energies

Review
Green Diesel: Biomass Feedstocks, Production
Technologies, Catalytic Research, Fuel Properties
and Performance in Compression Ignition Internal
Combustion Engines
Savvas L. Douvartzides 1,2, *, Nikolaos D. Charisiou 1 , Kyriakos N. Papageridis 1 and
Maria A. Goula 1, *
1 Laboratory of Alternative Fuels and Environmental Catalysis (LAFEC),
Department of Environmental and Pollution Control Engineering, Western Macedonia University of
Applied Sciences, GR-50100 Kozani, Greece; [email protected] (N.D.C.); [email protected] (K.N.P.)
2 Laboratory of Internal Combustion Engines, Department of Mechanical and Industrial Engineering,
Western Macedonia University of Applied Sciences, GR-50100 Kozani, Greece
* Correspondence: [email protected] (S.L.D.); [email protected] (M.A.G.);
Tel.: +30-2461-068296 (M.A.G.)




Received: 31 December 2018; Accepted: 25 February 2019; Published: 28 February 2019


Abstract: The present investigation provides an overview of the current technology related to the
green diesel, from the classification and chemistry of the available biomass feedstocks to the possible
production technologies and up to the final fuel properties and their effect in modern compression
ignition internal combustion engines. Various biomass feedstocks are reviewed paying attention
to their specific impact on the production of green diesel. Then, the most prominent production
technologies are presented such as the hydro-processing of triglycerides, the upgrading of sugars
and starches into C15 –C18 saturated hydrocarbons, the upgrading of bio-oil derived by the pyrolysis
of lignocellulosic materials and the “Biomass-to-Liquid” (BTL) technology which combines the
production of syngas (H2 and CO) from the gasification of biomass with the production of synthetic
green diesel through the Fischer-Tropsch process. For each of these technologies the involved
chemistry is discussed and the necessary operation conditions for the maximum production yield and
the best possible fuel properties are reviewed. Also, the relevant research for appropriate catalysts
and catalyst supports is briefly presented. The fuel properties of green diesel are then discussed in
comparison to the European and US Standards, to petroleum diesel and Fatty Acid Methyl Esters
(FAME) and, finally their effect on the compression ignition engines are analyzed. The analysis
concludes that green diesel is an excellent fuel for combustion engines with remarkable properties
and significantly lower emissions.

Keywords: green diesel; biofuels; biomass feedstocks; hydro-processing of triglycerides; compression

ignition (CI) engines

1. Introduction
The modern world is in a continuous search for improved sources of energy. This effort is
catalyzed by the gradual depletion of the reserves of crude oil, natural gas and coal, by the necessity for
national energy security, and by the detrimental impact of the conventional utilization of fossil fuels on
climatic conditions and the natural environment. Petroleum diesel is a distillate of fossil petroleum oil
rich in saturated hydrocarbons (also known as paraffins or alkanes) containing 8 to 21 carbon atoms per
molecule (C8 to C21 ). It also contains napthenes (cycloparafins) and aromatics and is produced through

Energies 2019, 12, 809; doi:10.3390/en12050809 www.mdpi.com/journal/energies

Energies 2019, 12, 809 2 of 41

the fractional distillation of crude oil at atmospheric pressure and temperatures between 250–360 ◦ C [1].
From the construction of the first compression ignition (CI) internal combustion engine by Rudolph
Diesel in 1897, petroleum diesel has dominated the transport sector, but also contributed significantly
to the environmental pollution and climate change due to the extensive emission of CO2 into the
atmosphere. Petroleum diesel is also burned in dedicated burners to provide hot water and space
heating in residential and commercial buildings. In an effort to mitigate the effects of global warming
and move towards energy independence, the European Union (EU) has set the target that all new
buildings must have near-zero environmental footprint until 2020 [2]. Biomass and biomass-derived
biofuels such as bio-hydrogen, bio-gas, bio-methane, bio-ethanol, green gasoline, biodiesel and green
diesel are in the crest of international interest, as they can mitigate CO2 levels in the atmosphere and
substitute fossil fuels in the future energy supply.
Biodiesel is produced by the transesterification of triglycerides contained in biomass matter such
as vegetable oils (e.g. rapeseed, soybean, cottonseed, palm, corn, sunflower, coconut, peanut, camelina,
carinata and jatropha oils), animal fats, micro-algal oils and used cooking oils [3]. Transesterification
is the chemical process of the biomass lipids usually with methanol, in which triglycerides are
transformed into Fatty Acid Methyl Esters (FAME or biodiesel) and glycerol in presence of a
homogeneous alkaline catalyst such as KOH or NaOH, at a temperature of about 60 ◦ C and atmospheric
pressure [4]. Although the biodiesel industry has experienced enormous growth between 2005 and
2015, with production rising from 10% of total biofuel output in 2005 to almost 25% in 2015, it relies
heavily of favorable policy instruments (i.e., economic subsidies) as its production costs are still very
high [5–7]. A further issue to be considered is the co-production of crude glycerol, as it undermines
the environmental credential of the industry, with efforts towards its energetic utilization still at
research level [8–11]. Biodiesel is a product of biological origin leading to significantly lower net CO2
accumulation in atmosphere since biomass is produced with an equal adsorption of atmospheric CO2
during the process of photosynthesis. At the same time, biodiesel is an oxygenated fuel which does
not contain any sulfur and its combustion is cleaner leading to reduced emissions of CO, unburned
hydrocarbons (HCs) and smoke. It also has enhanced lubricity which protects the engine components
of the fuel delivery system, such as fuel pumps and injectors. On the other hand, high oxygen content
means that biodiesel has some important disadvantages, such as low oxidative stability, high viscosity
and poor cold weather performance (due to high cloud point and high pour point). In addition,
biodiesel shows lower stability during storage and it also attacks certain metals such as copper, zinc,
tin and lead, causing corrosion or swells various elastomers used for the sealing of the engines. In 2006
about two thousand fuel stations in Europe were providing “pure” biodiesel (B100), but concerns over
the compatibility of B100 with the equipment of modern compression ignition engines (common rail
fuel injection systems, particulate filters etc.) have limited the maximum allowable concentration of
biodiesel for use in EU vehicles to 7% by volume (B7) [12]. Finally, biodiesel increases the emission
of nitrogen oxides (NOx ) and has a lower energy content than petroleum diesel [13,14]. As a result,
the utilization of B100 or biodiesel blends with high biodiesel content results in a noticeable drop of
the engine thermal efficiency and brake power output [15].
Green diesel is a new generation biofuel also known as “renewable diesel”, “second
generation diesel”, “bio-hydrogenated diesel”, “Hydrogenated Esters and Fatty Acids (HEFA)”,
“Bio-Hydrogenated Diesel (BHD)”, “Hydrogenation Derived Renewable Diesel (HDRD)”, “Hydro-
treated Vegetable Oil” or “Hydrogenated Vegetable Oil”. The last two names share the same acronym
HVO and have been used during the last decade due to the fact that the vegetable oils were the most
usual biomass feedstock for the production of this biofuel. Today, green diesel is also produced from
other biomass sources such as animal or fish fats but the term HVO is still in use in the industry as well
as in the fuel standards and the European regulation [16]. Green diesel is a mixture of straight chain and
branched saturated hydrocarbons which typically contain 15 to 18 carbon atoms per molecule (C15 to
C18 ). This composition resembles the fossil petroleum diesel and allows green diesel utilization in CI
engines in pure form or as a blend with any desired blending ratio without engine modifications [17,18].
Energies 2019, 12, 809 3 of 41

Energies 2019, 12, x FOR PEER REVIEW 3 of 42

Like biodiesel, green diesel is a product of biological origin with a reduced impact on the accumulation
of CO 2 in the atmosphere
petroleum diesel it is andfree in of contrast
aromatics to or
petroleum
naphthenes diesel
and it provides
is free of aromatics or naphthenes
a cleaner combustion. Unlike
and provides
biodiesel,a however,
cleaner combustion.
green diesel Unlike
doesbiodiesel,
not containhowever,
oxygengreenanddiesel does not
therefore it iscontain oxygen non-
more stable,
and therefore
corrosive itand is more
has astable,
heatingnon- valuecorrosive
similar and has a heating
to petroleum value
diesel. similar
Green to also
diesel petroleum diesel. cold
has superior
Green diesel also has superior cold weather behavior than biodiesel, it does not
weather behavior than biodiesel, it does not increase NOx emissions and has a higherx cetane number increase NO emissions
and has
(CN) a higher
whichcetane number
translates (CN) which
to easier translates
ignition in CI to easier ignition
engines. Finally, ingreen
CI engines.
diesel Finally,
produced green
by the
dieselhydro-processing
produced by the hydro-processing
of triglycerides has of propane
triglycerides has propane
as byproduct as byproduct
which is a gaseous whichfuelisof
a gaseous
high market
fuel of high This
value. marketfactvalue.
makes This
greenfactdiesel
makesproduction
green diesel production
more attractivemore attractive interms
in economical economical
when terms
compared
whentocompared to the of
the production production
biodiesel of biodiesel [19,20].
[19,20].
Green diesel
Green can can
diesel generally
generally be beproduced
producedfrom frombiomass
biomassthroughthrough four four technologies:
technologies: a)
(a) hydro-processing,
hydro-processing, (b)b)catalytic
catalytic upgrading
upgrading of sugars,
of sugars,starches andand
starches alcohols, (c) thermal
alcohols, conversion
c) thermal conversion
(pyrolysis) and upgrading
(pyrolysis) and upgrading of bio-oil and (c)
of bio-oil andbiomass
c) biomass to liquid (BTL)
to liquid thermochemical
(BTL) thermochemical processes.
processes.
Hydro-processing
Hydro-processing aims at the conversion of the triglycerides of the biomass oils and into
aims at the conversion of the triglycerides of the biomass oils and fats fats into
saturated
saturatedhydrocarbons
hydrocarbons through catalytic
through processing
catalytic with with
processing hydrogen.
hydrogen.The Thecatalytic upgrading
catalytic of of
upgrading
sugars and alcohols
sugars and alcoholsinvolves
involvesliquid phase
liquid technologies
phase technologiessuchsuch
as aqueous
as aqueous phase reforming
phase reforming(APR).
(APR).
Thermal
Thermalconversion involves
conversion the pyrolysis
involves of biomass
the pyrolysis and the
of biomass andproduction
the production of bio-oil which
of bio-oil is then
which is then
refined into green
refined diesel.
into green Finally,
diesel. BTL BTL
Finally, processes involve
processes the high
involve temperature
the high temperature gasification of the
gasification of the
biomass for the production of syngas which is rich in H and CO
biomass for the production of syngas which is rich 2in H2 and CO and the subsequent chemicaland the subsequent chemical
synthesis of liquid
synthesis green diesel
of liquid green through the wellthe
diesel through known
wellFischer-Tropsch
known Fischer-Tropsch(FT) process. (FT)The green diesel
process. The green
produced
dieselby the Fischer-Tropsch
produced method is sometimes
by the Fischer-Tropsch method is referred
sometimes as FT green as
referred diesel [21,22].
FT green diesel [21,22].

2. Biomass Feedstocks
2. Biomass Feedstocks
Biomass is any
Biomass is organic matter
any organic such such
matter as wood, crops,
as wood, seaweed
crops, and animal
seaweed or fish
and animal orwastes that can
fish wastes that can
be used as a source of energy. Information on the biochemical and chemical compositions
be used as a source of energy. Information on the biochemical and chemical compositions of various
of various
biomass feedstocks
biomass is presented
feedstocks in Table
is presented 1 [23–25],
in Table noting
1 [23–25], that the
noting thatvalues givengiven
the values are representative
are representative of of
each each
feedstock type. According to various studies [26–28] the use of biofuels in the EU reached
feedstock type. According to various studies [26–28] the use of biofuels in the EU reached 564 564 PJ
in 2012 and
PJ in is expected
2012 to reach
and is expected toabout
reach 1216
aboutPJ1216
in 2020,
PJ in accounting more more
2020, accounting than 90%
than of
90% theofrenewable
the renewable
energy that will
energy that be used
will in transportation.
be used Biodiesel
in transportation. production
Biodiesel by feedstock
production is summarized
by feedstock is summarized for the
for the
EU, USA and the world in Figure 1 [29,30].
EU, USA and the world in Figure 1 [29,30].

Figure 1. Feedstock
Figure inputsinputs
1. Feedstock for biodiesel production
for biodiesel in the European
production Union (2016),
in the European UnionUSA (2016)
(2016), USAand the and
(2016)
worldthe
(2013). Data from Ref. [29,30].
world (2013). Data from Ref. [29,30].
Energies 2019, 12, 809 4 of 41

Table 1. Biochemical and chemical analysis of various biomass feedstocks. Data taken from [23–25].

Structural Analysis (wt% dry) Ultimate Analysis (wt% daf) Ash Cell. +
Feedstock Group Feedstock
Cellulose Hemicellulose Lignin Sum C5 Sum C6 C H N S O (wt% dry) Semihell/Lignin

Sugar cane 31 12 8 - - 50 6.2 0.50 0.17 44 3.3 5.7

Sugar beet 26 28 5 - - 47 6.2 1.93 0.14 45 4.3 12.0
Food Crops Corn 40 30 12 27 31 47 6.2 0.63 0.08 46 2.4 5.7
Wheat 31 20 7 - - 48 5.8 1.40 0.22 44 8.1 7.3
Sorghum 39 24 9 - - 49 5.8 0.91 0.07 44 6.9 6.7
Spruce wood 45 21 28 6 63 49 5.9 0.17 0.02 45 0.9 2.3
Pine 44 25 26 7 57 52 6.3 0.14 0.10 41 0.7 2.7
Forestry
Oak 40 20 25 18 40 50 6.3 0.61 0.09 43 1.4 2.4
Birch 39 29 22 27 39 49 6.2 0.19 0.15 45 0.5 3.2
Bark 24 25 50 - - 53 5.9 0.41 0.05 40 4.1 1.0
Forest Industry
Thinnings 37 18 34 - - 51 5.7 0.59 0.09 42 1.5 1.7
Residues
Shaw dust & shavings 47 21 25 - - 52 5.8 0.12 0.03 42 0.6 2.8
Poplar 46 26 23 18 52 50 6.1 0.25 0.03 44 1.0 3.2
Short Rotation
Eucalyptus 43 23 25 11 52 51 6.1 0.27 0.04 42 1.6 2.6
Forestry/Coppice
Willow 39 18 26 16 41 50 6.1 0.62 0.05 43 2.0 2.1
Switch grass 37 31 23 28 41 49 6.1 0.64 0.12 44 6.3 3.0
Grassy Crops Miscanthus 45 24 21 17 45 50 5.6 0.54 0.06 44 3.7 3.2
Arundo donax 33 27 18 27 33 47 5.7 0.47 0.11 47 3.9 3.4
Straw 37 27 17 21 39 49 5.9 0.76 0.10 44 8.4 3.6
Olive tree prunings 30 18 21 - - 48 6.1 0.88 0.09 46 13.3 2.3
Agricultural Residues
Grape prunings 26 39 32 - - 49 6.0 0.83 0.03 44 2.6 2.0
Bagasse 39 31 18 24 41 49 6.0 0.55 0.10 44 5.8 3.9
Almond shell 36 29 29 29 30 50 6.2 0.89 0.04 43 3.7 2.3
Hazelnut shell 26 30 46 - - 49 5.9 0.77 0.46 45 1.4 1.2
Agro-industrial
Walnut shell 23 20 43 19 26 52 6.2 0.80 0.08 41 1.8 1.0
Residues
Orange peel 16 7 5 - - 50 6.6 1.29 0.07 42 3.8 4.6
Olive husk 23 25 47 - - 51 6.9 1.22 0.07 41 5.5 1.0
Macroalgae 9 7 0 - - 31 4.3 2.00 1.50 38 30.0 n/a
Paper pulp/sludge 59 17 14 12 68 42 5.5 0.79 0.39 52 18.9 5.5
Others
Municipal solid waste 14 2 16 - - 57 6.7 1.83 0.64 33 25.2 1.0
Food industry wastes 18 21 17 - - 50 6.7 1.58 0.21 41 6.6 2.3
 Energies 2019, 12, x FOR PEER REVIEW 5 of 42
Energies 2019, 12, 809 5 of 41
Biodiesel is the main biofuel used in EU transportation systems and in 2016 it was produced
mainly by triglycerides from edible vegetable oils such as sunflower oil (3%), soybean oil (7%), palm
Biodiesel is the main biofuel used in EU transportation systems and in 2016 it was produced
oil (15%) and rapeseed oil (47%). Non-edible yellow grease and animal fats contributed 18% and 8%,
mainly by triglycerides from edible vegetable oils such as sunflower oil (3%), soybean oil (7%), palm oil
respectively [28]. At the same time, bio-ethanol in the EU is produced using sugars and starches
(15%) and rapeseed oil (47%). Non-edible yellow grease and animal fats contributed 18% and 8%,
from edible crops such as sugar beet (57.9%), corn (19.8%), wheat (18.8%), barley (1.8%) and rye
respectively [28]. At the same time, bio-ethanol in the EU is produced using sugars and starches from
(1.8%) [28]. These numbers makeclear that the biofuel industry is heavily dependent on edible seeds
edible crops such as sugar beet (57.9%), corn (19.8%), wheat (18.8%), barley (1.8%) and rye (1.8%) [28].
and crops with obvious food security implications. In view of this problem a 2014 European Council
These numbers makeclear that the biofuel industry is heavily dependent on edible seeds and crops
decision has set that in 2020 first generation biodiesel and bio-ethanol from edible raw biomass must
with obvious food security implications. In view of this problem a 2014 European Council decision has
not contribute more than 7% of the transportation energy, promoting the production of second
set that in 2020 first generation biodiesel and bio-ethanol from edible raw biomass must not contribute
generation biofuels from lignocellulosic biomass [31].
more than 7% of the transportation energy, promoting the production of second generation biofuels
Liquid biofuels may be produced by a large variety of biomass feedstocks which can be
from lignocellulosic biomass [31].
classified by type as: a) triglycerides, b) sugars and starches and c) lignocellulosic biomass.
Liquid biofuels may be produced by a large variety of biomass feedstocks which can be classified
by2.1.
type as: (a) triglycerides, (b) sugars and starches and (c) lignocellulosic biomass.
Triglycerides
2.1. Triglycerides
Oil and fat triglycerides share a common chemical structure as shown in Figure 2a. They have
as a backbone the trialcohol glycerol (C3H8O3, Figure 2b) and they are formed by the substitution of
Oil and fat triglycerides share a common chemical structure as shown in Figure 2a. They have as
the H2 atoms of the three hydroxyl radicals (O–H) of the alcohol by three fatty acid residues.
a backbone the trialcohol glycerol (C3 H8 O3 , Figure 2b) and they are formed by the substitution of the
Although vegetable oils are preferred as the main lipid source for biodiesel and green diesel
H2 atoms of the three hydroxyl radicals (O–H) of the alcohol by three fatty acid residues. Although
production, animal and fish fats have also great potential for the production of biofuels. Rich
vegetable oils are preferred as the main lipid source for biodiesel and green diesel production, animal
triglyceride sources are also waste cooking oils (WCO) such as waste palm oil, waste rapeseed oil
and fish fats have also great potential for the production of biofuels. Rich triglyceride sources are also
and waste sunflower oil [32–34].
waste cooking oils (WCO) such as waste palm oil, waste rapeseed oil and waste sunflower oil [32–34].

a) Oil and fat triglycerides b) Glycerol (C3H8O3) c) Three different fatty acids

Figure
Figure2. (a)
2. a)The
Thecommon
common chemical
chemical structure of of
structure oiloil
and fatfat
and triglycerides, (b)b)
triglycerides, the glycerol
the molecule
glycerol and
molecule and
(c)c)symbolization
symbolizationofofthree different
three fatty
different acids.
fatty acids.

