair, endocytosis, cellular aging, protein transport and degradation, and
others.14–16 To a large extent, sphingolipid biosynthesis pathways as well as
sphingolipid functions are conserved from yeast to man.
In mammals, a specific class of sphingolipids termed ceramides serves
an additional important function related to formation and maintenance
of the epidermal permeability barrier, protecting skin from desiccation and
preventing chemicals from penetrating the skin into underlying tissues.17,18
Ceramides are amide-linked fatty acids containing a long-chain amino alcohol
(sphingoid base).
Skin barrier functions can be mainly attributed to the outermost layer of
mammalian epidermis, the stratum corneum (SC). This region consists of dead,
cornified cells embedded in a matrix of extracellular lipids, containing mainly
ceramides, cholesterol, cholesterol sulphate and free fatty acids. The SC lipids
are organized in a specific lamellar, quasi-crystalline structure, which is critical
for optimal skin barrier homeostasis. However, formation of the lamellar
structure requires presence of the lipid subclasses in a defined ratio, and
ceramides by weight comprise roughly 50% of total SC lipids. The structure
and formation of the epidermal lipid barrier is explained in Figure 12.15.
Mammalian SC ceramides contain one of four sphingoid bases, namely
sphingosine, 6-hydroxysphingosine, phytosphingosine and dihydrosphingosine
White Biotechnology 451
Despite volatility sugar remains a competitive feedstoc
2500,00

2000,00

1500,00
€/t Carbon

1000,00

500,00

0,00
1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008

Sugar Glycerol Propylene

Sources: Propylene West Europe contract-CMAI; Naphtha Amsterdam spot–CMAI;

Sugar # 11 contract; Crude Glycerol (80%) – ICIS; stand September 2008.

Figure 12.13 Prices of fossil and renewable carbon are coupled.

Recent Press Releases: Bio-Monomers & Polymers

Monomer Polymer
Supplier Production Marketing Market
Production

JV Mohawk Polyester
Tate&Lyle DuPont
1,3-PDO TheHomeDepot 2007 -45 kta
JV Telles Telles PHB
ADM Metabolix/ADM Telles
PHB 2008 -50 kta

Tianjin Green JV PHB

JV DSM
Bio-Science PHB 2009 -10 kta

JV Polyethylene
Odebrecht Braskem Braskem
Ethene 2009 -200 kta

JV Polyethylene
Crystallsev Dow Dow
Ethene 2011 -350 kta

JV PBS
Roquette DSM ???
Succinic acid 2011 -? kta

Carg./Novozy. Polyacrylate
Cargill ??? ???
3-HP 2011 -? kta

Figure 12.14 Biotechnological plants are announced worldwide.

452 Chapter 12

Figure 12.15 Formation of the lipid barrier of human skin. The top layer of the
epidermis called stratum corneum is a hornified and inert barrier. Its
primary functions are regulation of the skin’s moisture content and
protection of the underlying tissues against external influences. Due to
its structure it is often compared to a brick wall in which the non-
viable keratin-filled corneocytes are embedded like bricks in a matrix
of intercellular lipids. Synthesis of the stratum corneum lipids starts in
deeper skin layers, where lipids (mainly glucosylceramides and
sphingomyelin) are produced and packaged in so-called ‘‘lamellar
bodies’’. During differentiation and maturation, these lipids are
enzymatically converted to ceramides and finally assembled into den-
sely packed lamellar structures surrounding the corneocytes and filling
the intercellular spaces of the stratum corneum.
White Biotechnology 453
(sphinganine). To date, 11 different ceramide classes, with more than 300
molecular variants, have been identified in human skin. Their classification is
based on the sphingoid bases contained and the fatty acids they are linked to
(straight-chain fatty acids, a-hydroxylated fatty acids, o-hydroxylated and
esterified fatty acids). Depending on the sphingoid base present in a specific
ceramide, two or three asymmetric C-atoms occur, meaning that up to eight
different stereoisomers are conceivable. However, the sphingoid bases in nat-
ural skin ceramides have only one conformation for each base. Conformation
has proven crucial for SC skin barrier function, because interactions with other
lipids, and as a consequence formation of the lamellar structure of the SC lipid
layer, depend on proper ceramide stereochemistry.
Topical application of compositions comprising sphingolipids, such as
ceramides, improves the barrier function and moisture-retaining properties
of the skin.19–23 Moreover, sphingoid bases exhibit anti-inflammatory and
anti-microbial activities, making sphingolipids valuable active ingredients in
cosmetic formulations.24,25

12.2.1.2 Biotechnological Production of Phytosphingosine by

Fermentation of Pichia ciferrii
Sphingoid bases as core building blocks for ceramide production can be pro-
duced by extraction from different natural sources, such as brain or chicken
eggs. However, the amount of sphingoid bases gained from those resources is
fairly low. Moreover, due to concerns raised by the BSE crisis, products of
animal origin lack customer acceptance. Therefore, many companies producing
cosmetics generally banned those compounds from their portfolios.
Chemical production of sphingoid bases could represent an alternative, and
several routes have been described. However, due to the presence of several
stereocentres, chemical synthesis results in the production of racemic mixtures
rather than defined enantiomers. Moreover, extensive protection chemistry is
required due to the presence of several functional groups within the molecules,
making those processes very laborious and expensive.
For the sphingoid base phytosphingosine, an alternative production method
relies on fermentation of the non-conventional yeast Pichia ciferrrii. Originally
isolated in 1932, it was discovered in 1960 that certain isolates of this
yeast secrete substantial amounts of acetylated sphingoid bases, mainly
phytosphingosine, into the growth medium.26 The major form detected was
tetraacetyl phytosphingosine (TAPS), but other, not fully acetylated forms
were detected as well.27 It is assumed that acetylation of phytosphingosine in
this yeast is a prerequisite for secretion.28 The physiological significance of
sphingolipid secretion remains obscure. Growth inhibition of competing
microbial strains is one possibility. However, acetylated sphingoid bases
precipitate in the medium, and are likely inactive in this form. For the moment,
acetylation of sphingoid bases and subsequent secretion into the medium is a
unique trait of certain P. ciferrii strains.
454 Chapter 12
Soon after discovery, the production behaviour of P. ciferrii for TAPS was
investigated in large-scale fermentation.29 During the past decades, P. ciferrii
TAPS producers have been continuously improved by re-isolation and muta-
genesis/screening programs, and product titres in fermentation processes today
yield multigram dimensions. Several companies, such as Evonik Industries
and Doosan Corporation, produce TAPS by fermentation. After extraction
and purification from the fermentation broth, chemical deacetylation yields
the sphingoid base, which is then chemically acylated to yield the desired
ceramides. Alternatively, phytosphingosine may be directly incorporated as an
active ingredient into cosmetic formulations.

12.2.1.3 Sphingolipid Biosynthesis in the Yeast Pichia ciferrii

Sphingolipid biosynthesis in P. ciferrii has been extensively studied for
many years. An overview of the biosynthetic pathway is given in Figure 12.16.
For a more detailed description, the reader is referred to the excellent work of

Figure 12.16 Sphingolipid biosynthesis in Pichia ciferrii. Enzymes are shown as

ovals and named according to the corresponding homologues from
Saccharomyces cerevisiae. Abbreviations: AcTR, acetyl-CoA:long-
chain base acetyltransferase; TAPS, tetraacetyl phytosphingo-
sine; TriASa, triacetyl sphinganine; TriASo, triacetyl sphingosine;
IP, inositol phosphoryl. TAPS is by far the most abundant sphingo-
lipid formed in wild-type cells, as reflected by the strength of the
arrows.
White Biotechnology 455
30
Boergel. Biosynthesis starts with condensation of serine and palmitoyl-CoA
to form 3-ketosphinganine. The reaction is catalyzed by heterodimeric
serine palmitoyltransferase (Lcb1p, Lcb2p) and is considered rate-limiting in
the closely related yeast Saccharomyces cerevisiae. The gene encoding one
subunit (LCB2) was cloned and over-expressed, yielding two-fold increased
TAPS levels.31 Reduction of 3-ketosphinganine by NADPH-dependent
3-ketosphinganine reductase (Tsc10p) leads to formation of sphinganine
(dihydrosphingosine), the direct precursor of phytosphingosine.32 Hydroxyla-
tion of sphinganine at the C2-position to give phytosphingosine is catalyzed by
sphinganine hydroxylase (Syr2p/Sur2p). The corresponding gene was also
cloned and characterized by Bae et al.33
Acetylation of phytosphingosine (and to a minor extent also sphinganine) is
catalyzed by acetyl-CoA:long-chain base acetyltransferase.34,35 The enzyme
was partially purified and characterized from enriched membrane fractions.
It accepts various sphingoid bases as substrates, and experimental data suggests
that a single enzyme catalyzes both N- and O-acetylation.36
Besides free and acetylated sphingoid bases, P. ciferrii produces a range
of ceramides with long or very long acyl side chains attached to the base
via amide linkage.32 Those ceramides may comprise phytosphingosine,
sphinganine, sphingosine or sphingadienine as sphingoid base. They can be
further converted to complex glucosylceramides (glucocerebrosides) by
attachment of a glucose residue to the hydroxy group in C1-position of the
sphingoid base.37 Whether or not P. ciferrii like e.g. S. cerevisiae produces
phytoceramides containing myo-inositol is currently not known. Cere-
broside biosynthesis starts by transfer of a long acyl residue from acyl-CoA
to the amino group of sphinganine, catalyzed by the dimeric dihydroceramide
synthase Lag1p/Laf1p.38 Next, Des1p (dihydroceramide-D4-desaturase)
introduces a double bond at D4 position in the sphingoid base backbone,
leading to formation of sphingosine-based ceramide from sphinganine-
based dihydroceramide.39 Obviously, Des1p does not accept the free
sphingoid base sphinganine as substrate, but is only active on the corre-
sponding dihydroceramide. Ceramide represents a branching point in P. ciferrii
sphingolipid biosynthesis. It can be further converted to complex cere-
brosides (see above), or alternatively be hydrolyzed by action of the cera-
midase Yxc1p to give the free sphingoid base and fatty acid. So far,
Yxc1p represents the only ceramidase identified in P. ciferrii and, based
on homology studies and knowledge about closely related yeast species,
it is likely that Yxc1p from P. ciferrii represents a ceramidase hydro-
lyzing sphingosine- as well as sphinganine- and phytosphingosine-based
ceramides.38
Although P. ciferrii contains the complete genetic information required
for conversion of sphinganine to sphingosine, the pathway seems to be
largely inactive. Only traces of sphingosine are produced, acetylated
and secreted by P. ciferrii wild-type strains, whereas large amounts of
acetylated phytosphingosine (along with some acetylated sphinganine) are
produced.
456 Chapter 12

