Overview

Comparative analysis of biodiesel

versus green diesel
Andreas Vonortas and Nikolaos Papayannakos ∗

The use of biofuels is becoming more and more common because of both envi-
ronmental and economical concerns. Several attempts have been made for the
substitution of fossil fuels with other alternative fuels. An important feedstock
for the production of biofuels fully adapted to modern engine technology is es-
ter molecules derived from refined or crude vegetable oils and animal fats. Two
distinct techniques have been applied for the transformation of the vegetable
oil’s esters into molecules compatible with petroleum diesel that is transesterifi-
cation of ester molecules for the production of lighter esters by using an alcohol
and hydrogenation of ester bonds for the production of linear hydrocarbons. The
way both biofuels are produced is discussed in this work. Raw materials tested,
production methods and systems investigated, feasibility of production of these
fuels in plant and industrial scale and the main characteristics of the two fuels are
included.  C 2013 John Wiley & Sons, Ltd.

How to cite this article:

WIREs Energy Environ 2014 , 3 :3–23. doi: 10.1002/wene.78

INTRODUCTION final oil products). Though, these measures proved

to be insufficient for the environmental protection so
I n the previous century, with the rapid evolution
of industrial activity and the radical increase in
human population, the need for alternative energy
the need for use of sustainable energy resources was
made imperative. A successful substitute for diesel
fuel, used mainly in the transportation sector, was
sources became pressing. The extensive use of fossil
found to be the mixture of the ester derivatives from
resources and especially of petroleum and its deriva-
the vegetable oils and animal fats. This new feedstock
tives as fuel or as a raw material for other applica-
is environmental friendly, renewable, and totally in-
tions has given rise to serious environmental con-
dependent from petroleum. There are four distinct
cerns related mainly to the production of harmful
ways for vegetable oils to be used as fuels1 : by using
gases like SOx , NOx , and COx , which are mainly
neat vegetable oils or blends of the latter with petro-
held responsible for several environmental problems.
diesel,2–6 by forming microemulsions,7 by modifying
Additionally, to the environmental problems, both
them with thermal catalytic or noncatalytic treatment
economical and social concerns also arose because
like catalytic hydrodeoxygenation (HDO)8 or thermal
of the dwindling fossil fuel supplies. An increase in
cracking,9–14 and finally by reducing their size via
the final fuel price affected the cost of other es-
transesterification,15 which is the most widely used
sential products and services. Through regulations,
method for converting vegetable oils to appropriate
the European Union (EU) and other international
substitutes of diesel fuel.
or national organizations, at first, tried to make
Any fuel of biological origin can be called bio-
the existing fuels environmental friendly (e.g., by re-
fuel. However, when referring to the term biofuels
ducing the sulfur and nitrogen concentration in the
what instantly springs to mind is biodiesel. Biodiesel
is defined as the mono-alkyl esters of vegetable oils
or animal fats, obtained by transesterifying oils or
*Correspondence to: npap@central.ntua.gr fats with an alcohol, usually methanol or ethanol.
National Technical University of Athens, School of Chemical En- In US, the American Society for Testing and Materi-
gineering, Athens, Greece als (ASTM) D6751–08 defines the standards for the
DOI: 10.1002/wene.78 commercially used biodiesel, whereas in Europe, the

Volume 3, January/February 2014  2013 John Wiley & Sons, Ltd. 3333 3
Overview wires.wiley.com/wene