Table
Table 2 presents
2 presentstypical
typicalwt%wt%composition
compositionof of these fatty acids
these fatty acidsin inthe
themost
mostcommon
commonvegetable
vegetable oils
oils and in some animal and fish fats. Vegetable oils have high concentrations
and in some animal and fish fats. Vegetable oils have high concentrations of unsaturated fatty acids of unsaturated fatty
acids
suchsuch as linolenic
as linolenic (18:3),
(18:3), linoleic(18:2)
linoleic (18:2)andandoleic
oleic (18:1)
(18:1) acids.
acids. Instead,
Instead, animal
animalfatsfatshave
havehigher
higher
concentrations of saturated fatty acids such as stearic (18:0) and palmitic
concentrations of saturated fatty acids such as stearic (18:0) and palmitic (16:0) [35–37]. (16:0) [35–37].
Microalgae
Microalgae represent
representa new
a newbiomass
biomass family which
family is expected
which to support
is expected the production
to support the production of theofsothe
called “third generation” biodiesel and green diesel fuels. These are primary
so called “third generation” biodiesel and green diesel fuels. These are primary unicellular unicellular organisms
that are foundthat
organisms in abundance
are found in inabundance
all aquatic systems and can
in all aquatic serveand
systems as a can
plentiful
serve source of triglyceride
as a plentiful source of
oils [38,39]. Microalgae have significant growth rates and can be produced
triglyceride oils [38,39]. Microalgae have significant growth rates and can be produced in non-arable in non-arable places,
avoiding the undesirable
places, avoiding competition
the undesirable for cultivation
competition land. Moreover,
for cultivation research is
land. Moreover, underway
research on the
is underway
genetic manipulation of microalgae for the development of improved strains
on the genetic manipulation of microalgae for the development of improved strains for each desired for each desired final
product [40]. The most common fatty acids of microalgae are palmitic (16:0), stearic
final product [40]. The most common fatty acids of microalgae are palmitic (16:0), stearic (18:0), oleic (18:0), oleic (18:1),
linoleic
(18:1), (18:2),
linoleiclinolenic (18:3) and
(18:2), linolenic some
(18:3) andspecies may also
some species have
may alsoeicosapentaenoic acid (20:5)
have eicosapentaenoic acid and
(20:5)
docosahexaenoic acid (22:6), as shown for some microalgae species in Table
and docosahexaenoic acid (22:6), as shown for some microalgae species in Table 3 [41]. The methods 3 [41]. The methods
employed
employed forfor
thetheextraction,
extraction,characterization
characterization and
andpurification
purification ofof
the algae
the algaelipids
lipidshave
havebeen
beenrecently
recently
summarized by Santillan-Jimenez
summarized by Santillan-Jimenez et al. [42]. et al. [42].
.
Energies 2019, 12, 809 6 of 41

Table 2. Typical fatty acid composition of various vegetable oils, animal fats and fish fats. Data obtained from [35–37].

Typical Fatty Acid Composition, wt%

Fatty acid Vegetable Sources Animal and Fish Sources
Rapeseed Palm Soybean Sunflower Jatropha Camelina Beef Fat Chicken Fat 1 Yellow Grease Lard 2 Tallow Salmon 3
Capric (10:0) 0.56 0.48 0.10
Lauric (12:0) 0.09 0.09 0.10 0.09 0.36 0.19 0.19
Myristic (14:0) 1.05 0.09 0.10 0.28 2.56 3 1 0.78 2 2.55 3
Palmitic (16:0) 4.04 41.59 11.07 6.31 14.36 5.79 27 22 16.03 27 23.85 11
Palmitoleic (16:1) 0.09 0.19 0.18 0.10 0.93 11 6 0.85 4 2.55 5
Stearic (18:0) 2.1 3.6 3.72 3.55 5.88 2.66 7 6 6.90 11 17.86 4
Oleic (18:1) 57.26 40.41 22.61 21.39 38.94 15.96 48 37 43.34 44 41.42 25
Linoleic (18:2) 20.69 9.3 51.33 63.35 34.89 16.15 2 20 24.39 11 4.32 5
Linolenic (18:3) 8.08 0.29 5.63 1.46 0.28 33.81 1 1.07 0.88 5
Arachidic (20:0) 0.37 0.29 0.27 0.29 0.19 1.33 0.28 0.20
Eicosenoic (20:1) 2.02 0.10 0.27 0.19 0.09 13.68 0.47 0.59
Behenic (22:0) 0.28 0.10 0.27 0.58 0.19 0.81 0.38 0.10
Erucic (22:1) 0.46 0.09 0.10 0.09 2.94 0.09 0.10
Total Saturated 7.06 48.85 15.70 11.22 23.58 14.18 37 29 24.94 40 46.87 18
Total Unsaturated 88.80 50.28 80.39 88.69 75.31 84.87 61 65 75.06 59 51.21 80
1 Chicken fat corresponds also to turkey fat and contains also 1% gadoleic and 6% others. 2 Lard refers to hog fat. 3 Salmon is considered as skinned fillet and contains also 2% stearidonic

(18:4), 5% arachidonic (20:4), 2% eisositetrenoic (20:4), 2% eicosipentenoic (25:5), 2% docosatetrenoic (22:4), 7% docosapentenoic (22:5), 17% docosahexenoic (22:6).
Energies 2019, 12, 809 7 of 41

Green diesel can be produced by a larger range of feedstocks in comparison to biodiesel.

The transesterification of an unsaturated feedstock provides a biodiesel blend of unsaturated FAMEs
which is susceptible to oxidative instability or may react with the alkaline catalysts to give soaps.
As a result, biodiesel production needs special concern on the concentration of the unsaturated fatty
acids [13,32]. On the other hand, green diesel is produced through the saturation of the triglycerides
with H2 and results in a blend of saturated hydrocarbons regardless the initial feedstock [19,22].

Table 3. Typical fatty acid composition of various microalgae species. Data from [41]. sp.: species.

Typical Fatty Acid Composition, wt%

Fatty acid Nannochlopsis Picochlorum Phaeodactylum Amphidinium Bidduphia Extubocellulus
Oculata. sp. Tricornutum sp. sp. sp.
Capric (10:0) 0.07
Lauric (12:0) 0.41
Myristic (14:0) 5.76 0.55 3.29 0.79 21.50 6.61
Palmitic (16:0) 32.21 17.03 23.62 35.68 23.62 25.56
Palmitoleic (16:1) 29.57 1.22 48.16 1.08 33.36 60.52
Stearic (18:0) 0.98 3.45 0.81 4.10 0.73 0.95
Oleic (18:1) 20.10 15.73 3.61 19.35 1.47 3.21
Linoleic (18:2) 1.28 36.22
Linolenic (18:3) 15.07
Arachidic (20:0) 2.11 5.68
Eicosapentaenoic acid (20:5) 8.26 12.13 11.94 9.65
Docosahexaenoic acid (22:6) 20.21
Total Saturated 40.5 23.7 28.1 46.3 48.8 33.6
Total Unsaturated 59.5 76.3 71.9 53.7 51.2 66.4

2.2. Sugars and Starches

Simple sugars (e.g., sugar cane and sugar beet) or starches (e.g., corn, wheat and sorghum) may be
used as feedstocks for the production of renewable liquid biofuels [43]. The sugars contained into the
biomass are transformed into bio-ethanol and CO2 through enzymatic fermentation, a process which is
well established in the liquor industry for the production of alcoholic beverages [44]. Starch containing
biomass may also be of use after the pretreatment of enzymatic hydrolysis which converts the starch
into corresponding sugars [45]. Sugars and starches have been used mainly for the production of
bio-ethanol but recently endeavors have also appeared for the catalytic upgrading of carbohydrates
into higher hydrocarbons, as it will be discussed in Section 4.