12.2.1.4 Strain Improvement of Pichia ciferrii for Efficient

Production of Sphingosine
As sphingosine is one of the major sphingoid base components of human skin
ceramides, it is of considerable commercial interest to produce the corre-
sponding ceramides for cosmetic applications. Sphingosine can be produced
chemically from phytosphingosine, but the process is laborious and expensive,
adding significant costs to the final ceramide prices and preventing their broad
application in cosmetics so far. Therefore, Evonik Industries started a broad
research program several years ago, and since then has undertaken great
research efforts to redirect sphingolipid biosynthesis in P. ciferrii from phyto-
sphingosine to sphingosine production. The program included classical strain
improvement methods (random mutagenesis/screening) as well as rational
elements (metabolic engineering).
As a first step, P. ciferrii wild-type strains were subjected to treatment
with the antifungal drug syringomycin E, which is known to be toxic for yeast
strains carrying an intact SYR2 gene.33,40 A number of SYR2 strains with a
complete block of phytosphingosine production could be isolated.39 However,
initial expectations that a block in phytosphingosine production would directly
translate into elevated titres of acetylated sphingosine (triacetyl sphin-
gosine, TriASo) were not fulfilled. Rather, SYR2 strains secreted greatly
elevated levels of acetylated sphinganine (triacetyl sphinganine, TriASa),
pointing to one or more bottlenecks in the three-step pathway leading from
sphinganine to sphingosine formation. This finding suggested that a purely
classical strain improvement program probably would not be successful,
making a rational approach more promising. The toolbox for metabolic
engineering of P. ciferrii has so far been strictly limited. For instance, no
autonomously replicating plasmids are available, so gene over-expression can
only be achieved by stable chromosomal integration of the corresponding
expression cassettes. However, a transformation system based on a point-
mutated allele of a small ribosomal protein (PcL41*) conferring cycloheximide
resistance has been described.31 Together with a repetitive rDNA element for
targeted integration of heterologous DNA, the system has proven useful for
gene over-expression purposes, as it favours multi-copy integration into the
chromosome.
To identify and overcome metabolic bottleneck(s), a large number of dihy-
droceramide synthase, dihydroceramide-D4-desaturase and ceramidase genes
were functionally expressed in P. ciferrii, either alone or in different combi-
nations.30 The genes evaluated were taken from a diverse set of organisms,
including yeasts, mammals and viruses. Finally, it turned out that concerted
over-expression of all three enzyme types, covering the whole pathway from
sphinganine to sphingosine, was required for efficient sphingosine formation.
Moreover, large differences were observed concerning the impact of homo-
logous genes from various organisms on sphingosine titres, and many different
genes and gene combinations had to be screened prior to isolation of a strain
efficiently converting sphinganine to sphingosine.
White Biotechnology 457
Initially, over-expression of the different sphingosine biosynthesis genes
had only minimal effects, although expression in all cases was driven by strong
promoters driving expression of glycolytic genes. A closer inspection of the
known P. ciferrii open reading frames revealed that P. ciferrii coding DNA has
a GC content below 35%, accompanied by a very narrow codon usage with a
high bias towards A or T in third-base codon positions. Therefore, a number of
codons occur very rarely in P. ciferrii, and foreign genes seem to be only poorly
expressed unless their sequence is adapted to P. ciferrii codon usage. After the
foreign genes had been adapted accordingly, sphingosine productivity was
dramatically improved, resulting in titres several fold higher compared to the
starting strains.
Research work to further increase sphingosine production titres in recom-
binant P. ciferrii strains is still ongoing. Usually, production titres of biomo-
lecules are constrained by regulatory mechanisms like e.g. feedback inhibition,
a common biological principle applying to many biosynthetic pathways in
nature. Future work will hopefully help to elucidate the underlying regulatory
principles, and lead to a better understanding of sphingolipid biosynthesis
in the unique yeast Pichia ciferrii.

12.2.2 L-Cysteine
12.2.2.1 Biotechnical Production of L-Cysteine

12.2.2.1.1 L-Cysteine – Relevance in Nature and Industry. L-cysteine is an

important sulphur-containing compound in nature. Due to the accumulation of
several functional groups in close proximity (thiol, amino and carboxyl group)
this amino acid is predestined to participate in a wide variety of different
biochemical reactions and processes. For living organisms L-cysteine has an
outstanding relevance since it is involved in protein biosynthesis as one of the
21 canonical building blocks. In proteins or peptides L-cysteine residues often
constitute structural functions by the formation of either intra- or inter-
molecular disulfide bonds thus stabilizing the protein’s overall structure or
by the constitution of Fe/S clusters in the catalytic domain of enzymes. Apart
from its requirement in proteins, L-cysteine functions also as major donor of
reduced sulphur atoms in the biosynthesis of essential low molecular weight
sulphur-containing compounds of the cell, like L-methionine, lipoic acid,
biotin, thiamine, coenzyme A and others.
Due to its extraordinary reactivity L-cysteine plays not only a crucial role for
the cell’s metabolism but it has gained importance in several fields of humans’
daily lives as well.
Currently the world market of L-cysteine represents approximately
5,000 mto a1, approximately 55 Mio US$ sales and an annual growth rate of
4%, whereby its main fields of application are the pharmaceutical, food and
cosmetic industries. About 30% of the annual L-cysteine requirement is con-
verted into the derivatives N-acetylcysteine and S-carboxymethylcysteine
458 Chapter 12
as mucolytic pharmaceuticals for bronchial diseases. Also due to its strong
reductive ability L-cysteine is applied in the food industry; as baking additive
L-cysteine breaks up the disulfide bonds of gluten thus facilitating the kneading
of the dough and helping to increase its volume. Another significant portion of
L-cysteine is used as a flavour enhancer and for the production of meat flavour
in pet food. In cosmetics L-cysteine is used for the generation of permanent
waves, for anti-aging products and even for whitening creams.

12.2.2.2 Manufacturing of L-cysteine

12.2.2.2.1 Extraction from Natural Sources. Today, L-cysteine is one of the
few amino acids still to be produced by extraction from natural material in
industrial scale.41 Keratin-rich waste products like pig bristles, poultry feathers
and human hair are used as raw material for the isolation process. After acidic
hydrolysis of the keratin at elevated temperatures the low-solubility L-cysteine-
dimer L,L-cystine is precipitated easily upon pH neutralization. Finally, by
electrolytic reduction L-cysteine is formed from L,L-cystine. However, during
the extraction process approximately 27 kg of hydrochloric acid are needed to
receive 1 kg of L-cysteine, which means an immense challenge for waste
water treatment.42

12.2.2.2.2 Bioconversion of DL-2-Amino-Thiazoline-4-Carboxylic Acid.

Another process makes use of the ability of some bacteria belonging to
the genus Pseudomonas to convert DL-2-amino-thiazoline-4-carboxylic acid
(DL-ATC) into L-cysteine.43,44 DL-ATC is synthesized chemically from
2-chloroacrylic acid and thiourea. Formation of L-cysteine from DL-ATC
is a three-step process catalyzed by different enzymes inside the cells: 1)
racemization of DL-ATC to L-ATC by ATC racemase, 2) formation of
N-carbamoyl-L-cysteine (L-NCC) from L-ATC by L-ATC hydrolase and 3)
hydrolysis of L-NCC to L-cysteine, NH3 and CO2 by L-NCC-amino-
hydrolase.

12.2.2.2.3 Microbial Fermentation – a Powerful and Sustainable Process.

However, in order to face the increasing needs for L-cysteine and to provide
the market with a product meeting the highest quality standards a new pro-
cess for the large-scale production of L-cysteine has been established by
Wacker Chemie in 2001. This process is based upon microbial fermentation
using a special strain of Escherichia coli which has been generated by means
of metabolic engineering and produces large amounts of L-cysteine when
grown on glucose as carbon source. Already in 2004 the fermentative pro-
duction process shared more than 12% of the L-cysteine market representing
a volume of 500 mto and an annual growth rate of 10%.45 One important
aspect for the success of the Wacker process is the high quality of the pro-
duct which is needed for different applications. Especially for the pharmaceu-
tical industry fermentation based L-cysteine is desirable because the danger
of product contamination with agents like BSE or SARS can be excluded.
White Biotechnology 459
Another benefit of this new process is the environmental sustainability since
in contrast to the extraction process only 1 kg of hydrochloric acid is needed
to receive 1 kg of L-cysteine, which corresponds to an acid reduction of
more than 96%.42 This issue was honoured by the Federation of German
Industries (BDI) in June 2008 when Wacker won the environmental prize in
the ‘‘Environmentally Compatible Technology’’ category.

12.2.2.2.4 L-Cysteine Biosynthesis in Escherichia coli. In E. coli the amino

acid L-serine serves as a precurser for L-cysteine biosynthesis. L-serine in
turn is derived from 3-phosphoglycerate, an intermediate of the cell’s central
metabolism.46 The initial step of the specific L-serine biosynthetic pathway is
the oxidation of 3-phosphoglycerate to 3-phosphohydroxypyruvate catalyzed
by 3-phosphoglycerate dehydrogenase (SerA) (see Figure 12.17). For control
of the cell’s L-serine pool the SerA activity is subjected to an efficient feed-
back inhibition by L-serine (Ki ¼ 40 mM). In the second step an amino group
is inserted by phosphoserine transaminase (SerC) to give 3-phosphoserine.
Finally the phosphate is cleaved off by 3-phosphoserine phosphatase (SerB)
to end up with L-serine.
As in many other organisms in E. coli L-cysteine synthesis represents the sole
mechanism for incorporation of inorganic reduced sulphur atoms into organic
matter. Thus, due to the central position of L-cysteine in sulphur metabolism
the enzymatic activities of the different biosynthetic branches finally leading
to the formation of L-cysteine are stringently regulated and coordinated
on the expression level or on the enzyme activity level, respectively (see Figure
12.17).47 The final step in L-cysteine biosynthesis is the incorporation of a
reduced sulphur atom into O-acetylserine (OAS) to give L-cysteine. In the case

Glucose Sulfate

extracellular
intracellular
Degradation
Glucose-6-phosphate
CysB*
S2 - L-Cysteine Exp. L-Cysteine
3-Phosphoglycerate
CysK
SerA*
CysM
3-Phospho- L-Serine O-Acetylserine
hydroxypyruvate
CysE*

Figure 12.17 Important targets for the generation of an L-cysteine production

strain. Mutant proteins are marked with an asterisk. Exp.: cysteine
export proteins. SerA: 3-phosphoglycerate dehydrogenase. CysE:
serine transacetylase. CysB: transcriptional activator of the cystein
regulon. CysK: O-acetyl-L-serine (thiol)-lyase A. CysM: O-acetyl-L-
serine (thiol)-lyase B.
460 Chapter 12
of sulphate being the only available sulphur source the sulphur atom has to be
reduced to sulphide prior to incorporation via an energy-dependent multi-stage
process. However, when the cell is provided directly with a reduced sulphur
compound like sulphide or thiosulphate, respectively, L-cysteine biosynthesis is
a relatively simple two-stage process in which the hydroxyl group of L-serine is
replaced by a thiol group. The first step consists of the O-acetylation of L-serine
catalyzed by the L-serine transacetylase, the product of the cysE gene (see
Figure 12.17). Subsequently, the activated acetyl group of OAS is replaced by
reduced sulphur to give L-cysteine and acetate. This reaction is managed by
either of the O-acetylserine (thiol)-lyases, isoenzymes with different substrate
preferences, which are encoded by the cysK or the cysM gene, respectively. The
CysK enzyme (isoenzyme A) acts with sulphide as substrate and yields
L-cysteine directly as the end-product, whereas the CysM enzyme (isoenzyme B)
has a broader substrate specificity and is able to accept thiosulphate as a
sulphur donor as well.48 In the latter case S-sulphocysteine is formed as an
intermediate which requires hydrolysis or reduction to deliver L-cysteine.
Most of the genes coding for the enzymes involved in L-cysteine biosynthesis
(e.g. cysK, cysM and genes for uptake and reduction of sulphur compounds)
are integrated in a regulatory unit, the so-called cysteine regulon. The expres-
sion of these genes (except cysE) is under the control of the transcriptional
activator CysB which requires N-acetylserine (NAS) as a co-inducer molecule
as well as a sulphur limitation, because sulphide and thiosulphate act as
so-called anti-inducers. NAS is formed from OAS in an irreversible and purely
chemical reaction preferentially occurring in neutral solutions or even better at
an alkaline pH value.49 Thus NAS accumulates in the cell rather quickly under
conditions when OAS is formed by the CysE catalyzed reaction but cannot be
consumed due to the lack of reduced sulphur compounds.
The L-cysteine biosynthesis is also kinetically controlled by the end-product
L-cysteine, which efficiently inhibits the activity of serine transacetylase.50
By this means, the inhibition of the metabolic flux from L-serine to L-cysteine is
integrated into the regulation of the expression of all genes necessary for sul-
phate assimilation. Since CysB and its positive effector NAS are required for
transcriptional activation of the cysteine regulon the feedback inhibition of
OAS synthesis by L-cysteine (resulting in a reduced intracellular NAS accu-
mulation) elegantly counterbalances gene expression when the L-cysteine
pool of the cell is replenished. Stringent balance of L-cysteine biosynthesis is
essential, as it is the major sulphur donor for the synthesis of other organo-
sulphur compounds and also because higher levels of L-cysteine have been
reported to be inhibitory or even toxic.51–54