European Norm (EN)14214:2008 gives the corre- T A B L E 1 | Total Biodiesel Production Capacity in Tones for 2011
sponding specifications, although slight differences for EU-27
exist between the national versions of the EN stan- Country Thousand Tones
dards. According to ASTM D6751, biodiesel is de-
fined as the mono-alkyl esters of long-chain fatty Austria 560
acids derived from plant oils or animal fats, desig- Belgium 710
nated B100 and used as fuel for compression igni- Bulgaria 348
tion internal combustion piston engines. EN14214 Cyprus 20
defines biodiesel as a fuel suitable for use in compres- Czech Republic 427
Denmark 250
sion ignition (diesel) engines that is made off fatty
Estonia 135
acid mono-alkyl esters derived from biologically pro- Finland 340
duced oils or fats including vegetable oils, animal fats, France 2505
and microalgal oils. Nowadays, a new approach for Germany 4932
the production of renewable fuels from vegetable oils Greece 802
and their derivatives is proposed as an alternative sus- Hungary 158
tainable way of valorization of this type of biomass. Ireland 76
Green diesel or renewable diesel is produced from the Italy 2265
very same feedstocks as biodiesel, but by following Latvia 156
direct HDO of triglyceride and fatty acids molecules, Lithuania 147
and thus for its production, the complete knowledge Luxemburg 0
Malta 5
of HDO reactions is imperative.16 Despite the fact
The Netherlands 1452
that both biodiesel and green diesel are environmen- Poland 864
tally friendly, their cost is relatively high because of Portugal 468
the expensive raw material. The price of a refined oil Romania 277
can range between 4.05 and 10.40 $/gal17 depend- Slovakia 156
ing on its origin, type, and availability, whereas for Slovenia 113
waste/used vegetable oils and fats, an average price Spain 4410
is 3.30 $/gal.18 Therefore, refined vegetable oils ap- Sweden 277
pear to be not very attractive because of their high UK 404
prices. Additionally, the cultivation of plants from TOTAL 22117
which these oils derive in large amounts for energy Reproduced with permission from Ref 19. Copyright, European Biodiesel Board.
purposes occupies large fields that could be used for
the production of edible oils. Thus, the equilibrated
use of land for food and energy production will be Table 1. The total number of existing plants is calcu-
a challenge in our societies in the near future. More- lated as 254. In Table 2, a comparison of the world-
over, vegetable oils which are not edible, like Jatropha wide biodiesel production is presented for the years
or cottonseed oil, could be used for energy production 2005–2009.
purposes but the problem of valuable land used for Both biofuels are compatible with petroleum-
their production still persists. derived diesel and can be used either neat or in mix-
A number of alternative production processes tures with petro-diesel. In Table 3, some major repre-
already exists for the treatment of the vegetable oils; sentative properties of each fuel are given. It should
transesterification and esterification in the case of be noted that for green diesel cloud point is strongly
biodiesel and hydrogenation in the case of green affected by the existence of partial isomerization step
diesel. For the latter, the production can occur in in- process after the HDO reaction.
frastructure already possessed by oil refineries. This Life cycle analysis (LCA) for biodiesel or green
infrastructure is not only related to the reactor ves- diesel takes into account the whole process from the
sel that will carry out the conversion of triglycerides very beginning to the end use that is, from the grow-
to normal paraffins but also to hydrogen production ing of the plants at the fields to the final consumer
units. On the contrary, for the biodiesel production, of the produced biofuel.22 In general, the cumulative
initial investments should be made but in compari- and fossil energy demand appears to be strongly de-
son with green diesel, small-scale units can be built pendent on the raw material, whereas for green diesel,
and the production conditions are milder and thus the energy demand is lower than for biodiesel. It has
simpler than that used for green diesel. The biodiesel been reported that for biodiesel produced from palm
production capacity of 2011 for EU-27 is presented in oil, LCA suggests that the cumulative energy required

4  2013 John Wiley & Sons, Ltd. Volume 3, January/February 2014

 WIREs Energy and Environment Comparative analysis of biodiesel versus green diesel

T A B L E 2 | Comparison of the Worldwide Biodiesel Production

World Biodiesel Production by Region in Thousand Tones per Year

Region 2005 2006 2007 2008 2009

North America 303 848.8 1672.9 2278.5 1747.3

Central and South America 24.8 109.2 754.5 1916.1 2874.2
Europe 3380.4 5619.2 6825.5 7694.2 8567.9
Asia and Oceania 109.2 451.7 784.3 1429.6 1414.7
Other1 14.9 14.9 34.7 124.1 193.5
World 3832.2 7043.9 10071.9 13442.5 14797.6
Created using data from Ref 20.
1
Other includes Africa, Eurasia, and the Middle East.

