Accepted Manuscript

Review

A review on lignin structure, pretreatments, fermentation reactions and biore-

finery potential

Vinoth Kumar Ponnusamy, Dinh Duc Nguyen, Jeyaprakash Dharmaraja, Sutha

Shobana, Rajesh Banu, Rijuta Ganesh Saratale, Soon Woong Chang,
Gopalakrishnan Kumar

PII: S0960-8524(18)31323-3
DOI: https://doi.org/10.1016/j.biortech.2018.09.070
Reference: BITE 20486

To appear in: Bioresource Technology

Received Date: 20 August 2018

Revised Date: 11 September 2018
Accepted Date: 13 September 2018

Please cite this article as: Ponnusamy, V.K., Nguyen, D.D., Dharmaraja, J., Shobana, S., Banu, R., Saratale, R.G.,
Chang, S.W., Kumar, G., A review on lignin structure, pretreatments, fermentation reactions and biorefinery
potential, Bioresource Technology (2018), doi: https://doi.org/10.1016/j.biortech.2018.09.070

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A review on lignin structure, pretreatments, fermentation reactions and
biorefinery potential

Vinoth Kumar Ponnusamy1,2#, Dinh Duc Nguyen3#, Jeyaprakash Dharmaraja4, Sutha

Shobana5, Rajesh Banu6, Rijuta Ganesh Saratale7, Soon Woong Chang3, Gopalakrishnan
Kumar8*

1
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University,
Kaohsiung City, Taiwan
2
Research Center for Environmental Medicine, Kaohsiung Medical University, Kaohsiung
City, Taiwan
3
Department of Environmental Energy Engineering, Kyonggi University, Suwon, Republic of
Korea
4
Division of Chemistry, Faculty of Science and Humanities, Sree Sowdambika College of
Engineering, Aruppukottai, Tamil Nadu, India
5
Department of Chemistry and Research Centre, Aditanar College of Arts and science,
Virapandianpatnam, Tiruchendur, Tamil Nadu, India
6
Department of Civil Engineering, Regional Campus Anna University Tirunelveli,
Tamilnadu, India.
7
Research Institute of Biotechnology and Medical Converged Science, Dongguk University–
Seoul, Ilsandong–gu, Goyang–si, Gyeonggi–do 10326, Republic of Korea
8
Green Processing, Bioremediation and Alternative Energies Research Group, Faculty of
Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

# Authors have equal contribution to this work

* Corresponding author:
Dr. Gopalakrishnan Kumar, Green Processing, Bioremediation and Alternative Energies
Research Group, Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho
Chi Minh City, Vietnam. Email: [email protected]

1
Contents
Abstract ...................................................................................................................................... 3

1. Introduction ........................................................................................................................ 4

1.1. Green biomass processing .............................................................................................. 5

1.2. Lignin valorization .......................................................................................................... 6

2. Structural characteristics of lignin ......................................................................................... 9

2.1. Lignin derivatives and chemistry .................................................................................. 12

2.2. Possible mechanism for lignin degradation ................................................................. 13

3. Pretreatments for lignin separation and degradation ........................................................... 14

3.1. Biological pretreatment ................................................................................................ 15

3.2. Physical pretreatment ................................................................................................... 16

3.3. Chemical pretreatment.................................................................................................. 17

3.4. Hybrid pretreatment...................................................................................................... 18

4. Detrimental reactions in depolymerization of lignin ........................................................... 19

5. Liquid and gaseous biofuel production ................................................................................ 20

6. Biorefinery scheme .............................................................................................................. 21

6.1. High value–added chemicals production...................................................................... 22

6.1.1. Macromolecular products .................................................................................. 22

6.1.2. Aromatic compounds ......................................................................................... 25

6.2. Biochar and other valuable products ........................................................................... 27

7. Perspectives and Recommendations–Biorefinery scheme................................................... 27

8. Conclusions .......................................................................................................................... 31

Acknowledgements .................................................................................................................. 32

References ................................................................................................................................ 32

2
Abstract

In recent years, lignin valorization is commercially an important and advanced

sustainable process for lignocellulosic biomass-based industries, primarily through the

depolymerization path. The conversion of the lignin moieties into biofuels and other high

value-added products are still challenging to the researchers due to the heterogeneity and

complex structure of lignin-containing biomass. Besides, the involvement of different

microorganisms that carries varying metabolic and enzymatic complex systems towards

degradation and conversion of the lignin moieties also discussed. These microorganisms are

frequently short of the traits which are obligatory for the industrial application to achieve

maximum yields and productivity. This review mainly focuses on the current progress and

developments in the pretreatment routes for enhancing lignin degradation and also assesses

the liquid and gaseous biofuel production by fermentation, gasification and hybrid

technologies along with the biorefinery schemes which involves the synthesis of high value-

added chemicals, biochar and other valuable products.

Keywords: Lignocellulosic biomass; lignin; biorefinery; biofuel; hybrid–conversion;

sustainability

3
1. Introduction

Plant cell walls are composed of lignin which is a phenylpropanoid biopolymer, giving

mechanical strength to the plant structure. Cellulose and hemicellulose make up the entire

biomass and are firmly connected to the lignin molecules via covalent and hydrogenic

linkages which make the structure extremely strong and recalcitrant to pretreatment

techniques. Lignocellulosic biomass is primarily comprised of cellulose (38–50%),

hemicellulose (23–32%) and lignin (12–25%) components (Sun and Cheng 2002; Gonzalo et

al., 2016). The lignin component is familiar as the second greatest inexhaustible natural

organic polymer which conveys the greatest energetic substance of all the above, empowers

plants to build rigid chemical structures and also provides a probability against hydrolysis of

cellulose and hemicellulose in the lignocellulosic biomass (Saake et al., 2012; Zakzeski et al.,

2010). Accordingly, certain novel course of reactions are desirable to produce high value–

added products from the lignin moieties (Kleinert and Barth 2008). At present, the most

integrated bio–based refinery techniques comprise four key divisions that include the

harvesting and storage of the feedstock, pretreatment, enzymatic hydrolysis and fermentation

process of the released sugar to biofuels (Dale and Ong 2012). Moreover, lignin is the only

large–volume renewable feedstock that is comprised of an enormous number of aromatic

monomers (Tuck et al., 2012). The U.S. Energy Security and Independence Act of 2007

authorization announced that by 2022 the development of 79 billion liters of second–

generation biofuels wouldbe produced annually. Even if specific basic research has been

focused on the conversion of lignin to the platform chemicals, materials and fuels, the efforts

for commercialization are based on the bioengineering of lignin to easerecovery and

conversion. Moreover, advances in coupling the analytical chemistry, computational

designing and modelling dimensions of genetic engineering for lignin pretreatment have

rendered the lignin depolymerization and conversion easier (Ragauskas et al., 2014). It has

4
also been well demonstrated that lignin is more applicable trait than the other existing ones of

biomass and is attributed to the aromaticity and side chains on the carbon backbone (Dale and

Ong 2012). In a nutshell, the ease of extraction for lignin via a reduction in the cross–linkages

with the other polymers in the biomass and the depolymerization pathways of the inherently

complex lignin structure are two main process considerations which determine the

significance and value of lignin biorefineries.

1.1. Green biomass processing

Lignin is a heterogeneous biopolymer and consists of phenylpropanoid moieties via the

conjugation of a vast number of aromatic monomers with different bonds derived from three

mono lignols (p–coumaryl, coniferyl and sinapyl alcohols) (Pandey and Kim 2011).

Softwood lignin mainly comprises coniferyl alcohol, hardwood lignin contains both coniferyl

and sinapyl alcohols and grass lignin contains all the above three moieties (Duval and

Lawoko 2014). Lignin has a high recalcitrance to chemical and biochemical

depolymerization due to the existence of phenylpropanoid polymers, ether linkages (β–O–4)

(Azadi et al., 2013; Pandey and Kim 2011) and a range of functional groups namely methoxy,

aliphatic and aromatic hydroxy, benzyl alcohol, ether and non–cyclic benzyl ether and

carbonyls (Pandey and Kim 2011).Various green biomass processing procedures have been

adopted for the isolation of lignin from lignocellulosic biomass and these procedures can

generally be categorized according to the isolation mechanisms. One category targets

hydrolyzation/solubilization of cellulose and hemicellulose except for lignin residue. Another

one is based on the dissolution of lignin residue (Azadi et al., 2013; Pandey and Kim 2011).

The isolated lignin is observed with different structural modifications like the isolation of

organo-solv lignin (EOL) and is comparatively pure when the hydrolyzation/solubilization

procedure is followed and its interior structures also remain unchanged despite that its

5
formula weight is decreased because of partial cleavage of β–aryl ether linkages (Bauer et al.,

2012).The ethereal linkages get cleaved in the degradation paths whilst new bonds are formed

by way of condensation in the case of kraft lignin from the second category (Chakar and

Ragauskas 2004).Such structural changes can be considered as the most significant barriers

for the prolificutilization of lignin (Bugg and Rahmanpour 2015). Moreover, the biorefineries

together with the pulp and paper industries produce a large quantity of lignin

Moreover, the fungi and bacteriae significantly occupy vital role in the metabolic systems for

the destruction of lignin during biomass processing. However, such lignin deconstruction

processes often constitute barriers for industrial applications where high yields and high

lignin utilization efficiencies are sought (McLeod et al., 2006; Nelson et al., 2002). As a

result, research in this direction had led to the isolation of many enzymes which mediate

lignin degradation with acceptably good yields and conversion efficiencies.

Characteristically, kraft and organo-solv lignins are the two appropriate candidates for

industrial applications for converting lignin to value–added chemicals whereas ligno–

sulphonates yield low–value chemicals which necessitate complex processing. Since kraft

lignin envelops a range of applications which include high value–added platform chemicals

and products prodcution starting from the woody biomass by neans of pulping and paper

production processes., it is consequently considered as a useful intermediate between ligno–

sulphonates and organosolv lignin for green biomass processing (Chen and Wan 2017).

1.2. Lignin valorization

Lignin has also been utilized in the synthesis of binding agents, dispersing or emulsifying

agents, sequestrant agents as well as a raw material for synthetic polymers such as phenol–

formaldehyde resin, epoxy resin, polyurethane resin and polyester (Lin 1983; Sen and Patil

2015). Lignin hence offers a remarkable platform for valorizing lignocellulosic biomass and

6
promoting the lignin–based biorefineries (Bhaskar and Pandey 2015; Hatakeyama and

Hatakeyama 2010; Holladay et al., 2007). Lignin can also be a potential source of various

aromatic compounds and chemicals (Table 1). However, chemically modified lignin can be

used as a reinforcing agent or filler for polymer blends and composite materials (Kai et al.,

2016). The syngas (CO + H2) products derived from lignin can be transformed into methanol,

dimethyl ether, ethanol, blended or mixed alcohols, Fischer–Tropsch–fluids and C1–C7 gases.