2.3. Lignocellulose
Lignocellulose may be used for the production of useful chemicals and/or biofuels through
three technological routes: (a) biochemical conversion into sugars, (b) thermal pyrolysis, and (c)
thermochemical gasification. The biochemical conversion of lignocellulose aims at the production of
sugars which may then be used for the production of chemicals and/or biofuels through fermentation
or other methods. Both cellulose and hemicellulose are carbohydrate polymers which can be
transformed into sugars through hydrolysis. Hemicellulose can be hydrolyzed under mild acid
or alkaline conditions or by appropriate hemicellulase enzymes. The cellulose fraction is more
resistant and requires more potent pretreatment, especially when the lignin content is high. Lignin
is acknowledged as a major deterrent to enzymatic hydrolysis because it protects hemicellulose and
celullose and makes them less accessible to processing [46,47]. As a result, the biochemical conversion
of lignocellulosic biomass requires special lignin pretreatment techniques such as weak and strong
acid hydrolysis, lime hydrolysis, ammonia hydrolysis, oxidative delignification (extraction of lignin
by chemicals), organosolv processing, steam explosion, CO2 explosion, etc. [48–50]. Herbaceous
biomass feedstocks have more loosely bound fibers and lower lignin content. As a result, hemicellulose
and cellulose are less protected and the biomass is appropriate for biochemical conversion into
sugars. On the other hand, woody biomass is comprised of fibers with high lignin content and
requires significant lignin pretreatment before biochemical conversion. These feedstocks are more
 Energies 2019, 12, x FOR PEER REVIEW 8 of 42
Energies 2019, 12, x FOR PEER REVIEW 8 of 42
Energies 2019, 12, x FOR PEER REVIEW 8 of 42
high lignin content and requires significant lignin pretreatment before biochemical conversion.
high
Energieslignin
2019, 12,content
809 and requires significant lignin pretreatment before biochemical conversion. 8 of 41
high
These lignin contentare
feedstocks and morerequiresappropriate significant lignin pretreatment
for thermal or thermochemical before biochemical
conversion without conversion. any
These feedstocks are more appropriate for thermal or thermochemical conversion without any
These feedstocks are more appropriate for thermal
pre-processing. The last column of Table 1 provides the ratio of cellulose and hemicellulose to lignin, or thermochemical conversion without any
pre-processing. The last column of Table 1 provides the ratio of cellulose and hemicellulose to lignin,
pre-processing.
appropriate
which for The
may indicate thermal last
theor column of Table
thermochemical
appropriate 1 conversion
processingprovides the
for each ratio
without of
anycellulose
lignocellulosic and hemicellulose
pre-processing.
feedstock. The last column to lignin,
of
which
Table
may
1
indicate
provides the
the
ratio
appropriate
of cellulose
processing
and hemicellulose
for each to
lignocellulosic
lignin, which may
feedstock.
indicate the appropriate
which may indicate the appropriate processing for each lignocellulosic feedstock.
processing
3. Hydro-Processing for each lignocellulosic
of Triglycerides feedstock.
3. Hydro-Processing of Triglycerides
3. Hydro-Processing of Triglycerides
In a conventional
3. Hydro-Processing of refinery
Triglycerides hydro-processing describes the catalytic processes in which various
In a conventional refinery hydro-processing describes the catalytic processes in which various
In a conventional
petroleum distillates react refinery withhydro-processing
H2 at elevated temperature describes and the catalytic
pressure processes in which various
to form transportation fuels
petroleum distillates react
In a conventional with hydro-processing
refinery H2 at elevated temperature describes the andcatalytic
pressure to form transportation
processes in which various fuels
petroleum
and heating distillates
oil. Thisreact with H2 at elevated
is accomplished throughtemperaturethe destructive andhydrogenation
pressure to form of transportation
the heavy distillates fuels
petroleum
and heatingdistillates
oil. This is react with H2 at elevated
accomplished throughtemperature
the destructive and pressure
hydrogenation to formof transportation
the heavy distillates fuels
and
intoheating
lighteroil. with This is accomplished
appropriate boilingthrough point and the through
destructive the hydrogenation
non-destructiveofhydrogenation the heavy distillates of the
andlighter
into heatingwith oil. This is accomplished
appropriate boilingthrough point and the through
destructive thehydrogenation
non-destructive of the heavy distillates
hydrogenation of the
light
into distillates
lighter withwhich appropriate improves boilingtheir pointquality and [51,52].
through Destructive hydrogenation
the non-destructive or hydrocracking
hydrogenation of the is
into distillates
light lighter with which appropriate
improves boiling point and
their quality through
[51,52]. the non-destructive
Destructive hydrogenation hydrogenation
or hydrocracking of the is
favored
light by high
distillates which temperatures,
improves their highqualityhydrogen [51,52]. pressures
Destructive and hydrogenation
strong acid catalysts and catalyst
or hydrocracking is
light distillates
favored by highwhich improves their
temperatures, high qualityhydrogen [51,52]. Destructive
pressures and hydrogenation
strong acid catalysts or hydrocrackingand catalyst
supports
favored by(alumino-silicates,
high temperatures, silico-alumino-phosphates
high hydrogen pressures (SAPO) and
and strong
strong zeolites). Typical conditions
acidcatalysts
catalysts and catalystfor
supports (alumino-silicates, silico-alumino-phosphates (SAPO) and zeolites). Typicaland
is favored by high temperatures, high hydrogen pressures and acid catalyst
conditions for
the
supports hydrocracking
supports (alumino-silicates, of
(alumino-silicates, the petroleum distillates
silico-alumino-phosphates
silico-alumino-phosphates are 350–430 (SAPO)and
(SAPO) °C at 100-200
andzeolites). bar
zeolites). with
Typical
Typical a space velocity
conditions
conditions for forof
the
0.2–2
hydrocracking
h and H2/feed
−1 of the petroleum
ratios of 800–2000
distillates m /m3 are 3 350–430
[52,53].◦ C
°C at 100-200
Non-destructive
bar with a
hydrogenation
space velocity
is called
of
thethehydrocracking
hydrocracking ofofthe the petroleum
petroleum distillates
distillates are 350–430 °C atat100-200
100-200 bar with a space velocity of of
0.2–2 h−1−1 and H2/feed
hydrotreatment and is ratios
favored of by 800–2000
mild m33are/m33 350–430
temperatures, [52,53]. mild Non-destructive
pressures
bar
and
with a space
hydrogenation
catalysts of
velocity
mild isacidity.
called
0.2–2
0.2–2hh−1and andHH2/feed2 /feed
ratios
ratiosof of 800–2000
800–2000 m m3 /m /m 3 [52,53].
[52,53]. Non-destructive
Non-destructivehydrogenation hydrogenation is called
is called
hydrotreatment
Of these the most and is favored
common types by mild
are the temperatures,
sulfided Ni–W/Al mild2O pressures
3, Co–Mo/Αl
and2O catalysts
3 and Ni–Mo/Αl
of mild acidity.
2O3 [52]
hydrotreatment and is favored by mild temperatures,
hydrotreatment and is favored by mild temperatures, mild pressures and catalysts of mild acidity. mild pressures and catalysts of mild acidity.
Of these
which arethe most common types are the sulfided Ni–W/Al 2O3, Co–Mo/Αl2O3 and Ni–Mo/Αl2O3 [52]
Of Ofthese
these thealso
the most
most used common
common for thetypes hydrodesulfurization
types areare the the sulfided
sulfided of petroleum
Ni–W/Al
Ni–W/Al 2 O32,O
distillates
3, Co–Mo/Αl
Co–Mo/Al [54].
2 O32O 3 and
and Ni–Mo/Αl
Ni–Mo/Al 2 O32O 3 [52]
[52]
whichInare thealso used
biofuel for the
industry hydrodesulfurization
hydro-processing of petroleum
describes the distillates
chemical [54].
reaction of the triglycerides
which are also used for the hydrodesulfurization
which are also used for the hydrodesulfurization of petroleum distillates [54]. of petroleum distillates [54].
In the in
contained biofuel
biomass industry
lipids with hydro-processing
H2 for the production describes ofthethe
liquid chemical
hydrocarbon reaction fuelsof [55].
the triglycerides
H2 saturates
InInthe thebiofuel
biofuel industry
industry hydro-processing
hydro-processing describes
describes the chemical
chemical reaction
reaction of ofthethe triglycerides
triglycerides
contained
the double in biomass
bonds lipids
oflipids with
the triglycerides H 2 for the production of liquid hydrocarbon fuels [55]. H2 saturates
andproduction
under specific conditions mayfuels provide different liquid
contained
contained ininbiomass
biomass lipids with H H22 for
for thethe production ofofliquid
liquid hydrocarbon
hydrocarbon fuels[55].[55].
H2 H 2 saturates
saturates
the
fuels double
thedoublesuch
double bonds
bonds
as green
bonds of
of the
diesel triglycerides
(C –C ), and
green under
jet fuel specific
(C –C )conditions
and green may
naphtha provide (C –Cdifferent
). liquid
Obviously,
the ofthe thetriglycerides
triglycerides
15 18 and andunder under specificspecific
11conditions
13 conditionsmay providemay provide different5 liquid fuels
different
10 liquid
fuels
the such
suchproduction
as green as greendiesel diesel
of light (C15 –C(C15such
fuels –C
), 18), green jet fuel (C11–C13) and green naphtha (C5–C10). Obviously,
green as green
jet fuel naphtha
(C –C requires
) and conditions
green naphtha of high
(C –C temperature,
). Obviously, high
fuels such as green diesel (C15 18 –C 18 ), green jet fuel 11 (C 13
11 –C 13 ) and green naphtha 5 (C 10
5 –C 10 ). Obviously,
the
the production
pressureproductionand ofoflight
strong light fuels
acidic fuels such
catalysts
such asas green
and naphtha
supports
green naphtha thatrequires
promote
requires conditions
hydrocracking.
conditions of ofhigh On
high temperature,
the other
temperature, high
hand,
the production of light fuels such as green naphtha requires conditions of high temperature, high
pressure
highproduction and strong
pressure and acidicacidic
strong catalysts and
catalysts supports
and as supports that promote
that promote hydrocracking.
hydrocracking. On On the other hand,
the
pressure and strong of heavyacidicgreen catalysts fuels such
and supports green thatdieselpromote requires conditions
hydrocracking. that the the
On promote other other
mainly
hand,
the
hand,production
the production
hydrotreatment, of heavy
although green
of green
heavy fuels
greensuch
hydrocracking such as
fuelsassuch maygreen asalso diesel
green requires
be dieselused requires conditions
to conditions conditions
a limited that
extent promote
thattopromote causemainlythe
the production of heavy fuels green diesel requires that promote mainly
hydrotreatment,
mainly hydrotreatment, although hydrocracking
although hydrocracking may also
may be
also used
be used to a limited extent to cause the
isomerization
hydrotreatment, of although
the hydrocarbons. hydrocracking In this may respect, also the beconversion
used to toof
a atriglycerides
limited extent
limited extent intototocause
greencause the
diesel
the
isomerization
isomerization
requires mild of
of the
the
temperatures hydrocarbons.
hydrocarbons. in the In this
In
range thisofrespect,
respect,
280–450 the
the °C, conversion
conversion
pressures of of
of triglycerides
triglycerides
1–5 MPa andinto intogreen
solid green diesel
catalysts dieselof
isomerization of the hydrocarbons. In this respect, the
◦ C, pressures
conversion of triglycerides into green diesel
requires
requires
mild acidity mild
mild temperatures
temperatures
[56]. The sulfided in inthe the range
range of of 280–450
280–450 °C, pressures of 1–5 ofMPa1–5 MPa
and and
solid solid
catalysts catalysts
of mild of
requires mild temperatures in theNi–Mo/Αlrange of 2280–450 O3, Co–Mo/Αl °C, pressures 2O3 andof Ni–W/Al
1–5 MPa 2Oand
3 catalysts mentioned
solid catalysts of
mild
acidity
before acidity
[56].the
are [56].
The most The
sulfided sulfided
commonly Ni–Mo/Al Ni–Mo/Αl
used 2O catalysts 2O3, Co–Mo/Αl
3 , Co–Mo/Al also O3 the
2for O3 and Ni–W/Al
andhydrotreatment
2Ni–W/Al 2 O3 catalysts
of 2O3 catalysts
the mentioned
triglycerides mentioned
before
and an
mild acidity [56]. The sulfided Ni–Mo/Αl2O3, Co–Mo/Αl2O3 and Ni–W/Al2O3 catalysts mentioned
before
are theare
advantage most thecommonly
most commonlyused catalysts used catalysts
also for the also for the hydrotreatment
hydrotreatment of the triglyceridesof the triglycerides
anditancan advantage and an
before are theofmost the commonly
hydro-processing used catalysts route for
alsogreenfor thediesel production
hydrotreatment ofisthethat
triglycerides beand easily
an
of the
advantage
accomplishedhydro-processing
of the route
hydro-processing
in hydro-processing
the existed refinery for green diesel production
route for green is
diesel that it can
production be easily accomplished
is that it can in the
be hydro-
easily
advantage of the routefacilities
for green used diesel for production
the hydro-processingis that it can andbe easily
existed
accomplished refinery
desulfurizationinof the infacilities
the used
existed
the petroleum for the
refineryhydro-processing
facilities
fractionsfacilities usedand hydro-
for the desulfurization
[55,56]. used for the hydro-processing and hydro- hydro-processing of the petroleum
and hydro-
accomplished existed refinery
fractions
desulfurization
The [55,56]. of the petroleum
hydro-processing of a fractions [55,56].
triglyceride initiates with the saturation of the double bonds of its
desulfurization
Thehydro-processingof the petroleum
hydro-processing fractions [55,56].
of aa triglyceride initiates with
The
fattyThe acid chains by hydrogen of triglyceride
(hydrogenation) initiates withthe
and continues thesaturation
saturation
with the removal
of ofthethedouble
double
of oxygen
bonds bonds of its
from of its
fatty acid hydro-processing
chains by hydrogen of a(hydrogenation)
triglyceride initiates and with thewith
continues saturation
the removalof theofdouble
oxygen bonds
from of the
the its
fatty acid chains
triglyceride by hydrogen
molecules, which (hydrogenation)
converts them into and continues
saturated with the removal
hydrocarbons. The of oxygen
reactions from the
causing the
fatty acid chains
triglyceride by hydrogen
molecules, whichconverts(hydrogenation)
convertsthem theminto intoandsaturated
continues with the removal
hydrocarbons. of oxygen
Thereactions
reactions from the
causing
triglyceride
oxygen removal molecules, fromwhich which
the triglyceride molecule saturated
are commonly hydrocarbons.termed The The
as reactions causing
of selectivethe
triglyceride
the oxygen molecules,
removal from the converts
triglyceride them into
molecule saturated
are commonly hydrocarbons.
termed as reactions
reactions of causing
selective the
oxygen
deoxygenation removal (SDO) from the triglyceride
andtriglyceride
may be further molecule are commonly
classified into the reactions termed asof reactions hydrodeoxygenationof selective
oxygen
deoxygenationremoval(SDO) fromand the may be furthermolecule classified into are the commonly
reactionstermed as reactions
of hydrodeoxygenation of(HDO),
selective
deoxygenation
(HDO), decarbonylation (SDO) and may
(deCO) be be further
andfurther
decarboxylationclassified into
(deCO the reactions of hydrodeoxygenation
2), as shown in the following reactions
deoxygenation
decarbonylation(SDO) (deCO) and andmay decarboxylation classified
(deCO 2 ), as into
shown the in reactions
the following of hydrodeoxygenation
reactions [55,56]:
(HDO), decarbonylation (deCO) and decarboxylation
[55,56]:decarbonylation (deCO2), as shown in the following reactions
(HDO), (deCO) and decarboxylation (deCO2), as shown in the following reactions
[55,56]:
[55,56]:
(1)
(1)
(1)
(2)
(2)
(2)
(3)
(3)
Decarboxylation and decarbonylation are commonly referred as deCOx reactions. (3) In
Decarboxylation
decarboxylation the Oand decarbonylation
2 molecules are removed areincommonly
the form ofreferred
CO2 whileas indeCO x reactions. the
decarbonylation In
Decarboxylation and decarbonylation are commonly referred as deCOx reactions. In
decarboxylation the O molecules are removed in the form of CO while
oxygen molecules are removed as CO and H2O. In both these deCOx cases the saturated
2 2 in decarbonylation the
decarboxylation the O2 molecules are removed in the form of CO2 while in decarbonylation the
oxygen molecules
hydrocarbon are removed
produced has one C as COless
atom and H2the
than O. parent
In bothfatty
these
aciddeCO
chainx incases the saturated
the triglyceride. In
oxygen molecules are removed as CO and H2O. In both these deCOx cases the saturated
hydrocarbon produced
HDO the oxygen has one
molecules are C atom less
removed than the as
exclusively parent
H2O fatty
and theacid chain inhydrocarbon
saturated the triglyceride.
has anIn
hydrocarbon produced has one C atom less than the parent fatty acid chain in the triglyceride. In
HDO the oxygen molecules are removed exclusively as H2O and the saturated hydrocarbon has an
HDO the oxygen molecules are removed exclusively as H2O and the saturated hydrocarbon has an
Energies 2019, 12, 809 9 of 41

Decarboxylation and decarbonylation are commonly referred as deCOx reactions.

In decarboxylation the O2 molecules are removed in the form of CO2 while in decarbonylation the
oxygen molecules are removed as CO and H2 O. In both these deCOx cases the saturated hydrocarbon
produced has one C atom less than the parent fatty acid chain in the triglyceride. In HDO the oxygen
molecules are removed exclusively as H2 O and the saturated hydrocarbon has an equal number
of C atoms with the corresponding fatty acid bound in the triglyceride. As a result, the saturated
hydrocarbons produced by the hydro-processing process will have about the same C atoms with the
fatty acid chains of the triglycerides. The three SDO reactions form a complex mechanism in which the
accurate determination of their individual contribution is generally difficult. However, the catalytic
preference to deCOx or HDO reactions may be estimated by the distribution of the liquid hydrocarbons
and the C17 /C18 ratio and the preference between the deCO2 and deCO reactions may be found
through the CO2 /CO ratio [55,57]. The conversion of the triglycerides, the degree of deoxygenation
(DOD) and the yield of normal saturated hydrocarbons tend to increase with the reaction temperature
in both batch and continuous reactors. However, the yield of C15 –C18 hydrocarbons maximizes at
an optimal temperature and then reduces due to hydrocracking and reverse water gas shift (RWGS)
reactions. Higher H2 pressures have been observed to enhance both the yield of hydrocarbons and the
selectivity to green diesel. Also, the higher H2 pressures promote the HDO reaction pathway [39].
The H2 consumption obviously depends on the chemistry of the feedstock. Highly unsaturated oils
such as rapeseed oil and fish oils require higher H2 consumption since they have more double bonds.
Finally, in all cases, propane (C3 H8 ) is produced as a side product together with H2 O, CO and CO2
from the SDO reactions.
The deoxygenation of triglycerides provides a green diesel consisting mainly of normal (straight
chain) saturated hydrocarbons in the C15 –C18 range. These hydrocarbons have a high cetane number
but poor cold flow properties since they have a high freezing point above 15 ◦ C [58]. One solution to
this problem is to blend green diesel with petroleum diesel as a cetane number improver. Another
solution to this problem comes with the hydroisomerization of the normal saturated hydrocarbons
into branched chain isomers with lower freezing point appropriate for use in engines under cold
weather and cold start conditions, though with the cost of lower cetane numbers [55,56]. Isomerization
changes the structure of a molecule leaving its molecular weight the same. Given that saturated
hydrocarbons are not prone to direct isomerization they must be processed in an appropriate way
and hydroisomerization is an appropriate technique in this direction. The hydroisomerization of a
saturated hydrocarbon takes place in three steps starting with its dehydrogenation into the same carbon
atom alkene and proceeds with the skeletal isomerization of the alkene and its final hydrogenation
into the branched isomer saturated hydrocarbon. This three step process is feasible in light saturated
hydrocarbons with less than 7 carbon atoms but it is generally difficult for heavier molecules without
some extent of hydrocracking [59]. In the case of the heavy saturated hydrocarbons of the green diesel,
isomerization needs a balanced action of hydroisomerization and hydrocracking over an appropriate
heterogeneous catalyst that can increase selectivity to the desired isomer hydrocarbons [60,61]. This
is achieved by using acidic catalysts such as commercial FCC catalysts, zeolites or other supports.
The hydromerization of green diesel may lower the freezing point from 20 ◦ C below −10◦ causing also
a drop of the cetane number from about 100 to 70.
The global market of green diesel is growing in great volumes, from 330 × 106 gallons in 2011 to
2.1 × 109 gallons in 2017 [62]. A list of the main green diesel producers is given in Table 4 [63]. Most of
the producers have developed proprietary technologies (Neste NExBTL, UOP/Eni EcofiningTM ,
UPM BioVerno etc.) and standalone plants comprised by the biomass cleanup and pretreatment
section, the deoxygenation (hydrotreatment) section, a hydroisemarization reactor and a separation
column, as shown in Figure 3a. Given that green diesel can be mixed with conventional petroleum
diesel to satisfy the automotive fuel specifications, some oil refineries have developed methods
for the simultaneous co-processing of triglyceride feedstocks with petroleum intermediates such
as straight run gas oil and/or vacuum gas oil, as shown in Figure 3b [55,56]. This is economically
 Energies 2019, 12, x FOR PEER REVIEW 10 of 42

hydrodesulfurization of the gas oil in the same reactor and over the same sulfided catalysts such as
Energies 2019, 12,2809
Co–Mo/Al O3 and
Ni–Mo/Al2O3. The co-processing typically takes place at 350–450 °C and 10 50–100
of 41

bar by mixing 5–20% vegetable oils with 80–95% gas oil and leads to gas phase products such as
C1–C4 saturated hydrocarbons, green propane, CO, CO2 etc., and liquid phase products such as
attractive for the existing refineries which can combine the hydrotreating of the triglycerides with the
straight C5–C30 hydrocarbons with high yields to C15–C18 green diesel [55].
hydrodesulfurization of the gas oil in the same reactor and over the same sulfided catalysts such as
Co–Mo/Al2 O3 and Ni–Mo/Al2 O3 . The co-processing typically takes place at 350–450 ◦ C and 50–100
bar by mixing Table
5–20%4.vegetable
List of the oils
mainwith
green diesel producers
80–95% gas oil andcurrently
leads toingas
operation. Data from
phase products [62].as C1 –C4
such
saturated
Company hydrocarbons, green propane, CO, CO 2 etc., and liquid phase products such as straight
C5 –C30 Location Feedstocks
hydrocarbons with high yields to C15 –C18 green diesel [55]. Capacity Technology
Name
Neste The Netherlands Vegetable oil and waste animal fat 1,000,000 tn/year NExBTL
Neste List of the main greenVegetable
Table 4.Singapore diesel producers currently
oil and waste in operation.
animal Data tn/year
fat 1,000,000 from [62]. NExBTL
Diamond Green Non-edible vegetable oils and
Company Name USA Location Feedstocks Capacity
900,000 tn/year Technology
EcofiningTM
Diesel animal fats
Neste The Netherlands Vegetable oil and waste animal fat 1,000,000 tn/year NExBTL
Vegetable oils, animal fats and
Neste
UOP/Eni Singapore
Italy Vegetable oil and waste animal fat 1,000,000 tn/year
780,000 tn/yearNExBTLEcofiningTM
Diamond Green used cooking
Non-edible oils oils and
vegetable
USA 900,000 tn/year EcofiningTM
Neste
Diesel Finland Vegetable
animal fats oil and waste animal fat 380,000 tn/year NExBTL
Renewable Vegetable oils, animal fats and TM
UOP/Eni Italy High and low free fatty acid 780,000 tn/year Ecofining
Dynamic Fuels
used cooking oils
Energy Group USA 250,000 tn/year
Neste Finland feedstocks
Vegetable oil and waste animal fat 380,000 tn/year NExBTLLLC
(REG) Inc. Energy
Renewable High and low free fatty acid Dynamic Fuels
USA Non-edible 250,000 tn/year
Group (REG) Inc. feedstocks natural oils and LLC
AltAir Fuels USA 130,000 tn/year EcofiningTM
Non-edible natural
agricultural waste oils and
AltAir Fuels USA 130,000 tn/year EcofiningTM
UPM Biofuels Finland agricultural
Crude waste
tall oil 100,000 tn/year UPM BioVerno
UPM Biofuels Finland Crude tall oil 100,000 tn/year UPM BioVerno
NOTES: Also, there are a number of companies co-processing vegetable oils with petroleum distillates such as
NOTES: Also, there are a number of companies co-processing vegetable oils with petroleum distillates such as
Petrobras (Brazil), Cepsa (with several refineries in Spain), Preem (Sweden), Repsol (with several refineries in
Petrobras (Brazil), Cepsa (with several refineries in Spain), Preem (Sweden), Repsol (with several refineries in Spain)
Spain)
andand British
British Petroleum
Petroleum (Australia)
(Australia).

(a)

(b)

Figure
Figure 3. 3.Schematic
Schematicrepresentation
representationof of a standalone
a standalone biomass
biomass hydroprocessing
hydroprocessing plant
plant (a) (a)
andand
a a
co-prosessing hydroprocessing plant for biomass and petroleum distillates
co-prosessing hydroprocessing plant for biomass and petroleum distillates (b). (b).