12.2.2.2.5 Generation of an L-Cysteine Production Strain by Metabolic Engi-

neering. In order to overcome the natural regulation and the limitations of
L-cysteine biosynthesis several targets have to be engineered to finally end up
with an effective overproduction of the metabolite (see Figure 12.17). One
major task is the generation of feedback-resistant enzymes which are no
longer inhibited by intermediates or by the end-product of the L-cysteine
White Biotechnology 461
biosynthetic pathway. For example, variants of the 3-phosphoglycerate dehy-
drogenase with a tremendously increased resistance towards L-serine were
isolated by means of a sophisticated mutagenesis/screening strategy. The
most effective SerA mutant protein described has a 3750-fold higher resis-
tance against L-serine compared to the wild-type SerA.55 Besides point muta-
tions, which are described in the European patent EP1496111, a complete
removal of the regulatory domain of the 3-phosphoglycerate dehydrogenase
could be an interesting starting point for further optimization of the cysteine
production process.56 The proof of this concept was demonstrated in an
engineered strain of Corynebacterium glutamicum for an improved L-serine
production.57
The second important feedback mechanism which has to be eliminated
regulates the penultimate reaction in L-cysteine biosynthesis. The L-serine
transacetylase CysE is normally inhibited effectively by the end-product L-
cysteine (KiB1 mM). Also for this enzyme various muteins were generated
showing a very efficient decoupling of feedback regulation by the end-product.
Most powerful is the mutant allel named cysE23 encoding a protein with a Ki
value of 2.3 mM.58
An alternative issue for avoidance of feedback inhibition by L-cysteine is the
use of heterologous L-serine transacetylases. Very promising proteins can be
found in plants which are summarized in the review by Wada and Takagi.59
Besides elimination of feedback regulation mechanisms a very fundamental
subject is the enhancement of end-product excretion for an effective L-cysteine
overproduction. Recently four different export systems for L-cysteine belong-
ing to various classes of membrane proteins could be identified in E. coli, which
implies the importance of such proteins for the cell. The first exporter identified
was the YdeD (EamA) protein which belongs to the PecM family of transport
proteins.60 Even in a wild-type strain over-expression of the ydeD gene leads to
the excretion of both L-cysteine and its precursor OAS. YfiK (EamB) was
detected by the same group and belongs to the RhtB type of transporters. Like
YdeD YfiK also excretes both L-cysteine and OAS but only in strains already
containing a deregulated CysE enzyme.61 Over-expression of a third trans-
porter confers resistance to high extracellular L-cysteine concentrations. This
L-cysteine transport system, encoded by the operon cydDC, belongs to the
group of ABC transport proteins and is required for cytochrome assembly.62
The L-cysteine export protein identified most recently can be assigned to the
large group of multidrug resistance transporters. The discovery of the Bcr
protein as an L-cysteine exporter displays that global screening procedures are
valuable tools for metabolic engineering.63 For effective L-cysteine production
a highly sophisticated balance is needed when several export proteins are
combined in the production process.
Since even a slightly elevated L-cysteine concentration is inhibitory or pos-
sibly toxic for the cells E. coli possesses another mechanism for detoxification
of this compound in addition to excretion: degradation of L-cysteine. Five
enzymes with L-cysteine desulfhydrase activity have been identified so far
in this organism: L-tryptophanase (TnaA), L-cystathionine b-lyase (MetC),
462 Chapter 12
O-acetyl-L-serine (thiol)-lyase A (CysK), O-acetyl-L-serine (thiol)-lyase B
(CysM) and MalY.64 Thus in order to engineer a potent L-cysteine over-pro-
ducer excessive degradation of the amino acid must be prevented by inactiva-
tion of the genes encoding the major L-cysteine desulfhydrase activities.
Finally, an efficient and elegant tool for the deregulation of L-cysteine bio-
synthesis in general is the expression of a constitutively active variant of the
transcriptional activator CysB no longer being dependent on the co-inducer
molecule NAS. Thus expression of the genes belonging to the L-cysteine reg-
ulon is ensured under all physiological conditions.
Although good progress has been achieved so far by application of con-
ventional metabolic engineering tools (e.g. mutagenesis and screening, targeted
genetic engineering), new comprehensive approaches like genome sequencing
and metabolic flux analysis of production strains are necessary to identify new
genetic targets for further manipulation which will help to improve the process
for future demands.

12.2.3 Lipid Biotechnology

The microbial production and the biotechnological transformation of lipids
and lipid soluble compounds are summarized under the term ‘‘Lipid Bio-
technology’’. Target substances are triacylglycerols including their different
fatty acid types and to a minor extent phospholipids, sphingolipids, glycolipids,
sterols, carotenoids and other lipid soluble compounds (Figure 12.18). Excel-
lent overviews about the different lipid classes, a lipid glossary and fatty acid
structures of seed oils can be accessed online.65–68 Several classes of biocatalysts
including lipases, esterases or phospholipases may be utilized for the

O
B OH
O A
O OH
NH
O
O O

O O O
A1
O O D O C
HO O
O O
O O
O HO O A2
O O O
O
HO
C P N+
OH
O O-
D

HO
E

Figure 12.18 Examples of lipid structures and oil soluble compounds: A) tria-
cylglycerol; B) ceramide; C) phospholipid (with enzymatic modifica-
tion sites); D) sophorose lipid; E) carotene; F) sitosterol.
White Biotechnology 463
Table 12.3 Typical examples for Lipid Biotechnology. Commercialized
lipid (including glycerol) based products manufactured
biotechnologically.
Product Process (typical)

Microbial oils (polyunsaturated) Fermentation of mainly marine micro-

organisms
‘‘Designer Lipids’’/Structured lipids/ Enzymatic modification with regioselective
Margarine lipases
Carotenoids (Carotene/Astaxanthin)80,81 Fermentation of Dunaliella or
Haematococcus
Cosmetic esters82 Lipase catalyzed synthesis
Sophorose lipids83 Fermentative production with Candida
bombicola
Sphingolipids84 Fermentative production with Pichia ciferrii
Steroid hormones (sterol based)85 Transformations with several
microorganisms
Decalactone (aroma compound)86,87 Biocatalytic production with Yarrowia
lipolytica
Hexenal (+other grass aroma Lipoxygenase and Hydroperoxide Lyase
compounds)86,87
Dicarboxylic acids (mainly from Biocatalytic production with Candida
alkanes)88,89 tropicalis
Biodiesel (in development)90,91 Lipase catalyzed transesterification
Dihydroxyacetone (glycerol based)92 Production with Gluconobacter oxydans
1,3-Propanediol (glycerol based)93 Production with Clostridium sp. or Klebsiella
sp.

modification of lipids, fats and oils. Several of these enzymes from microbial,
plant and animal origin are available commercially from different suppliers.69
An excellent book supplying a broad overview about biocatalysts for lipid
modification is available.70
Lipases are the most versatile catalysts in the field of Lipid Biotechnology
with a variety of industrial applications e.g. in the food, cosmetic, pharma-
ceutical, leather, pulp and paper or detergent industries (Table 12.3).70,71 Most
of them display certain fatty acid selectivity; some possess regioselective
properties and show enantioselective catalytic behaviour. Fatty acid selectivity
and regioselecticity are especially interesting properties in the field of lipid
biotechnology. The lipases are not only able to modify ester bonds of lipids but
may also catalyze non-natural reactions like the modification of hydrophilic
polyol compounds, the peroxidation of fatty acids or the transformation of
amine based compounds.70–73 Additionally the lipase-catalyzed synthesis of
several polyester compounds has been shown.74,75 The availability of high-
throughput screening methods for lipases makes them ideal targets for modern
biotechnology including e.g. metagenome screening approaches for the iden-
tification of new catalysts or genetic engineering for alteration or optimization
of the catalyst properties.76–79
464 Chapter 12
Microbial production of oils and the enzymatic synthesis of ‘‘Designer
Lipids’’ will be exemplified in this chapter in more detail.

12.2.3.1 Production of Microbial Lipids

Microbial lipid production has been known for more than a century; however,
the economics of microbial oil production utilizing yeasts and fungi could
not compete with that of plant-derived oils for commodity products. Therefore
the concept of commodity oil production by fermentation was generally
abandoned.94,95

12.2.3.1.1 Microbial PUFA Oils. Micro-organisms, mainly of marine ori-

gin, are able to synthesize polyunsaturated fatty acids (PUFAs). In contrast
to plants, micro-organisms and animals are able to build up fatty acids with
chain lengths of 4C18 via sequential elongase and desaturase cycles.
Recently a completely separate pathway for the synthesis of polyunsaturated
long-chain fatty acids was detected in marine bacteria and some marine
algae, which uses a polyketide synthase system.96,97
Several species are of commercial interest for the fish feed industry and as
natural sources of PUFAs for health food and infant nutrition formulas.
Health food applications focus on products containing eicosapentaenoic (EPA)
and docosahexaenoic acid (DHA) while infant formulas contain arachidonic
acid (ARA) and DHA as PUFA components. EPA enriched products are
mainly based on purified fish oils, whereas ARA and DHA are also produced
microbially in an industrial scale.96–98
Mortierella alpina was identified to be an excellent production organism with
up to 70% ARA in the storage lipid fraction and it is the only commercially
used micro-organism for ARA manufacturing.99,100 With the application of
molecular technology, increases in the total ARA content of Mortierella have
been achieved.101
DHA-rich oils are produced industrially with micro-organisms of either the
Thraustochytrid genus or Crypthecodinium cohnii. These micro-organisms are
able to grow phototrophically or heterotrophically. For commercial produc-
tion, heterotrophic conditions are applied for cost reasons.96 Several other
micro-organisms are able to produce PUFAs including marine bacteria; how-
ever, they are not of commercial importance for the time being.102 A promising
approach is the introduction of gene clusters encoding for PUFA synthesis into
lipid-accumulating yeasts. The engineering of a Yarrowia lipolytica strain with
an EPA content of 39% of the total fatty acids was reported recently.96

12.2.3.2 Enzymatic Synthesis of ‘‘Designer Lipids’’

The term ‘‘Designer Lipids’’ comprises artificial glycerides, synthesized either
chemically or enzymatically, with a specific fatty acid composition and/or a
specific regioselective pattern, the latter ones called structured lipids. Enzymatic
White Biotechnology 465
O
OH O
O C R1
H2C HO C R1
H2C
HC OH + +
HC OH
O
O H2C
H2C OH HO C R2
O C R2

1,3-regioselective
pancreas lipase

OH
O
H2C O
O C Oleic
HC O C Palmitic
H2C O

H2C +
HC O C Palmitic
OH
O O
H2C
O C Oleic HO C Oleic

Figure 12.19 Simplified scheme of the pancreatic hydrolysis of structured lipids (top:
1,3-diacylglycerols; bottom: human milk fat replacers).

processes have several advantages over chemical processes: the regioselectivity

of enzymes can be exploited to obtain specific structures and fewer by-products
are formed due to lower reaction temperatures. Several structured lipids have
been synthesized enzymatically and concepts for reactor designs for the pro-
duction of these lipids have been elucidated.103–105 Structured lipids are inter-
esting products for infant and medical nutrition as well as for dietetic products.
The structure of the lipid influences e.g. the gastric emptying, the fecal loss of
lipids and the lipid profiles in tissues after resynthesis.106 The pancreatic lipase
is a 1,3-regioselective enzyme, thus the structure of a lipid determines the
composition of fatty acids and glyceride species absorbed in the intestine
(Figure 12.19).