Lignin was oxidized under different oxidation conditions to produce vanillic acid, aliphatic

acids, aromatic acids, aromatic aldehydes, quinones, cyclohexanol, dimethyl sulphoxide and

–keto adipate (Bhaskar and Pandey 2015). The depolymerization of lignin has been assessed

through the oxidation pathway in the presence of alkaline medium using nitrobenzene or CuO

as mild oxidants to produce phenolic aldehydes like vanillin and syringaldehyde (Pandey and

Kim 2011; Ruoshui et al., 2018; Villar et al., 2001; Zakzeski et al., 2010). Lignin can also be

converted to certain high value–added products: aromatic hydrocarbons such as benzene,

phenol, substituted phenols or polyols, catechols, cresols, eugenol, resorcinols, syringols,

coniferols and guaiacols. In addition, lignin can also find an application in the production of

carbon fiber fillers, polymer extenders, substituted lignins, thermoset resins or gums,

composites, adhesives or glues, binders, additives or preservatives, pharmaceuticals bio–

compounds and some other polyols (Bhaskar and Pandey 2015; Jong et al., 2012). The

various existing linkages (ether, C–C and ester) patterns in lignin have been catalytically

depolymerized into various aromatic value–added monomeric units or compounds through

cracking, hydrolysis, dehydroxygenation, reduction and oxidation processes to produce

biofuels.

7
 Table 1: Lignin valorization for aromatics and bio–oils

Sl. No Lignin type Conditions Solvent used Catalyst Liquid products (%)
1 Klason birch lignin 200 oC, 15 h, 4 MPa H2 Methanol Pd / C 4–n–Propanolsyringol (35 %)
o
2 Oxidized birch lignin 200 C, 6 h, 1 MPa H2 Methanol Ni / MgAlO–C Mixed aromatics (22 %)
o
3 Diphenyl ether 120 C, 10 h, no H2 Isopropanol Ru / C Mixed aromatics (90–98 %)
4 Acetophenone 320 oC, 2 h, no H2 Ethanol FeNiB Ethylbenzene (64 %)
5 Alkali lignin 260 oC, 5 h, 4MPa H2 Methanol Pd / C + CrCl3 Monomeric phenols (28.5 %)
6 Enzymatic acidolysis 260 oC, 4 h, 3 MPa H2 Methanol MoOx / Carbon nanotube Monomeric phenols (47 %)
lignins
7 Lignin –O–4 models 42 oC, 4 h, Ar Acetonitrile ZnIn2S4 Monomeric phenols (71–91%)
8 Vanillin 100 oC, 2 h, 1 MPa H2 Water Pd / PRGO / Ce–MOF 2–Methoxy–4–methylphenols (10 %)
9 Poplar sawdust 200 oC, 3 h, 2 MPa H2 Methanol Pd / C – H3PO4 Monomeric phenols (45 %)
10 Klason Miscanthus lignin 180 oC, 6 h, 1 MPa H2 Methanol Co@Nb2O5@Fe3O4 C20–C28 and C29–C37 fragments (54 %)
11 2–Aryloxy–1– 80 oC, 12 h, 10 mol % EtOAc Pd / C Aryl ketones (98 %)
arylethanols NaBH4
12 Olive tree lignin 80 oC, 12 h, no H2 Tetralin Ni10 % Al – SBA Monomers, dimmers and trimmers (17 %)
13 Benzophenone 100 oC, 4 h, 2 MPa H2 Methanol [Pd(tpy)Cl]Cl Diphenylmethane (99 %)
14 Guaiacylglycerol – 100 oC, 24 h, no H2 DMSO Vanadium Schiff base Monomeric phenols (90 %)
guaiacyl ether catalyst
15 1,3 – dilignol 160 oC, 16 h, no H2 o – xylene [Ru(Cl)(H)(PPh3)3)3 Guaiacol (89 %)
16 Aryl ethers 80 – 100 oC, 2 – 10 h, m – xylene Ni(o) / ligand Mixed aromatics (> 80 %)
0.1 MPa H2
(Modified from source: Cao et al., 2018)

8
Furthermore, there are a number of commercially essential phenolic compounds which can be

efficiently derived from the degradation of lignin (Fachuang 2014). Using dehydroxygenation or

zeolite upgrading, lignin can be transformed to automobile or transportation fuels. For example,

studies have been conducted to investigate the hydrogenation of C=C bonds and deoxygenation

of C–O bonds under sulfide NiMo/CoMo catalysts on Al2O3 (alumina) or Cr as well as aromatic

moieties or zeolite at 250–450 oC to produce oil form of phenol, cyclohexane, benzene,

naphthalene and phenanthrene (Fachuang 2014; Oasmaa et al., 1993). Moreover, there is a vast

growing enthusiasm for developing a novel lignin–based derivative by the fact that lignin can be

an alternate substitute of aromatic compounds to fossil resources (Isikgor and Becer 2015).

In this regard, intensive research efforts have been continually deployed to explore the potential

routes for lignin valorization process. This article reviews the current developments in the

pretreatment routes for enhancing lignin degradation and then assesses liquid and gaseous

biofuel production by fermentation, gasification and hybrid technologies along with the

biorefinery scheme which involves the synthesis of highly value–added chemicals, biochar and

other valuable products.

2. Structural characteristics of lignin

Lignin is a complex, amorphous, three dimensional long–chain and heterogeneous high

molecular weight (6×105–15×106 kg kM–1) aromatic polymer of phenylpropanes of 3C attached

with 6C atom rings, methoxy groups and non–carbohydratic polyphenolic substances, which are

connected by ether linkages (Anwar et al., 2014). It is present approximately about 10–25% of

the biomass by weight in plant primary cell wall and makes up a rigid, impermeable and resistant

structure towards microbial attack and oxidative stress, and contains well–built cellulose

microfibrils because of a different variety of alkyl– / aryl–ether inter–unit linkages (Hu and

Ragauskas 2012). Generally, lignocellulosic biomass or its feedstocks mainly contain cellulose,

9
hemicellulose, lignin and a small amount of ash as well as extractives. The lignin content present

in different lignocellulosic biomass feedstocks is shown in Table 2.

Table 2: Lignin content in various lignocellulosic biomass feedstocks

Lignin
Lignocellulosic biomass References
(%)

Bagasse 24.8 Kim 2018

Barley hull 13.8–19.0 Isikgor and Becer 2015

Barley hull 19.3 Kim 2018

Barley straw 6.3–9.8 Isikgor and Becer 2015

Beech 20.0 Zhou et al., 2016

Birch 22.0 Zhou et al., 2016

Corn cobs 6.1–15.9 Isikgor and Becer 2015

Corn cobs 15.0 Bajpai 2016, Khalid et al., 2017

Corn fiber 8.4 Kim 2018

Corn pericarp 4.7 Kim 2018

Corn stalks 17.5 Zhou et al., 2016

Corn stalks 7.0–18.4 Isikgor and Becer 2015

Corn stover 19.9 Zhou et al., 2016

Corn stover 18.6 Kim 2018

Corn straw 11.0 Zhou et al., 2016

Corncob 20.8 Zhou et al., 2016

Douglas fir 27.0 Isikgor and Becer 2015

Eucalyptus 21.5 Isikgor and Becer 2015

Fir 18.0 Zhou et al., 2016

Grasses 10.0–30.0 Isikgor and Becer 2015, Bajpai 2016, Khalid et al.,
2017

10
Miscanthusgiganteus 12.02 Zhou et al., 2016

Newspaper 18.0–30.0 Khalid et al., 2017

Nut shells 30.0–40.0 Khalid et al., 2017

Oak 24.1 Isikgor and Becer 2015

Oat straw 10.0–15.0 Isikgor and Becer 2015

Olive tree pruning 16.2 Kim 2018

Paper 0.0–15.0 Khalid et al., 2017

Pine 27.3 Zhou et al., 2016

Pinewood 20.0 Isikgor and Becer 2015

Pinewood 27.7 Kim 2018

Pinewood 27.3 Zhou et al., 2016

Poplar 15.5–16.3 Isikgor and Becer 2015

Poplar 29.1 Kim 2018

Ray straw 9.9–24.0 Isikgor and Becer 2015

Red maple 29.1 Kim 2018

Rice husks 15.4–20.0 Isikgor and Becer 2015

Rice straw 17.0–19.0 Isikgor and Becer 2015

Rice straw 13.3 Kim 2018

Rice straw 12.2 Zhou et al., 2016

Solid cattle manure 2.7–5.7 Khalid et al., 2017

Sorghum straw 15.0–21.0 Isikgor and Becer 2015

Sorted refuse 20.0 Khalid et al., 2017

Spruce 28.3 Kim 2018

Spruce 27.9 Isikgor and Becer 2015

Spruce 28.2 Zhou et al., 2016

Sugar cane 10.7 Zhou et al., 2016

11
Sugarcane bagasse 15.0–25.0 Isikgor and Becer 2015

Sugarcane bagasse 11.4 Kim 2018

Sweet sorghum bagasse 14.3 Kim 2018

Switchgrass 15.0–20.0 Isikgor and Becer 2015

Switchgrass 12.0 Bajpai 2016, Khalid et al., 2017

Switchgrass 17.8 Kim 2018

Waste papers from 5.0–10.0 Khalid et al., 2017

chemical pulp

Wheat straw 12.0–16.0 Isikgor and Becer 2015

Wheat straw 15.0 Bajpai 2016, Khalid et al., 2017

Wheat straw 17.0 Kim 2018

Wheat straw 18.0 Zhou et al 2016

2.1. Lignin derivatives and chemistry

Lignin is an irregular and randomly cross–linked phenolic polymer which is composed of three

different primary phenylpropanes monomer or monolignol units of (i) p–coumaryl alcohol

(abbreviated as “H” unit; p–hydroxy phenyl propanol or 4–hydroxycinnamyl; grasses: 5 %); (ii)

coniferyl alcohol (abbreviated as “G” unit; guaiacyl propanol or 3–methoxy4–hydroxycinnamyl;

softwoods: 90–95%; hardwoods: 50% & grasses: 75%) and (iii) sinapyl alcohol (abbreviated as

“S” unit; syringyl alcohol or 3,5–dimethoxy 4–hydroxycinnamyl;softwoods: 5–10%; hardwoods:

50% & grasses: 25%) through a series of oxidation steps (Brunow 2004; Staley and Barlaz

2009). The monolignol unit has hydroxy (–OH) and methoxy(–OCH3) substituted

phenylpropane unit (Azadi et al., 2013; Boerjan et al., 2003; Weng et al., 2008) which are joined

through several dissimilar linkages to form the lignin structure. The basic distinction in the latter

three phenylpropane units are the number of methoxy (–OCH3) groups appended to an aromatic

12
ring. Generally, softwood lignin has a rich (~ 90 %) content of guaiacyl or p–coniferyl alcohol

(G) unit with very low content of p–coumaryl alcohol (H) unit whereas hardwood lignin contains

a blend of guaiacyl (G) and syringyl (S) units and grass lignin contains a mixture of above the

three G, H and S units (Li et al., 2013; Zakzeski et al., 2010).