Catalytic research
Catalytic researchon onthethe
hydrotreatment
hydrotreatment of the triglycerides
of the hashas
triglycerides mostly focused
mostly focusedon on
thethe
sulfided
sulfided
catalysts Ni–Mo/Al
catalysts Ni–Mo/Al 2 O2O
3 [64–80], Co–Mo
3 [64–80], Co–Mo[71,75,77,80–85],
[71,75,77,80–85], and
andPtPt
onon
various
varioussupports
supports[74,84,86]. Ni–,
[74,84,86]. Ni–,
Co– andand
Co– Mo–Mo–based catalysts
based are preferred
catalysts to noble
are preferred metals
to noble as they
metals asshow high activity,
they show while they
high activity, also
while they
have low
also cost.low
have Srifa et al.
cost. [87]et
Srifa have
al. examined
[87] have the monometallic
examined catalysts Ni,catalysts
the monometallic Co, Pt and
Ni,Pd supported
Co, Pt and Pd
on Al2 O3 and found that the catalytic activity was of the order Co > Pd > Pt > Ni. They also observed
Energies 2019, 12, 809 11 of 41

that only Co promotes HDO stronger than deCOx reactions. Ni and Co are often used as promoters
to increase the activity of molybdenum sulfide, as it is believed that they donate electrons to Mo,
which weakens the metal–sulfide bond. However, it has been found that the activity of the sulfided
catalysts decreases over time due to a loss in MoS2 active sites and to the presence of water due to HDO.
This means that a continuous supply of a sulfiding agent, such as H2 S, is necessary in order to avoid
either the oxidation of the sulfide catalyst or the reduction by H2 of the sulfide phase [88]. Kubı̆cka
and Kaluža [72] have examined the deoxygenation of rapeseed oil over sulfided Ni, Mo and Ni–Mo
catalysts supported over Al2 O3 and observed that Ni produces exclusively n-C17 H36 and no n-C18 H38
while Mo produces only a small fraction of C17 H36 and almost exclusively C8 H18 . This behavior
implies that Ni promotes exclusively the deCOx of the fatty acids while Mo promotes their HDO.
This is explained by the inherently different electronic properties of the Mo and Ni sulfided phases.
In the Ni-Mo catalyst, both n-C17 H36 and no n-C18 H38 were observed as products in appreciable
quantities with a C17 /C18 weight ratio equal to 0.36 (at 260–280 ◦ C, 35 bar and Liquid Hour Space
Velocity, LHSV, = 0.25–0.4 h−1 ). Given that Ni was used as a promoter in lower concentration than
Mo, it was deduced that over Ni-Mo the main product is n-C18 H38 and the main reaction pathway
is HDO [72]. Laurent et al. [89], examined the impact that H2 O and H2 S have on the HDO of
guaiacyl, carboxylic and carbonyl groups, using NiMo/CoMo catalysts that were based on γ-Al2 O3 ,
and concluded that Brønsted acidity of the sulfide phase increases in the presence of H2 S during the
reaction. Toba et al. [80] have examined the hydrotreatment of waste cooking oil (WCO) using sulfided
Ni–Mo/Al2 O3 , Co–Mo/Al2 O3 , and Ni–W/Al2 O3 catalysts and observed that although all catalysts
have high catalytic activity for production of C15 –C18 hydrocarbons there exists a small difference
in the order Ni–Mo > Ni–W > Co–Mo. At the same study, the effect of the support was examined
on Ni–Mo/Al2 O3 and Ni–Mo/B2 O3 –Al2 O3 catalysts and it was shown that due to higher acidity,
B2 O3 –Al2 O3 increases the production of branched isomers and improves the cold fuel properties of the
biofuel. Phosphorus has also been tried as a promoter of Mo-based catalysts during hydrotreatment
of bio-oil and model compounds. It was concluded that phosphorus enhances the dispersion of Mo
on to the support, helps reduce the formation of coke, favors the creation of new Brønsted and Lewis
acid sites on the surface of the support and increases the packing of MoS2 crystallites [90]. As is well
understood, the nature of the support can have a significant effect on the performance of a catalytic
system and as a result a number of different metal oxides, such as Al2 O3 , TiO2 , ZrO2 and CeO2
have been tested as carriers [91]. As alumina supports have been used extensively for the removal
of sulfur from crude oil (upgrading of oil), a number of authors have examined its performance for
hydrodeoxygenation in bio-oil upgrading. The main issues identified are the susceptibility of alumina
to attack by acidic water at elevated conditions and its reaction with H2 O which leads to a reduction of
surface area [92]. Moreover, as alumina is not inert (as it possesses acid centers, mainly of Lewis type),
promoters such as Ni and/or Co can react with Al2 O3 and take up tetrahedral and octahedral sites
found in the external layers [93]. As a consequence, a strong interaction develops between the support
and the modifier, which in turn inhibits the dispersion of the Mo sulfide phase and affects HDO
activity in a negative way [94]. The effect of the support has been examined also by Kubı̆cka et al. [75]
who examined the hydrotreatment of rapeseed oil over Co-Mo supported on Al2 O3 , MCM-41 and
Organized Mesoporous Alumina (OMA) and shown that the formation of branched isomers follows
the order OMA > Al2 O3 > MCM-41. A promising supporting material for HDO is activated carbon
(AC) due to its thermal stability, high surface area and pore volume, presence of both meso and macro
pores and hydrophobic nature [95,96]. Supelveda et al. [95], using a Mo2 N/AC catalyst reported that
the high mesoporosity of the activated carbon facilitated the diffusion of the reactants to the internal
surface area, i.e., at the location of the active centers. Moreover, Echeandia et al. [96] argued that
the hydrophobic nature of activated carbon prevents the water produced during HDO from being
adsorbed on the catalyst’s active sites. SiO2 has also been used in HDO reactions as it is known to be
inert and to have a small interaction with the sulfide phase. For example, Popov et al. [97] studying
the HDO of phenolic molecules reported that the phenolic compound interacted through H bonding.
Energies 2019, 12, 809 12 of 41

The authors also reported that phenate formation on the silica surface was very low in comparison
to Al2 O3 support. MgO has also been used as supporting material in hydroprocessing reactions; for
example, Yang et al. [90] investigated CoMo catalysts supported on MgO for the hydroprocessing of
phenol and reported high coke resistance which they attributed to the acidic nature and high dispersion
of MoO3 /MoS2 on the MgO surface.
By comparing the three deoxygenation reactions one observes that hydrogen consumption is
higher in the order HDO > deCO > deCO2 and, therefore, deCOx reactions are preferable despite
the expense of carbon loss into CO and CO2 . Also, HDO reaction over sulfided metal catalysts can
contaminate the products with sulfur [91] and requires high H2 pressures that are mostly available
only in centralized refineries. From the discussion above it is clear that there is great need for the
development of deoxygenation catalysts that will be free of sulfur, and at the same time be highly
active and selective and also resistant to deactivation in low H2 pressure. The deCOx reactions are
catalyzed by simpler supported metal catalysts and also need lower H2 pressures. Due to these
advantages research was undertaken for the selective deoxygenation of triglycerides over catalysts
that promote the deCOx such as Pt, Pd [74,84,86,98] and especially Ni-based catalysts which show
comparable activity to noble metals at a much lower cost [91,99–101]. Peng et al. examined the
HDO of stearic acid over Ni catalysts supported on two types of zeolites, HZSM-5 and HBeta [102].
The authors reported that Ni/HBeta catalysts were more selective to C17 and C18 alkanes promoting
the HDO reaction and eliminating cracking. In contrast, the narrower pores and higher concentration
of Brönsted acid sites of the Ni/HZSM-5 catalysts led to a higher effective residence time, which in turn
resulted at an increased degree of cracking. Thuan Minh et al. [103] investigated the catalytic HDO of
phenol over Ni–Cu/HZSM-5 and Ni–Co/HZSM-5 bi-metallic catalysts and found that the conversion
and selectivity was decreased with the addition of Cu, and attributed this behavior to a negative
synergistic effect. In contrast, the addition of Co (10Ni–10Co) resulted in an increase of activity and
selectivity, due to the formation of a NiCo2 O4 spinel phase, which also improved resistance to coke
deposition. Wu et al. [104] examined the effect of the support on non-sulfided catalysts that were based
on Al2 O3 , ZrO2 and SiO2 for Ni2 P catalyst on the HDO of guaiacol. The acidic strength decreased in
the order of Al2 O3 > ZrO2 > SiO2 , which was also the case for the Ni2P catalysts (i.e., the different
supports had analogous acidic strengths). SiO2 , being the support with the lowest acidity, led to the
strongest association with Ni and also allowed P to maintain its fully phosphided state; it also led
to decreased coke deposition. Lercher et al. [105] used a number of different supports and active
phases in order to investigate the HDO of palmitic acid and reported that activity decreased in the
order of: 15%Ni/ZrO2 = 5%Ni/HZSM-5 (Si/Al = 200) > 5%Ni/HBEA[d] (SiAl = 180) > 10%Ni/ZrO2
> 5%Ni/ZrO2 > 5%Pd/ZrO2 > 5%Pt/ZrO2 > 3%Ni/ZrO2 > 5%Ni/Al2 O3 > 5%Ni/SiO2 > 5%Pt/C
> 5%Pd/C. The zeolites and ZrO2 with weak and medium acid sites on the surface exhibited much
higher catalytic activity than the SiO2 , Al2 O3 and activated carbon, with the same nickel content.
The authors also argued that ZrO2 participated in the HDO process, leading to the much higher
activity. Kumar et al. [106] examined the deoxygenation of stearic acid over Ni/HZSM-5, Ni/Al2 O3
and Ni/SiO2 , with weak and medium acidity. The results showed that the Ni/HZSM-5 was more
active (two times higher) than the Ni/Al2 O3 and Ni/SiO2 , however, the Ni/HZSM-5 exhibited high
selectivity to octadecane while the other two catalysts were more selective to heptadecane. Similarly,
Zuo et al. [107] prepared sulfur-free Ni catalysts supported on SiO2 , γ-Al2 O3 , SAPO-11, HZSM-5,
and HY and tested them in the HDO of methyl palmitate to produce renewable diesel. The acidic
strength of the catalysts increases in the order of: 7wt% Ni/SiO2 < 7 wt% Ni/ SAPO-11 < 7wt%
Ni/γ-Al2 O3 < 7wt% Ni/HZSM-5 < 7wt% Ni/HY. Moreover, the Ni/SAPO-11 catalyst exhibited higher
catalytic activity in comparison to the other samples, which the authors attributed to the presence of
both weak and medium strength acid sites present in the SAPO-11 support. An extensive review on
the development of Ni-based catalysts for the transformation of the natural triglycerides into green
diesel has been published recently by Kordulis et al. [91]. A review of the catalytic research on the
hydro-processing of the triglycerides is presented in Table 5 [72–119].
Energies 2019, 12, 809 13 of 41

Table 5. Catalysis research on hydrotreating of vegetable oils, waste cooking oils, greases and animal fats. LHSV: Liquid Hour Space Velocity. LDH: Layered Double
Hydroxide. n.a.: Not available. b.p: Boiling point.
Reactor H2 /Oil LHSV Duration Conversion Selectivity among
Catalyst Oil T (◦ C) P (bar) Main Products 1 Ref.
Type Ratio (h−1 ) (h) % Oil Product (wt%)
Ni/Al2 O3 Continuous Rapeseed 50 260–280 35 0.25–4 n.a. 98 59 (C17) C17 (zero C18) 72
Mo/Al2 O3 Continuous Rapeseed 50 260–280 35 0.25–4 n.a. 100 82 (C18) C18 (only 2 wt% C17) 72
Ni–Mo/Al2 O3 Continuous Rapeseed 50 260–280 35 0.25–4 n.a. 100 94 (C17 and C18) C15–C18 (C17/C18 = 0.36) 72
Ni–Mo/Al2 O3 Continuous Rapeseed 250 340 40 1 n.a. n.a. 91.64 (C15–C18) C15–C18 (C17/C18 = 1.32) 73
Ni–Mo/Al2 O3 Batch Rapeseed n.a. 350 80 n.a. 3 n.a. 70 (C15–C18) C15–C18 (C17/C18 = 1.63) 74
Ni–Mo/Al2 O3 Continuous Rapeseed 100 310 70 1.5 n.a. 100 >90 (C17 and C18) C17–C18 (C17/C18 = 0.25) 75
Ni–Mo/MCM-41 Continuous Rapeseed 100 310 70 1.5 n.a. 100 >90 (C17 and C18) C17–C18 (C17/C18 = 0.5) 75
Ni–Mo/OMA Continuous Rapeseed 100 310 70 1.5 n.a. 100 >90 (C17 and C18) C17–C18 (C17/C18 = 0.07) 75
Pt/HZSM-5 Batch Rapeseed n.a. 380 110 n.a. 3 n.a. 43 (C5–C12) Gasoline (C5–C12) 74
FCC equilibrium catalyst Continuous 2 Rapeseed n.a. 525 1 n.a. n.a. n.a. 15.7 (C12–C20) Gasoline (C5–C12) 32.4 wt% 107
FCC-ZSM-5 Continuous 2 Rapeseed n.a. 525 1 n.a. n.a. n.a. 13.2 (C12–C20) Gasoline (C5–C12) 32.3 wt% 107
Ni–Mo/Al2 O3 Continuous Palm n.a. 350 40 2 n.a. n.a. 80 (C15–C18) C15–C18 (C17/C18 = 0.58) 76
Ni–Mo/Al2 O3 Continuous Palm 250 350 45 0.6 n.a. n.a. 92.69 (C15–C18) C15–C18 (C17/C18 = 0.78) 73
Ni–Mo/zeolite Batch Palm n.a. 300–320 1 n.a. n.a. n.a. 47.24 (C15–C19) C15–C19 and also 52.76% C8–C13 108
MCM-41 Palm n.a. 450 1 2.5 n.a. n.a. 26 (Diesel) Also gasoline 23.9% and kerosene 13 wt% 105
Al–MCM-41 Continuous Palm n.a. 450 1 2.5 n.a. n.a. 11.2–20.3 (Diesel) Gasoline 30.1–31.7% and kerosene 10.6–20.7 wt% 104
Ni–Mo/Al2 O3 Batch Soybean n.a. 400 92 n.a. 2 92.9 64.45 (C15–C18) C15–C18 (C17/C18 = 2.49) 102
Pd/Al2 O3 Batch Soybean n.a. 400 92 n.a. 2 91.9 79.22 (C15–C18) C15–C18 (C17/C18 = 11.9) 102
Co–Mo/Al2 O3 Batch Soybean n.a. 400 92 n.a. 2 78.9 33.67 (C15–C18) C15–C18 (C17/C18 = 2.16) 102
Ni/Al2 O3 -SiO2 Batch Soybean n.a. 400 92 n.a. 2 60.8 39.24 (C15–C18) C15–C18 (C17/C18 = 29.3)) 102
Pt/Al2 O3 Batch Soybean n.a. 400 92 n.a. 2 50.8 37.71 (C15–C18) C15–C18 (C17/C18 = 0.92) 102
Ru/Al2 O3 Batch Soybean n.a. 400 92 n.a. 2 39.7 32.00 (C15–C18) C15–C18 (C17/C18 = 39.6) 102
Ni/Al2 O3 Batch Soybean n.a. 350 6.9 n.a. 4 68 51.20 (≥C18) ≥C18 99
Ni–Al/LDH Batch Soybean n.a. 350 6.9 n.a. 4 74 52.90 (C8–C17) C8–C17 99
Ni–Mg–Al/LDH Batch Soybean n.a. 350 6.9 n.a. 4 49 54.1 (≥C18) ≥C18 99
Mg–Al/LDH Batch Soybean n.a. 350 6.9 n.a. 4 72 47.80 (C8–C17) C8–C17 99
Co–Mo/Al2 O3 Continuous Sunflower 450 340–350 50–80 1 n.a. 94.0–99.8 63.1–71.5 91 cetane number Diesel fuel 77
Co–Mo/Al2 O3 Continuous Sunflower 500–600 380 40–60 1 n.a. 100 83.1–89.2 C15–C18 (C17/C18 = 0.15) 92
Ni–Mo/Al2 O3 Continuous Sunflower 450 340–350 50–80 1 n.a. 81.8–97.4 42.0–51.9 92 cetane number Diesel fuel 77
Ni–Mo/ Al2 O3 Continuous Sunflower 500 350 45 0.8 n.a. n.a. 86.59 (C15–C18) C15–C18 (C17/C18 = 0.86) 73
Ni–W/Al2 O3 Continuous Sunflower 450 340–350 50–80 1 n.a. 86.7–95.6 39.4–49.3 91 cetane number Diesel fuel 77
Ni–Mo/Al2 O3 -F Continuous Sunflower 500 350–370 20–40 1 n.a. 91–96 73.2–75.6 C15–C18 of which 37–38% isomers 78
Pd/SAPO-31 Continuous Sunflower 1000 310–350 20 0.9–1.6 n.a. n.a. 83.4–100 nSH 1 and iSH 1 of which 46.8–90.7% C17 and C18 98
V2 O5 /α-Al2 O3 Batch Sunflower n.a. 355 1 n.a. 0.66 92.1 48 (Heavy Diesel) also about 23% gasoline and 4% kerozene 109
V2 O5 /α-Al2 O3 Batch Sunflower n.a. 390 1 n.a. 0.5 85 68 (b.p > 200 ◦ C) Liquid oil products with boiling point > 200 ◦ C 110
Co3 O4 /α-Al2 O3 Batch Sunflower n.a. 390 1 n.a. 0.5 68 60 (b.p > 200 ◦ C) Liquid oil products with boiling point > 200 ◦ C 110
KOH/α-Al2 O3 Batch Sunflower n.a. 390 1 n.a. 0.5 65 53 (b.p > 200 ◦ C) Liquid oil products with boiling point > 200 ◦ C 110
MoO3 /α-Al2 O3 Batch Sunflower n.a. 390 1 n.a. 0.5 56 59 (b.p > 200 ◦ C) Liquid oil products with boiling point > 200 ◦ C 110
NiO/α-Al2 O3 Batch Sunflower n.a. 390 1 n.a. 0.5 66 57 (b.p > 200 ◦ C) Liquid oil products with boiling point > 200 ◦ C 110
ZnO/α-Al2 O3 Batch Sunflower n.a. 390 1 n.a. 0.5 84 70 (b.p > 200 ◦ C) Liquid oil products with boiling point > 200 ◦ C 110
Ni–Mo/Al2 O3 Continuous Jatropha 800 350 40 7.6 n.a. 100 97.2 (C11–C20) C11–C20 (iSH/nSH 1 = 0.08) 79
Ni–Mo/SiO2 Continuous Jatropha 800 350 40 7.6 n.a. 100 99.1 (C11–C20) C11–C20 (iSH/nSH 1 = 0.03) 79
Ni–Mo/Al2 O3 -SiO2 Continuous Jatropha 800 350 40 7.6 n.a. 100 89.6 (C11–C20) C11–C20 and also 9.8 wt% C5–C10 (iSH/nSH 1 = 0.26) 79
Ni–Mo/H-Y Continuous Jatropha 800 350 40 7.6 n.a. 100 50.9 (C11–C20) C11–C20 and also 48.9 wt% C5–C10 (iSH/nSH 1 = 0.87) 79
Ni–Mo/H-ZSM-5 Continuous Jatropha 800 350 40 7.6 n.a. 100 22.1 (C11–C20) Also 77.8 wt% C5–C10 (iSH/nSH 1 = 1.21) 79
Ni–HPW(30%)/nHA Continuous Jatropha 600 360 30 2 n.a. 100 83.4 C10–C22 [(C15 + C17)/(C16 + C18)] = 4.4, (iSH/nSH 1 = 1.64) 100
Energies 2019, 12, 809 14 of 41