12.2.3.2.1 Human Milk Fat Replacers. Human milk fat is a structured

lipid with an amount of more than 70% of saturated fatty acids, mainly pal-
mitic acid, in the sn-2 position of the triglyceride backbone. This structure,
in comparison to a randomized glyceride with human milk fat composition,
guarantees a high absorption of energy-rich palmitic acid and a low loss of
calcium in the faeces.107 Human milk fat substitutes are produced enzymati-
cally on an industrial scale. The process is based on the regioselective
exchange of oleic acid with palmitic acid at the sn-1 and sn-3 positions of tri-
palmitin.108 Alternatively the regioselective alcoholysis of tripalmitate yields
466 Chapter 12
2-monoacylglycerols, which are then re-esterified at the 1- and 3-positions
with oleic acid.

12.2.3.2.2 1,3-Diacylglycerols. 1,3-diacylglycerols are produced enzymati-

cally on a commercial scale as dietetic cooking oil and have been a great
success especially in Japan. Long-term clinical studies including a recent
1-year human study suggest that the exchange of standard cooking oils with
diacylglycerol oil results in a moderate loss of body weight.109,110 The work-
ing principle of the oil is a decreased formation of 2-monoglyceride after
hydrolytic action of pancreatic lipase, resulting in a lower re-synthesis and
storage of triglycerides and in an increase of metabolic fat oxidation.109 The
oil is produced enzymatically in a 1,3-regioselective synthesis of fatty acid
with glycerol.111 Acyl migration from the sn-1 to the sn-2 position decreases
the content of 1,3-diacylglycerol, thus reaction conditions must be controlled
carefully to obtain a high concentration of the desired product.

12.2.3.2.3 Triglyceride Concentrates. Triglycerides of concentrated PUFAs

and conjugated linoleic acid (CLA) are produced enzymatically by several
companies starting from either free fatty acids or the corresponding ethyl
esters. The triglycerides are advantageous for food applications, because free
fatty acids and ethyl esters cannot be formulated into food products directly.
Due to the oxidative instability of the products, enzymatic processes are
favoured over chemical routes. The enzymatic synthesis is possible without
the use of solvents under a high vacuum at moderate temperatures.112,113 The
removal of water or ethanol from the reaction is a critical step; improve-
ments in the synthesis reaction were achieved with nitrogen as strip gas.114

12.2.3.2.4 Margarine Production. Enzymatic interesterification at low

reaction temperatures for the production of trans fat free margarine and
confectionary fats is a recently developed process, which is now running
industrially at several manufacturers.115 The ban of trans fats, which were
identified as causing a variety of negative health effects in humans,116 has
given the enzymatic process a competitive advantage over classical margarine
production.

12.2.4 PLA (Polylactic Acid)

12.2.4.1 Introduction
Polylactide or Polylactic Acid (PLA) is a synthetic, aliphatic polyester from
lactic acid (Figures 12.20 and 12.21).
For industrial applications, such as fibres, films and bottles, the chain length n
should be between 700 and 1400. This is significantly higher than with partially
aromatic polyesters like PET and PBT, where n is between 100 and 200.
Therefore, the requirements on both raw material purity and technical effort are
much higher.
White Biotechnology 467

Figure 12.20 Ring opening polymerization of lactic acid dimer yielding polylactide
(reproduced from Wikipedia: Polylactic Acid).

Figure 12.21 Synthesis of polylactic acid (PLA).

At temperatures below its glass transition point (e.g. 55 1C, depending on

comonomer content) PLA is as stable as PET or PBT. Only in an industrial
composting facility, the high temperature (60 1C) and humidity required for the
hydrolysis are achieved. After hydrolysis, PLA is biologically degradable by
common micro-organisms. Lactic acid, the monomer building block of PLA,
can frequently be found in plants and animals as a by-product or intermediate
product of metabolism. Lactic acid is non-toxic by its nature.

12.2.4.2 Non-depleting Properties of PLA

Lactic acid can be industrially produced from a number of starch- or sugar-
containing agricultural products. Competition between human food, industrial
lactic acid and PLA production is not to be expected: for example, using PLA
468 Chapter 12

Consumption of Polymers: ca. 16.1 Mio. tons in 2007

33 % for packaging: ca. 5.3 Mio. tons

(5%) Substitution Potential at least (based on current application range)

Market potential ca. 265,000 tons

Agricultural area necessary: 37,100 ha sugar beets

= 10 percent of acreage used for sugar beets in Germany

= 0.2 percent of total acreage in Germany
Source: Wirtschaftsdaten und Grafiken, VKE e.V. Internet Version, 16.10.2008

Figure 12.22 Packaging and acreage.

as substitute for 5% of the German packaging plastics consumption requires

only 0.5% (sugar beet) to 1.25% (wheat) of the agricultural area available
(Figure 12.22). At the same time, approximately 30% of the available area lies
fallow mainly for economic reasons. Research is in progress on processes and
micro-organisms that produce lactic acid from cellulose coming from agri-
cultural residues such as maize stalks or straw.
Several recycling methods can be applied to waste PLA:

 Industrial composting
–– Most attractive method of disposal based on public acceptance
–– No recovery of material and energy

 Mechanical recycling
–– Loss of product properties cannot be recovered
–– ‘‘Downcycling’’

 Burning (energy recycling)

–– Recovers ‘‘green energy’’

 Chemical recycling
–– Back into polymerisation
–– Collecting and sorting yet to be solved

Composting allows only moderate benefits. In future, sorting, purification of

PLA waste and re-feeding into the polymerization plant seems to be the most
attractive way of recovery.
White Biotechnology 469

140
Total Fossil Energy [GJ/ mto plastic] fossil fuel
120 fossil raw material

100

80

60

40

20

0
PA 6 HDPE PET PLA
Source: M. Patel, R. Narayan, in Natural Fibers, Biopolymers and
Biocomposites, A. Mohanty, M. Misra, L. Drzal, Taylor & Francis Group,
2005, Boca Raton.

Figure 12.23 Consumption of fossil resources by PLA vs. polymers from fossil
feedstock, ‘‘cradle to gate’’.

PLA – like other biopolymers – is often criticized for the need of process
energy from fossil resources. Even if this is the case at present, 1 kg of PLA
represents fewer energy equivalents than 1 kg of polymers from petrochemical
feedstock (Figure 12.23). Consequently, PLA producers can also reap financial
benefits by trading CO2 emission certificates (Figure 12.24).
If process energy is supplied by biomass, e.g. biogas, the fossil energy
required for 1 kg PLA can be cut by half, thus duplicating the benefits
from trading CO2 emission certificates. Additionally, significant potential exists
for saving process energy by improving lactic acid and polymerization
technologies.

12.2.4.3 Market Potential of PLA

The first marketplace for PLA is Europe, with Italy, Germany, The Nether-
lands, the United Kingdom and France in the frontline, followed by Japan,
USA and South Korea. In Germany and France the governments have
issued specific regulations to give preference to renewable and biodegradable
polymers.
As PLA is a rather young polymer, many companies are developing appli-
cations. These are mainly focused on the field of packaging fresh food, but
other applications are emerging. Processing PLA is possible on standard
polymer equipment for the various process techniques.
470 Chapter 12

6
[kg CO2eq/kg]

0
PA 6 HDPE PET PLA
Source: M. Patel, R. Narayan, in Natural Fibers, Biopolymers and Biocomposites,
A.Mohanty, M. Misra, L. Drzal, Taylor & Francis Group, 2005, Boca Raton.

Figure 12.24 CO2 emissions by PLA vs. polymers from fossil feedstock, ‘‘cradle to
gate’’.

Table 12.4 PLA producers, production capacity. State: 09/2008; no claim to

completeness.
Producer Trade Name Route Capacity t/y Country

Nature Works Ingeo ROP 70,000 USA

Mitsubshi Lacea DP-S 500 Japan
Chemicals
Toyota Eco Plastic ROP 1,000 Japan
Hisun Hisun ROP 5,000 PR China
Toray Ecodea ROP 5,000 RO Korea
Shimadzu Lacty ROP 1,000 Japan

Besides some smaller suppliers (Table 12.4) NatureWorks LLC is the only
producer of PLA based on a 70,000 mto a1 facility which has been brought to
full capacity over the last years and intends to increase capacity to 140,000 mto
a1 in 2009.

12.2.4.4 Process Routes to PLA

Several process routes have been developed or are practised on industrial scale:
Ring Opening Polymerization (ROP), Direct Polycondensation in high boiling
solvents (DP-S) and Direct Polymerization in bulk followed by chain extension
with reactive additives.
White Biotechnology 471
ROP (Figures 12.20 and 12.21) is the route which delivers by far the highest
proportion of PLA chips available on the market. The other routes produce
only minor amounts or did not get past the pilot scale. Figure 12.21 depicts the
steps of an ROP process, starting from lactic acid. In the first part lactide is
formed, which – after fine purification – is converted by ROP to PLA.

12.2.4.5 Processing of PLA

A major advantage of PLA is the possibility to process the polymer on common
process equipment. Especially the converters of polyolefins do not require a
change to other process equipment. They only need to change the handling of
granulate. It is very important to dry the polymer before processing otherwise it
will degrade. Water and high temperatures (up to 240 1C) facilitate fast
degradation.
PLA is a polymer which can be processed by:

 injection moulding;
 sheet extrusion;
 extrusion blow moulding;
 thermoforming;
 injection stretch blow moulding;
 fibre spinning;
 non woven spinning, spun bonding.

12.2.4.6 Properties of PLA

PLA is a crystal clear, transparent material when amorphous that becomes
hazier the higher the crystallinity. Crystallized material is opaque. When pro-
ducing lactide, meso-lactide is formed as a by-product. It is difficult to separate
the meso-lactide from the L-lactide in the purification step. When polymerizing
L-lactide with small contents of meso-lactide a co-polymer is formed.
Increasing meso-lactide leads to decreasing crystallinity. With more than
10–15% meso-lactide the polymer is amorphous.
By varying the amount of meso-lactide the properties of the polymer can be
adjusted for specific applications.
One of the reasons for the limited consumption of PLA up to now is the low
thermal resistance. The Tg (glass transition temperature) is about 55 1C
depending on comonomer content to a small extent (Table 12.5).
Methods of improving thermal resistance are to prepare a stereo complex
(sc PLA) or a stereo-block copolymer (sbc PLA). Melting point and heat
distortion temperature (HDT) will increase significantly.
Improving the thermal properties can extend the applications of PLA
considerably in the future.
There are also various additives that improve the properties of PLA with
respect to impact strength, melt viscosity, HDT, crystallinity etc.
472 Chapter 12
Table 12.5 Properties of PLA type.
Type Tm Tg sn Eb

PLLA 160–180 1C 55–65 1C 45–55 MPa 3–5 %

PL/DLA – 55 1C 50–200 %
sc PLA 220–230 1C 60 1C 3–5 %
sbc PLA 185–195 1C 55 1C 5–10 %

Tm-melting temperature Eb-elongation at break

Tg-glass transition temperature sn-tensile strength at break

12.2.4.7 Perspective
PLA combines all prerequisites of sustainability with important properties of
well-established polymers. Applications have already been found in many niches
of packaging and textile products. Within those niches fast growth of con-
sumption is expected to continue depending on the availability of PLA polymer.
High research activity is dedicated to overcome typical weaknesses of PLA –
low impact strength and low heat distortion temperature – and to develop
tailor-made PLA grades in order to serve special applications. These activities
will conquer new niches for PLA and will help to increase PLA consumption at
high velocity.
Other growth factors are the availability and prices of raw oil, agricultural
products and production plants and technology.
Within the foreseeable future PLA will not become a commodity polymer
like PE, PP and PS – this is considered to be an advantage for both PLA
producers and converters. However, this could change in the long term.