The phenylpropane building units or blocks of lignin distribution depend on the types of plant

biomass (Itoh et al., 2003; Suhara et al., 2012). Herbaceous plants like grasses (10–19%) have

the lowest lignin contents which have all the three phenylpropane units collectively together with

p–hydroxycinnamic acids (p–coumaric acid, ferulic acid and sinapic acid) (Hendriks et al., 2009;

Itoh et al., 2003) while softwoods (25–35%) and hardwoods (18–25%) have the highest lignin

content (Silverstein et al., 2007; Valaskova et al., 2007). The digestibility of biomass increases

by applying suitable pretreatment techniques (Vidal and Molinier 1988) which can assist the

deconstruction and depolymerization of the lignin structural composition. Lignin can be further

classified into three types namely Type–G (softwood lignin), Type–G–S (hardwood lignin) and

Type–H–G–S (grass lignin). However, these moieties can frame the lignin matrix through

different linkages (aryl– or alkyl–ether, ester and C–C) with various functional groups (–OH, –

OCH3, C=O, –C–OH, propyl moiety, etc) resulting in extremely convoluted lignin structures

(Wang et al., 2017).

2.2. Possible mechanism for lignin degradation

Lignin contains a different variety of alkyl– or aryl–ether inter–unit linkages (~ 60–70 %),

carbon–carbon (~ 25–35 %) and very low ester bonds (< 5% in herbaceous plants) which include

–O–4, –5, ––––– –O–4, –O––O––O–4–O–5–5–5 and 6–5

(Holtman et al, 2007; Zakzeski et al, 2010). Based on the literature, seven major linkages namely

–O–4–aryl ether (–O–4), –O–4–aryl ether (–O–4), –O–5–diaryl ether (–O–5), –5–

phenylcoumaran (–5), –5–biphenyl (5–5), –1–(1,2–diarylpropane) ( –1) and  – (resinol)

13
are present in the lignin molecules (Dorrestijn et al., 2000; Wang et al., 2017; Zhou et al., 2016).

The correct linkage structures in native lignin of biomass are not completely known. But aryl–

or alkyl–ether linkages (C–O–C of  –O–4,  –O–4 etc.) are more predominant than the ester

bonds or carbon–carbon bond linkages. Additionally, lignin can act as an adhesive medium,

among the dissimilar components of lignocellulosic biomass cell walls, consequently making it

water–insoluble (Fengel and Wegener 1984). The degradation path of the lignin moiety involves

hydrolysis followed by cleavage of aryl–/alkyl–ether, ester and C–C bonds, demethoxylation,

alkylation and condensation reactions (Barbier et al., 2012). The cleavage of Cα–Cβ bond is

easier as well as the cleavage of β–O–4 ether bond is superior to other bond cleavages (Ehara et

al; 2002; Wang et al., 2009). However, the aromatic phenyl rings remain unaltered or unaffected

and the biphenyl type moieties persist in their stability (Ehara et al., 2002). Under mild

conditions of very low temperature with a short period of reaction time, the phenolic monomeric

and dimeric compounds are derived from lignin, consequently a cleavage of the ether and C–C

bonds occur. At high temperatures (250–550 °C) and pressures (5–25 MPa), the lignin is

converted by way of demethoxylation and alkylation reaction pathways to produce many desired

compounds (Singh et al., 2015).

3. Pretreatments for lignin separation and degradation

Pretreatments are vital to modify biomass particle size, its structure and its chemical

composition. It is essential for reducing the recalcitrance of biomass to deconstruction. There are

a number of studies which support that pretreatments work by deconstructing the lignin structure

as well as subsequently expanding enzyme accessibility to cellulose in the biomass for an

effective separation from other bio components especially from hemicellulose and cellulose (Li

et al., 2013). As part of the pretreatment steps, hydrolysis of the carbohydrate part in the biomass

materials into monomeric sugars can be accomplished more quickly and with higher yield of

sugars. A perfect pretreatment strategy ought to endow a number of key advantages. The main

14
advantages are decrease in biomass particle size, quick enzymatic hydrolysis to enhance the

monosaccharide (glucose) yield to avoid the degradation of carbohydrate, a decrease in

enzymatic action inhibition and in the energy needs (Duque et al., 2016; Parveen et al., 2009). In

general, the saccharification of lignocellulosic biomass without pretreatment can yield fewer than

20% of aggregate sugars. However, after the pretreatment, the yield can ascend to 90% with

various pretreatment like biological, physical, chemical and physico–chemical methods. The

pretreatment methods are presumably the most energy–demanding activity in biomass

conversion for biofuels and synthesis of high value–added chemicals. Pretreatment of lignin

taking place in the biorefineries will probably be used for isolating all the fractions of

lignocellulosic biomass materials and obtain high purity unadulterated feedstocks. However, the

pretreated lignin in the pulp and paper industries is an appropriate candidate which may be

expected to support the lignin valorization process (Valaskova et al., 2007). Moreover, the

different lignin pretreatments utilize different, and at times harsh, conditions of temperature,

pressure, pH range and solvents.

3.1. Biological pretreatment

Currently, the biological pretreatment of lignocellulosic biomass materials has been received

more and more research attention by reason of its many favourable characteristics. The merits of

this process are the cost–effectiveness, eco–friendliness and high propensity in degrading plant

cell materials. A relatively wide variety of microorganisms are capable of degrading lignin by

way of enzymatic and/or chemical pathways and make the plant biomass more amenable to

saccharification via the polysaccharide sugar units (Valaskova et al., 2007). During biological

pretreatment, there are also a number of fungi which are capable of secreting enzymes that can

subsequently degrade the lignin, hemicellulose and polyphenols, present in the crude biomass.

White and soft–rot fungi have been associated in the degradation of lignocellulose materials.

15
However, white–rot fungi show remarkably more significant effects, when compared to the red–

rot fungi as they are employed to mediate some form of biological pretreatment of

lignocellulosic biomass (Agbor et al., 2011; Sun and Cheng 2002). Brown–rot fungi, on the other

hand, first attack the cellulose, while soft and white–rot fungi attack both lignin and cellulose

moieties through lignin deconstruction pathways mediated by enzymes such as lignin

peroxidases, manganese–dependent peroxidases, polyphenoloxidases and laccases which are

capable of degrading the lignin effectively (Agbor et al., 2011). Some of the selected white–rot

fungi such as Phanerochaete chrysosporium, Phlebia radiata, Dichmitus squalens, Rigidosporus

lignosus and Junguasepar abilima shows excellent delignification of wood and wheat straw. By

the latter, lignin depolymerization with the fungi species takes a very long time but it can be very

effective and selective (Hatakka 1994). Moreover, such fungal biomass depolymerization has

also been found to save approximately 15–20% of the electrical energy requirements needed for

the ethanolysis of beech wood with white–rot fungi (Itoh et al., 2003). Moreover, nearly fifty–

one white–rot basidiomycetes of Punctularia sp. are available. TUFC20056 and TUFC20057

have shown efficient and selective lignin degradation by way of the enzymatic hydrolysis of

bamboo culms for the production of bioethanol (Suhara et al., 2012).

3.2. Physical pretreatment

In general, the physical pretreatment methods include mechanical (e.g. grinding,

chipping, milling, knife milling and scissor cutting), microwave irradiation, low frequency

ultrasound irradiation, steam explosion and liquid hot water treatments. The mechanical

pretreatment methods lead to a reduction of particles size between 5 cm to few millimeters which

can further decrease the degree of crystallinity of cellulose and thereby an eventual increase in

the accessible surface area and pore size of the substrate. However, the microwave irradiation

pretreatment has been found particularly efficient in increasing the solubilization of lignin and

16
cellulose, available from lignocellulosic biomass. However, ultrasound and microwave

irradiation pretreatments have a number of demerits and these may be summarized in terms of

energy–insensitivity, production of possible inhibitory phenolic acids like byproducts, complex

operation procedures and strict monitoring of equipments – that all collectively limit their

commercial applications.

3.3. Chemical pretreatment

Using strong acids (HCl, H2SO4 and HNO3), alkalis (NaOH, KOH, Ca(OH)2, ammonia and

hydrazine), organic solvents (benzene, ether, cyclohexane, hexane, ethanol and methanol), ozone

(O3) and ionic liquids (ILs), the chemical pretreatment methods have been reported to bring

significant positive effects on the native structure of lignocellulosic biomass. Generally, the

strong acids are not favoured because they are more corrosive and may be cost–intensive.

Similarly, the alkaline pretreatment disturbs the lignin structure and breaks the linkages (such as

aryl–ether, ester and C–C bonds), amongst the lignin and the other sugars or carbohydrate

fragments from lignocellulosic biomass and thence making the starch in the heteromatrix more

open (Saratale and Oh 2015). This pretreatment method is an excellent approach with low–lignin

content biomass like agricultural residues. In the chemical pretreatment method, when cotton

stalks were autoclaved with 2% of sulfuric acid and hydrogen peroxide medium, a 25% and 30%

decrease in lignin content for 90 and 60 minutes at 121 oC/15 psi, respectively, were recorded

(Silverstein et al., 2007). The mnewspaper, pretreated with 35% acetic acid together with 2%

nitric acid (HNO3) resulted in the reduction of lignin by 80% (Vidal and Molinier 1988). Ozone

(O3) pretreatment is another way of reducing the lignin content of lignocellulosic wastes and this

type of approach results in an increase of the in vitro digestibility of the treated materials and it

does not produce any toxic residues. After the ozonolysis pretreatment of poplar sawdust under

enzymatic hydrolysis, the lignin content decreased from 29% to 8% (Xiao and Clarkson 1997).

17
In addition, the acid pretreatment can be effectively utilized to remove hemicelluloses

competently by breaking ether bonds in lignin/phenolics–carbohydrates complexes without

dissolving the lignin. The pretreatment of cane bagasse with hydrogen peroxide (H2O2) greatly

enhances its susceptibility to enzymatic hydrolysis. About 50% of the lignin and most of the

hemicellulose were solubilized by 2% H2O2 at 30 °C within 8 hours, and 95% efficiency of

glucose production from cellulose was achieved by the subsequent saccharification by cellulases

at 45 °C for 24 hour (Azzam 1989). Recently, certain imidazonium salts of ionic liquids (ILs) are

being widely used in biomass fractionation (Agbor et al., 2011). Generally, ILs show very low

environmental impact because of their low–volatility, low vapour pressure, high solvent power,

non–toxic character, non–flammability and eco–friendly solvent characteristics in contrast to

many other organic solvents. Thus, ILs can be expected to reduce the cost of solvent usage and

also be recycled (Agbor et al., 2011; Brodeur et al., 2011). After the pretreatment with N–

methylmorpholine–N–oxide, rice straw substrates gave a 60–68% enhancement in methane

production at 130 °C during 1hour (Teghammar et al., 2011). ILs can also selectively extract the

unaltered lignin from the lignocelluloses while simultaneously yielding a highly degradable

cellulose fraction (Wyman et al., 2009).