Table 5. Cont.
Reactor H2 /Oil LHSV Duration Conversion Selectivity among
Catalyst Oil T (◦ C) P (bar) Main Products 1 Ref.
Type Ratio (h−1 ) (h) % Oil Product (wt%)
Pt/H-ZSM-5 Batch Jatropha n.a. 270 65 n.a. 12 100 78.9 (C15–C18) C15–C18 (C17/C18 = 0.40) 93
Pt/USY Batch Jatropha n.a. 270 65 n.a. 12 31.2 68.15 (C15–C18) C15–C18 (C17/C18 = 0.51) 93
ZSM-5-Zn-20 Continuous Camelina n.a. 500 1 0.6 n.a. 76.8 52.39 (C13–C15) C13–C15 and also C7–C8 25.09 wt% 111
Mo-Zn/Al2 O3 Batch Carinata n.a. 350 21–58 n.a. n.a. >92 83 (C12–C18) C12–C18 112
Ni/Al2 O3 Continuous Hemp seed 3 300 350 40 4.7 n.a. 100 90% (C10–C17) C10–C17 (C17 equal to 49–62 wt%) 101
Ni–Cu/Al2 O3 Continuous Hemp seed 3 300 350 40 4.7 n.a. 100 100 (C10–C20) C10–C17 (C17 equal to 80 wt%) 101
Ni–Mo/Al2 O3 Batch WCO 4 666 300 70 2.8 3 99.6 93 (C15–C18) C15–C18 (iSH/nSH 1 = 1.4/97.5) 80
Co–Mo/Al2 O3 Batch WCO 4 666 300 70 2.8 3 99.3 84.7 (C15–C18) C15–C18 (iSH/nSH 1 = 6.4/89.7) 80
Ni–W/Al2 O3 Batch WCO 4 666 300 70 2.8 3 100 92.8 (C15–C18) C15–C18 (iSH/nSH 1 = 2.2/97.3) 80
Ni–Mo/Al2 O3 Batch WCO 4 666 350 70 2.8 3 99.8 90.7 (C15–C18) C15–C18 (iSH/nSH 1 = 3.8/94.8) 80
Ni–Mo/B2 O3 -Al2 O3 Batch WCO 4 666 350 70 2.8 3 99.9 87.1 (C15–C18) C15–C18 (iSH/nSH 1 = 7.5/91.4) 80
Ru/SiO2 Continuous WCO 4 400 350 20 15.2 n.a. n.a. 98.9 (C11–C20) C11–C20 (iSH/nSH 1 = 0.08) 106
Ru/Al13-montmorillonite Continuous WCO 4 400 350 20 15.2 n.a. 100 89.8 (C11–C20) C11–C20 and 9.1 wt% C5–C10 (iSH/nSH 1 = 0.2) 106
Ru/H-Y Continuous WCO 4 400 350 20 15.2 n.a. n.a. 56.5 (C11–C20) C11–C20 and 42.8 wt% C5–C10 (iSH/nSH 1 = 0.43) 106
HZSM-5 Batch WCO 4 n.a. 400–420 10 n.a. 1 n.a. 30.55-36.3 (Gas oil) also 15.57–16.76% gasoline and 9.99–11.83% kerozene 113
Sulfated Zr2 O3 Batch WCO 4 n.a. 400–420 10 n.a. 1 n.a. 41.18-44.61 (Gas oil) also 10.04–14.68% gasoline and 6.51–10.32% kerozene 113
Ni–Mo/B2 O3 -Al2 O3 Batch LTG 5 666 350 70 2.8 3 99.8 92.1 (C15–C18) C15–C18 (iSH/nSH 1 = 2.6/96) 80
Ni–Mo/B2 O3 -Al2 O3 Batch STG 6 666 350 70 2.8 3 99.3 86.6 (C15–C18) C15–C18 (iSH/nSH 1 = 3.4/94.8) 80
Ni/Al2 O3 Continuous 75 wt% YG 7 2400 375 40 2 3 inadequate - Gas products and unconverted liquids 101
Ni–Cu/Al2 O3 Continuous 75 wt%YG 7 2400 375 40 2 3 100 92% (Diesel) Diesel (34wt% C17) 101
Ni–Cu/Al2 O3 Continuous 75 wt% YG 7 2400 375 40 2 8 100 94% (Diesel) Diesel (74 wt% C17) 101
Ni–Mo/Al2 O3 Continuous Lard 250 350 45 0.8 n.a. n.a. 86.11 (C15–C18) C15–C18 (C17/C18 = 0.47) 73
1 nSH = normal Saturated Hydrocarbons, iSH=isomer (branched) Saturated Hydrocarbons; 2 FCC hydrocracking microactivity test unit; 3 25% hemp seed oil dissolved on dodecane; 4

WCO =Waste Cooking Oil; 5 LTG = Liquid Trap Grease; 6 STG = Solid Trap Grease; 7 75 wt% Yellow Grease in dodecane.
Energies 2019, 12, 809 15 of 41

Energies 2019, 12, x FOR PEER REVIEW 16 of 42

4. Catalytic Upgrading of Sugars, Starches and Alcohols

4. Catalytic Upgrading of Sugars, Starches and Alcohols
Since 2006 Virent Energy Systems Inc. (Madison, WI, USA) has developed a platform of processes
Since 2006 Virent Energy Systems Inc. (Madison, WI, USA) has developed a platform of
for the conversion of carbohydrates into liquid fuels like green gasoline, green jet fuel and green diesel,
processes for the conversion of carbohydrates into liquid fuels like green gasoline, green jet fuel and
as shown in Figure 4 [120].
green diesel, as shown in Figure 4 [120].

® platform for the production of renewable transportation fuels from

Figure4.4.Virent’s
Figure Virent'sBioForming
BioForming® platform for the production of renewable transportation fuels from
biomass
biomassfeedstocks
feedstocks[120].
[120].Reproduced
Reproducedwith
withpermission
permissionfrom
from[120].
[120].Virent:
Virent:Copyright
Copyright2008.
2008.

The ®
The platform
platform isis known known as as BioForming
BioForming® and and involves
involves liquid liquid phase
phase technologies
technologies such such asas
hydrolysis,
hydrolysis, hydrogenation, hydrogenolysis, dehydration, isomerization, oxidation, aqueous phase
hydrogenation, hydrogenolysis, dehydration, isomerization, oxidation, aqueous phase
reforming
reforming (APR)
(APR) and andaldol aldolcondensation
condensation[121–125].
[121–125]. Biomass
Biomass (lignocellulosic,
(lignocellulosic, sugars,
sugars, starches)
starches) isis
initially pretreated with dilute sulfuric acid catalyst (0–3 wt%) at about 130–220 ◦ C for 2–30 min.
initially pretreated with dilute sulfuric acid catalyst (0–3 wt%) at about 130–220 °C for 2–30 min. This
This breaks
breaks down down the the biomass
biomass forfor a subsequent
a subsequent enzymatichydrolysis
enzymatic hydrolysiswith withthethe cellulase
cellulase enzyme
enzyme which which
converts
converts polysaccharides like cellulose, hemicellulose, starch and inulin into a hydrolysate slurryof
polysaccharides like cellulose, hemicellulose, starch and inulin into a hydrolysate slurry of
monosaccharides
monosaccharidessuch suchasas xylose,
xylose, fructose andand
fructose glucose. The The
glucose. slurry is then
slurry is purified from insoluble
then purified solids,
from insoluble
proteins and inorganic
solids, proteins compounds
and inorganic which arewhich
compounds problematic for the operation
are problematic for the ofoperation
the plantof equipment
the plant
and catalysts and after possible hydrogenation or hydrogenolysis
equipment and catalysts and after possible hydrogenation or hydrogenolysis in pretreatment in pretreatment reactors it is finally
routed to the catalytic reactor of aqueous phase reforming (APR) with a sugar
reactors it is finally routed to the catalytic reactor of aqueous phase reforming (APR) with a sugar concentration between 10
and 15 wt% [125].
concentration During10APR
between andthe 15 hydrolysate slurry reacts
wt% [125]. During APR with water whichslurry
the hydrolysate converts the sugars
reacts and
with water
sugar alcohols into H
which converts the 2sugars , CO , lower saturated hydrocarbons, and condensable
2 and sugar alcohols into H2, CO2, lower saturated hydrocarbons, and chemical intermediates at
temperatures about 175–300 ◦ C and pressures of 10–90 bar over supported metal or metal alloy catalysts
condensable chemical intermediates at temperatures about 175–300 °C and pressures of 10–90 bar
such
overassupported
Pt or Ni-Sn [125–127].
metal or metal Thealloy
specific mixturesuch
catalysts composition
as Pt or depends on the reactor
Ni-Sn [125–127]. design, process
The specific mixture
conditions, feed concentration, solution pH, catalyst support and
composition depends on the reactor design, process conditions, feed concentration, solution pH, catalyst. The reactions involved
are considered
catalyst support to and
be (a) the reforming
catalyst. of the involved
The reactions sugars which produces H
are considered to2 ,be
(b)a)the
thedehydrogenation
reforming of the
of
sugars which produces H2, b) the dehydrogenation of alcohols, c) the hydrogenationhydrogenolysis
alcohols, (c) the hydrogenation of carbonyls, (d) deoxygenation reactions, (e) of carbonyls, d)
and (f) cyclization.
deoxygenation In situ
reactions, e) generation
hydrogenolysis of Hand
2 from APR is considered
f) cyclization. of key importance
In situ generation of H2 fromfor APR theis
de-functionalization
considered of key importance of the very forreactive carbohydrate to aofless
the de-functionalization the reactive mono-oxygenated
very reactive carbohydrate to species
a less
(alcohol, ketone or aldehyde) which can then be converted into a non-oxygenated
reactive mono-oxygenated species (alcohol, ketone or aldehyde) which can then be converted into a hydrocarbon through
conventional
non-oxygenated catalytic condensation
hydrocarbon and hydrotreating
through conventionaltechniques
catalytic [120]. Any excess
condensation and H2 hydrotreating
is recycled to
upgrade
techniquesthe [120].
aqueous Any solution
excessof Hcomplex C5 and
2 is recycled C6 sugar the
to upgrade mixtures
aqueous upstream
solution theofAPR reactorCthrough
complex 5 and C6
the reactions of hydrogenation and hydrogenolysis. Hydrogenation
sugar mixtures upstream the APR reactor through the reactions of hydrogenation and takes place in the presence of
hydrogen at 100–150 ◦ C and 10–30 barplace
causing thepresence
saturation of the C=C, C=O and
hydrogenolysis. Hydrogenation takes in the of hydrogen at 100–150 °CC–O–C
and 10–30 bondsbar
over metal catalysts such as Ru, Pt, Pd and Ni. Hydrogenolysis occurs
causing the saturation of the C=C, C=O and C–O–C bonds over metal catalysts such as Ru, Pt, Pd and in presence of hydrogen at
125–230 ◦ C and 14–300 bar causing the selective cleavage of C–C or C–O bonds of specific molecules
Ni. Hydrogenolysis occurs in presence of hydrogen at 125–230 °C and 14–300 bar causing the
like glycerol
selective for theof
cleavage production
C–C or C–O of more
bondsvaluable polyols
of specific or diols
molecules which
like are useful
glycerol for thein the production
production of moreof
valuable polyols or diols which are useful in the production of chemical polymers [128].
Hydrogenolysis takes place under alkaline conditions over supported metal catalysts such as Ru, Pd,
Energies 2019, 12, 809 16 of 41

chemical polymers [128]. Hydrogenolysis takes place under alkaline conditions over supported metal
catalysts such as Ru, Pd, Pt, Ni and Cu [128–131]. The effluent of the APR reactor contains oxygenated
molecules such as alcohols, ketones, aldehydes and organic acids with less than six carbon atoms
that can be converted into the desired liquid fuel in subsequent chemical processes. Green gasoline is
produced through direct catalytic condensation using acid catalysts such as solid acids and zeolites
like the ZSM-5 zeolite catalyst employed by Virent. On the other hand, green jet fuel is produced
through a base catalyzed route. Finally, green diesel may be produced through dehydration, alkene
oligomerization and alkene saturation.
Alkenes or olefins are unsaturated hydrocarbons with one double bond (C=C) and general
chemical formula Cn H2n . Traditionally they are produced by the steam or catalytic cracking of
fossil hydrocarbons but as oil resources are decreasing production routes are becoming increasingly
expensive. Catalytic dehydration is an alternative pathway for the production of alkenes from
oxygenated feedstocks and a first step for the production of higher hydrocarbons. The dehydration
of an alcohol takes place through acidic catalysis and provides the corresponding alkene with the
same number of carbon atoms. SAPO-34 has shown excellent performance on the dehydration of
methanol [132–136] and high activity on the dehydration of ethanol and butanol [126,127]. Zeolites such
as HZSM-5 [137–142] and mesoporous Si-based materials such as Ni-MCM-41 and Zr-KIT-6 [143–147]
have also shown good dehydration activity. According to various studies [145,148,149] materials with
fewer Brønsted and more Lewis acid sites provide higher selectivity to the desired alkenes and show
better stability since they are less conducive to carbon formation and deposition. In the case of the
APR effluent the dehydration of alcohols is straightforward but the ketones, aldehydes and organic
acids which are present can also be dehydrated after catalytic hydrogenation which will cause their
reduction to the respective primary or secondary alcohols.
Oligomerization describes a reaction which produces molecules with only a few monomer units
in contrast to polymerization which produces large molecules of high molecular weight. Alkene
oligomerization describes the conversion of lower alkenes such as propylene, butylene and pentene to
heavier alkenes in the boiling range of gasoline and petroleum diesel. The reaction may proceed over
acid catalysts such as zeolites or over supported Ni catalysts [150–154]. Two commercial processes
of alkene oligomerization are the Mobil Olefins to Gasoline and Distillates (MOGD) [154,155] and
Conversion of Olefins to Diesel (COD) ones [156–158]. The MOGD process appeared in 1982 at the
former Mobil refinery in Paulsboro in New Jersey, USA, in combination with Mobil’s successful
fluidized bed Methanol to Olefin (MTO) technology. The success of these technologies lies on the
unique properties of Mobil’s shape selective zeolite catalysts like H-ZSM-5 which inhibit carbon
formation reactions and promote the selective production of high quality diesel range (C10 to C20 )
iso-alkenes. After hydrogenation these provide a mixture of saturated hydrocarbons on the diesel
boiling point with a cetane number slightly above 50. On the other hand, the COD process was
developed by Air Liquide (formerly Lurgi) during the 1990s. A COD reactor normally operates at
about 120 ◦ C with a zeolite catalyst like H-ZSM-5. The reactor operates discontinuously due to the
deposition of heavy hydrocarbons on the catalyst which reduce its activity. As a result, at the end of
each catalyst cycle the operation is discontinued and the catalyst is regenerated. Due to this three or
more COD reactors are operated in a staggered sequence. The effluent stream of the COD reactors
contains alkenes with a wide range of carbon atoms, starting from a small amount of propylene (C3 H6 )
and up to heavy C23 H46 . The distribution curve shows a dominant maximum on the gasoline range,
for C12 H24 . After hydrogenation the effluent produces a diesel fuel with a cetane number close to 56.

5. Thermal Conversion of Lignocellulosic Biomass

5.1. Biomass Pyrolysis and Production of Bio-Oil

Pyrolysis is the endothermic reaction that takes place by heating lignocellulosic biomass at
300–900 ◦ C in absence of air. Most of the pyrolysis research has been conducted using different types
Energies 2019, 12, 809 17 of 41

of woods but other feedstocks have also been tested such as forest residues and agricultural residues
such as straw, willow, olive pits and nut shells [159,160]. The pyrolysis products are biochar (a black
solid residue), syngas (a mixture of H2 and CO), and bio-oil (a brown liquid).
Bio-char is a high carbon, fine-grained solid residue. It has potential as a solid fuel for the
generation of heat and power or as a soil improver and a ground storage medium for the atmospheric
greenhouse gases. It was found to benefit soil health by retaining both water and water soluble
nutrients [161]. This can increase crop production in soils that are degraded and nutrient poor and
can provide cost benefits decreasing the needs for irrigation and fertilizers [162]. Land bio-char
applications are also environmentally desirable as they remove CO2 from the atmosphere and facilitate
long term carbon sequestration. Bio-char can also store large amounts of greenhouse gases in the
ground [163–166].
Apart from H2 and CO, the pyrolysis syngas also contains small amounts of CO2 , H2 O(g) ), N2 , CH4 ,
ethylene (C2 H4 ), ethane (C2 H6 ), tar and ash in a quantitative composition that depends on the process
conditions and the biomass feedstock. H2 production is due to the thermal cracking and gaseous
reforming of hydrocarbons and generally increases with temperature. On the other hand, CO and CO2
are produced by the thermal cracking of oxygenated organic compounds such as cellulose. Methane,
ethylene and ethane are also formed by the thermal cracking of higher hydrocarbons. The syngas
formed by pyrolysis may be combusted to provide heat or may be used as a fuel in industrial processes,
internal combustion engines and Solid Oxide Fuel Cells (SOFCs). Moreover, syngas may be used
as the reactant mixture for the production of synthetic chemicals and fuels through the well-known
Fischer-Tropsch process, especially when the H2 /CO molar ratio is close to 2.
Bio-oil contains highly oxygenated organic molecules such as carbohydrates, phenols, alcohols,
aldehydes, organic acids and lignin-derived oligomers with a specific composition which depends on
the biomass feedstock as shown for some typical cases in Table 6 [94,167–169].