T A B L E 3 | Typical Physical/Chemical Properties of the Two Fuels Biodiesel

Discussed and Comparison With Petro-Diesel Biodiesel is produced by the contact of vegetable oils,
Property Diesel Fuel Green Diesel Biodiesel animal fats, and their derivatives (VOFD) with an al-
cohol. Then, the alcohol reacts with the triglycerides,
Oxygen content (%) 0 0 11 which constitute more than 98% of the oils, for the
Stability Good Good Marginal production of a mixture of mono-alkyl esters. These
Sulfur [ppm(mass)] <10 <1 <1 esters have better properties than the triglycerides they
Density (g/cm3 ) 0.84 0.78 0.88
come from because of their smaller size.25 In Figure 1,
Cetane number 40 70–90 50–65
the reaction route of a typical triglyceride contained
Cloud point (◦ C) −5 −20 to +20 −5 to +15
Cold flow properties Good Poor Poor in VOFD with methanol is presented. The reaction
Heating value (MJ/kg) 43 44 38 occurs in three steps. In the first step, a triglyceride
reacts with an alcohol molecule producing a diglyc-
Reproduced from Ref 21. Copyright 2007, UOP. eride and a mono-ester and then the diglyceride reacts
with another alcohol molecule producing a monoglyc-
for the production of 1 MJ energy is 3.2 MJ, whereas
eride and another mono-ester, and finally, the mono-
a slightly less amount of energy is required for green
glyceride reacts with another alcohol molecule giv-
diesel (3.0 MJ). However, the corresponding nonre-
ing glycerin and another mono-ester.26, 27 Methanol
newable, fossil energy demand appears to be 0.45 MJ
is mainly used for the production of biodiesel world-
for biodiesel and 0.40 MJ for green diesel. The same
wide. Other alcohols that can be used are ethanol,
trend is observed with tallow as feedstock but with
propanol, and butanol.
much better cumulative energy efficiency (about 1.3
Apart from triglycerides, crude vegetable oils
and 1.2 MJ, respectively).23 It should be noted that
contain phospholipids that are removed during the
to correctly estimate the overall LCA of various liq-
degumming stage of refining as a crude mixture
uid biofuels, several disciplines should be combined
(lecithin).28 This valuable product is the basis of the
making the estimation process a matter that requires
phospholipid industry, and phospholipids are used
serious attention.24
extensively in food products, in animal feeds, and
The aim of this work is to present an analysis of
in industrial processes. Each vegetable oil contains
the existing production technologies of both biodiesel
different amount of phospholipids like soybean oil
and green diesel and compare their main characteris-
(3.2%), rapeseed oil (2.5%), and sunflower seed
tics. An overview of all the methods applied for the
oil (1.5%), whereas palm oil contains little or no
conversion of vegetable oils to the desired fuel prod-
phospholipids.29, 30 Because of the high value of the
uct, the vegetable oils used, and the main properties
phospholipid-based products, the removal of phos-
of these biofuels is presented.
pholipids from the vegetable oils before their treat-
ing for biofuel production is suggested. The waste
PROCESS ANALYSIS vegetable oils, cooking oils, or edible oil refinery by-
In this section, the comparative analysis of the two products scarcely contain any phospholipids as their
biofuels is carried out. The chemistry, production pro- starting materials are degummed.
cess, characteristics of final products, and economics The parameters affecting the transesterification
for each biofuel, biodiesel, and renewable diesel are reaction are temperature, molar ratio of alcohol
included. to oil, type and quantity of catalyst, the type of

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Overview wires.wiley.com/wene

F I G U R E 1 Transesterification of typical triglycerides using methanol.

the process, and the composition of the reactants T A B L E 4 | Effect on the Relative Amounts of Toxic Gases Emit-
mixture. ted When Biodiesel is Used for Fuel
Molar ratio of alcohol to oil is one key factor Emission B100 B20
for the transesterification reaction. Three molecules of
alcohol are needed for full conversion of each triglyc- Carbon monoxide (CO) −48% −12%
eride molecule giving three molecules of methyl esters Total hydrocarbons (THC) −67% −20%
and glycerol. In actual processes, though, a greater Particle matter (PM) −47% −12%
molar ratio is used which is strongly connected to the Nitrogen oxides (NOx ) +10% +2%
type of catalyst selected. An excess of alcohol favors Sulfur oxides (SOx ) −100% −20%
Toxic gases −60 to −90% −12 to −20%
the product formation but on the other hand makes
the separation of glycerol more difficult, increasing Reproduced with permission from Ref 42. Copyright 2005, American Chemical Society.
the process cost.
The advantages of biodiesel considering the im-
pact of its use on the environment are focused on
the fact that it is biodegradable and has lower sul-
fur, nitrogen, and aromatics content than diesel.31, 32
It has also been reported33, 34 that biodiesel can be
biodegraded within 21 days. Moreover, its use sig-
nificantly reduces toxic gas emissions like carbon
monoxide, sulfur oxides, hydrocarbons (total hydro-
carbon or THC), and particulate matter (PM) ex-
cept for NOx .35–39 Schumacher et al.38 conducted ex-
periments with a diesel engine showing that when
20% (wt/wt) biodiesel derived from soybean oil was
introduced in the engine (B20) CO, SOx , THC,
and PM were reduced, whereas NOx increased. Lin
et al.40 found that polycyclic aromatic hydrocar-
bons, carcinogenic potencies (BaPeq ), and PM de-
creased with the use of palm oil-derived biodiesel.
They found that B15 showed the best performance
as fuel. Lin et al.41 found that when waste cook-
ing oil-derived biodiesel was used, B20 blends ap-
peared to have the lowest emissions, whereas ni-
trogen oxides emissions increased while increasing F I G U R E 2 Typical industrial process involving alkali catalysis.
biodiesel percentage in the fuel. In Table 4, the ef-
fect on the amounts of some major toxic gases emit-
ted when using neat biodiesel (B100) or 20% blend Homogeneous Catalysis
in petro-diesel (B20) is shown.42 Except environ- Homogeneous catalysis of vegetable oils transesteri-
mental advantages, biodiesel shows higher combus- fication can be distinguished in acid and basic catal-
tion efficiency and higher cetane number than diesel ysis. The alkali-catalyzed transesterification of veg-
fuel.43 etable oils is about 4000 times quicker than the acid
For the production of biodiesel, both homoge- catalyzed.44 Because of this fact, but also because
neous and heterogeneous catalyses have been used. these catalysts are less corrosive than the acid ones
The most important of them are described in the fol- (like inorganic acids), typical industrial processes are
lowing section. built based on the use of alkali catalysts. In Figure 2,