3.4. Hybrid pretreatment

Hybrid pretreatments in the case of deconstructing the lignin, a number of studies have shown

that a combination of two pretreatment methods such as biological pretreatment with chemical or

physical method is more effective when compared to pretreatments with a chemical or biological

method alone. Ultrasound–assisted and oxidative (H2O2) medium pretreatment procedures were

studied by Yu et al., (2009), in this work, combined pretreatment shows better lignin removal

than in the case of the one–step pretreatment with a 2% H2O2 for 48 hour (Yu et al., 2009). The

combined ultrasound and alkali pretreatments of birch and pine saw dusts. Kadimaliev et al.,

18
(2003) explored that there had been an increase in the intensity of lignin degradation. Ultrasound

treatment loosened the wood structure by weakening the bonds amongst and within

polysaccharide and lignin molecules and therefore led to an increase in the accessibility of fungal

enzymes. The results in the work of Kadimaliev et al., (2003) indicated that the pretreatment of

the lignocellulosic substrate with alkali or ultrasound is essential for intensification for the

bioconversion of lignin. In another study, the hybrid pretreatment (which comprised both

biological and acid pretreatments) using Echinodontium taxodii or Antrodia sp. 5898 with 0.25%

H2SO4 was found to be more effective than a one–step pretreatment (Ma et al., 2010). In the later

work, the reducing sugar yield increased by 1.13–2.11 folds than in the case of the acid

pretreated water hyacinth, and this result indicated that a hybrid combination of biological and

mild acid pretreatment can be regarded to be promising enough a strategy for the improvement

of enzymatic hydrolysis and ethanol production from water hyacinth having low lignin content.

4. Detrimental reactions in depolymerization of lignin

The depolymerization of lignin involves the formation of a considerable amount of detrimental

high molecular weight compounds from the highly reactive intermediates like 4–vinylphenol, 2–

methoxy–4–vinylphenol, isoeugenol, quinone methide etc., after the main primary reaction path,

a secondary repolymerization route mainly via coupling of the odd electron species,

condensation of vinyl functional unit (Patwardhan et al., 2011; Ye et al., 2012). It is due to the

fact that some of the chief functional units of the lignin moiety like Ar–OH (free aromatic

hydroxyl), certain linkages like β–O–4 ether & Cα–Cβ bonds and high reactivity of formaldehyde

(phenol–formaldehyde resin) like products from the cleavage of Cγ position in the lignin side

chains play a vital role in certain secondary reactions via condensation coupled repolymerization

paths which lead to a substantial restriction in the vale added as well as fuels yield and finally the

decomposition of lignin occurs (Bai et al., 2014; Fossey et al., 1995; Huang et al., 2015; Saisu et

al., 2003). In addition, the initially generated odd electron species involve the paths viz

19
abstraction, rearrangement and irreversible radical–radical coupling mechanistic reactions to

yield a number of undesirable components (Kim et al., 2017). Thereby, inducing rapid

stabilization characteristics of the lignin derived intermediates can only prevent such reaction

pathways (Toledano et al., 2014). In this concern, certain compounds have been used as capping

agents like boric acid, water–ethanol–phenol mixture etc, to block addition as well as

condensation reactions among the primary products and stabilize the functional units Ar–OH, Cγ

respectively etc. In addition, a rapid quenching process of the reactive odd electron species and

hydrogenolysis in the presence of certain metal catalysts like Ru, Pt, Pd, Ni, etc can minimize

reactions of the lignin side chains (Deuss and Barta 2016; Sun et al., 2018).

5. Liquid and gaseous biofuel production

During the gasification of lignin, it is converted to hydrogen (H2), carbon monoxide (CO),

carbon dioxide (CO2) and methane (CH4). The generalized and well recognized methods for

gasification of lignin are (i) conventional gasification at high temperatures and almost

atmospheric pressure with oxygen (O2) and/or water (> 800oC, 1 bar), and (ii) catalytic

gasification in supercritical water at moderate temperatures under high pressures (350–500 oC,

250 bar) (Yamaguchi et al., 2008; Kang 2015). Generally, temperature, pressure, steam,

concentration of oxygen (O2), heating rate, composition of lignin content and impurities present

in the biomass materials affect the yield of the products. The syngas products (CO + H2) from

lignin materials have already been developed in different industries and thus produced syngas

can be converted to a wide range of high value–added products like alcohols, ethers, paraffin and

aromatic hydrocarbons through the Fischer–Tropsch (FT) synthesis reaction (Yamaguchi et al.,

2012; Farzaneh 2014). Further, the lignin gasification is focused on the conversion of black

liquor or black alcohol (containing C, O, Na, S, H and K) which is the direct byproduct of the

papermaking process. At very high temperatures (>900 oC), the conventional gasification process

suffers from high corrosion due to soluble base or alkali compounds and also diminishing the

20
sulfur/sodium (S/Na) ratios of the recouped chemicals, which eventually increase the separation

charge or cost.

In the conventional perspective of a biorefinery of lignin, the isolated fragments are the

monosaccharides of glucose and lignin. There involves physical, chemical as well as biological

pretreatments followed by enzymatic hydrolysis. The carbohydrate sugar parts are then

converted into bio–alcohols like methanol, ethanol, butanol and other bio–based value–added

products. In general, the liquefaction of lignin present in the lignocellulosic biomass occurs very

quickly through the early stages of the liquefaction process since lignin has an amorphous

structure and it is easily accessible for liquefaction (Ge et al., 2018). The hydrothermal

liquefaction of lignin moiety takes place via hydrolysis and cleavage of aryl–/alkyl–ether, ester

and C–C linkages. Thereby, demethoxylation, alkylation and condensation reactions take place

(Barbier et al., 2012). Further, the lignin can be converted into phenolic and several alkyl

phenolic compounds through demethoxylation and alkylation reactions by the side of high

temperatures (250–550 °C) and pressures (5–25 MPa) (Singh et al., 2015).

6. Biorefinery scheme

These days, the biorefineries are focusing on the production of biofuels from the feedstocks with

high sugar content. In this regard, the valorization of lignin involves a new potent technique

which is the hybrid chem–biorefinery or hybrid biorefinery route that can bring the merits of

higher efficiency of lignin depolymerization through certain chemical approaches and excellent

selectivity of the targeted high value–added biocompounds or chemicals using green microbial

approaches (Wild 2015; Wu et al., 2017).

Commercially, lignin has been mobilized around 300 million dollars (Schutyser et al., 2018).

The aggregates of lignin accessibility in the biosphere surpass 300 billion tons and there are an

every year increments by around 20 billion tons (Smolarski 2012). With this economic

21
performance, lignin may be expected to turn into the principal sustainable resource for both the

biofuel and platform chemicals industries. Moreover, lignin can be utilized as an eco–friendly

alternative to numerous petro–derived substances, rubber additives, thermoplastics and

pharmaceuticals (Zakzeski et al., 2010). Due to the lack of innovative processing techniques,

there are some hurdles which hamper the full–fledged development and implementation of

lignin–based biorefineries. As a result, the commercial productions of biochemicals from lignin–

based feedstocks become a complex process strategy (Li et al., 2015).

6.1. High value–added chemicals production

The macromolecular structure of lignin brings the possibility to valorize the lignin substrate into

an extensive variety of high value–added products. Only a few articles are showing up the

essentials of the various valorization paths for making high value–added products from the lignin

(Li et al., 2015; Pandey and Kim, 2011; Zakzeski et al., 2010). The valorized products from

lignin fall into two categories, namely, macromolecules and aromatics.

6.1.1. Macromolecular products

At present, lignin–derived products are synthesized via the depolymerization pathways which

include reductive catalytic fractionation, non–reductive, reductive (mild, harsh and bifunctional

hydroprocessing) with hydrosilanes, oxidative, acid– and base–catalyzed, solvolytic and thermal

processes (Holladay et al., 2007).

6.1.1.1. Carbon fibers

Carbon fiber, starting from 2011, has been occupied a yearly worldwide market of about 46,000

metric tons which valued itself at $1.6 billion and this market is projected to an increment up to

140,000 metric tons through an estimation of $4.5 billion constantly with years by 2020

(Smolarski 2012). However, the fundamental processing is cost–intensive (Smolarski 2012) and

22
this is due to the bioprocessing of its precursor polyacrylonitrile ($15 kg–1) (SAE International

2013). Moreover, the lignin as a characteristic natural, low–cost carbon source with high carbon

content of about more than 60% carbon by mass has been turned into a cost–effective precursor

for the synthesis of carbon fiber via melting spin, oxidative stabilization of lignin fiber,

carbonization under N2, surface treatment and sizing (Baker and Rials 2013; Ragauskas et al.,

2014). Two main advantages for the utilization of lignin are the lower melting temperature and

faster stabilization capability than the polyacrylonitrile precursor (Baker and Rials 2013). As the

significant source of lignin originates from kraft lignin, it is hard to recover the pure lignin for

further processing to get lignin–based carbon fiber of poor mechanical properties in comparison

with conventional PAN–derived carbon fiber (Ragauskas et al., 2014). Exceptionally, the

shapeless amorphous structure of lignin brings about the development of disordered glassy

carbon, by the pyrolysis process (Saha et al., 2013). These days, a significantly specialized

challenge for the utilization of the lignin as carbon fiber originates from the dilemma, arising in

the process of melt spinning (Department of Energy 2007). A few research, findings have been

made which could be employed to deal with the related issues of purification and structural

modification of lignin. Lignin that has been purified in an organic solvent which has been found

to have magnificent spin ability (Baker et al., 2012), making it a precursor for the generation of

carbon fiber in comparison with the untreated lignin. Furthermore, structural modifications of

lignin by the utilization of acetic, succinic, phthalic and maleic like anhydrides with

tetrahydrofuran (THF) and methanol solvents indicate similar outcomes (Chatterjee et al., 2014).

It has been accounted for that about 40–50% of auxiliary steel could be supplanted with carbon

fiber composite materials (Ragauskas et al., 2014) and this could occupy a crucial commercial

segment, especially in the automotive sector when compared to the carbon fiber from PAN (Jahn

et al., 2012). Moreover, the statistical analysis has demonstrated that such sectors would not pay

more than $7–11 kg–1 for carbon fiber material (Smolarski 2012). The Oak Ridge National

23
Laboratory (ORNL) is an American multi–program science and technology national laboratory,

sponsored by the U.S. Department of Energy and is of now the pioneer in the production of

lignin–based carbon fiber (Smolarski 2012). It constructs $8 per kg, which could be

commercially available for about $12 per kg. An ongoing estimation by ORNL showed that the

lignin–based carbon fiber could be sold at $12 kg–1 and this estimate is very near to the objective

range sale price in these sectors (Smolarski 2012).

6.1.1.2. Polyurethane products

Polyurethanes are remarkable polymeric compounds and are amongst the most flexible polymers

for their intended range of applications. Its commercial scope was in the range of about $52

billion in 2015 and it is expected to gain $77 billion by the year of 2023 (Global Market Insights

2016). The polyurethane synthetic pathway incorporates the reaction of diisocyanates and

polyols with terminal hydroxyl functionals (Engels et al., 2013) and polyurethane exists both in

the rigid and flexible frames. Polyurethanes are usually utilized as insulation and floating

materials by the reason of their rigid form and also in their flexible frames for cushioning and

packaging materials (UNEP 1996).

Additionally, the lignin can be consolidated as a polyol in polyurethane synthesis (Strassberger et

al., 2014) and hence structurally modified before being utilized. Such modifications depend on

the diisocyanates moiety as the utilization of the kraft lignin and methylene diphenyldiisocyanate

(Duong et al., 2014) forms a high atomic weight polyurethane (920,000 g mol–1) at a temperature

at 80 oC for 3 hours (Nadji et al., 2005; Duong et al., 2014). Furthermore, in the synthesis of

polyurethane, the lignin polymer with hydroxyl (–OH) functional can replace polyols effectively

(Zhang et al., 2015). The incorporation of amino functional (–NH2) into lignin enhances its water

dissolvability and reactivity with isocyanate, and consequently the formation of polyurethane

with enhanced mechanical, anti–aging, rigid and brittle characteristics becomes possible in

comparison with the conventional one. Aniceto et al., (2012) demonstrated that oxypropylation

24
could be employed to graft polypropylene oxide into lignin and this procedure eventually is

leading to the formation of liquid polyols in which the hydroxyl functional groups have been

rationalized for polyurethane characterization.