12.3 Outlook of White Biotechnology

White Biotechnology has an enormous future potential, simply because today
enzymes and micro-organisms can be rationally designed. In addition the
biotechnologic processes are characterized by water-based, harmless and less
toxic conditions.
At present the unique performance of biotechnological products is the main
driver of this technology, especially in the pharma and cosmetic markets. API’s,
active pharma ingredients, are often protein based, like antibodies. These are
one of the backbones of red biotechnology. But also other API’s and nutrition
ingredients, which can only be synthesized in a complex series of chemical steps
are nowadays synthesized in microbes. Examples are insulin or vitamins,
examples of White Biotechnology. Many of these are described in the beginning
of this chapter.
Nevertheless the share of White Biotechnology for all chemical processes
and products today is only 5%. This share will grow steadily. But the growth
White Biotechnology 473
will take time, on the one hand because of the high complexity of the biological
systems and on the other hand because of missing solutions for the interface of
biology and chemistry. One of the important interfaces is the downstream
processing of the aqueous biotechnological process solutions. To work up these
solutions energy efficiently, achieving chemical products in a high purity, more
biochemical engineering breakthroughs are needed. Therefore in the near
future White Biotechnology will still mainly grow in chemical niches, but
as soon as solutions for the biochemical interfaces are provided, White Bio-
technology will also grow into chemical bulk product markets.
Another important factor for the development of White Biotechnology will
be simply the oil price. Bulk chemicals derived from renewables will be unlikely
at low prices.
But with the next economic recovery in addition to the climate change
derived CO2-debate new, white biotech derived processes will be in place and
take their share of the new economic growth.
A large amount of effort in research and development is necessary for White
Biotechnology to become a significant part of a green future.

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Subject Index

acarbose precursor 247–8 Alwörden’s reaction 390

acetate/mevalonate pathway 347–9 amino acids
acetylation 330 α-amino acids 375–80
acetylserine 459–60 in white biotechnology 438, 439–42
active ingredients 247 amphoteric 376
in cosmetics 395–6 surfactants 387–8
activity-based criteria, exclusion 17–18 amylopectin 239–41, 244
acylglycerols 179, 462, 465, 466 amylose 239–41, 244, 281, 288–9
adenosine triphosphate 279 amylosucrase 288
adhesion 426 anaerobic biodegradability 386
adhesives 425–34 anaerobic digestion 110–13
aesculin 317, 318 biogas from 115
AFNOR reference model 39 methane from 142
Agenda 21 6, 398 process scheme 111
agility, logistic 45–6 animal fats and oils 167
agricultural land fatty acids in 182
increased biomass use 116, 121 global production/demand 169
polymer consumption 468 production 178–9
agriculture see also fats; milk
changes in usage 171, 172 animal feed 30–3, 187
dairy farming 71–80 additives 437–8, 440
greenhouse gas emissions 56 cattle feed 74–80
product utilization 8 animal fibres 368, 374–80
production 69 sourcing 383–4
see also cereals; crops; pesticides structure 379
alchemy 407 anti-parallel β-sheet 379
alcohol see ethanol antibiotics 72, 249, 438, 441
algae 157, 182, 212–13 antioxidants 202, 203, 207, 208
algal oil 212–13 APG® surfactants 60, 226, 252–3
alkaline neutralization 177 aquatic toxicity 62, 414, 415, 419
alkyl glucosides 225–6 arachidonic acid 464
alkyl polyglycosides 60, 226, 252–3 ARBOFORM® 312, 328–9
allergies 387 Argan oil 402
480 Subject Index

Argan tree 399–404, 405 property comparisons 141

Arganyl™ 403 from rapeseed 198
Argatensyl™ 403 from vegetable oils 138–40
asbestos fibres 369 worldwide capacity 8
L-ascorbic acid 251–2 see also biofuels; diesel fuel; synthetic
ash 306, 318–19 biofuels
asset management 16–22 bioethanol 109, 114, 127–37
asset value 13–14 bio-ethylene from 272
automatic fed combustion technologies 99 in Brazil 121, 127, 136
automotive industry 391 plant materials for 127–8
autothermal process 152 production processes 128–37
as transportation fuel 136
babassu oil 195 bio-ethylene 272
bacteria biofuels 125–58
amino acid fermentation 439–40 carbon costs 450, 451
anaerobic digestion 110–13 combustion technologies 99
bioethanol fermentation 134–5 EU directives 125–6, 138
in biopolymer production 446–7, 448 first-generation 126–37
fuel-producing 157–8 global trade 173
see also Corynebacterium lipid-based 137–42, 143
glutamicum; Escherichia coli major forms of 89–90
bacterial inulin 287–8 market expansion 114–15
bagasse 266, 269 second-generation 142, 144–57
banking 12–23 syngas-based 145–57
BASIL process 33–4 third-generation 157–8
bast fibres 381–3, 385 usage 86–8
best available technology 320 from vegetable oils 107–9
best-in-class 18 see also biodiesel; bioethanol;
betaines 387–8 synthetic biofuels
betulin 317, 318 biogas
beverages 246–7 production 110–13, 114–15
bio-SNG see synthetic natural gas yield targets 111
biobutanol 144 bioliq®-process 156–7
bio-chemical conversion biological diversity 6, 396–7, 401
biomass 90, 109–13 biomass 86–123
biomethane 114, 115 bioethanol from 128–32
biodegradability biofuels from 126
plastics 249–51 competition, effects on 118–19
surfactants 62, 384, 386 competition areas 116–18
test methods 62 configuration approaches 119–22
biodiesel definition 164
flow diagram 143 demand 116
glycerine market 222 different options for use 120
HTU diesel 145 electricity from 88, 114, 115
jet-based 142 energy content and elements in 91
from palm 193 environment/climate advantages 88
Subject Index 481
gasification 96–7, 98, 104–7, 144, carbon
150–1, 152 budget 344–5
for green chemistry 164–6 costs 450, 451
heat, power and fuels from 89 in plants 343
market expansion 119 carbon dioxide emissions
potential 93–5, 113–15 from cattle 80
properties 90–2 from polylactic acid and polymers 470
thermo-chemical conversion 89–90, potential 414–15, 417, 419
95–107 carbon monoxide 96, 97
uses 113–15, 122, 301 carbonization 384
see also feedstock; renewable carrier oils 218–21
resources; wood castor oil 209–11, 216
biomass conversion caterpillars 384–5
bio-chemical 90, 109–13 cationic surfactants 387
new technologies 121 cattle feed 74–80
physico-chemical 90, 107–9 cavitation 344
thermo-chemical 89–90, 95–107 cedar trees 3
biomethane 112, 114–15, 142 cell membrane 213
see also synthetic natural gas cellulose 130, 131, 132, 133, 307–9
biopolymers 443–7, 448, 451 lignocellulose 129, 130–2, 142
fats and oils as precursors 214–16 see also hemicellulose
from fermentation 441 cellulose esters 324
Biosphere Reserves 401 cellulose fibres
biosyncrude 156 chemistry and structure 372–4
biotechnology see white biotechnology regenerated 324
bleaching 320–1, 389 ceramides 450, 452–7
blow-in combustion units 101–2 cereals
Botryococcus braunii 157 bioethanol production 128, 129, 130,
Brundtland, Mrs Gro Harlem 4 133
BtL fuels see synthetic biofuels in starch production 239, 240, 241
BTL process 155–6 see also individual cereals
bubbling fluidized bed (BFB) 152–3 Cerenol® 444–5
building materials 305–6, 327 cetane 140, 141
Business and Biodiversity Initiative 397 channel relationships 39
butter 178, 204–5 charcoal 102
cheeses 80
cadaverine 443 chemical fibres 370, 391
calcium oxide 267 Chemical Industry Responsible Care®
calendula oil 208 168
Camelina oil 207–8 chemical pulping 319–20, 321, 322
Cannabis sativa 381 applications 323
CANOLA 197 chemical refining 175–7
caoutchouc 339 chemically processed biofuels 89–90
capryl dimethylamide 220 China wood oil 208
carbohydrates 343, 346, 355, 357–8 Chlorella vulgaris 157
see also starch; sucrose; sugar Choren CarboV® 155–6
482 Subject Index

CHRIGAS project 155 Corynebacterium glutamicum 439, 440,

circulating fluidized bed 153, 154–5 443
cis-fatty acids 179, 180 cosmetics 193, 195, 203, 205, 224
cleaning, fabrics 388–9 from ceramides 456
Clostridia 134, 144 plant-based ingredients for 394–405
coal 91 from white biotechnology 439
briquettes 256 cossettes 267
gasification 106 costs
coalescents 419–20 logistic 44–5
coalification 102 see also prices
coating 258, 259 cotton 370, 373, 380–1, 382
fabrics 389–91 properties 385
cobalt catalysts 149–50 Cotton Belt 381
cocoa butter 204 cottonseed 381, 382
coconut oil 59, 60, 193–5 cottonseed oil 200, 381
Cognis 401–4, 405 cradle-to-grave analysis 26
cohesion 426 crops
Collaborative Planning, Forecasting energy crops 93, 94, 95, 113, 121, 212
and Replenishment 44 protection 185, 228, 420–2
colouring, fabrics 390 silage 75
combined heat and power plants 114 see also cereals
combustion 95–6 crude oil
direct combustion 98–102 extraction 226
technologies 99 prices 174, 249, 261
compaction, detergents 64, 65 see also petrochemicals; petroleum oil
competitive advantage 41 crude palm oil 189, 191, 192
composting 109, 468 crystallization 268, 269, 270
confectioneries 246 strain-induced 360
construction industry 305–6, 327 Cuphea seed oil 195, 196
consumer products 53–65, 68 curing systems 29–30, 31, 34, 431, 432
washing process life-cycle 57–62 cuticle 377, 379
consumer purchasing behaviour 54–6 L-cysteine 457–62
contamination, toleration levels 151 cysteine regulon 460
Convention of Biological Diversity 6, cytosol 356
396, 401
cooperatives, dairy 72–4 dairy farming
coppicing 404 cattle feed 74–80
copra 193 milk procurement 71–4
corn 75 deforestation 172, 188, 400
corn oil 200–1, 239 degumming 175–6
corn syrup, high fructose 246–7 dehydrated castor oil 211
corporate social responsibility 12, 394, dehydration 135–6
397–8 delthametrin 421
and Argan tree products 399–404, 405 demographic dynamics 54–7, 58
corrugated board 259 deodorization 177
cortex 377, 379 derivatized starches 242
Subject Index 483
design strategy, SOLVSAFE 412–16 dry adhesives 429
designer lipids 464–6 dry cleaning 408
detergents 57–62 dry fractionation 191
from fatty alcohols 222 dry-milling 130, 201
sustainability profiles 62–5 dry rubber 354, 355, 358
using white biotechnology 437 DVFA framework 13, 14
developed countries DXP-MEP pathway 347–9
biofuel usage 87 dyes 390
consumer purchasing behaviour 54–6 Dynamin 127
developing countries, biofuel usage 87, 88
development megatrends 54–7, 58 e-commerce 40
dextran 281, 289–90 easy-care finishing 390
dextransucrase 289 ECN, Netherlands 155
dextrins 243 ecobalance 26
dextrose 244, 247, 253 eco-efficiency analysis 26–8
dextrose equivalent value 243, 244 beneficial uses 34–5
diacids 442–3 conducting 27–8
1,3-diacylglycerols 465, 466 curing systems 29–30, 31
diamines 442–3 ionic liquids 33–4
diesel fuel 137–8 vitamin B2 production 30–3
selected properties 108 ecological cleansers 63, 64
specifications 139–40 ecological disasters, first 3
see also biodiesel; gasoline ecological risk assessment 62
dilute acid hydrolysis 132 eco-logistics 46–8
dimethoate 421 economic circuit 13
dimethyl isosorbide 260 Eco-packaging program 46
dimethylether 147, 148 ecosystems, forests 303
dimethylol dihydroxy ethylene urea 330–1 edible rendering 179
direct combustion 98–102 effectiveness 43
direct supply chain 39 efficiency, logistic 43–5
disasters, natural and ecological 3 EHS Guidelines see Environmental
Disponil® 227 Health and Safety Guidelines
disposal phase 62 eicosapentaenoic acid 464
dissolving grade pulp 323–4 EIG Targanine 401–4, 405
distillation 135–6 elasticity 360
DL-2-amino-thiazoline-4-carboxylic elastomer market 340, 341
acid 458 electricity
DMAPP 347, 349, 350 from biomass 88, 114, 115
DMDHEU 330–1 generation 98
docosahexaenoic acid 464 elemental chlorine-free bleaching 320
Domini 400 Social Index 15 elongation phase 348, 349–50
double-metal cyanide catalysis 211 emollients 439
Dow Jones Sustainability Indexes 15, 16 emulsifiable concentrates 420–1
downstream processing 136, 173, 473 emulsifiers 224, 226–7, 277, 421
drugs see pharmaceuticals emulsion polymerization 226–7
dry acid degumming 175 (end-)energy sources 117–18
484 Subject Index