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 WIREs Energy and Environment
F I G U R E 3 Mechanism of alkali catalyzed transesterification. (Reproduced with permission from Ref 27. Copyright 1998, S.B.Q., Sociedade
Brasileira de Quı́mica.)
a typical industrial process is depicted using an alkali
homogeneous catalyst.
Homogeneous Base-Catalyzed Production of
Biodiesel
The catalysts used today in alkali-based catalysis
are sodium and potassium hydroxide (NaOH and
KOH) and the corresponding methoxides (CH3 ONa
και CH3 OK). The typical molar ratio of methanol
to vegetable oil used in alkali transesterification
is 6:1 molmeth /moloil , reaction temperature resides
within the range of 55–62◦ C, while the reaction time
is between 20 and 40 min. The proposed mechanism
of the alkali catalysis for the transesterification reac-
tion of VOFD is presented in Figure 3.27
Several works using alkali catalysts have been
published in literature studying the effect of starting
oils and process conditions on the product proper-
ties and process economics. Qiu et al.45 investigated
the production of biodiesel [(fatty acid methyl esters
(FAME)] by transesterifying a mixture of soybean and
rapeseed oil with NaOH as a catalyst. Temperature,
molar ratio of methanol to oil, catalyst amount, and
reaction time were studied and the optimum condi-
tions (94% yield of methyl esters) found to be 55◦ C,
5:1 molar ratio, 0.8 wt%, and 2 h, respectively. Phan
and Phan46 converted waste cooking oils to FAME in
Volume 3, January/February 2014  2013 John Wiley & Sons, Ltd.
Comparative analysis of biodiesel versus green diesel
a laboratory scale reactor, using potassium hydrox-
ide. Again, the effect of temperature, molar ratio of
methanol to oil, and catalyst concentration were stud-
ied. They concluded that the produced fuel in blends
with petroleum-derived diesel, at wt% ratios below
30, could be used to engines without major modifi-
cations, having physical properties within EN14214
standard.
But, alkali homogeneous catalysis has one im-
portant drawback that is related to the quality of the
vegetable oil available. When the raw oils or fats con-
tain not only triglycerides but also water and free
fatty acids (FFAs), water has the ability to hydrolyze
the triglycerides forming more FFAs, whereas the al-
kali catalyst will react with the acids for the for-
mation of soaps.1 Thus, a significant amount of the
raw material is lost through side reactions, the cost
of the product purification increases, and the prob-
lem of disposing the produced soaps emerges. Lotero
et al.42 reported that waste cooking oil with more
than 6% FFAs is not suitable feed for alkali cataly-
sis. Literature proposes that to use bases as catalysts,
a vegetable oil with less than 1% FFAs should be
used.47, 48 If waste oils or oils with high FFAs concen-
tration are meant to be used, pretreatment is required
for the removal of both water and FFAs to avoid
aftertreatment.
7
Overview
F I G U R E 4 Mechanism of acidic catalyzed transesterification. (Reproduced with permission from Ref 27. Copyright 1998, S.B.Q., Sociedade
Brasileira de Quı́mica.)
Homogeneous Acid-Catalyzed Biodiesel
Production
Another option is the acidic catalysis of the transester-
ification reaction. The acids mostly used are sulfuric
acid (H2 SO4 ) and sulfurous acid (H2 SO3 ), whereas in
some cases HCl is also used. These types of homo-
geneous catalysts give high conversions to alkyl es-
ters but they are slow and require high temperatures
(above 100◦ C). The typical molar ratio of alcohol to
vegetable oil is 30:1. Pryde and coworkers49 showed
that for the methanolysis of soybean oil in the pres-
ence of 1 mol% H2 SO4 and molar ratio of methanol
to oil 30:1 at 65◦ C, 50 h were required for full con-
version of vegetable oil (>99%). The proposed mech-
anism of the acidic catalysis of the transesterifica-
tion reaction of vegetable oils and fats is presented in
Figure 4.27
These catalysts can be used in the transester-
ification of waste oils or highly acidic oils that are
considered to be useless by the food industry. Mo-
hamad et al.50 used sulfuric acid and various concen-
trations of HCl for the conversion of waste palm oil
with ethanol to biodiesel. Higher concentrations of
acid catalysts produced biodiesel with better physical
characteristics and in shorter periods of time. Di Se-
rio et al.51 used a variety of acid catalysts (bivalent
cations) for the synthesis of biodiesel. Slightly acidic
soybean oil was used in each test. Both esterification
and transesterification reactions are catalyzed by these
cations. Liu et al.52 compared two acid catalysts, sul-
furic acid and SAC-13 (Nafion/silica composite solid
acid catalyst), for the conversion of carboxylic acids