6.1.1.3. Other macromolecular products

Thermoset and resin macromolecules have a large commercial market and the value of lignin–

valorized macromolecular materials is significantly higher than using lignin as a source of power

and fuel (Holladay et al., 2007). Lignin can commercially be valorized for some other

macromolecular materials such as polymeric modifiers, adhesives and resins (Ragauskas et al.,

2014; Strassberger et al., 2014; Upton and Kasko 2016; Zhao and Abu–Omar 2015).

6.1.2. Aromatic compounds

6.1.2.1. Butane, Toluene and Xylene (BTX) moieties

Phenols, benzene, toluene, xylene (BTX) and terephtalic acid can be synthesized more efficiently

from lignin than from fossil–based resources. The innovation to change the lignin molecules into

BTX is a two–step process. The initial step incorporates a depolymerization of the lignin into

oxygenated aromatic monomers, then followed by a second step hydrodeoxygenation (HDO) and

demethoxylation (Jongerius 2013). The most employed noble metal catalysts in the latter BTX

production process are Pt, Rh, Pd and Ru. It results in cyclic aliphatic hydrocarbons via

hydrogenation of the aromatic monomers (Lee and Deng 2015; Zhao and Lercher 2012;

Jongerius 2013) which demonstrates that the application of a novel catalytic system namely Co–

Mo/Al2O3 and Mo2C/CNF could assist the lignin conversion effectively in to BTX, after

reforming treatment of liquid phase. Moreover, BTX is the precursor for a series of materials

such as resins, nylon fibers, polyurethane and polyester. Productive advancement to get BTX

from lignin can possibly expand the utilization of lignin–based waste materials. The worldwide

generation of BTX was around 100 million metric tons (1.0 × 1011 kg) in 2010 (Jongerius 2013)

25
and it is expected to develop at the rate of ca. 4.4% CAGR (Compound annual growth rate),

every year from this year to 2020 (Smolarski 2012). At present, the greater part of the BTX

originates from fossil derived oils are becoming replaced by the lignin based biomass. Such a

BTX generation is at present in the R & D stage and is expected to reach the commercial

innovation stage within 10–20 years (ACC 2011).

6.1.2.2. Phenolic compounds

Phenol is mostly produced using cumene, which is a product obtained from alkylation of lignin–

derived benzene. The worldwide market for phenol is around 8 million metric tons and estimated

to have a commercial value of about USD12 billion, out of the year 2010 (Brzonova et al., 2014).

Lignin–to–phenol depolymerization needs a further one to two decades to capture the

commercial market stages. Lignin is rich in both aliphatic and phenolic hydroxyl functional

groups and the HDO process of lignin yields phenolics with various methoxylation degrees. The

methoxy functional group (–OCH3) can be replaced through demethoxylation by utilizing certain

catalysts namely Mo2N and CoMo/Al2O3 (Liu et al., 2012; Wu et al., 2015). Phenols are broadly

utilized in the synthesis of formaldehyde resins and polyurethanes (Freitas et al., 2009; Malaviya

and Rathore 2007). Today, the cost of phenol is specifically influenced by oil, and hence getting

the innovation of transforming lignin into phenol.

6.1.2.3. Vanillin

Vanillin has been economically derived from lignin since 1937, and the worldwide market for

vanillin in 2011 was assessed to be 16,000 metric tons with an estimated value of $230 million.

Around 20% of the manufactured vanillin originates from valorization of lignin, and the

remaining 80% originates from unrefined petroleum (Borregaard 2015). Vanillin is outstanding

in its utilization as one the world's mostly used flavoring agent (Yang et al., 2013) and is

26
produced from lignin through the oxidative catalytic pathway rather than the hydrogenolytic

pathway (Hua et al., 2007).

6.2. Biochar and other valuable products

Lignin is a precursor to lignite coal throughout a three–step geochemical process that changes

lignin into lignite coal. This procedure is known as coalification, which incorporates

microbiological degradation of cellulose to transform the lignin into humic yield and inturn they

build coal particles (Miller 2011). The lignin particle is evaluated to understand a

dehydroxylation procedure in which cleavage of the –O–4 etherial bond and a demethylation

procedure to coalify lignin into lignite coal have taken place (Hatcher and Clifford 1997).

Because of the similitudes between lignin and lignite coal, lignin has the potentiality as a

feedstock for the generation of powdered activated carbon for the mercury sequestration.

7. Perspectives and Recommendations–Biorefinery scheme

The biorefinery scheme of lignin biopolymer by depolymerizationis is briefly depicted in Figure

1. In general, the lignin derived compounds are the mixture of lignin products obtained from

depolymerization and also isolation of the pure compounds is technically challenging as well as

the yield of individual derivative has economically low values. During the depolymerization

process of lignin the products like alkyl, alkenyl, carbonyl, alcohol, carboxyl and ester

compounds are utilized as biorenewable fuels, solvents, polymers and aromatic chemical

reagents. One of the largest challenges associated with lignin valorization is that there are

economic pathways for conversion of lignin to value–added fuels and chemicals. In primary core

transformations that affect the phenolic core is done through hydrodeoxygenation (HDO) i.e.,

HDO of lignin depolymerization products often form an essential and primary upgrading step.

Figure 1 clearly shows that the HDO constituents can be divided in four sub–classes based on the

targeted products like cycloalkanes, aromatics, phenols and cyclohexanols/cyclohexanones and

27
also these four classes show a characteristic O/C and H/C ratio. The lignin derived HDO

products of cyclohexanes may serve as mid–range fuel additives which are derived from

methoxylated phenols through the combined action of both noble (Ru, Pd, Pt) or nickel–based

metal catalysts (hydrogenation) followed by Bronsted acidity (dehydration and / or

demethoxylation) (Zhang et al., 2014, Luska et al., 2015). The higher value HDO products of

aromatic hydrocarbons like propylbenzene were obtained as selective deoxygenated aromatics

followed by direct C–O hydrogenolysis which is preferred over ring hydrogenation and also the

selectivity is favored in gas phase at very high temperature and low pressure (< 1 bar H2) under

sulfided CoMo– and NiMo–based catalysts (Joshi and Lawal 2013, Ruiz et al., 2012) in this

transformation. Another higher value added lignin derived HDO compounds of phenolics are

also obtained from noble (Pd/C, Ru/C) and base metal (Fe/C, MoCx/C, WP/SiO2) catalysts under

selective demethoxylation (Sun et al., 2013). The last lignin derived HDO products of

cyclohexanols via demethoxylation followed by aromatic ring hydrogenation without removal of

functionality under suitable selective catalysts like Ni/CeO2, Raney Ni, CoNx/C, Ru–MnOx/C,

etc can be utilized for this transformation in liquid phase (Wang and Rinaldi 2012, Liu et al.,

2016, Ishikawa et al., 2016). Moreover, the alkylated cyclohexanols (like propylcyclohaxanol)

can be oxidized towards the corresponding cyclohexanones and successively converted into

alkylated caprolactone (via Baeyer–Villiger oxidation) which is a potential polyester building

block, adipic acid and caprolactam (Schutyser et al., 2015). Furthermore, the side chain

transformations can also be performed separately, while leaving the phenolic core unchanged

and the high value–added products are obtained through oxidation, hydrogenation,

hydrogenolysis and dehydration processes (Schutyser et al., 2018).

Lignin, usually a waste product of paper and pulp and biorefining industries, is presently pulling

in more consideration than ever. The field of lignin valorization has seen critical development

and advances from the previous decades. The aromaticity of lignin has a solid commercial

28
potentiality. Its usage is both ecologically and economically valuable. Current innovations with

lignin usage are still to a great extent and constrained to moderately low fuel and power

consumption. Commercialization of lignin as a precursor for the selected macromolecular

materials and aromatic products requires additional innovative effort. There are still hindrances

existing between the examination of inherent lignin structure, handling of lignin

depolymerization, and applications of the final products. Even though such a zone is being

contemplated thoroughly. However, there are some serious efforts needed, regarding a strong

collaboration across different disciplines in science and engineering. There is likewise

dependably the topic of feedstock fluctuation from area to area and in addition starting with one

growing season then onto the next. With these difficulties, lignin can be a substitute for the

fossil–based feedstock for some items. Moreover, the government can assume an essential part in

catalyzing commercialization by setting strong approaches that push for fossil feedstock

substitutions. Multidisciplinary and shared collaborative team look into the lignin valorization is

relied upon to proceed, develop and flourish sooner rather than later. At long last, to manage and

enhance future research on fractionation/depolymerization, we might to bring up a couple of

basic comments as learnt from the above review, the structure and reactivity of the detached

lignins has to be administered via the biomass kind, the fractionation strategy, and the nature of

the fractionation technique which decide the confined lignin yield or assay. In this manner,

reasonable examinations of basic qualities must be made by decoupling these three deciding

viewpoints from each other.

29
Fig 1. Biorefinery scheme of lignin biopolymer (modified from Source: Schwartz et al., 2016).

An optimal valorization of lignin into chemicals requires optimal use of the entire lignin portion

in the feedstock, which thus necessitates the combination of an effective (high yield) lignin

isolation and depolymerization step. Similarly, as for the depolymerization of lignin, the viability

depends on the facts that the depolymerization technique and the chemical composition of the

lignin substrate. Not only the improvement in the cost–effective approaches is at a standstill

height due to the complex characteristics of lignin which can influence strongly the involved

reaction pathways in the lignin valorization but also the implicated processes considerably distort

the structural individuality for the lignin composition. Thereby, it has limited the yield towards

the production of the present and future biorefineries along with certain high value added

platform chemicals. Furthermore throughout the lignin conversion process, there are the

possibilities for a certain detrimental reactions among the formed intermediate products. Though,

the isolation and utilization processes of the lignin were practiced back to the near beginning of

1900s, the researchers yet are seeking the successful lignin valorization techniques. A reasonable

correlation between various depolymerization requires that the lignin substrate be the same, and

the other way around. At the point when these essentials are satisfied, fractionation and

30
depolymerization techniques can be assessed over various investigations. In any case, an extra

obstacle is a variation in the analytical techniques that exist between different investigations,

prompting various results. Subsequently, to encourage a reasonable and dependable appraisal of

the different fractionation and depolymerization techniques, similar examinations that

remembers the proposed criteria and apply a similar analytical technique which can give

significant consideration. As last, we might want to fortify the research towards lignin molecules

to consider the whole (local) lignin fraction in future fractionation and lignin depolymerization

examinations. An ideal valorization of lignin into synthetic products needs an ideal utilization of

the whole lignin from the feedstock, which in this manner requires the blend of a powerful (high

return) lignin confinement and depolymerization process.

8. Conclusions

Lignin valorization to value added chemical and biofuels have been discussed in a brief manner.