Table 6. Comparison of the properties of pyrolysis bio-oil produced by various lignocellulosic

feedstocks and common distillate fuels. Data taken from [94,167,169].

Properties Wood Willow Straw Sweet Grass Petroleum Distillate Fuel

Water Content, wt% 15–30 17.4 47.4 24.7 0.1
Carbon, wt% 54–58 43.17 28.2 38.3 85
Hydrogen, wt% 5.5–7 7.15 8.78 7.42 11
Oxygen, wt% 35–40 49.49 62.83 54.08 1
Nitrogen, wt% 0–0.2 0.1 0.1 0.1 0.3
Ash, wt% 0–0.2 0.1
pH 2–3 2.68 3.45 2.87 -
Viscosity, mm2 /s 40–100 53.2 17.2 34.2 2.39
Density, kg/m3 1.2 0.94
Higher Heating Value (HHV), MJ/kg 16–19 18.4 13.6 16.4 40
Solid Particulates, wt% 0.2–1 1
Distillation Residue, wt% up to 50 1

It is also shown that bio-oil is significantly different to any petroleum distillate fuel. Bio-oil has a
high content of water which is produced during pyrolysis through chemical dehydration of cellulose
and hemicellulose and also it is acidic with a pH of approximately 2–3 due to the presence of organic
acids [167]. The elemental composition of bio-oil is close to the composition of biomass and as a
result it has a similar heating value of 16–19 MJ/kg which is, however, significantly lower than the
heating value of petroleum fuels [94]. Due to low heating value, high viscosity, low pH and high water
content crude bio-oil is generally regarded as inappropriate for direct use in CI engines or turbines.
Bio-oil’s acidity is corrosive to the engine parts (injection nozzles, fuel pumps, pressure valves, seals,
gaskets etc.) and its high water content impedes autoignition. For this reason it is generally agreed
that bio-oil is not appropriate in high speed engines. Furthermore, various tests have shown that crude
bio-oil produces also a number of engine problems such as excessive carbon deposition inside the
engine cylinders, poor atomization during injection and increased engine wear. Although bio-oil is a
Energies 2019, 12, 809 18 of 41

poor Energies
engine2019,and12,burner fuelREVIEW
x FOR PEER it is a valuable intermediate for the production of biofuels and 19 pyrolysis
of 42
optimization for high bio-oil yield is important [169].
deposition inside
Depending on thethe engine
heatingcylinders,
rate of poorthe atomization during injection
biomass feedstock three and increased
pyrolysis engine are
processes
distinguished: a) slow pyrolysis, b) fast pyrolysis and c) flash pyrolysis. Slow pyrolysis takes the
wear. Although bio-oil is a poor engine and burner fuel it is a valuable intermediate for place in
production of biofuels and pyrolysis optimization for high bio-oil yield is important [169].
batch reactors at 550–950 ◦ C heating biomass particle sizes of 5–50mm with a heating rate of about
Depending on the heating rate of the biomass feedstock three pyrolysis processes are
0.1–1 ◦ C/s for periods of 5–30min. It typically produces biochar, uncondensed gases and bio-oil in
distinguished: a) slow pyrolysis, b) fast pyrolysis and c) flash pyrolysis. Slow pyrolysis takes place in
the approximate
batch reactorsproportions
at 550–950 °Cofheating
35, 35 biomass
and 30 wt%,
particlerespectively
sizes of 5–50mm [170].with
Fast pyrolysis
a heating ratetakes place in
of about
continuous
0.1–1 °C/sflow
for reactors
periods ofby5–30min.
rapidlyItheating
typicallydry biomass
produces particles
biochar, (<1 mm)gases
uncondensed withand a heating rate of
bio-oil in
aboutthe10–200 ◦ C/s up to about 850–1250 ◦ C within 0.5–10s and typically yields biochar, syngas and
approximate proportions of 35, 35 and 30 wt%, respectively [170]. Fast pyrolysis takes place in
bio-oil at the proportions
continuous flow reactors of by
15–25,
rapidly10–20 and dry
heating 60–75 wt%,particles
biomass respectively.
(<1 mm)Finally,
with aflash pyrolysis
heating rate of may
about 10–200 °C/s up to about 850–1250 °C within 0.5–10s and typically
be accomplished by an extremely fast heating of biomass particles (<0.2 m) up to 1050–1300 yields biochar, syngas and◦ C in
bio-oil at the proportions of 15–25, 10–20 and 60–75 wt%, respectively. Finally,
less than 0.5s and is capable to provide biochar, syngas and bio-oil at proportions 12, 13 and 75 wt%, flash pyrolysis may
be accomplished
respectively. Maximum by an extremely
bio-oil fast heating
production of biomass
requires particlesreaction
a moderate (<0.2 m) up to 1050–1300(about
temperature °C in less
500 ◦ C),
than 0.5s and is capable to provide biochar, syngas and bio-oil at proportions 12, 13 and 75 wt%,
fast heating of the biomass particles, short residence time of the feedstock in the reactor (typically
respectively. Maximum bio-oil production requires a moderate reaction temperature (about 500 °C),
less than 2 s), fast removal of product char to minimize vapor cracking and the quick dampening
fast heating of the biomass particles, short residence time of the feedstock in the reactor (typically
of theless
pyrolysis
than 2 s),vapors in order
fast removal to condense
of product char tothe bio-oilvapor
minimize [171].cracking
These conditions
and the quick aredampening
feasible through
of
properly
the pyrolysis vapors in order to condense the bio-oil [171]. These conditions are feasible through fuel
controlled fast or flash pyrolysis. Then bio-oil may be upgraded to liquid transportation
through a) hydrotreating,
properly controlled fastb) orcatalytic vapor (zeolite)
flash pyrolysis. Then bio-oilcracking
may beorupgraded
c) through gasification
to liquid into syngas
transportation
and subsequent
fuel throughFischer-Tropsch
a) hydrotreating,synthesis.
b) catalyticBio-oil
vapor hydrotreating
(zeolite) cracking andorzeolite cracking
c) through are analyzed
gasification into in
syngas and
the following subsequentGasification
paragraphs. Fischer-Tropsch synthesis. Bio-oil
and production hydrotreating
of synthetic andbe
fuels will zeolite cracking
discussed are
in Section 6.
analyzed in the following paragraphs. Gasification and production of synthetic fuels will be
5.2. Bio-Oil Upgrading
discussed through
in Section 6. Hydrotreating
A
5.2.typical
Bio-Oilpyrolysis
Upgradingand bio-oil
through hydrotreating pathway is shown schematically in Figure 5. Biomass
Hydrotreating
is reduced in particle sizes of about 2–6 mm and is dried at approximately 10 wt% water. Fast or flash
A typical pyrolysis and bio-oil hydrotreating pathway is shown schematically in Figure 5.
pyrolysis follows with the rapid heating of the feedstock at about 500 ◦ C in less than 1 s, usually in a
Biomass is reduced in particle sizes of about 2–6 mm and is dried at approximately 10 wt% water.
fluidized
Fast or bed reactor.
flash Any
pyrolysis solidwith
follows matter and solid
the rapid heatingchar is removed
of the feedstock through cyclones
at about 500 and
°C in less the1 bio-oil
than s,
vaporusually
exits the reactor. Bio-oil vapor is then quickly liquefied in a condenser providing
in a fluidized bed reactor. Any solid matter and solid char is removed through cyclones and the brown
liquidthe
bio-oil
bio-oilwith
vaporanexits
approximately 75% yield
the reactor. Bio-oil vaporonisathen
dry weight basis. Then,
quickly liquefied in a the bio-oil providing
condenser hydrotreating
occurstheinbrown
two stages,
liquidas shown
bio-oil in an
with Figure 5 [172]. At75%
approximately the first
yieldstage
on a the
dry mild
weighthydrotreating of bio-oil
basis. Then, the bio-oiltakes
placehydrotreating ◦ C andin
at about 240 occurs 170twobarstages, as shown
in excess in Figure
of hydrogen over5 a[172]. At the first
conventional stage the mild
hydrotreating catalyst
hydrotreating of bio-oil takes place at about 240 °C and 170 bar in
such as the sulfided Co–Mo/Al2 O3 or Ni–Mo/Al2 O3 . This is used to hydrogenate and stabilizeexcess of hydrogen over a
conventional hydrotreating catalyst such as the sulfided Co–Mo/Al 2O3 or Ni–Mo/Al2O3. This is used
various active species such as carbonyl and phenolic compounds which are present in the bio-oil and
to hydrogenate and stabilize various active species such as carbonyl and phenolic compounds which
can undergo reactions of depolymerization and condensation which will promote carbon formation
are present in the bio-oil and can undergo reactions of depolymerization and condensation which
and catalyst deactivation [173]. At the second stage heavy hydrotreating takes place at about 370 ◦ C
will promote carbon formation and catalyst deactivation [173]. At the second stage heavy
and 140 bar in excess
hydrotreating takesof place
hydrogen over370
at about sulfided
°C andCo–Mo/Al
140 bar in2 O 3 or Ni–Mo/Al
excess of hydrogen 2 O3over
. This causes the
sulfided
deoxygenation
Co–Mo/Al2Oof bio-oil
3 or and the
Ni–Mo/Al 2O3. production.
This causes the of adeoxygenation
mixture of saturated
of bio-oil hydrocarbons
and the productionwhich. of is
a then
distilled to provide
mixture fractions
of saturated of light gases,
hydrocarbons naphtha,
which is thengreen diesel
distilled and heavy
to provide distillates.
fractions Thegases,
of light latter will
undergo additional
naphtha, processing
green diesel through
and heavy hydrocracking
distillates. and undergo
The latter will they willadditional
provide extra yieldsthrough
processing of naphtha
hydrocracking
and green diesel. and they will provide extra yields of naphtha and green diesel.

Figure
Figure 5. Typical
5. Typical flowflow chart
chart forfor theproduction
the production of
of green
green diesel
dieselfrom the
from pyrolysis
the of biomass
pyrolysis and the
of biomass and the
hydrotreatment
hydrotreatment of bio-oil.
of bio-oil.
Energies 2019, 12, 809 19 of 41

Bio-oil hydrotreating involves deCOx reactions but proceeds mainly through hydrodeoxygenation
(HDO), as shown on the following conceptual reaction proposed by Bridgwater [171]:

C1 H1.33 O0.43 + 0.77H2 → CH2 + 0.43H2 O (4)

where CH2 represents an unspecified hydrocarbon product. The catalysts which were originally
examined were the sulfided Co-Mo and Ni-Mo supported on Al2 O3 or alumino-silicate which are
well known for their efficiency in the desulfurization of petroleum distillates [174]. However, these
catalysts suffered from low stability due to the high water content of the bio-oil. Also, due to gradual
loss of sulfur they were requiring frequent re-sulfurization. Research was then focused to noble metal
catalysts on various supports like Pd/C, Pt/Al2 O3 -SiO2 , Ru/Al2 O3 , Ru/C and Ru/TiO2. A brief
review of the research of bio-oil hydrotreating on these catalysts is presented in Table 7 [175–179].

Table 7. Review of the catalysis research for the hydrotreating of bio-oil.

Catalyst Reactor Type Time, h Temperature, ◦ C Pressure, bar DOD 1 , % Yield of Oil, wt% Ref.
Co–Mo/Al2 O3 Batch 4 350 200 81 26 175
Co–Mo/Al2 O3 Continuous 4 370 300 100 33 176
Ni–Mo/Al2 O3 Batch 4 350 200 74 28 175
Ni–Mo/Al2 O3 Continuous 0.5 400 85 28 84 177
Pd/C Batch 4 350 200 85 65 175
Pd/C Continuous 4 340 140 64 48 178
Pt/Al2 O3 -SiO2 Continuous 0.5 400 85 45 81 177
Ru/Al2 O3 Batch 4 350 200 78 36 175
Ru/C Continuous 0.2 350-400 230 73 38 179
Ru/C Batch 4 350 200 86 53 175
Ru/TiO2 Batch 4 350 200 77 67 175
1DOD is the Degree of Deoxygenation calculated as: DOD = (1 − (wt% of O in the products/wt% of O in the feed))
× 100%.

5.3. Bio-Oil Upgrading through Catalytic Vapor (Zeolite) Cracking

In a conventional refinery fluid catalytic cracking (FCC) is used to convert the high molecular
weight and high boiling point fractions of petroleum into more valuable lighter products such as
gasoline or gases. The cracking of these heavy distillates was originally accomplished by thermal
cracking, but it has been replaced almost completely by catalytic cracking because it produces higher
yields of gasoline with high octane rating. Bio-oil upgrading can take place through chemical reactions
similar to FCC in a process known as catalytic vapor cracking or zeolite cracking. Zeolite cracking
removes oxygen from the bio-oil as CO2 , as shown in the following conceptual reaction [171]:

C1 H1.33 O0.43 + 0.26O2 → 0.65CH1.2 + 0.33CO2 + 0.27H2 O (5)

where CH1.2 represents an unspecified hydrocarbon product. The process typically takes place between
300 and 600 ◦ C over zeolite catalysts which are also used in the FCC industry. A brief review of the
research of bio-oil zeolite cracking is presented in Table 8 [180–183].

Table 8. Review of the research for the catalytic vapor cracking of bio-oil.

Catalyst Time, h Temperature, ◦ C Pressure, bar DOD 1 , % Yield of Oil, wt% Ref.
GaHZSM-5 0.32 380 1 n/a 18 180
H-Modernite 0.56 330 1 n/a 17 181
H-Y 0.28 330 1 n/a 28 181
HZSM-5 0.32 380 1 50 24 180
HZSM-5 0.91 500 1 50 12 182
MgAPO-36 0.28 370 1 n/a 16 183
SAPO-11 0.28 370 1 n/a 20 183
SAPO-5 0.28 370 1 n/a 22 183
ZnHZSM-5 0.32 380 1 n/a 19 180
1 The Degree of Deoxygenation (DOD) is calculated by the relation given in Table 7.
Energies 2019, 12, 809 20 of 41

HZSM-5 is considered a good catalyst for bio-oil upgrading through zeolite cracking as it provides
high yields of liquid oil and propylene.

5.4. Hydrothermal Liquefaction of Biomass and Upgrading of Bio-Crude

Hydrothermal liquefaction (HTL), also known as hydrous pyrolysis or direct liquefaction,
is another thermal technology used for the conversion of biomass into a liquid product similar to
bio-oil which is usually called bio-crude. During the HTL process the biomass is converted directly
into bio-crude and other aqueous, gaseous and solid phase byproducts in presence of a solvent and
sometimes of a catalyst. The most common solvent is water but it usually produces low yields of
bio-crudes with higher oxygen content and lower heating values. Other organic solvents such as
alcohols, phenol, esters, ketones, tetralin and various alcohol-water mixtures can provide higher
bio-crude yields with lower oxygen content and can serve also as donors of hydrogen during the
process [184]. The catalyst may be used to inhibit the formation of char and tar [185]. This is usually
a homogeneous catalyst such as sulfuric acid, oxalic acid, hydrochloric acid, sodium hydroxide or a
metallic salt but various heterogeneous catalysts are also under investigation.
The HTL process usually takes place at temperatures of 200–400 ◦ C and at elevated pressures of
50 to 200 bar with relative long residence times of 10–60 min. The high process pressure sustains the
produced solvents in the liquid state and increases the yield of liquid bio-crude but also increases the
cost of the HTL technology. The mechanism of the HTL process is complex and still under investigation.
It proceeds with the depolymerization of the biomass macromolecules into smaller compounds
and with various chemical and thermal decompositions of monomers by cleavage, dehydration,
decarboxylation and deamination (removal of aminoacids) which create smaller fragments and
remove oxygen from the biomass product. Finally the created fragments are rearranged through
condensation, cyclization and repolymerization [184,186]. Ramirez et al. [187] have reported that the
chemical composition of bio-crudes varies significantly and contains various groups of chemicals
such as phenolics, esters, aromatics and heterocyclics, aldehydes, carboxylic acids, ketones, saturated
hydrocarbons and nitrogenates. A general comparison of HTL bio-crudes with the pyrolysis bio-oils
shows that bio-crude has a higher carbon content (68–81% vs. 56–66%), lower oxygen content (9–25%
vs. 27–38%), lower water content (6–25% vs. 24–52%) and higher heating value equal to about
28–41 MJ/kg [187,188]. On the other hand, HTL bio-crude has a much greater viscosity than bio-oil,
petroleum diesel and biodiesel.
Although similar to the biomass pyrolysis, the HTL does not need the preliminary drying of
the feedstock and therefore wet feeds of lower cost can be exploited such as the microalgae which
are cultivated in aqueous media. Dimitriadis and Bezergianni [189] have reviewed the most useful
biomass feedstocks studied for HTL including lignocellulosic (woody) biomass, wastes (sewage sludge,
solid wastes, swine manure, pulp/paper sludge powder, agricultural residues and food processing
wastes) and microalgae. According to their review, the yield of bio-oil from these sources ranges
between 15 and 68 wt% depending on the feedstock type and size, the operation parameters, catalyst
and solvent type and solvent to biomass mass ratio. Xu et al. [190] have reviewed the catalytic HTL of
algae over homogeneous catalysts such as CH3 COOH, HCOOH, KOH and Na2 CO3 and have reported
that Na2 CO3 provides the highest bio-crude yields between 20.4 and 51.6% for various algae varieties at
280–360 ◦ C and with residence times of 30 and 60 min. The same study also reviewed the HTL of algae
over various heterogeneous catalysts such as Pd/C, Pt/C, Ni/SiO2 -Al2 O3 , CoMo/Al2 O3 , Ce/HZSM-5
and Ru/C and concluded that Ni/SiO2 -Al2 O3 is the best option in terms of bio-crude yield and cost
and Ce/HZSM-5 is the best option in terms of bio-crude quality providing high hydrogen content,
high heating value, high yield and low heteroatom content.
Due to the similarity of pyrolysis bio-oil and HTL bio-crude, the upgrading of the bio-crude
is accomplished with the same hydrotreating and zeolite cracking technologies mentioned before
in the Sections 5.2 and 5.3. The hydrotreatment of bio-crude may proceed in two stages as it was
discussed also for bio-oil and over the same catalysts. The initial mild hydrotreatment stage is useful
Energies 2019, 12, 809 21 of 41