with methanol at 60◦ C. The effect of carbon chain
length was measured and proved that the reaction
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rate decreased as the number of carbon atoms in-
creased for both H2 SO4 and SAC-13. The transfor-
mation of FFAs with acidic catalysts is also proposed
for the pretreatment of acidic vegetable oils and fats
before feeding them into the transesterification reac-
tor in which a base catalyst is used. In Figure 5, an in-
dustrial process including pretreatment of waste feed
and homogeneous alkali catalysis is presented.
Heterogeneous Catalysis
Research done in the sector of heterogeneous catalysis
for the production of biodiesel led to some interesting
findings. Major goal of these efforts was the creation
of a catalytic system that would be able to function
in relatively low temperatures and pressures and give
a good conversion in short times. The important fea-
tures of the effective catalysts should be their ability
to convert fats and low grade oils with high concen-
tration of FFAs and water and their stability.
Literature proposes a variety of solid catalysts
for the production of biodiesel from different feed-
stocks. The successful selection of a catalyst depends
on its cost, the energy and materials required for the
transesterification reaction, and the final quality of
the biodiesel fuel. Early attempts have been made
for the use of heterogeneous catalysts53 but the reac-
tion rates were very slow being controlled by mass
transfer limitations due to the three phase system
(alcohol–vegetable oil–solid catalyst). High molar ra-
tios of alcohol to oil were required in some cases54–56
and in general more severe conditions than the ones
used in homogeneous catalysis, to achieve the same
conversion.
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 WIREs Energy and Environment
F I G U R E 5 Industrial process steps for biodiesel production using waste oil with high concentration in FFAs. A pretreatment stage of the fatty
acid is required before the transesterification for avoiding the formation of soaps or ester molecule’s hydrolysis.
Heterogeneous Base-Catalyzed Biodiesel
Production
A number of alkali heterogeneous catalysts have been
developed and presented in literature for the transes-
terification reaction of vegetable oils.
The predominant solid catalysts used for the
production of FAME are metal oxide catalysts like
MgO and CaO. Several studies exist57–61 utilizing
CaO for the transesterification of edible and waste
oils. Preparation of CaO catalyst plays a very impor-
tant role to their activity, which is strongly related to
porosity, surface area and crystallite size.62 Different
precursors were used for a series of CaO solids, which
have been prepared by different means of thermal
treatment. During the reaction, calcium methoxide
is formed on the surface of CaO, which is thought
to be the actual catalyst of the transesterification
reaction.63 It slightly dissolves in methanol so it acts
primarily as heterogeneous catalyst. Bai et al.64 found
that soybean conversion to biodiesel was 98.72%.
Kouzu et al.65 conducted experiments in a batch re-
actor with soybean oil and methanol. It was found
that the catalyst had no measurable deactivation. In
another communication,60 it was reported that the
FAME yield dropped significantly when waste cook-
ing oil was used. The authors stated that the catalytic
activity was dropped because of the poisoning of the
basic sites of CaO by strong adsorption of FFAs on
the catalytic surface. Lopez Granados et al.,66 how-
ever, carried out experiments with sunflower oil and
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Comparative analysis of biodiesel versus green diesel
proved that when carbon dioxide or water is added,
the poisoning of CaO is far from negligible. The study
showed that CaO quickly carbonated and hydrated
in the presence of CO2 and H2 O resulting in cata-
lysts deactivation. However, this deactivation is re-
versible at high temperatures where both species are
removed from the active catalytic sites. Di Serio et
al.67 found that MgO was active only at high temper-
atures (180◦ C) when soybean oil was used. In lower
temperatures, the results are in accordance with other
works58, 68 where the similar behavior was observed,
that is, very low or even negligible conversion.
Hydrotalcites indicated a very important solid
catalyst for the production of FAME. The most widely
used is Mg–Al hydrotalcite. Georgogianni et al.69
compared three different solids for the conversion of
soybean with methanol. Among those catalysts, Mg–
Al hydrotalcite showed the highest activity (97%).
Zeng et al.70 and Xi and Davis71 reported a yield of
FAME about 90.5% when using the same catalyst