energy consumption ester solvents 411

Germany 86, 87 esterification 219, 220, 253, 277–8
pulp and paper production 321 see also transesterification
rubber 342 Esterquats 387
sugar production 268 ethanol
washing process 61, 62 fermentation 109–10
energy content, biomass and coal 91 selected properties 109, 110
energy crops 93, 94, 95, 113, 121, 212 from syngas 147
energy generation, from biomass 86–123 see also bioethanol
energy prices 118 ethyl-tertiary-butyl-ether 127, 136
engagement 19 European Sustainable Development
Enhanced Analytics Initiative 18, 21 Strategy (2006) 48
entrained-flow gasifiers 153, 154 European Union
environment impacts biofuels directives 125–6, 138
Argan tree 400, 404 climate objectives 302
cotton 381 REACH standard 342
RENEW project 155
fabric production 390
SOLVSAFE project 412
natural fibres 370
evening primrose oil 205, 206
pulp and paper processing 320–1
Evian mineral water 80–4
solvents 409, 414–15
evolution, human 2
surfactants 386, 387
ex ante screening 17
wool 384 ex post monitoring 17
see also recycling excess air ratio 97, 98
Environmental Health and Safety exclusion 17–18
Guidelines 174, 175, 410, 412, 416 expanded polystyrene 250
enzymes exposure, control of 410
in cosmetics 439 extended supply chain 39
degumming 175, 176 external lubrication 219
designer lipid synthesis 464–6 extra-financial criteria 16–17, 22
feedback-resistant 460–1 extra virgin olive oil 206
in food, feed and households 437–8 extractives 306, 307, 308, 313–18
hydrolysis 132, 133 examples 315
production 441 solubility 316
reactions 279–80, 281–4
see also fermentation fabric conditioners 386–8
epichlorohydrin 222 fabrics 388–91
epoxidized oils 214 FAME see fatty acid methyl ester
epoxidized soybean oil 187 FASAL® 312, 328–9
erucamide 198 fat replacers 278
erucic acid 196, 197, 198 fats 76
Escherichia coli 157–8, 440, 446–7, 448 biopolymers precursors 214–16
in L-cysteine biosynthesis 458–60 chemical composition 179–213
ESG (Environmental, Social, fatty acid compositions 183
Governance) 13, 14, 16–22 processing 217
essential fatty acids 76, 77, 78 production, use and trade, changes to
essential oils 182, 224 168–74
Subject Index 485
for synthetic biofuels 140–1 fibres
value chain 213–28 global production 371
see also animal fats and oils; fatty properties of glass and natural 385
acids; lipids see also natural fibres; individual
fatty acid dimethylamides 419 fibres
fatty acid esters 218, 219–21 fibrils 308, 372, 373, 376, 377–8, 379
hydrogenation 223 fibroin 374–5, 376, 379–80
sucrose 278 FICFB gasifier 155
fatty acid methyl ester 90, 107–9 finance, sustainability 12–23
hydrogenolysis 140–1 fine chemicals 416–18, 439–42
selected properties 108 first-generation biofuels 126–37
synthesis of 138–9 Fischer glycosidation 253
fatty acids 76–80, 137, 194 Fischer–Tropsch process 149–50, 155
in animal fats and oils 182 fish meal 179, 187
biodiesel specifications and 140 fish oil 179, 182, 213
chemical composition 179–80 fixed-bed gasifiers 105, 152, 153, 154
flammability 414, 415
in neutral lipids 358–9
flash pyrolysis 103, 145
nut oils and olive oil 209
flax 75, 381–3
in oils and fats 183
flax oil 206–7
as oleochemicals 216–18
flexible fuel vehicles 126, 136
in vegetable oils 182
fluidized-bed gasifiers 105, 152–3, 154–5
see also omega-3 fatty acids; omega-6 food
fatty acids; trans-fatty acids; eating habits 56
unsaturated fatty acids enzymes in 437
fatty alcohols 222–4 functional 208, 287
Fischer glycosidation 253 prices 60
synthesis 140–1 processed 246
feedstock safety 70
biodiesel 138–40 sustainability in 69–84
biogas production 112, 113 food applications, starch 240, 241, 245–7
see also biomass; renewable resources Food-Based Dietary Guidelines 71
fermentation 31, 32, 60 forest residues 93, 94
bacteria 134–5, 439–40 forests
ethanol 109–10 deforestation 172, 188, 400
glucose syrups used in 248–9 as ecosystem and resource 303
main products from 249 historical sustainability 4
microbial 458–9 pressure on 60–1
new molecules 261–2 reforestation 404
products produced by 441 see also wood
and saccharification 132 formaldehyde-based resins 251
sucrose in 264 fossil fuels 88, 116, 126, 447
vitamin C production 252 alternatives to 142, 301
yeast 132–4 carbon costs 450, 451
see also enzymes; white environmental health and safety 410
biotechnology polymer and polylactic acid
fertilizers, mineral 266, 267 consumption 469
486 Subject Index