Biorefinery approach is necessary towards the practical considerations of depolymerization

techniques. Additionally, ideal valorization of lignin into synthetic chemicals, fuels and products

needs the utilization of the whole lignin from the feedstock, which in this manner requires the

blend of a powerful (high return) lignin confinement and depolymerization process. In spite of

such challenges related to the asymmetrical structure of lignin, the valorization of this aromatic

biopolymer has been emerged that bring many defined products via depolymerization in the

presence of catalysts/ biocatalysts.

31
Acknowledgements

The authors thank the Ministry of Science and Technology-Taiwan, Kaohsiung Medical

University (KMU)-Taiwan and Research Center for Environmental Medicine-KMU for research

grant supports. Author GK would like to acknowledge the financial assistance from Ton Duc

Thang University, Vietnam. This work was supported by the New & Renewable Energy Core

Technology Program of the Korea Institute of Energy Technology Evaluation and Planning

(KETEP) granted financial resource from the Ministry of Trade, Industry & Energy, Republic of

Korea (No. 20173010092470).

References

1. ACC (American Chemistry Council), 2011. Guide to the business of chemistry. ACC,
Washington, DC.
2. Agbor, V.B., Cicek, N., Sparling, R., Berlin, A., Levin, D.B., 2011. Biomass
pretreatment: Fundamentals toward application. Biotechnol. Adv. 29(6), 675–685.
3. Aniceto, J.P.S., Portugal, I., Silva, C.M., 2012. Biomass–based polyols through
oxypropylation reaction. ChemSusChem. 5(8), 1358–1368.
4. Anwar, Z., Gulfraz, M., Irshad, M., 2014. Agro–industrial lignocellulosic biomass a key
to unlock the future bio–energy: A brief review. J. Radiat. Res. Appl. Sci. 7(2), 163–173.
5. Azadi, P., Inderwildi, O.R., Farnood, R., King, D.A., 2013. Liquid fuels hydrogen and
chemicals from lignin: A critical review. Renew. Sust. Energy Rev. 21, 506–523.
6. Azzam, A.M., 1989. Pretreatment of cane bagasse with alkaline hydrogen peroxide for
enzymatic hydrolysis of cellulose and ethanol fermentation. J. EnViron. Sci. Health B. 24
(4), 421–433.
7. Bai, X., Kim, K.H., Brown, R.C., Dalluge, E., Hutchinson, C., Lee, Y.J., Dustin, D.,
2014. Formation of phenolic oligomers during fast pyrolysis of lignin. Fuel 128, 170–
179.
8. Bajpai, P., 2016. Pretreatment of Lignocellulosic Biomass for Biofuel Production,
SpringerBriefs in Green Chemistry for Sustainability, Springer Verlag, Singapore.

32
9. Baker, D.A., Gallego, N.C., Barker, F.S., 2012. On the characterization and spinning of
an organic–purified lignin toward the manufacture of low–cost carbon fiber. J. Appl.
Poly. Sci. 124(1), 227–234.
10. Baker, D.A., Rials, T.G., 2013. Recent advances in low–cost carbon fiber manufacture
from lignin. J. Appl. Poly. Sci. 130(2), 713–728.
11. Barbier, J., Charon, N., Dupassieux, N., Loppinet–Serani, A., Mahe, L., Ponthus, J.,
Courtiade, M., Ducrozet, A., Quoineaud, A–A., Cansell, F., 2012. Hydrothermal
conversion of lignin compounds. A detailed study of fragmentation and condensation
reaction pathways, Biomass Bioenerg. 46, 479–491.
12. Bauer, S., Sorek, H., Mitchell, V.D., Ibáñez, A.B., Wemmer, D.E., 2012.
Characterization of Miscanthus giganteus lignin isolated by ethanol organosolv process
under reflux condition. J. Agric. Food Chem. 60(33), 8203–12.
13. Bhaskar, T., Pandy, A., 2015. Advances in Tehrmochmical conversion of Biomass –
Introduction, – Chapter 1, Recent Advances in Thermochemical Conversion of Biomass,
Pandey, A., Bhaskar, T., Stöcker, M., Sukumaran, R., (Ed.), First Erition, Elsevier.
14. Boerjan, W., Ralph, J., Baucher, M., 2003. Lignin biosynthesis. Annu Rev Plant Biol. 54,
519–546.
15. Borregaard, 2015. The home of sustainable vanillin. Availed at: www.smartvanillin.com.
Accessed 28 Jan 2016.
16. Brodeur, G., Yau, E., Badal, K., Collier, J., Ramachandran, K. B., Ramakrishnan, S.,
2011. Chemical and Physicochemical Pretreatment of Lignocellulosic Biomass: A
Review. Enzy Res. 2011, 1–17.
17. Brunow, G., 2004. Methods to reveal the structure of lignin in Biopolymers. Weinheim,
Wiley–VCH.
18. Brzonova, I., Kozliak., E, Kubátová, A., Chebeir, M., Qin, W., Christopher, L., Ji, Y.,
2014. Kenaf biomass biodecomposition by basidiomycetes and actinobacteria in
submerged fermentation for production of carbohydrates and phenolic compounds.
Bioresour Technol. 173, 352–360.
19. Bugg, T.D.H., Rahmanpour, R., 2015. Enzymatic conversion of lignin into renewable
chemicals. Curr. Opin. Chem. Biol. 29, 10–17.
20. Cao, L., Yu, I.K.M., Liu, Y., Ruan, X., Daniel, Tsang, D.C.W., Hunt, A.J., Ok, Y.S.,
Song, H., Zhang, S., 2018. Lignin valorization for the production of renewable
chemicals: State–of–the–art review and future prospects. Bioresource Technol.
https://doi.org/10.1016/j.biortech.2018.08.065.

33
21. Chakar, F.S., Ragauskas, A.J., 2004. Review of current and future softwood kraft lignin
process chemistry. Ind Crop. Prod. 20(2), 131–41.
22. Chatterjee, S., Jones, E.B., Clingenpeel, A.C., McKenna, A.M., Rios, O., McNutt, N.W.,
Keffer, D.J., Johs, A., 2014. Conversion of lignin precursors to carbon fibers with
nanoscale graphitic domains. ACS Sustainable Chem. Engg. 2(8), 2002–2010.
23. Chen, Z., Wan, C., 2017. Biological valorization strategies for converting lignin into
fuels and chemicals. Renew. Sust. Energ. Rev. 73, 610–621.
24. Dale, B.E., Ong, R. G., 2012. Energy, wealth, and human development: why and how
biomass pretreatment research must improve. Biotechnol. Prog. 28(4), 893–898.
25. Department of Energy, (2007). Alternative, renewable and novel feedstocks for
producing chemicals. Washington, DC: Department of Energy [DOE]. Available at:
http://www1.eere.energy.gov/manufacturing/pdfs/v2020_alternate_feedstock_report.pdf.
26. Deuss, P.J., Barta, K., 2016. From models to lignin: Transition metal catalysis for
selective bond cleavage reactions. Coordi. Chem. Rev. 306(2), 510–532.
27. Dorrestijn, E., Laarhoven, L.J.J., Arends, I.W.C.E., Mulder, P., 2000. The occurrence and
reactivity ofphenoxyl linkages in lignin and low rank coal. J. Anal. Appl. Pyrol. 54(1-2),
153–192.
28. Duong, L.D., Nam, G-Y., Oh, J.S., Park, I.K., Luong, N.D., Yoon, H.K, Lee, S.H., Lee,
Y., Yun, J.H., Lee, C.G., Hwang, S.H., Nam, J.D., 2014. High molecular-weight
thermoplastic polymerization of kraft lignin macromers with diisocyante. BioResources
9(2), 2359–2371.
29. Duque, A., Manzanares, P., Ballesteros, I., Ballesteros, M., 2016. Steam Explosion as
Lignocellulosic Biomass Pretreatment, Chapter 15. Biomass Fractionation Technologies
for a Lignocellulosic Feedstock Based Biorefinery. Mussatto, S.I., (Ed.), Elsevier,
Amsterdam, Netherlands.
30. Duval, A., Lawoko, M., 2014. A review on lignin–based polymeric, micro and
nanostructured materials. React. Funct. Polym., 85, 78–96.
31. Ehara, K., Saka, S., Kawamoto, H., 2002. Characterization of the lignin–derived products
from wood as treated in supercritical water. J. Wood Sci. 48(4), 320–325.
32. Engels, H.W., Pirkl, H.G., Albers, R., Albach, R.W., Krause, J., Hoffmann, A.,
Casselmann, H., Dormish, J., 2013. Polyurethanes: Versatile material and sustainable
problem solvers for today’s challenges. Angew. Chem. Int. Edit. 52(36), 9422–9441.
33. Fachuang, L., (Ed.), 2014. Lignin: Structural Analysis, Applications in Biomaterials and
Ecological Significance, Nova Science Publishers Inc, New York.

34
34. Farzaneh, A., Richards, T., Sklavounos, E., Heiningen, A.V., 2014. A kinetic study of
CO2 and steam gasification of char from lignin produced in the SEW process.
BioResources 9(2), 3052–3063.
35. Fengel, D., Wegener, G., 1984. Wood: Chemistry, ultrastructure, reactions. Walter de
Walter de Gruyter, Berlin, New York.
36. Fossey, J., Lefort, D., Sorba, J., 1995. Free Radicals in Organic Chemistry. Ist Ed., Wiley,
Paris.
37. Freitas, A.C., Ferreira, F., Costa, A.M., Pereira, R., Antunes, S.C., Gonçalves, F., Rocha-
Santos, T.A., Diniz, M.S., Castro, L., Peres, I., Duarte, A.C., 2009. Biological treatment
of the effluent from a bleached kraft pulp mill using basidiomycete and zygomycete
fungi. Sci. Total Environ. 407(10), 3282–3289.
38. Ge, X., Chang, C., Zhang, Lu., Cui, S., Luo, X., Hu, S., Qin, Y., Li, Y., 2018. Chapter
Five – Conversion of Lignocellulosic Biomass into Platform Chemicals for Biobased
Polyurethane Application. Advances in Bioenergy, 3, 161–213.
39. Global Market Insights [GMI] (2016) Polyurethane (PU) market size by product. Ocean
view: Global market insights [GMI]. Available at:
https://www.gminsights.com/industryanalysis/polyurethane–PU–market
40. Gonzalo., G., Colpa, D.I., Habib, M.H.M., Fraaije, M.W., 2016. Bacterial enzymes
involved in lignin degradation, J. Biotechnol. 236, 110–119.
41. Hatakeyama, H., Hatakeyama, T., 2010. Lignin Structure, Properties, and Applications.
In: Abe A., Dusek K., Kobayashi S. (Eds.) Biopolymers. Lignin, Proteins. Springer-
Verlag GmbH Berlin, Heidelberg, 1 – 63.
42. Hatakka, A., 1994. Lignin–modifying enzymes from selected white–rot fungi: production
and role from in lignin degradation. FEMS Microbiol. Rev. 13, 125–135.
43. Hatcher, P.G., Clifford, D.J., 1997. The organic geochemistry of coal: from plant
materials to coal. Org. Geochem., 27(5–6), 251–274.
44. Hendriks, A.T., Zeeman, G., 2009. Pretreatments to enhance the digestibility of
lignocellulosic biomass. Bioresour Technol. 100(1), 10–18.
45. Holladay, J.F., Bazell, J.J., White, J.F., Johnson, D., 2007. Top value-added chemicals
from biomass. Volume II–Results of Screening for potential candidates from biorefinery,
Lignin, Pacific Northern National Laboratory [PNNL], Richland, Washington.
46. Holtman, K.M., Chang, H. M., Kadla, J. F., 2007. An NMR comparison of the whole
lignin from milled wood, MWL, and REL dissolved by the DMSO/NMI procedure. J.
Wood Chem. Technol. 27, 179−200.