for 4 h, 6:1 alcohol to oil ratio, and 65◦ C temper-
ature. Cantrell et al.68 by using a series of hydro-
talcite materials studied the reactivity of Mg–Al hy-
drotalcites. They found that all the materials tested
were capable of catalyzing the transesterification of
glyceryl tributyrate with methanol but the reactivity
was increasing by adding more Mg. Replacing mag-
nesium with other metals like zinc did not have any
impact on catalytic activity.72 Another hydrotalcite
used for the conversion of poultry fats and waste
9
Overview
vegetable oils is quintinite-3T. Its major advantage is
its ability to convert triglycerides and FFAs simulta-
neously into biodiesel.73 As with the sulfated zirconia
catalysts, a polyvinyl alcohol (PVA) membrane was
tested for the production of FAME from soybean oil
and methanol. The experiments were carried out at
60◦ C with methanol to oil ratio 12:1, whereas the
catalyst was in pellet form and dispersed in a poly-
mer matrix.74 Finally, hydrotalcite-like compounds
containing magnesium, nickel, and aluminum were
tested for the transesterification of soybean oil with
methanol. The catalysts were prepared by the copre-
cipitation method and calcined at 773 K for 10 h. Fi-
nal conversion reached 87%.75 Barakos et al.76 used
a basic Mg–Al–CO3 hydrotalcite for the conversion
of both acidic and refined cottonseed oil to methyl
esters. The experiments were performed in a batch re-
actor with temperature ranging from 180 to 210◦ C,
methanol to oil ratio of 6:1, and 1 wt% catalyst.
The catalyst showed high activity in the production
of biodiesel, whereas diglycerides and monoglycerides
produced during the transesterification reaction were
reduced by removing the produced glycerin. One im-
portant remark is that the catalyst exhibited high ac-
tivity when it was tested with animal fat-containing
water.
Heterogeneous Acid-Catalyzed Biodiesel
Production
Acid catalysts have the advantage of the simultaneous
treatment of both FFAs and triglycerides. Their devel-
opment is directly connected with the replacement of
homogeneous acid catalysts.77 In fact, the advantages
of solid acid catalysts over liquid acid catalysts are
mainly related with the operational mode of the reac-
tor. A continuous process could minimize operational
costs and contribute in making biodiesel produced an
attractive alternative of diesel.78
Several solids have been used as acid catalysts,
the most important of which are presented below.
Ion-exchange resins are insoluble macroporous
polymeric matrices with the ability to exchange ions
with a solution or a reaction medium. Their surface
can easily exchange ions because of their pore struc-
ture. Ion-exchange resins with strong acidic behavior
are used for biodiesel synthesis. Common types of
acidic ion-exchange resin are such as Purolite CT-
275, Amberlyst-15, Amberlyst-35, and Nafion SAC-
13. Pasias et al.79 conducted experiments in a batch
reactor with a super acid Purolite CT-275 catalyst us-
ing a by-product of a vegetable oil refinery with high
concentration of FFAs. Reaction temperature was set
to 90–120◦ C, whereas methanol to oil ratio was kept
constant at 6.6:1. Using a kinetic model, both acti-
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vation energy and frequency factor were calculated
and model verification performed by using oils with
higher concentration of FFAs. Catalyst deactivation
was monitored and it was reported that no deacti-
vation occurs for the first 84 h. Heidekum et al.80
used an Amberlyst-15 and found that it can achieve
faster conversion (90%) for the esterification reaction
than Nafion-NR-50 or sulfated zirconia can. How-
ever, poor performance in catalyzing the transester-
ification reaction was shown. Dos Reis et al.81 re-
ported that the transesterification of Babassu coconut
oil using Amberlyst-15 was about 80% but only if the
methanol to oil ratio was as high as 100:1. But for
low temperatures (<90◦ C), as with all the other solid
acid catalysts, the reaction rate was extremely low.82
So, higher reaction temperatures are required for ac-
ceptable reaction rates to occur but Lotero et al.42
reported that this resins become unstable for temper-
atures higher than 140◦ C, limiting their wider use for
biodiesel synthesis.
Titanium dioxide (TiO2 ) is a metal oxide used
as a catalyst for biodiesel production. Addition of
sulfuric acid into the reactant’s mixture can signifi-
cantly enhance its catalytic activity.82 Chen et al.83
compared the catalytic activity of sulfated zirconia
to sulfated titania for the conversion of acid cot-
tonseed oil to biodiesel. High temperatures (230◦ C)
required making this catalyst unattractive for indus-
trial use. To enhance its reactivity, Peng et al.84 pro-