see also coal; crude oil; glass fibres 385

petrochemicals; petroleum oil Global Commerce Initiative 49–50
fractionation 191 Global Ethic 2
Freshfields Bruckhaus Deringer study 20 Global Food Safety Initiative 70
Frey-Wyssling particles 356 Global Product Strategy 6
fructans 286–8 global production/demand
fructose 133, 266, 273, 280 adhesives and sealants 428–9, 430, 433
high fructose corn syrup 246–7 biodegradable polymers 251
oligofructose 287 fibres 371
fructosyltransferase 287–8 oils and fats 169, 170, 171
FTSE4Good Index Series 15 papermaking 325
fuel-ethanol 135 pulp 322, 324
fuels solvents 408
from biomass 89, 114, 120 global trends, demographics 54–7, 58
from producer gas 106–7 global warming 2, 56
selected properties 108 glucoheptonic acid 254, 255
gluconic acid 254, 255
see also bioethanol; biofuels; diesel
glucono delta-lactone 256
fuel; transportation fuels
D-glucopyranose 307, 372
full oxidation 97
glucose 132, 133, 266
full-solid adhesives and sealants 431
D-glucose 239, 243, 244, 245, 255, 280
functional foods 208, 287
glucose syrups 243–4, 246–7, 261
functional unit 26, 57 in fermentation 248–9
fungal diseases 185 glucosinolates 196–7
furan fatty acid 358–9 glues 325
furanose ring 287 L-glutamic acid 440
furfural 275 glycerine 139, 222, 248
furfurylation 330, 331 glycerol 446–7
fusible solids 411 glycerol formal 417–18
glycerol isobutyral 417, 420
gamma-linolenic acid 205 glycerolipids 213
gas cleaning 105, 106, 151 glycolipids 358
gasification 96–7, 98, 104–7, 144, glycosidation 253
150–1, 152 glyphosphate 184–5
gasifiers good governance 69–70
current developments 154–6 Gossypium hisutum 380
types 105, 152–3 grasslands 171
gasoline 110, 147–9, 148 green chemistry 6–7
see also diesel fuel biomass for 164–6
gel phase 353 principles 334
gelatinization 240, 242 starch-related 247–56
genetic modification 24 principles of 7, 8
cotton 381 green diesel see biodiesel; biofuels;
organisms 136 synthetic biofuels
rapeseed 197 green gas see biomethane
soya bean 184–5 green solvents 220, 407–23
Gingko biloba 317 commercially available 411
Subject Index 487
green strength 361 hotmelts 431
greenhouse gases 37–8, 342 HTU diesel 145
agriculture 56 hubs, logistic 40, 50
from cattle 80 human milk fat replacers 465–6
transportation 41, 50 humectant 248
see also carbon dioxide emissions hunger 69, 70
Grenelle Environment meeting (2007) 41 hybrid products 45
gross calorific value 92 hydrochloric acid scavengers 33
groundnut oil 200 hydrodeoxygenation step 145
groundwaters 81–2 hydroformylation 224
GSP gasifier 154 hydrogen, from biomass gasification 144
gypsum boards 257 hydrogen bridges, cellulose 308, 309,
372–3
hardening 219 hydrogen peroxide 389
hardwoods 306, 307, 308 hydrogenated castor oil 211
extractives contents 314 hydrogenation 177–8, 180, 219, 223,
lignin in 311 275, 285
polyoses in 310 hydrolysate 244, 249
hay 75 hydrolysis
hazard, control of 410 cellulose 132, 133
health hazards 419 starch 243–4
categories 409 hydrophilic extractives 314
SOLVSAFE 413–15 hydrophilization 191
HEAR (high erucic acid rape seed) hydroxyethyl starches 247
197, 198 7-hydroxymatairesinol 317–18
heartwood 314 5-(hydroxymethyl)furfural 272–5
heat build-up 360
heat production, from biomass 89, 90, immobilized cells 283–4
113–14, 120 import, biomass 117
heating and drying 95, 96 impregnation modification 330–1
α-helices 376, 377 indigenous communities 172, 188, 205
hemicellulose 95, 130, 132, 307, 308, industrial binders 240, 256–7
309–10 industrial biotechnology see white
hemp 381–3 biotechnology
HERA project 62 industrial cleaning applications 225–6
herbaceous residues 93, 94 inerts 220, 228
herbicides 184–5, 266 infectious diseases 56–7, 58
Hevea brasiliensis see rubber tree infiltrating 389–91
hexane 175 inorganic chemicals 59, 306, 318–19
High Environment Quality method 46–7 in natural rubber 355, 359
high fructose corn syrup 246–7 inositols 357–8
high oleic sunflower oil 199, 200 insect fibres 374–5
higher heating value 92 insecticides see pesticides
horse chestnut 318 intensive farming 74–5
hot gas cleaning 106, 151 intercompany collaboration 44–5
hot rotating wheel 103 intermediate filaments 376, 378
488 Subject Index
internal lubrication 219 levan 281, 286–7, 288
internal optimization 44 levansucrase 288
inulin 281, 286–8 levulinic acid 274–5
invert sugar 270, 280 LHV see lower heating value
investments 12–13 life-cycle, washing process 57–62
see also socially responsible life-cycle assessment 26–8, 335
investment curing systems 30
ion exchange process 280 washing process 57–8, 60
ionic liquids 33–4 life-cycle impact assessment 26
iron catalysts 149–50 life-cycle interpretation 26
ISO 14000 standards 26, 27, 46 life-cycle inventory 26
isomalt 282, 285–6 lignan 207, 317
isomaltulose 280–6 lignin 130, 132, 307, 308, 311–13
isopentenyl diphosphate 347–50 basic units of 312
isosorbide 260 in pulping 319–20
lignocellulosic feedstock 129, 130–2, 142
Jatropha oil 211–12 Limits to Growth (Club of Rome) 3
jet fuels 141–2 Linium usitatissimum 381
‘Jockey’ 78, 79, 80 Linola™ 207
jojoba oil 181 linoleic acid 198–9, 200, 203, 208, 209
Just-in-Time 40 linseed 75, 78–80
linseed oil 206–7
Karlsruhe Institute of Technology 156–7 linters 381, 382
keratin 374–7, 383, 458 lipases 463, 465, 466
key performance indicators 13, 14 lipids 76–80
Klebsiella pneumoniae 447, 448 biofuels based on 137–42, 143
knotwood extractives 317–18 biotechnology 462–6
Kraft pulping 312, 319–20, 321, 322 designer lipids 464–6
Kyoto Protocol 37 jet fuels based on 141–2
in natural rubber 355, 358–9
lactic acid 443, 466–7 sphingolipids 449–57
see also polylactic acid see also fats; fatty acids; oils
lactide 471 Lipofructyl™ 403
lamellae 380 lipophilic extractives 314, 316
lamellar structures 450, 452–3 liquefied petrol gas 147
land area, biomass 116 localization, rubber biosynthesis 351
landfill gas 110 logistic agility 45–6
latex yield 344–5, 346 logistic efficiency 43–5
laticifer vessels 344, 345 logistic reliability 42–3
laurics 182, 192, 193 logistics 37–51
lead-times, reduction 45 current situation 40–1
lecithin 175 definition and role 38–40
legislation detergent life-cycle 61
hazardous chemicals 410 employment in 47
pension funds 20 four drivers 41–8
see also European Union sustainable 48–50
Leuconostoc mesenteroides 289 see also transportation
Subject Index 489
LOHAS (Lifestyle Of Health And methyl isobutyl ketone 417–18
Sustainability) 54–5, 397 methyl soyate 187
low-density lipoprotein-cholesterol 180 metrics, sustainability 25–35
lower heating value 90–2 mevalonic acid 347–9
ethanol 109, 110 microalgae 157, 182, 212–13
lubricants 218–21 microbial fermentation 458–9
lumen 380 microbial lipids 464
lutoid particles 356 micro-credit instrument 69
lysine 440, 442, 443 micro-emulsions 421
microfibrils 308, 372, 373, 376, 377, 379
macroalgae 212 microgel 353, 354–5
macrofibrils 308, 373, 377, 379 microorganisms see bacteria;
macrogel 353, 354 Escherichia coli; Pichia ciferrii;
macrostructure, rubber 351, 352 Saccharomyces cerevisiae
maize oil 200–1 microstructure, rubber 351, 352
maltodextrins 243–4, 246, 247, 261 MILENA gasifier 155
maltotriose 248
milk 178
mannans 310
chemical composition 182
manually fed combustion technologies 99
human milk fat replacers 465–6
Marco Polo programme 48–9
procurement 71–4
margarine production 466
quotas 171
mass customization 45
Mater-bi® 250 milk production, cattle feed for 74–80
mechanical extraction 175 modified solid wood products 329–34
mechanical pulping 319–20, 321, 322 modified starches 242–3, 261
mechanically processed biofuels 89 MOGD process 148
medicines see pharmaceuticals molar mass distribution 353
Mediterranean diet 71, 205 molasses 269, 270
medium-chain fatty acids 194 molecular sieves 135
melt process 278 monomers 442–7, 451
mercaptodextran 290 Mortierella alpina 464
mercerization 373, 374, 389 mother liquor 268–9
mesostructure, rubber 352–5 MTG process 147–9
metabolic engineering 460–2 MTS process 148–9
metabolites best 62 mulesing 383–4
metal degreasing 418–19 multi-modal transport 46, 48–9
methacrylic acid 272, 273 MVA pathway 347–9
methane 56, 80, 97
in biogas 111 natural fibres 368–9
via anaerobic digestion 142 classification 370
see also biomethane processing 385–91
methanol sourcing 380–5
contamination levels tolerated 151 structure 371–80
from syngas 146–7, 148 sustainable 369–71
methionine 442 natural gas grid 114–15, 142
methyl esters 193, 218, 219, 221, 223 nature 2–3
see also fatty acid methyl ester Neo-amylose™ 281, 288–9
490 Subject Index

net calorific value 90–2 polyols 214, 215

nettle cloth 368 utilization 8
neutral lipids 358–9 value chain 218, 220
neutral oil 177 see also biodiesel; fats; fatty acids; oils
NExBTL 141 Olestra 200
NF X 50-600 standard 38 oligofructose 287
non-ionic surfactants 388 olive oil 205–6, 209
non-isoprene components, natural omega-3 fatty acids 76–80, 182, 207,
rubber 355–9 208, 213
non-timber-forest-products 301–2 omega-6 fatty acids 76–80, 213
norm-based screening 18 organic chemicals 59–60
novaluron 421 organic solvents 408
NuLin™ 207 safer functional 411–16, 420, 421
NuSun 199–200 organosolv pulping 320
nut oils 209 Our Common Future (Brundtland
nutrition 68–85 Commission) 4, 5
definition 70–1 oven, wood chips 100–1
see also food over-fishing 179
oxidation 96–8
‘Observatory’ 84 oxidative bleaching 320
occupational exposure 414, 415 oxidized starches 242–3
octane index 136 Oxo-process 224
oil extraction 175
oil palm see palm oil packaging materials 250–1, 468
oil seeds 167 recycling 46, 80–1
global production 169, 170, 171 paints 419–20
global trade 174 Palatinose™ 282–6
production 174–5 palm-kernel oil
oils composition and uses 192–3
biopolymers precursors 214–16 production 189–92
carrier oils 218–21 palm oil 59, 60–1, 172, 187–93
chemical composition 179–213 composition and uses 192
essential oils 182, 224 production 189–92
fatty acid compositions 183 sustainable cultivation 61, 188–9
processing 217 palm olein 191, 193
production, use and trade 168–74 palm stearin 191, 193
for synthetic biofuels 140–1 palmitic acid 78
value chain 213–28 pancreatic lipase 465, 466
see also vegetable oils paper grade pulp 323
oilseed rape see rapeseed oil papermaking 258–9, 319–25
oleic acid 216 pasture 75
oleics 182, 203 peanut oil 200, 201
oleochemicals pellet combustor 99–100
chemical composition 180 pension funds 20
fatty acids as 216–18 People for the Ethical Treatment of
global consumption 170 Animals 384
Subject Index 491
per capita consumption, raw materials 55 plasticizers 214, 220, 251, 260
persistant organic pollutants 410 plastics
pesticides 220, 228, 381, 383, 420–1 biodegradable 249–51
see also herbicides wood-plastic-composites 326–8
petrochemicals 164–5, 369–70, 428–9 platform molecules 412–13
see also crude oil; fossil fuels; PLATO process 332–3
petroleum oil plugging index 346
petroleum diesel see diesel fuel pollution see environment impacts;
petroleum oil 8, 173 health hazards
Phakopsora pachyrhizi 185 polyamides 443
pharmaceuticals 205, 208, 210, 213 poly(cis-1,4-isoprene) 347–51, 352
from dextran 290 polydimethylsiloxane 388
formulations 247 polyether polyols 254, 255
green solvents in 417 polyethylene 272
plant-based 396, 397 polyethyleneterephthalate 260
from starches 240, 247–8, 260 polyhydric alcohols 275–6
using white biotechnology 438, 442 polyisoprenoids 347–9
from wood extractives 317–18 polylactic acid 443, 466–72
see also antibiotics market potential 469–70
phosphatides 175, 177 non-depleting properties 467–9
phospholipids 358 process routes 470–1
photosynthesis 127, 305, 343–4 processing 471
phthalates 260 properties 471–2
physical refining 177 polylactic fibres 369
physico-chemical conversion, biomass polymers
90, 107–9 biodegradable plastics 249–51
phytase 437–8 carbon dioxide emissions 470
phytochemicals 71, 396, 403 fossil fuel consumption 469
phytoplankton 212–13 packaging and acreage in
phytosphingosine 453–4, 455 consumption 468
Pichia ciferrii 453–7 see also biopolymers
pigment printing 390 polymorphs, cellulose 373–4
Pimozide 417 polyoses see hemicellulose
plant fibres 368, 372–4 polysorbates 253–4
sourcing 380–3 polyunsaturated fatty acids 206–9, 213
plant inulin 287 microbial oils 464
plants polyurethane foams 214, 215, 254, 279
bioethanol production 127–8 polyurethanes 210–11, 278–9
carbon and water in 343 polyvinyl chloride 272
for cosmetics 394–405 postponement 45
essential oils 182 pot marigold 208
feed from 440, 442 potatoes 239
see also forests; phytochemicals; poverty, and hunger 69, 70
wood power, from biomass 89, 114, 120
plasma expanders 247, 289 practice-based criteria, exclusion 18
plasterboards 257 pre-treatment, cellulose 130, 131, 132
492 Subject Index