35
47. Hu, F., Ragauskas, A., 2012. Pretreatment and lignocellulosic chemistry. Bioenerg. Res.
5, 1043–1066.
48. Hua, D., Ma, C., Song, L., Lin, S., Zhang, Z., Deng, Z., Xu, P., 2007. Enhanced vanillin
production from ferulic acid using adsorbent resin. Appl. Microbiol. Biotechnol. 74(4),
783–790.
49. Huang, X., Korányi, T.I., Boot, M.D., Hensen, E.J., 2015. Ethanol as capping agent and
formaldehyde scavenger for efficient depolymerization of lignin to aromatics. Green
Chem. 17, 4941-4950.
50. Ishikawa M., Tamura, M., Nakagawa, Y., Tomishige, K., 2016. Demethoxylation of
guaiacol and methoxybenzenes over carbon–supported Ru–Mn catalyst, Appl. Catal., B,
182, 193–203.
51. Isikgor, F.H., Becer, C.R., 2015. Lignocellulosic Biomass: a sustainable platform for
production of bio–based chemicals and polymers, Polym. Chem. 6, 4497–4559.
52. Itoh, H., Wada, M., Honda, Y., Kuwahara, M., 2003. Bioorganosolve pretreatments for
simultaneous saccharification and fermentation of beech wood by ethanolysis and white–
rot fungi. J Biotechnol. 103(3), 273–280.
53. Jahn, B., Karl, D., Witten, E., 2012. Composites Market Report 2012. Carbon
Composites. Available at http://www.carbon-composites.eu/sites/carboncomposites.
54. Jong, Ed. de, Higson, A., Walsh, P., Wellisch, M., 2012. Bio–based Chemicals: Value
Added Products from Biorefineries. IEA Bioenergy – Task 42 Biorefinery.
55. Jongerius, A.L., 2013. Catalytic conversion of lignin for the production of aromatics.
Doctoral Thesis. Utrecht University, The Netherlands.
56. Joshi, N., Lawal, A., 2013. Hydrodeoxygenation of 4–Propylguaiacol (2–Methoxy–4–
propylphenol) in a Microreactor: Performance and Kinetic Studies, Ind. Eng. Chem. Res.
52(111), 4049–4058.
57. Kadimaliev, D.A., Revin, V.V., Atykyan, N.A., Samuilov, V.D., 2003. Effect of
woodmodification on lignin consumption and synthesis of lignolytic enzymes by the
fungus Panus (Lentinus) tigrinus. Appl. Biochem. Microbiol. 39(5), 488–492.
58. Kai, D., Tan, M.J., Chee, P.L., Chua, Y.K., Yap, Y.L., Loh, X.J., 2016. Towards lignin–
based functional materials in a sustainable world. Green Chem. 18, 1175–1200.
59. Kang, K., Azargohar, R., Dalai, A.K., Wang, H., 2015. Noncatalytic gasification of lignin
in supercritical water using a batch reactor for hydrogen production: an experimental and
modeling study. Energy Fuel 29(3), 1776–1784.

36
60. Khalid, K.A., Ahmad, A.A., Yong, T.L.K., 2017. Lignin Extraction from lignocellulosic
Biomass Using Sub–and Supercritical Fluid Technology as Precursor for Carbon Fiber
Production, J. Jpn. Inst. Energy. 96(8), 255–260.
61. Kim, D., 2018. Physico–Chemical Conversion of Lignocellulose: Inhibitor Effects and
Detoxification Strategies: A Mini Review. Molecules, 23(2), 309.
62. Kim, K.H., Singh, S., Custodis, V., Bokhoven, J.V., 2017. Role of Free Radicals in Fast
Pyrolysis. In Fast Pyrolysis of Biomass: Advances in Science and Technology, Brown,
R.C., Wang, K., (Ed.), Chapter 7, Royal Society of Chemistry, 117–137.
63. Kleinert, M., Barth, T., 2008. Towards a lignocellulosic biorefinery: Direct one–step
conversion of lignin to hydrogen–enriched biofuel. Energy Fuels 22(2), 1371–1379.
64. Lee, A., Deng, Y., 2015. Green polyurethane from lignin and soybean oil through non–
isocyanate reactions. Eur. Polym. J. 63, 67–73.
65. Li, J., Lin, J., Xiao, W., Gong, Y., Wang, M., Zhou, P., Liu, Z., 2013. Solvent extraction
of antioxidants from steam exploded sugarcane bagasse and enzymatic convertibility of
the solid fraction. Bioresour. Technol. 130, 8–15.
66. Lin, S., 1983. Lignin utilization: potential and challenge, in: Tillman, D.A., Jahn, E.C.,
(Eds.), Progress in Biomass Conversion, Academic Press, Inc, 31–78.
67. Liu X., Xu, L., Xu, G., Jia, W., Ma, Y., Zhang, Y., 2016. Selective Hydrodeoxygenation
of Lignin–Derived Phenols to Cyclohexanols or Cyclohexanes over Magnetic
CoNx@NC Catalysts under Mild Conditions, ACS Catal. 6(11), 7611–7620.
68. Liu, Y., Zeng, Z., Zeng, G., Tang, L., Pang, Y., Li, Z., Liu, C., Lei, X., Wu, M., Ren, P.,
Liu, Z., Chen, M., Xie, G., 2012. Immobilization of laccase on magnetic bimodal
mesoporous carbon and the application in the removal of phenolic compounds.
Bioresour. Technol. 115, 21–26.
69. Luska, K.L., Migowski, P., Sayed, S. El., Leitner, W., 2015. Synergistic Interaction
within Bifunctional Ruthenium Nanoparticle/SILP Catalysts for the Selective
Hydrodeoxygenation of Phenols. Angew. Chem., Int. Ed., 54(52), 15750–15755.
70. Ma, F., Yang, N., Xu, C., Yu, H., Wu, J., Zhang, X., 2010. Combination of biological
pretreatment with mild acid pretreatment for enzymatic hydrolysis and ethanol
production from water hyacinth. Bioresour. Technol. 101, 9600–9604.
71. Ma, R., Guo, M., Xiao, Z., 2018. Recent advances in oxidative valorization of lignin,
Catalysis Today, 302, 50–60.
72. Malaviya, P., Rathore, V.S., 2007. Bioremediation of pulp and paper mill effluent by a
novel fungal consortium isolated from polluted soil. Bioresour. Technol. 98, 3647–3651.

37
73. McLeod, M.P., Warren, R.L., Hsiao, W.W., Araki, N., Myhre, M., Fernandes, C.,
Miyazawa, D., Wong, W., Lillquist, A.L., Wang, D., Dosanjh, M., Hara, H., Petrescu, A.,
Morin, R.D., Yang, G., Stott, J.M., Schein, J.E., Shin, H., Smailus, D., Siddiqui, A.S.,
Marra, M.A., Jones, S.J., Holt, R., Brinkman, F.S., Miyauchi, K., Fukuda, M., Davies,
J.E., Mohn, W.W., Eltis, L.D., 2006. The complete genome of Rhodococcus sp. RHA1
provides insights into a catabolic powerhouse. Proc. Natl. Acad. Sci. U.S.A. 103(42)
15582–15607.
74. Miller, B.G., 2011. The chemical and physical characteristics of coal BT – Clean Coal
engineering technology, Boston, Butterworth–Heinemann, 53–68.
75. Nadji, H., Bruzzese, C., Belgacem, M.N., Benaboura, A., Gandini, A., 2005.
Oxypropylation of lignins and preparation of rigid polyurethane foams from the ensuing
polyols. Macromol. Mater. Eng. 290, 1009–1016.
76. Nelson, K.E., Weinel, C., Paulsen, I.T., Dodson, R.J., Hilbert, H., Martins dos Santos,
V.A., Fouts, D.E., Gill, S.R., Pop, M., Holmes, M., Brinkac, L., Beanan, M., DeBoy,
R.T., Daugherty, S., Kolonay, J., Madupu, R., Nelson, W., White, O., Peterson, J.,
Khouri, H., Hance, I., Chris Lee, P., Holtzapple, E., Scanlan, D., Tran, K., Moazzez, A.,
Utterback, T., Rizzo, M., Lee. K., Kosack, D., Moestl, D., Wedler, H., Lauber, J.,
Stjepandic, D., Hoheisel, J., Straetz, M., Heim, S., Kiewitz, C., Eisen, J.A., Timmis,
K.N., Düsterhöft, A., Tümmler, B., Fraser, C.M., 2002. Complete genome sequence and
comparative analysis of the metabolically versatile Pseudomonas putida KT2440.
Environ. Microbiol. 4(12), 799–808.
77. Oasmaa, A., Alen, R., Meier, D., 1993. Catalytic hydrotreatment of some technical
lignins, Bioresource Technol. 45(3), 189–194.
78. Pandey, M.P., Kim, C.S., 2011. Lignin depolymerization and conversion: A review of
thermochemical methods. Chem. Eng. Technol. 34(1), 29–41.
79. Parveen, K., Barrett, D.M., Delwiche, M.J., Stroeve, P., 2009. Methods for Pretreatment
of Lignocellulosic Biomass for Efficient Hydrolysis and Biofuel Production, Ind. Eng.
Chem. Res. 48(8), 3713–3729.
80. Patwardhan, P.R., Brown, R.C., Shanks, B.H., 2011. Understanding the Fast Pyrolysis of
Lignin. Chem. Sus. Chem. 4(11), 1629–1636.
81. Ragauskas, A.J., Beckham, G.T., Biddy, M.J., Chandra, R., Chen, F., Davis, M.F.,
Davison, B.H., Dixon, R.A., Gilna, P., Keller, M., Langan, P., Naskar, A.K., Saddler,
J.N., Tschaplinski, T.J., Tuskan, G.A., Wyman, C.E., Lignin valorization: Improving
lignin processing in the biorefinery, Science, 344(6185), 1246843.