posed the introduction of SiO2 for the production of
SO2−4 /TiO2 − SiO2 . This new catalyst was used for
the transesterification of blends of cottonseed oil with
50% oleic acid. Maximum conversion achieved again,
at high temperature (200◦ C). Considering that the
corresponding homogeneous catalyst required tem-
peratures between 60 and 100◦ C still research is
needed if TiO2 is to be used industrially.
More effort has been put, though, for the re-
search of zirconium oxides’ (ZrO2 ) catalytic activ-
ity. The use of anions, like sulfate and tungstate, for
the enhancement of its acidity is a common practice.
Sulfated zirconia or tungstated zirconia proved to be
a catalyst with strong acidity.85 Comparing the two
solids, the latter proved to be more stable and recy-
clable, whereas the other was more active.86 Park et
al.87 used a WO3 /ZrO2 with higher stability (no ex-
tensive leaching of WO3 species) than sulfated zir-
conia, for the transesterification of waste cooking
oil. Selecting 75◦ C as reaction temperature, activity
was kept almost constant giving an 85% yield to
biodiesel for about 20 h but it decreased and stabi-
lized thereafter at 65%. The deactivation attributed
to leaching of WO3 species. Liquid phase transesterifi-
cation of triglycerides took place in a batch reactor at
Volume 3, January/February 2014
 WIREs Energy and Environment
120◦ C and 6.8 atm pressure. Tricaprylin’s number of
carbons affected the activity of the catalyst probably
because of the steric hindrances, whereas SO2− 4 were
leached out causing a further deactivation.88 Omota
et al.89 found that despite sulfated zirconias’ higher
acidity, it suffered from rapid deactivation due to
SO2−4 leaching. To quantify this leaching, they dis-
solved sulfated zirconia in water and PH measures
were taken. pH was found to decrease quickly because
of the formation of sulfuric acid from hydrolysis of
SO2−4 . So, in actual reaction conditions, the formation
of H2 SO4 had a masking effect on the determination
of catalytic behavior of the solid catalyst.
Tests were also performed with zeolites. Zeolites
are microporous crystalline solids that contain silicon
(Si), aluminum (Al), and oxygen in their framework.
The main characteristic of zeolites, which also serves
as their main advantage, is that their structure can be
altered according to the function they are destined for.
Corma and Garcia90 reported that by modifying the
aluminosilicate framework its acidic strength changes
and thus it can be used for a variety of reactions. But
zeolites indicate poor performance in the transesterifi-
cation of triglycerides.91, 92 When zeolites with small
pores are used triglycerides’ conversion is restricted
by mass transfer limitations. This problem can be
confronted by changing the ratio of Si–Al. Thus, it
may result in zeolites with larger pore diameter but
with lower acidity.93 For this reason, zeolites are
not yet considered as a good alternative for biodiesel
production.
The most important advantage of the use of the
solid catalysts is that they are not consumed, they are
not corrosive and the treatment of the transesterifica-
tion and esterification reaction products is very simple
and effective. A serious problem of the solid catalysts
is the leaching of the active phases from the catalytic
support leading to fast deactivation. In some cases, it
is not possible to distinguish the catalytic effect of the
solid catalysts from the effect of the dissolved active
material, which acts as a homogeneous catalyst.
Enzymatic Catalysis
The third type of catalysts used for biodiesel produc-
tion is biocatalysts. The most common biocatalysts
are the enzyme lipases.94 Enzymes present several ad-
vantages compared with acid or alkali catalysts. They
can catalyze feeds with water or FFAs and they seem
to be more stable than the acid catalysts when water is
present in the feed. The main advantage of the biocat-
alysts is the low temperature, which is required, below
50◦ C, for the esterification and transesterification re-
Volume 3, January/February 2014  2013 John Wiley & Sons, Ltd.
Comparative analysis of biodiesel versus green diesel
actions. Moreover, high grade glycerol can easily be
removed. Nevertheless, some important drawbacks
exist when an enzymatic catalyst is used, which are
strongly related with process feasibility from an eco-
nomic point of view. The cost of lipases remains high,
the reusability of them is still under investigation94
and the reaction rates remain very low. In some cases,
a cosolvent is required, which also increases the pro-
cess cost.
Several lipases have been developed for biodiesel
production, like Novozyme 435, Lipozyme TL IM,
and PS-C lipase. A detailed list of microorganisms and