also in this case to avoid carbon deposition due to the bio-crude content in carbonyls but it was shown
that the upgrading of HTL bio-crude may also proceed in a single step [191,192]. For example an
oxygen removal higher than 95% was achieved in wood derived bio-crude at 300 ◦ C over a sulfided
CoMo/Al2 O3 catalysts resistant to carbon formation due to its desalting pretreatment [192]. The second
stage heavy hydrotreatment process may follow over the same catalysts proposed in Table 7. Grlic
et al. [193] investigated the hydrotreatment of lignocellulosic biomass bio-crude over NiMo/Al2 O3 ,
Pd/Al2 O3 , Pd/C, Ni/SiO2 -Al2 O3 and bulk MoS2 at 300 ◦ C, 80 bar and 60 min. Their results have shown
that the sulfided NiMo/Al2 O3 catalysts provide a liquid product with appropriate HHV, rheological
properties and yield. The Pd/Al2 O3 and Pd/C catalysts exhibited low catalytic activity and the bulk
MoS2 catalysts was found promising for further investigation due to the low cost, relatively high
activity and HDO selectivity. Duan and Savage [194–196] investigated the upgrading of bio-crude
obtained from the non-catalytic liquefaction of Nannochlopris sp. at 320 or 340 ◦ C and shown that
Pt/C is an effective catalyst. At the same time, using 5 wt% Pd/C at 400 ◦ C, they examined the effects
of catalyst loading (5 to 80 wt%) and residence time (1 to 8 h) on the composition of the upgraded
bio-crude and shown that an in increase of either of these parameters is beneficial causing the decrease
of the O/C and N/C atomic ratios and an increase in the H/C ratio and the higher heating value
(HHV) of the product [196]. Finally, only few studies have examined the catalytic cracking of HTL
bio-crude. Adjaye and Bakshi [197] examined the upgrading of wood bio-crude at 330–410 ◦ C, 1 bar,
and 3.6 h−1 over HSZM-5, silicalite, H-mordenite, H-Y and SiO2 -Al2 O3 . For HSZM-5 the maximum
hydrocarbon yield was 39.3 wt% at 370 ◦ C and included mostly hydrocarbons in the gasoline range.
Over the rest catalysts the hydrocarbon yield was maximized at the maximum temperature examined
(410 ◦ C) following the order H-mordenite (27.5 wt%), SiO2 -Al2 O3 (26,1 wt%), silicalite (21.8 wt%), H-Y
(21 wt%). Among these catalysts H-mordenite and H-Y have shown high selectivity of green jet fuel
while the other catalysts mainly produced lighter hydrocarbons in the green naphtha boiling range.
Gevert and Otterstedt [198] investigated two commercial catalysts, EKZ-4 and EKZ-2, and α-Al2 O3 at
483, 500 and 562 ◦ C for the upgrading of wood bio-crude which was then hydroprocessed over sulfided
CoMo/Al2 O3 at 370 ◦ C and 100 bar. It was shown that EKZ-4 provides about 30.5 wt% gasoline and
20.1 wt% gas oil at 500 ◦ C. The discussion above shows that the production of green diesel from the
upgrading of HTL bio-crude has not been investigated in depth and therefore more research is needed.

6. Biomass to Liquid (BTL) Conversion of Lignocellulosic Biomass

Gasification is the exothermal reaction which converts biomass or carbonaceous fuels into
synthesis gas (syngas) by partial oxidation. It takes place by heating the material at temperatures above
700 ◦ C with a controlled sub-stoichiometric amount of O2 and/or steam and leads to the production
of mixtures containing syngas (i.e., CO and H2 ) and smaller amounts of CO2 and CH4 . Syngas was
previously introduced as one of the three products of the pyrolysis of biomass. Although pyrolysis
may be optimized for the production of syngas, biomass gasification is considered a better route for its
production as it provides higher yields of syngas without any significant byproduct competition.
Gasification is an established process for the production of syngas from coal, char, oil sands,
biogas and natural gas [199]. In a carbonaceous fuel the following reactions take place:

C + 1/2O2 → CO ∆H = −111 kJ/mol (6)

C + H2 O → CO + H2 ∆H = +131 kJ/mol (7)

where (6) is the exothermic partial oxidation of carbon and (7) is the endothermic water gas reaction.
Both these reactions cause the conversion of carbon into H2 and CO. In the case of biogas or natural
gas, which are already in the gas state, the endothermic catalytic steam reforming reaction is usually
employed which is written as:

CH4 + H2 O ↔ CO + 3H2 ∆H = +206 kJ/mol (8)

Energies 2019, 12, 809 22 of 41

The reactions (6)–(8) take place at high temperature and the final composition of the products is
controlled also by the equilibrium of the water gas shift (WGS) reaction:

CO + H2 O ↔ CO2 + H2 ∆H = −41 kJ/mol (9)

Due to the high gasification temperatures, methane is the only byproduct that can be present in
the products in any significant amount. An increased temperature reduces the methane production
as well as the H2 /CO molar ratio of the syngas by promoting the production of CO. High pressures
reduce the amounts of CH4 and CO2 . When gasification is optimized to provide a syngas mixture rich
in CO and H2 , temperatures above 1250 ◦ C and pressures at 25–80 bar are usually used [199]. A syngas
rich in H2 and CO is particularly useful for the synthesis of useful chemicals and fuels through the
well-known Fischer-Tropsch (FT) process.
The Fischer-Tropsch reaction was discovered in 1923 by Franz Fischer and Hans Tropsch,
when they observed that CO and H2 may react to provide gasoline, diesel and other heavy distillate
oils over iron (Fe) and cobalt (Co) catalysts [200]. Ever since the method has found success in various
industrial applications for the production of useful chemicals and fuels from syngas produced by the
gasification of coal or from the partial oxidation/steam reforming of natural gas. The technologies
using gasification of coal and production of liquid fuels from syngas through Fischer-Tropsch synthesis
are usually symbolized as XTL, where X refers to the raw material of the gasification process. Hence,
one can discern the CTL, GTL, WTL and BTL technologies which produce liquid fuels from the
Fischer-Tropsch synthesis by syngas produced by the gasification and/or steam reforming of coal
(X = C), gas (X = G), wastes (X = W) or biomass (X = B).
Fischer-Tropsch synthesis is a highly exothermic surface polymerization reaction which converts
H2 and CO into saturated or unsaturated hydrocarbons of 1–40 carbon atoms over heterogeneous
catalysts such as iron (Fe) or cobalt (Co). H2 and CO are absorbed on the surface of the catalyst and
dissociate to form monomer units such as CH2 which represents a methylene group of a normal
saturated hydrocarbon. The reaction proceeds with the surface polymerization of these groups into
larger chains according to the scheme:

2nH2 + nCO → (CH2 )n + nH2 O ∆Ho 250 ◦ C = -185.8 kJ/mol for n = 1 (10)

which eventually produces a crude oil mixture of saturated hydrocarbons, unsaturated hydrocarbons,
alcohols and carbonyls according to the following reactions [201,202]:

(2n + 1)H2 + nCO → Cn H2n+2 + nH2 O (11)

2nH2 + nCO → Cn H2n + nH2 O (12)

2nH2 + nCO → H(CH2 )n OH + (n − 1)H2 O (13)

nCO + (2n − 1)H2 → (CH2 )n O + (n − 1)H2 O (14)

At the same time, several other simultaneous reactions may occur such as the reversible WGS
reaction (9) which forms CO2 . The main products of the Fischer-Tropsch process are straight
saturated hydrocarbons and unsaturated hydrocarbons (alkenes) through reactions (11) and (12),
respectively, but the exact composition of the crude oil product depends on the H2 /CO molar ratio,
the thermodynamic conditions and the catalyst used on the reaction bed.
According to the reaction (11) the production of one monomer CH2 requires approximately
2.1 mol of H2 and therefore a H2 /CO molar ratio equal to 2.1. Fe catalysts promote the WGS
reaction (9) and therefore allow the utilization of syngas with H2 /CO molar ratios below 2.1 [203].
Co catalysts, on the other hand, inhibit the WGS reaction and as a result require H2 /CO molar ratios
between 2.06 and 2.16 [204]. The Fischer-Tropsch process usually takes place at 200–350 ◦ C and
10–60 bar over Fe or Co catalysts. However, two technologies may be further recognized: (a) high
Energies 2019, 12, 809 23 of 41

temperature Fischer-Tropsch (HTFT) and (b) low temperature Fischer-Tropsch (LTFT). HTFT synthesis
take place at 300–350 ◦ C over Fe catalysts and produces gasoline, oxygenates and linear C3 –C6 alkenes.
The latter may be transformed into diesel range hydrocarbons through alkene oligomerization, as
it was discussed in Section 4, and the resulting green diesel has a maximum yield of 40% and a
cetane number equal to about 50. LTFT synthesis, on the other hand, occurs at 200–240 ◦ C in either
Fe or Co catalysts producing high yields of saturated hydrocarbons and high molecular weight
linear waxes. LTFT synthesis provides high quality diesel range hydrocarbons, either directly
on the effluent product (about 20 wt% yield) or through the hydrocracking of the heavy waxes
(>C23 and boiling point above 350 ◦ C) into C15–C18 saturated hydrocarbons (green diesel) or other
lighter fuels (jet fuel, naphtha etc.). Hydrocracking combines catalytic cracking and hydrogenation.
Therefore, hydrocracking catalysts are bifunctional with an acidic support like SiO2 -Al2 O3 and an
appropriate hydrogenating metal such as Pt or sulfided Co–Mo, Ni–Mo or Ni–W [205]. The unsulfided
Pt/SiO2 -Al2 O3 catalysts allow wax hydrocracking with 100% conversion and 75–80% selectivity to
the desired products [206–209]. As a result Pt/SiO2 -Al2 O3 is considered superior to the conventional
sulfided metal catalysts. The hydrocracking of LTFT waxes is different to the typical hydrocracking
used for the petroleum distillates since it is not exothermal but almost isothermal. Also, it is not
conducive to carbon deposition and can take place in milder conditions, typically at 325–375 ◦ C and
35–70 bar with a space velocity of 0.5–3 h−1 and a H2 /feed ratio of 500–1800 m3 /m3 . LTFT typically
provides 80 wt% green diesel with a cetane number of about 75, 15 wt% green naphtha and 5 wt%
light gases (C1 to C4 ).

7. Green Diesel Properties and Performance in CI Engines

7.1. Green Diesel Properties

Petroleum diesel fuel falls under the specifications outlined by the standards EN 590 in
Europe [210] and ASTM D975 in the United States [211] which are presented in Table 9, together
with EN 14214 [212] which applies in Europe for oxygenated biodiesels comprised of FAME and
“EN15940: Automotive fuels-Paraffinic diesel fuel from synthesis or hydrotreatment-Requirements
and Test Methods” [213] which specifically applies to non-oxygenated Green Diesel fuels made by
hydro-processing or Fischer-Tropsch synthesis. In the USA and Canada the biodiesel standard is the
ASTM D6571. EN 590 defines the properties of the petroleum diesel used in the European automotive
market with an upper biodiesel limit of 7% (B7). It does not pay attention on how the diesel fuel was
made, as for example the renewable or fossil origin, but only states the regulations that the diesel fuel
must meet. Therefore, EN 590 permits the blending of petroleum diesel or B7 with green diesel in any
ratio and the only concern is that the final product must meet its regulations. It also specifies that the
maximum blending ratio of biodiesel in green diesel is 7%. Table 9 also presents the typical properties
of No.2 petroleum diesel (for use in CI engines with a maximum sulfur content of 15 ppm according to
ASTM D975), biodiesel and green diesel [29,35,210–215]. As one can observe green diesel produced by
either hydro-processing or Fischer-Tropsch meets the specifications of EN15940 but differs significantly
to biodiesel (FAME) due to chemical composition and to petroleum diesel due to various properties.
Energies 2019, 12, 809 24 of 41

Table 9. Standards and typical properties of petroleum Diesel (No.2), biodiesel and Green Diesel. Data from [29,35,210–215].
Petroleum Diesel Petroleum Diesel Green Diesel Biodiesel
European Standard USA Standard European Standard European Standard Typical Fuel Properties
Property
EN590:2013+A1:2017 ASTM D975-17a EN15940:2016/A1:2018 EN14214/A2:2018-A2
No.2 Petroleum Biodiesel
Min Max Min Max Min Max Min Max Green Diesel FT Diesel
Diesel (FAME)
Carbon (wt%) - - - - - - - - 86.8 76.2 84.9
Hydrogen (wt%) - - - - - - - - 13.2 12.6 15.1
Oxygen (wt%) - - - - - - - - 0.0 11.2 0.0
Cetane Number (CN) 51 - 40 - 70/51 - 51 - 44.5–67 45-55 >70 74–80
Cetane Index 46 - 40 - - - - -
Lower Heating Value (LHV) MJ/kg - - - - - - - - ≈43.1 ≈37.2 43.7–44.5 ≈43.5
◦C 765 800
Density at 15 (kg/m3 ) 820 845 - - 860 890 796–841 ≈880 770–790 774–782
780 810
Polycyclic Aromatic Hydrocarbons (wt%) - 8 - - - - - - 1.5–4.4 <0.1 <0.2
Aromaticity - - - 35 vol% - 1.1 wt% - - 35 vol% max 0 max
Sulfur Content (mg/kg) - 10 - 15 - 5 - 10 3.8–15 <5 <5
Manganese Content (mg/lt) - 2 - - - - - -
Flash Point (◦ C) 55 - 52/38 - 55 - 101 - 54–148 100–180 >59 ≈71
Cloud Point (◦ C) Down to −34 - - Down to −34 - - 10.5...−13 −5...−34
Ash Content (wt%) - 0.01 - 0.01 - 0.01 - - 0.01 <0.001
Water Content (mg/kg) - 200 - - - 200 - 500 <200
Carbon Residue on 10% Distillation (wt%) - 0.3 - 0.35 - 0.3 - 0.3 <0.1
Total Contamination (mg/kg) - 24 - - - 24 24 <10
Water and Sediment (vol%) - - - 0.05 - 0.02 - - ≤0.02
Copper Strip Corrosion Rating Class 1 - No. 3 Class 1 Class 1 No.3 Class 1 Class 1
Fatty Acid Methyl Esters (FAME) (vol%) - 7 - 5 - 7 96.5 wt% - 0
Oxidation Stability 20 h 25g/m3 - - 20 h 25 g/m3 6h - 2–15 h <25 g/m3 ≈0.8
>700 420–570 (additive
Lubricity, Wear Scar Diameter at 60 ◦ C (µm) - 460 - 520 - 460 - - 226–354
(additive required) required)
Viscosity at 40 ◦ C (mm2 /s) 2 4.5 1.9/1.3 4.1/2.4 2 4.5 3.5 5.0 1.9–4.1 2.9–11 2–4 2–4.5
Distillation
vol% Recovered at 250 ◦ C - <65 - - - <65 - - -
vol% Recovered at 350 ◦ C 85 - - - 85 - - - -
Distillation Temperature (◦ C)
90 vol% Recovered - - 282 282–338 - - - - 279–360 282–338 ≈305.8
95 vol% Recovered - 360 - - - 360 - - - <320 ≈312.2
Conductivity (pS/m) - - 25 - 25 - - ≥50
Acid Number (mg KOH/g) - - - 0.1 - 0.1 - 0.5
Energies 2019, 12, 809 25 of 41