38
82. Ruiz, P.E., Frederick, B.G., Sisto, W.J.De., Austin, R.N., Radovic, L.R., Leiva, K.,
Garcia, R., Escalona, N., Wheeler, M.C., 2012. Guaiacol hydrodeoxygenation on MoS 2
catalysts: Influence of activated carbon supports. Catal. Commun. 27, 44–48.
83. Saake, B., Lehnen, R., 2012. Lignin, in Ullmann’s encylopedia of industrial chemistry.
Weinheim: Wiley–VCH Verlag GmbH & Co. KGaA, 21–36.
84. SAE Automotive Engineering Magazine, 2013. Cutting costs of carbon composites -
SAE International, Pennsylvania, Michigan. Available at: http://articles.sae.org/11618.
85. Saha, D., Payzant, E.A., Kumbhar, A.S., Naskar, A.K., 2013. Sustainable mesoporous
carbons as storage and controlled–delivery media for functional molecuels. ACS Appl.
Mater. Interfaces 5(12), 5868–5874.
86. Saisu, M., Sato, T., Watanabe, M., Adschiri, T., Arai, K., 2003. Conversion of lignin with
supercritical water–phenol mixtures. Energy Fuels 17(4), 922–928.
87. Saratale, G.D., Oh, M.K., 2015. Improving alkaline pretreatment method for preparation
of whole rice waste biomass feedstock and bioethanol production, RSC Adv. 5, 97171–
97179.
88. Schutyser, W., Bosch, S.V., Dijkmans, J., Turner, S., Meledina, M., Tendeloo, G.V.,
Debecker, D.P., Sels, B.F., 2015. Selective Nickel‐Catalyzed Conversion of Model and
Lignin‐Derived Phenolic Compounds to Cyclohexanone‐Based Polymer Building Blocks,
Chem. Sus. Chem. 8(10), 1805–1818.
89. Schutyser, W., Renders, T., Bosch, S.V., Koelewijn, S.F., Beckham, G.T., Sels, B.F.,
2018. Chemicals from lignin: an interplay of lignocellulose fractionation,
depolymerisation, and upgrading. Chem. Soc. Rev. 47(3), 852–908.
90. Schwartz, T.J., Shanks, B.H., Dumesic, J.A., 2016. Coupling chemical and biological
catalysis: a flexible paradigm for producing biobased chemicals Curr. Opin. Biotechnol.
38, 54–62.
91. Sen, S., Patil, S., Argyropoulos, D.S., 2015. Thermal properties of lignin in
copolymers,blends, and composites: a review. Green Chem. 17, 4862–4887.
92. Silverstein, R.A., Chen, Y., Sharma–Shivappa, R.R., Boyette, M.D., Osborne, J.A., 2007.
Comparison of chemical pretreatment methods for improving Saccharification of cottons
talks. Bioresour. Technol. 98(16), 3000–3011.
93. Singh, R., Prakash, A., Balagurumurthy, B., Bhaskar, T., 2015. Hydrothermal
Liquefaction of Biomass, Recent Advances in Thermo–Chemical Conversion of
Biomass, Chapter 10, 269–291.

39
94. Smolarski, N., 2012. High–value opportunities for lignin: Unlocking its potential.
Smolarski, N., Frost and Sullivan Market Research. Available at:
http://www.frost.com/sublib/display–marketinsight–top.do?id=269017995
95. Staley, B., Barlaz, M., 2009. Composition of municipal solid waste in the United States
and implications for carbon sequestration and methane yield. J. Environ. Eng. 135, 901–
909.
96. Strassberger, Z., Tanase, S., Rothenberg, G., 2014. The pros and cons of lignin
valorization in an integrated biorefinery. RSC Advances 4, 25310–25318.
97. Suhara, H., Kodama, S., Kamei, I., Maekawa, N., Meguro, S., 2012. Screening of
selective lignin–degrading basidiomycetes and biological pretreatment for enzymatic
hydrolysis of bamboo culms. Int. Biodeter. Biodegr. 75, 176–180.
98. Suhas, Carrott, P.J.M., Ribeiro Carrott, M.M., 2007. Lignin – from natural adsorbent to
activated carbon: a review. Bioresour. Technol. 98(12), 2301–2312.
99. Sun, J., Karim, A.M., Zhang, H., Kovarik, L., Li, X.S., Hensley, A.J., McEwen, J.S.,
Wang, Y., 2013. Carbon–supported bimetallic Pd–Fe catalysts for vapor–phase
hydrodeoxygenation of guaiacol. J. Catal. 306, 47–57.
100. Sun, Y., Cheng, J., 2002. Hydrolysis of lignocellulosic materials for ethanol production: a
review. Bioresour. Technol. 83(1), 1–11.
101. Sun, Z.H., Fridrich, B., Santi, A., Elangovan, S., Barta, K., 2018. Bright Side of Lignin
Depolymerization: Toward New Platform Chemicals. Chem. Rev. 118(2), 614–678.
102. Teghammar A., Karimi, K., Horvath, I.S., Taherzadeh, M.J., 2012. Enhanced biogas
productionfrom rice straw, triticale straw and softwood spruce by NMMO pretreatment.
Biomass Bioenerg. 36, 116–120.
103. Toledano, A., Serrano, L., Labidi, J., 2014. Improving base catalyzed lignin
depolymerization by avoiding lignin repolymerization. Fuel 116, 617–624.
104. Tuck, C.O., Pérez, E., Horváth, I.T., Sheldon, R.A., Poliakoff, M., 2012. Valorization of
biomass: Deriving more value from waste. Science 337(6095), 695–699.
105. UNEP (United Nation Environmental Programme), 1996. Flexible and rigid foams.
France, Paris. Available at: http://www.unep.fr/ozonaction/information/mmcfiles/1350-
e.pdf.
106. Upton, B.M., Kasko, A.M., 2016. Strategies for the conversion of lignin to high–value
polymeric materials: Review and perspective. Chem. Rev. 116(4), 2275–2306.
107. Valaskova, V., Snajdr, J., Bittner, B., Cajthaml, T., Merhautova, V., Hofrichter, M.,
Baldrian, P., 2007. Production of lignocellulose–degradingenzymes and degradation of

40
 leaf litter by saprotrophic basidiomycetes isolatedfrom a Quercus petraea forest. Soil
Biol. Biochem., 39(10), 2651–2660.
108. Vidal, P.F., Molinier, J., 1988. Ozonolysis of lignins Improvement of invitro digestibility
of poplar sawdust. Biomass 16(1), 1–17.
109. Villar, J.C., Caperos, A., García–Ochoa, F., 2001. Oxidation of hardwood kraft–lignin to
phenolic derivatives with oxygen as oxidant. Wood Sci. Technol. 35(3), 245–255.
110. Wang, H.M., Wang, B., Wen, J.L., Yuan, T.Q., Sun, R.C., 2017. Structural
Characteristics of Lignin Macromolecules from Different Eucalyptus Species. ACS
Sustainable Chem. Eng. 5(2), 11618−11627.
111. Wang, S., Gongxin, D., Haiping Yang, Zhongyang L., 2017. Lignocellulosic biomass
pyrolysis mechanism: A state–of–the–art review, Prog. Energ. Combust. Sci., 62, 33–86.
112. Wang, X., Rinaldi, R., 2012. Exploiting H–transfer reactions with RANEY® Ni for
upgrade of phenolic and aromatic biorefinery feeds under unusual, low–severity
conditions, Energy Environ. Sci. 5(8), 8244–8260.
113. Wang, Zhao, H., Wang, Y., Fu, C., Yao, G., Qingxiang, 2009. Theoretical study on the
pyrolysis process of lignin dimer model compounds, Acta. Chim. Sinica. 67(9), 893–900.
114. Weng, J.K., Li, X., Bonawitz, N.D., Chapple, C., 2008. Emerging strategies of lignin
engineering and degradation for cellulosic biofuel production. Curr. Opin. Biotechnol.
19(2), 166–172.
115. Wild Paul J.de, Chapter 8 – Biomass Pyrolysis for Hybrid Biorefineries, Industrial
Biorefineries & White Biotechnology, 2015, Pages 341–368.
116. Wu, J., Xiao, Y–Z., Yu, H–Q., 2005. Degradation of lignin in pulp mill wastewaters by
white-rot fungi on biofilm. Bioresour. Technol. 96(12), 1357–63.
117. Wu, W., Dutta, T., Varman, A.M., Eudes, A., Manalansan, B., Loqué D., Singh, S., 2017.
Lignin Valorization: Two Hybrid Biochemical Routes for the Conversion of Polymeric
Lignin into Value–added Chemicals, Scientific Reports, Vol. 7, Article number: 8420
(2017).
118. Wyman, C.E., Dale, B.E., Elander, R.T., Holtzapple, M., Ladisch, M.R., Lee, Y.Y.,
Mitchinson, C., Saddler, J.N., 2009. Comparative sugar recovery and fermentation data
following pretreatment of poplar wood by leading technologies. Biotechnol. Progr. 25(2),
333–339.
119. Xiao, W., Clarkson, W.W., 1997. Acid solubilization of lignin and bioconversion of
treated newsprint to methane. Biodegradation, 8(1), 61–66.

41
120. Yamaguchi, A., Hiyoshi, N., Sato, O., Osada, M., Shirai, M., 2008. Lignin gasification
over supported ruthenium trivalent salts in supercritical water. Energy Fuel 22(3), 1485–
1492.
121. Yamaguchi, A., Hiyoshi, N., Sato, O., Shirai, M., 2012. Gasification of organosolv–lignin
over charcoal supported noble metal salt catalysts in supercritical water. Top. Catal.
55(11–13), 889–896.
122. Yang, W., Tang, H., Ni, J., Wu. Q., Hua, D., Tao, F., Xu, P., 2013. Characterization of
two Streptomyces enzymes that convert ferulic acid to vanillin. PLoS ONE 8(6), e67339.
123. Ye, Y., Fan, J., Chang, J., 2012. Effect of reaction conditions on hydrothermal
degradation of cornstalk lignin. J. Anal. Appl. Pyrol., 94, 190–195.
124. Yu J., Zhang, J., He, J., Liu, Z., Yu, Z., 2009. Combinations of mild physical or chemical
pretreatment with biological pretreatment for enzymatic hydrolysis of rice hull.
Bioresour. Technol. 100(2), 903–908.
125. Zakzeski, J., Bruijnincx, P.C.A., Jongerius, A.L., Weckhuysen, B.M., 2010. The catalytic
valorization of lignin for the production of renewable chemicals. Chem. Rev. 110(6),
3552–3599.
126. Zhang, C., Xing, J., Song, L., Xin, H., Lin, S., Xing L., Li, X., 2014. Aqueous–phase
hydrodeoxygenation of lignin monomer eugenol: Influence of Si/Al ratio of HZSM–5 on
catalytic performances. Catal. Today, 234, 145–152.
127. Zhang, Q., Zhang, G., Xu, J., Gao, C., Wu, Y., 2015. Recent advances in lignin derived
polyurethane polymers. Rev. Adv. Mat. Sci. 40, 146–154.
128. Zhao, C., Lercher, J.A., 2012. Selective hydrodeoxygenation of lignin–derived phenolic
monomers and dimers to cycloalkanes on Pd/C and HZSM–5 catalysts. Chem. Cat.
Chem. 4(1), 64–68.
129. Zhao, S., Abu–Omar, M.M., 2015. Biobased epoxy nanocomposites derived from lignin–
based monomers. Biomacromolecules 16(7), 2025–2031.
130. Zhou, X., Broadbelt, L.J., Vinu, R., 2016. Mechanistic Understanding of
Thermochemical Conversion of Polymers and Lignocellulosic Biomass, Chapter 2,
Kevin, M.V.G., (Ed.), Advances in Chemical \ Engineering, Academic Press, Cambridge,
49, 95–198.

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Graphical Abstract

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 Highlights

 Valorization of lignin towards chemicals and fuels is reviewed

 Various process routes are evaluated for efficient lignin depolymerization
 Detrimental reactions in depolymerization of lignin are discussed
 Biorefinery aspects for value added products generation are outlined
 Perspectives towards the biorefinery scheme is recommended

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