predicted environmental quality management

concentration 62 adhesives and sealants 432, 433
predicted no-effect concentration 62 Evian water 84
prenyltransferases 349–50 high environment quality method
pressure sensitive adhesives 426 46–7
prices milk 72
crude oil 174, 249, 261 olive oil 206
energy market 118 Total Quality Management 44
food 60 quebrachitol 357–8
fossil fuels and renewable carbon
450, 451 radiation curing 431, 432
increased biomass use 116, 117, 118, rainforests see forests
120, 121 rapeseed methyl ester 139–40
natural rubber 342 rapeseed oil 171, 195–8
sugar 264, 265 ‘00-rape’ 197, 198
primary extractives 314, 316 selected properties 108
principal component statistical raw materials 59–61
analysis 413, 414 bioethanol production 127–8
Principles for Responsible Investment developmental megatrends 55, 58
21 plant-based 396–7, 398–9
printing inks 220, 221 price increases 116, 117, 118
probiotics 71 production 55
processed foods 246 for synthetic biofuels 140–1
producer gas 98, 104, 106–7 see also feedstock; renewable
product-specific requirement 26 resources; individual raw
Project Village Farm 72 materials
1,3-propanediol 444–7, 448 raw sugar 270
1,2-propylene glycol 275–6 REACH standard 342
Protaminobacter rubrum 283, 284 reactivity 45
protein–fatty acid condensates 224, recharge area 84
225 rectification 135–6
proteins Rectisol process 151
fibres 374–80 recycling 426
in natural rubber 355, 357 bioethanol production 136
small rubber particle 350, 357 packaging 46, 80–1
in soya beans 185–7 polylactic acid 468
see also amino acids; enzymes wood-plastic-composites 328
protoporphyrinogen oxidase 421, 422 red palm oil 193
pulp oils 167, 169, 174 reductive bleaching 320
pulping 312, 314, 319–25 refining 175–7
global production 322, 324 reforestation 404
trade flow 323 regenerated cellulose fibres 324
pure plant oils 139 regeneration 373, 374
pyrolysis 97–8, 102–4 Reichskraftstoff 127
decomposition 95–6 reliability, logistic 42–3
pyrolysis oil 103–4, 145 rendering 178–9
Subject Index 493
RENEW project 155 rubber tree 340, 341
renewable mass index 414–15, 417, 419 photosynthesis and water in 343–4
renewable resources tapping, latex yield and carbon
in adhesives and sealants 432–3 budget 344–5
consumption 165 tapping and water budget 345–6
energy 86, 88 Rubisco 344
fibres 369, 370 RuBP 344
historical depletion 4
renaissance of 7–9 saccharides 286
sucrose 264–5 saccharification 130, 132
wood 304 Saccharomyces cerevisiae 127–8,
yielding chemical intermediates 166 132–4, 136, 280
see also biomass; feedstock; recycling in biopolymer production 447, 448
resins, formaldehyde-based 251 sphingolipids in 449
response surface methodology 282 safer organic solvents 411–16, 420, 421
Responsible Care® 6–7 safety
food 70
Responsible Care Global Charter 6
see also Environmental Health and
responsible investment see socially
Safety Guidelines; health hazards
responsible investment
safflower oil 204
retrogradation 241, 243
sanforizing 389
retting 382
sanitary defence perimeter 84
reverse logistics 46 saponification 217
rewetting 191 sapwood 314
rice bran oil 202 saturated fatty acids 76, 80, 140, 209
ricin 209 saw mill industry 326
ricinoleic acid 216 ‘schmoo’ 226
Ricinus communis agglutinin 209–10 scouring 384, 388
ring opening polymerization 470–1 scutching 382
Rio Earth Summit (1992) 5–6, 397, 398 sealants 425–34
risk management 84 seaweed 212
Roundtable on Sustainable Palm Oil second-generation biofuels 142, 144–57
61, 188–9 secondary extractives 314, 316
Roundup Ready® soya beans 184 SEEBALANCE 35
rubber, natural 339–40 seed oils see oil seeds
see also rubber tree; synthetic rubber semi-chemical pulping 319, 322
non-isoprene components 355–9 Sephadex® 290
poly(cis-1,4-isoprene) biosynthesis sericin 376, 379–80
347–51 L-serine 459–60, 461
prices 342 serum 356
production 341 sesame oil 202–4
specific properties 359–61 shareholder advocacy 19
structure 351–5 shea butter 204–5
supply chain 340–2 sheep 383–4
rubber clonal typology 345 Shikimate biosynthesis 311
rubber cream 356 short-chain fatty acids 194
rubber elongation factor 350, 357 silk 374–5, 376, 379–80, 384–5
494 Subject Index
simultanaeous saccharification and speciality chemicals 439–42
fermentation 132 speciality solvents 411
Single-Minute Exchange of Die 45 sperm oil 168, 181
sizing 258 sphinganine 455, 456
skin barrier functions 450, 452–3 sphingolipids 449–57
skin care active ingredients 395 sphingosine 456–7
slenderness ratio 326 Splenda® 276
small and medium enterprises 408 splitting 220
logistics 40, 41, 48, 50 fats 217, 219
small rubber particle protein 350, 357 stabilizing, fabrics 389
smallholders 188, 204, 340, 341 stakeholders 397, 405
soaps, manufacture 217 logistics reliability 43
socially responsible investment 15–19 natural rubber 340, 341
best-in-class 18 palm oil 189
engagement 19 standards
exclusion 17–18 biodiesel 138
mainstreaming of 19–22 environmental management 26, 27, 46
principles for 21 logistics 38
softwoods 306, 307, 308 REACH standard 342
extractives contents 314 starch
lignin in 311, 313 in bioethanol production 128, 129, 130
polyoses in 310 food applications 240, 241, 245–7
solar energy 88 industrial binder applications 240,
Sollbruchstelle 215 256–7
solvent-based adhesives 430, 431 markets 238–9, 240, 241
solvents modified 242–3, 261
environment impacts 409 outlook for 259–62
environmental health and safety 410 paper and board applications 240,
extraction 175 257–9
fractionation 191 pharmaceutical and chemical
green solvents 220, 407–23 applications 240, 247–56, 260
history 407–8 product family tree 261
safer organic 411–16, 420, 421 refinery products 243–5
SOLVSAFE 411–16 structure and properties 239–42
industrial applications 416–22 steam explosion 132
soot 87 storage organs, plant 127–8
sorbitan esters 253–4 strain-induced crystallization 360
sorbitol 244–5, 248, 252, 253–5, 260 stratum corneum 450, 452
Sorona® 444–6 structural adhesives 427, 432
soya bean 172, 175, 184–5 substitution, biomass 117
composition and uses 185–7 sucralose 276–7
soya bean oil 184–7 sucrose 127–8, 133, 264–5
soya polyols 187 chemistry 270–90
space heating 87 outlook 290–1
Span® 253 production 266–70
SPC model, Sustainability Master® in the rubber tree 344–5, 357
63, 64 see also sugar
Subject Index 495
sucrose acetate isobutyrate 278 four dimensions 398
sucrose derivates green solvents 407–23
degradation of framework 271, 272–6 history of 1–9
maintaining carbohydrate structure metrics 25–35
271, 279–90 palm oil cultivation 188–9
maintaining sucrose skeleton 271, Sustainability Master® 63, 64
276–9 sustainability profiles, detergents 62–5
sucrose esters 277–8 sustainability zone 63
sucrose isomerases 280, 282 sustainable chemistry see green
sucrose polyesters 278 chemistry
sugar 109 sustainable development, logistics
bioethanol production 128, 129, 133 and 48–50
as carbon feedstock 450, 451 SVZ gasifiers 154
invert sugar 270, 280 sweeteners 283, 286
prices 264, 265 syngas 106, 144
replacer 282, 285–6 based biofuels 145–57
see also sucrose based products 146–50
sugar beet/cane 264, 265, 266 current developments 154–7
sugar manufacture from 267–70 generation 150–4
sulphite pulping 311, 312, 314, 319–22 synthetic biofuels 115, 120
sunflower oil 171, 198–200 fats and oils as raw material 140–1
supercritical gases 411 flow diagram 143
supply chain 38–9, 51 property comparisons 141
eco-logistics 47 see also biofuels
efficiency 44–5 synthetic natural gas 114–15, 120, 144
natural rubber 340–2 synthetic rubber 217, 341, 360
problems with 40 syrup 268–9
reliability 43
sustainable logistics 49–50 tack 361
Supply Chain Event Management 43 tall oil 180, 181, 217
Supply Chain Management 39, 50 ‘tank mix’ 420
Supply Chain Wheel 47–8 tanning industry 437
supramolecular structure, rubber 352 tapping 344–6
surfactants 59–60, 62, 63–4, 193, 384 Targanine network 401–4, 405
from fatty alcohols 222 technical biomass potential 93–5, 113–15
in fibre processing 386–8 temperature
fossil vs renewable base stock 223 anaerobic digestion 110, 112
green 224–8, 252–3 Fischer–Tropsch process 149–50
from sucrose 290–1 heat build-up 360
sustainability 302, 369 and photosynthesis 343–4
adhesives and sealants 425–34 tetraacetyl phytosphingosine 453–4
Argan tree products 399–404, 405 textile manufacturing 369
concept 397–8 textile softeners 386–8
fibres 369–71 thermal energy, conversion 98
finance 12–23 thermal modification, wood 331–4
in food and nutrition 69–84 thermal properties, polylactic acid 471–2
496 Subject Index

thermo-chemical conversion UN Conference on Environment and

biomass 89–90, 95–107 Development (1992) 5–6
biomethane 114, 115 UN Stockholm Conference on the
wood 95, 96 Human Environment (1972) 3, 6
thermophilic clostridia 134 UN World Commission on Environment
thermoplastic starch 250, 261 and Development 4, 5
‘thick juice’ 268, 270 UNEP FI 16, 20
‘thin juice’ 268, 270 unsaponifiables 359
thinned starches 243 unsaturated fatty acids 76, 80, 209
third-generation biofuels 157–8 chemical composition 179–80
threonine 442 polyunsaturated 206, 207, 208, 209, 213
TIGAS process 148 use phase 61
timber 306 UV curing 29–30, 31, 34
TOE (tonnes of oil equivalent) 342
toothpaste 248 value chain, fats and oils 213–28
Total Quality Management 44 Värnamo demonstration plant 154–5
toxins, castor oil 209–10 varnishes 419–20
trace elements, in biomass 90 vegetable fats 177–8, 204–5
trans-fatty acids 179, 180, 182, 199 vegetable oils
transesterification 107, 108, 138–9, as biodiesel feedstock 138–40
217, 218, 219, 220 from biomass 90, 107
transpiration 343 in cattle feed 76–80
transportation chemical composition 182–213
capacity utilization 40 classification 167
drawbacks to 37, 50 global production 169
eco-logistics 46 major uses 167–8
forecast rates 37, 49 polymer building blocks 216
greenhouse gas emissions 41 production 174–8
sustainable logistics 48–9 raw materials 59–61
see also logistics as transportation fuels 137–8
transportation fuels uncertain market 115
bioethanol as 136 see also oils; individual vegetable oils
jet fuels 141–2 Vendor-Managed Inventory 44
vegetable oils as 137–8 vernonia oil 181
see also bioethanol; biofuels; diesel viscosity, starch 241, 243
fuel; synthetic biofuels vitamin B2 production 30–3
trees see forests; wood vitamin C 251–2
trehalulose 282–6 volatile organic chemicals 226, 317,
triacylglycerols 462 389, 414, 415, 419, 420
trichloroethylene 418, 419 vulcanization 361
triglycerides 179, 466
tung oil 208 walnut oil 209
Tween® 253 washed bottom fraction particles 350
tyres 341, 360 washing process, life-cycle 57–62
washing temperature 61
ultimate supply chain 39 waste paper 321
Subject Index 497
water wood
budget 345–6 chemical composition 307
degumming 175 chemistry 306–19
in plants 343 coalification 102
retting 382 commercial species 306, 308
in the rubber tree 343–4 increasing demand 116
stress 344 lower heating value 92
water-based adhesives 430, 431 modification 329–34
water-based emulsion 226–7 from resources to products 303–6
water resources sustainability, perspectives 302
developmental megatrends 56–7, 58 thermo-chemical conversion 95, 96
Evian mineral water 80–4 uses 301
water use efficiency 343 see also forests
waxes, natural 182 wood-based composites 325–9
wet adhesives 429 wood chips, oven 100–1
wet-end 258 wood gas 126
wet gas cleaning 106, 151 wood pellet combustor 99–100
wet-milling 130, 201 wood-plastic-composites 326–8
whaling, banning of 168 wood residues 93, 94, 304
white biotechnology 165, 436–7 wool 370, 371, 374–5, 376, 383–4, 385
L-cysteine 457–62 wool fabric 389, 390
drivers 447–9
lipids 462–6 xylans 310
market segments 437–47 xylose 310
outlook 472–3
plant announcements 451 yarns 388
polylactic acid 466–72 yeast see Pichia ciferrii;
sphingolipids 449–57 Saccharomyces cerevisiae
vitamin B2 production 31–2
see also enzymes; fermentation zeolite ZSM-5 catalyst 147, 148
Who Cares Wins initiative 20–1 zero-waste operations 128, 168, 192
whole-cell systems 437 Ziegler technology 224
winterization 191 Zymomonas mobilis 134–5