Green diesel has a higher cetane number (above 70) than petroleum diesel or biodiesel. Cetane
number (CN) is a measure of the ignition quality of a diesel fuel in a reciprocating CI internal
combustion engine. It is measured according to the ASTM D613 standard and quantifies the ignition
delay which is the time interval from the injection of the fuel to the beginning of the combustion process
(see Section 7.2). The higher the cetane number of a fuel the shorter is the ignition delay and usually
this means that the engine may operate with a higher thermal efficiency and lower fuel consumption.
Fuels such as green diesel which contain high concentrations of normal (straight chain) saturated
hydrocarbons have high cetane numbers because the activation energy required for the formation of
free radicals to begin the combustion process is low compared to branched hydrocarbons or aromatics
which are more stable and need higher pressures and temperatures to autoignite. When green diesel is
mixed to petroleum diesel the cetane number increases almost linearly to the blending ratio and the
automotive manufacturers claim that such a CN enhancement is preferable to the utilization of CN
improvement additives [216].
As discussed previously, the normal saturated hydrocarbons that provide green diesel its high
CN rating also cause the cloud point of the fuel to be above 20 ◦ C. The cloud point is measured
experimentally according to the ASTM D2500 standard and signifies the highest temperature below
which the formation of solid wax particulates make the fuel hazy. The high cloud point makes the
liquid impractical for use as an engine fuel or blendstock and isomerization is required which reduces
both the cloud point and the CN rating. Isomerization has the advantage that it does not change the
density of the fuel. Instead, the regulation of the low temperature operability of the fossil petroleum
is made through distillation which provides lighter hydrocarbons. This lowers the density and the
viscosity of the fuel and increases fuel consumption. Finally, it is important to notice that green diesel
is much more adjustable for low temperature operation than biodiesel in which the cold properties
depend on the feedstock.
Smagala et al. [217] examined the effect of the isomerization on the CN number and the cloud
point and shown that an initial mixture of normal saturation hydrocarbons with a CN rating of about
118 and a cloud point of 20 ◦ C can be converted into a practical green diesel fuel of a cloud point
down to −30 ◦ C while keeping the CN number above 70. Another property which indicates the low
temperature operability of the diesel fuel is the Cold Filter Plugging Point (CFPP). This is measured by
the constant cooling of a sample at a rate of 40 ◦ C/h and signifies the highest temperature at which
20 ml of the fuel fail to pass through a 45-micron wire mesh under a pressure of 2 kPa in less than
60 s. In petroleum diesel the CFPP may be improved by means of Cold Flow Improver (CFI) additives.
However, due to the narrow distillation range of the green diesel hydrocarbons between C15 and C18
the effect of these additives in the green diesel is small. Neste [216] claims that the CFPP is usually
equal or marginally lower than the cloud point of the fuel and that the low temperature operability is
controlled mainly by adjusting the cloud point.
Green diesel has a lower density than biodiesel or petroleum diesel [108]. This means that the
volumetric heating value of the fuel is reduced and the engine fuel consumption increases. Luckily,
the lower heating value (LHV) of green diesel on mass basis is higher than petroleum diesel and this
counteracts the adverse effect of the lower density to some extent. This is due to the higher H2 content
of green diesel. The lower density may also offer to some extend financial benefits since it can allow
the blending with heavier petroleum products of lower cost.
Lubricity is extremely important in a CI engine since both the fuel pumps and the fuel injectors
are high precision equipment manufactured with the highest possible geometrical accuracy and
operating with highly loaded contacts [218,219]. These are essential to the accurate quantification of
the fuel injection and play a key role to the optimization of the engine performance for high efficiency
and low fuel consumption. Consequently, the high fuel lubricity is particularly important for the
unproblematic engine operation with minimal wear [219,220]. The lubricity of a diesel fuel can be
estimated experimentally through the High Frequency Reciprocating Ring (HFRR) method according
to the ASTM D6079 standard. A hardened steel ball oscillates across a hardened steel plate under
Energies 2019, 12, 809 26 of 41

a constant load for 75 min. The result of the test is reported as a wear scar diameter and hence a
high diameter value is an indication of a fuel with low lubricity [219]. Diesel fuels that have low
concentration of heteroatom molecules such as the Ultra-low Sulfur Content (ULSD) fuels used in
modern engines, the FT diesel and the green diesel produced through hydro-processing generally
have low lubricities with typical wear scar diameters above 700 µm. This is lower than the minimum
lubricity required by all European and US standards and therefore a lubricity enhancer is usually added
as in the cases of petroleum diesel. The typical chemical structure of a lubricity additive consists of a
polar functional group attached to an oleophilic part Ri . Typical functional groups are carboxylic acid,
carboxylic acid ester and carboxylic acid amide [218]. Then, the oxidation stability and the thermal
stability of a diesel fuel are evaluated through the ASTM D2274 and ASTM D6468 tests, respectively.
Both these tests have been designed for diesel fuels containing more than 500 ppm of sulfur and since
the sulfur content of green diesel is extremely low (below 5 mg/Kg) may not be accurate in its case.
Smagala et al. [217] have tested various green diesel samples and found that the oxidative and thermal
stability of green diesel are comparable to petroleum diesel. Finally, conductivity is important for the
safe handling of the fuel during transport. This can be adjusted with antistatic additives.

7.2. Green Diesel Performance in CI Engines

Compression ignition (CI) engines are heat engines that convert the chemical energy of a fuel
into mechanical work. The fuel is injected as a liquid spray inside the cylinder (or in an appropriate
pre-chamber) under pressure through a fuel injector and after evaporation and mixing with air it
autoignites due to the excessive compression produced by a moving piston. The piston reciprocates
inside the cylinder between two zero-velocity positions called bottom dead center (BTC) and top
dead center (TDC), which define the maximum piston travel distance known as a stroke [221,222].
Depending on the engine type, four or two strokes are necessary to complete one engine operation cycle
which may be separated on the phases of air induction, air and fuel compression, combustion product
expansion and combustion product exhaust. Fuel injection and autoignition sequentially take place at
the final stages of the compression phase just before the piston reach at the TDC. After autoignition the
combustion process begins, the chemical energy of the fuel is released as heat, and since the available
volume inside the cylinder is small the combustion products are formed at high pressure and high
temperature. These will push the piston from the TDC to the BTC during the expansion phase of the
engine cycle and will produce positive mechanical work which is higher than the negative energy
needs during intake, compression and exhaust. The reciprocating movement of the piston is finally
converted into rotational shaft work by means of a piston - crank rod - crankshaft kinematic assembly.
Each instant of the engine cycle may be signified by the angular position θ of the cranskshaft
which is measured relative to the θ = 0◦ value assigned for the piston position at the TDC [221,222].
Figure 6 illustrates a typical variation of the cylinder pressure versus the instant angular position θ of
the crankshaft. Starting from the left of the diagram the compression stroke take place as the piston
approaches the TDC (θ = 0◦ ) and the air pressure increases gradually as the available volume decreases.
At a crankshaft angle equal to about 20◦ before the TDC the fuel injection starts and the droplets of
the fuel spray start to evaporate and mix with the cylinder air by diffusion and turbulent air motion.
The pressure and the temperature inside the cylinder continues to increase and at a certain instant
the autoignition of the fuel occurs and combustion begins. The time period or the crankshaft angle
interval between the start of the injection and the instant of autoignition is the ignition delay period
which depends on the cetane number of the fuel and other parameters such as the fuel volatility and
viscosity, the pressure and angle of the injection, the piston and cylinder geometry etc. The exothermic
combustion then takes place with the propagation of a flame front which travels inside the cylinder
with a subsonic velocity and eventually reaches the cylinder walls and quenches.
 since the available volume inside the cylinder is small the combustion products are formed at high
pressure and high temperature. These will push the piston from the TDC to the BTC during the
expansion phase of the engine cycle and will produce positive mechanical work which is higher than
the negative energy needs during intake, compression and exhaust. The reciprocating movement of
the piston
Energies is 809
2019, 12, finally converted into rotational shaft work by means of a piston - crank rod - crankshaft
27 of 41
kinematic assembly.

Figure6.6.Cylinder
Figure Cylinderpressure,
pressure,pump
pumpdelivery,
delivery,injection
injectionrate
rateand
andheat
heatrelease
release rate
rate curves
curves in
in aa typical
typical CI
CI
internal combustion engine.
internal combustion engine.

Optimally the autoignition of the diesel fuel must take place 0–8◦ before the TDC [223] so that the
completion of the combustion and the maximum pressure to be attained at about 15◦ after the TDC,
at the very start of the productive expansion stroke. For this to take place, the timing of the injection
must be appropriately controlled at an angle before TDC which depends on the ignition delay for the
specific fuel, on the engine design and the operating conditions. For example, given that the time of
flame propagation is generally constant an increase of the engine speed will require the advance of the
injection timing at a greater angle before TDC.
Figure 6 also shows in parallel a typical heat release curve during the combustion process and
a typical injection rate of the fuel versus the crankshaft angle. As observed, the autoignition of the
fuel and a significant part of the combustion process happen simultaneously with the injection of
the liquid fuel. This is true for fuels with high cetane numbers which have short ignition delay and
cause the pressure rise and heat release to proceed at about the slow rate of fuel injection and air-fuel
mixing. For fuels with low cetane number with long ignition delay, most of the fuel is injected before
the autoignition and this means that after the beginning of the combustion the burning rates are very
high leading to high rates of pressure rise and high maximum pressures [222].
After autoignition the combustion process generally proceeds in three phases. Initially,
combustion takes place between the air and the fuel that has reached the gas state and formed a
homogeneous mixture with air during the ignition delay period. This phase of combustion is knows
as premixed or rapid combustion phase and takes place within just a small crankshaft angle interval
with a high heat release rate. After the consumption of the premixed air-fuel mixture, the combustion
and the heat release rates slow down as they are now controlled by the mixing rate of the fuel
Energies 2019, 12, 809 28 of 41

and air. Finally, the combustion process continues also after the quench of the flame front into the
expansion stroke in the so-called late combustion phase. This is due to the appearance of equilibrium
thermal decomposition reactions and also due to mixing which promotes more complete combustion.
Fuels with low cetane numbers have a long ignition delay that increases the phase of premixed
combustion and give rise to higher pressure and heat release rates inside the cylinder [222].
Green diesel has been tested as a CI engine fuel in various studies [224–244]. In the majority
of them it was reported that, when compared to petroleum diesel, green diesel decreases both the
maximum cylinder pressure and the rate of pressure increase [224–230]. The lower maximum pressures
and the lower rates of pressure increase are attributed to the higher cetane number of green diesel
which shortens the ignition delay period and the premixed combustion phase, in agreement to the
conclusions of the previous discussion. Also, a possible lower viscosity of green diesel allows a better
mixing of the liquid fuel droplets with air and reduces the ignition delay [229]. Caton et al. [224]
has reported that at almost all engine loads and speeds the maximum cylinder pressure for green
diesel is about 2–6% lower than for petroleum diesel. Aatola et al. [231] have tested green diesel
on a turbocharged 8.4 L common rail engine and observed that the heat release was lower due to
the lower ignition delay, as it was discussed above, and also due to the lower volumetric heating
value of the biofuel. The same observation was also made in various other reports [226,232–234].
Also, almost all of the above studies concluded that green diesel increases the crankshaft interval of
the combustion process by approximately 0.5–2◦ [224,225,228,231–234]. This is reasonable since the
higher cetane number and the shorter ignition delay reduce the phase of rapid premix combustion
and lengthen the slower phase were the combustion is controlled by the mixing rate of air and fuel.
In terms of torque and brake power it was observed that the utilization of green diesel is comparable
to petroleum diesel. Kim et al [235] used green diesel in a 1.5 L direct injection common rail engine and
observed that the brake power was marginally lower than in the petroleum diesel operation. Similarly,
Sugiyama et al. [232], have used green diesel in a 2.2 L direct injection common rail engine and found
that the brake power was practically unchanged. On the other hand, Ogunkoya et al. [226] has tested
green diesel in a 418 cm3 single cylinder engine and observed that the indicated power in the case of
green diesel was higher. The authors attributed this behavior to effects such as the fuel ignition delay,
the combustion phasing relative to the TDC, injection fuel quality etc. The same authors also observed
that green diesel reduces the brake specific fuel consumption (bsfc) of the engine when comprised
by either normal or branched saturated hydrocarbons. This was also reported in numerous other
investigations [224,230,231,233–238] and is especially important since bsfc is the ratio of the mass of
the fuel consumed per brake power output. The lower bsfc values translate into higher fuel economy
during engine operation and also to lower emissions, since less fuel is burned for the same power
output. In the case of pure green diesel the reduction of the bsfc may be by 5–10% and it is attributed to
the higher H2 content and the higher calorific value (LHV, in mass basis). Finally, of major importance
in the analysis of the internal combustion engines is the brake thermal efficiency, defined as the ratio
of the brake power output to the rate of fuel energy consumption of the engine. In most research
reports green diesel was found able to increase the brake thermal efficiency of the engine by up to
10%. For example, Kumar et al. [230] have tested green diesel in a 661 cm3 single cylinder engine and
observed that it increased the brake thermal efficiency from 21.76 to 23% at 20% load, from 25.8 to
34.24% at 40% load, from 31.74 to 35.9% at 80% load and from 31.6 to 31.66% at full load conditions at
1500 rpm. This is attributed to the higher calorific value and to the lower ignition delay which shifts
the combustion process so that a larger fuel fraction to be oxidized near the TDC. These two factors are
considered to supersede the effect of the lower fuel density and lower volumetric heating value.

7.3. Green Diesel Emissions in Internal Combustion Engines

Neste [216] has reported results of exhaust emission tests that have been performed over 36 trucks
and buses or their engines and nine passenger car vehicles or engines in real road conditions and
artificial driving cycles in test beds. Three of the passenger car engines were utilizing neat green
Energies 2019, 12, 809 29 of 41

diesel and six a blend of 85% green diesel and 15% petroleum diesel. Results showed that in all
these Euro 2 to Euro 4 engines the operation with green diesel reduced the emissions of CO, CO2 ,
unburned hydrocarbons (HC), nitrogen oxides (NOx ) and solid particulates. CO emissions were
on average 27, 38 and 45% lower than the EN 590 levels in the case of trucks-buses, passenger cars
with pure fuel and passenger cars with blend fuel, respectively. At the same vehicle categories CO2
emissions were on average lower by about 4, 5 and 6%, respectively, HC were lower by 31, 55 and
40%, respectively, NOx were lower by 9, 1 and 1% and solid particulates were lower by 27, 30 and
13% respectively. The reduction of CO usually means higher CO2 due to more complete combustion,
but Neste claims that CO2 emissions also reduce due to the higher H/C atomic ratio on the green
diesel fuel. However, Neste also reported that the difference between individual engines was so large
that some bus or truck engines showed lower solid particulates by 47% and a slight increase of the
NOx emissions. In a similar study Kumar et al. [230] reported 25–30% lower CO emissions at part
load, almost constant CO2 emissions at all loads, 25–30% lower HC emissions at low and part load,
5–15% lower NOX emissions at all loads and 49–75% lower smoke at all loads. Two phenomena were
considered responsible for the lower emissions. At one hand, the mixing of green diesel with air is
better since the fuel is comprised by hydrocarbons in narrow carbon atom (C15–C18) and narrow
molecular length chain ranges. This reduces the emissions of CO, HC and smoke by promoting more
complete combustion. Secondly, the higher cetane number of green diesel reduces the heat release rate
and the maximum flame temperature in the cylinder. Reduced flame temperatures are known to inhibit
both the thermal dissociation of CO2 into CO at the late combustion phase and also the Zeldovich
mechanism of thermal NOx formation which is responsible for the production of the majority of NOx
emissions in an internal combustion engine. The flame temperature with green diesel is also lower
due to the higher H/C atomic ratio of the fuel. The reduction of NOx emissions is an advantage
of green diesel over biodiesel and petroleum diesel and it was verified experimentally also in other
communications [226,227,231,239–243]. However, some ambiguity exists since other communications
have reported unchanged or increased green diesel NOx emissions [232,233,236,237,244]. Finally,
most communications [228,232,235–237,239,241–243] claim that green diesel reduces the emission of
the solid particulates by up to 45%, in agreement to the Neste report [216] mentioned previously.
This is attributed to the higher cetane number of green diesel and also to the lower content in sulfur
and aromatics.

8. Conclusions
The hydro-processing of triglyceride oils and fats has been investigated as the most commonly
used technology for the production of green diesel throughout the world. As shown, the appropriate
selection of the operating conditions and the utilization of an optimally acidic catalyst and catalyst
support is able to provide high yields of C15–C18 saturated hydrocarbons with the desired
isomer/normal composition ratios which determine the cetane number and cold flow properties
of the biofuel. The review of the relevant research has shown that such appropriate options are
the sulfided Ni–Mo/Al2 O3 and Co–Mo/Al2 O3 catalysts which are the most common choice in
the industrial production facilities, together with the sulfided Ni–Mo/SiO2 and the non-sulfided
Pd/Al2 O3 , Pd/SAPO-31, ZnO/α-Al2 O3 and Ni–Cu/Al2 O3 catalysts which were found highly active
in the hydrotreatment of various feedstocks. The catalytic upgrading of sugars and starches into
green diesel was also examined paying specific attention on Virent’s BioForming® platform and the
relative liquid phase processes of aqueous phase reforming, hydrogenation, hydrogenolysis, catalytic
dehydration and alkene oligomerization. Although innovative, the method has found great success on
the production of green diesel of sufficiently high cetane number (>50) and also opened a valuable new
route of production from sugars obtained by the treatment of crops or lignocellulosic matter which,
however, must be susceptible to the existed lignin pretreatment methods. Due to this disadvantage
the upgrading of bio-oil or bio-crude and the BTL production technologies seem more promising as
they can exploit the entire variety of biomass feedstocks through pyrolysis, hydrothermal liquefaction
Energies 2019, 12, 809 30 of 41

and gasification processes, respectively. Bio-oil upgrading through hydrodeoxygenation was found
feasible with high yields of liquid hydrocarbons over sulfided Ni–Mo/Al2 O3 and Ru/TiO2 . On the
other hand, bio-oil upgrading through zeolite cracking was found to provide lower yields of liquids
and higher yields of gases such as propylene. Finally, BTL conversion of lignocellulosic biomass
was identified as an important technological route for the production of high quality green diesel
through Fischer-Tropsch synthesis. HTFT conversion of syngas over Fe catalysts provides mainly
gasoline and C3 –C6 alkenes. The latter can only yield up to 40% green diesel with a cetane number
about 50 through further oligomerization. LTFT conversion over Fe or Co catalysts, on the other hand,
provides about 20% saturated hydrocarbons of the appropriate boiling point range and about 50%
higher hydrocarbons with a boiling point above 350 ◦ C (waxes) which may be hydrocracked over
Pt/SiO2 -Al2 O3 to provide an overall FT green diesel yield of approximately 80% and a cetane number
equal to about 75.
The diesel fuel produced by the hydroprocessing-hydroisomerization and the BTL technologies
has a significantly higher CN, LHV and H/C atomic ratio than No.2 petroleum diesel, appropriate
cold flow properties, and through improvement with common additives it easily complies also the
lubricity standards of the automotive engine industry. Numerous studies which have tested green
diesel in road vehicles and laboratory internal combustion engines have shown improved combustion
characteristics during the engine cycle resulting in higher thermal efficiencies by up to 10% and lower
brake specific fuel consumptions by 5–10%. They have also shown significantly lower engine emissions
of CO, HC, smoke, solid particulates and also of NOx which are known to increase in the case of
biodiesel. CO2 emissions have been observed to be at the levels of the petroleum diesel, but one
must also account for the renewable nature of the green diesel which does not contribute to net CO2
accumulation in atmosphere. Given the plethora of non-edible biomass resources which can be used
for its production, green diesel can play a key role in replacing fossil petroleum in the transportation
and residential sectors.

Funding: This research received no external funding.

Acknowledgments: K.N.P is grateful for the support of the Hellenic Foundation for Research and Innovation
(HFRI) and the General Secretariat for Research and Technology (GSRT), under the HFRI PhD Fellowship grant
(GA. no. 359).
Conflicts of Interest: The authors declare no conflict of interest.

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