the lipases they produce can be found in a previous
study.94 The way lipases are used further distinguishes
them in intracellular and extracellular lipases.
Intracellular lipases are not used as pure, namely
they reside within the cell or the microorganism they
are produced by, whereas extracellular lipases are re-
covered from the cells producing them and conse-
quently purified to be ready for further use.
Intracellular lipases have a significant lower cost
than extracellular lipases because they can directly be
used for biodiesel production, but they fail to achieve
high yields because of the mass transfer limitations.
On the other hand, extracellular lipases exhibit
a better catalytic performance because of restricted
mass transfer limitations.95 However, their produc-
tion cost is high, which should be countervailed only
by long deactivation periods if they are to be used in
industry.
Various types of vegetable oils and alcohols
have already been tested. Sunflower, soybean, and
Jatropha oils are the most commonly used oils.96–98
The price of methanol and ethanol makes them the
most appealing option for the biodiesel production,
but the two alcohols can deactivate the enzyme if large
amounts of them are introduced to the bioreactor.98
But in many occasions, a high molar ratio of al-
cohol to oil is required for an adequate conver-
sion of the vegetable oil molecules. Chen et al.99 re-
ported that the longer the carbon chain of the alcohol
is, the smaller the deactivation rates are. Such alco-
hols, though, like methyl or ethyl acetate, are more
expensive. Another option is the use of organic sol-
vents that can dilute both alcohol and oil. The main
problem is that these cosolvents should dilute the pro-
duced glycerol as well because if pure glycerol is not
dissolved then it forms a new liquid phase that resides
on the enzyme’s surface and causes fast deactivation
on it.100 The use of cosolvent may increase reaction
rates96 but the production cost is increased substan-
tially because purification and reuse of the organic
cosolvent is required.
11
Overview
Thermal Production of Biodiesel
Another method used for the production of biodiesel,
besides alkali and acid transesterification, is the
thermal treatment without catalyst. For this method,
high temperature (above 180◦ C) and pressure (above
30 bar) is required.101 Pasias et al.102 found that this
method is applied for both refined and acid oils and
fats. In the case of FFAs, they play the role of an acidic
catalyst. The major advantage of this method is that
biodiesel and glycerol produced are pure, whereas the
latter is colorless and clear. On the contrary, glycerol
obtained by using the classic catalytic methods has a
brown color. The drawbacks of the thermal treatment
are the low reaction rates and the severe conditions
required for the transesterification reaction.
An alternative of this method is using super-
critical methanol. In this state, methanol can achieve
high solubility in the oily phase.103 As a result, reac-
tion times are minimized, whereas the cleaning of the
products is more environmentally friendly than it is
with the classical methods. Saka and Dadan104 state
that this method offers low production costs by using
simple technology for the production of biodiesel.
Overview
The most commonly used biodiesel production pro-
cesses throughout the world are based on homoge-
neous alkali catalysis. Its major advantages are the
fast reaction rates and the milder conditions required
to achieve the desired conversion. On the other hand,
the presence of water or FFAs in the feed leads to
undesired side reactions. Both types of homogeneous
catalysis have the drawback of further cost increase
because the removal of catalyst is required from the
final product. Another disadvantage is that continu-
ous operation cannot be easily employed is such type
of catalysis. On the contrary, heterogeneous catalysts
can support continuous operation improving the pro-
cess economics. More severe conditions are required
than with homogeneous catalysis to achieve the same
reaction rates. A certain advantage of the process
based on heterogeneous catalysis is the production
of glass-clear glycerine as by-product. Another option
for biodiesel production is the use of biocatalysts such
as lipases. They can operate at very low temperatures
with feeds containing from low to high concentration
of FFAs and water. Their main drawback is their high
cost and the small reaction rates they achieve. Also,
their sensitivity to the alcohol used as a reactant and to
impurities present in crude oils is one more factor that
affects their stability. For the improvement of the pro-
duction processes, research should be focused on fully
understanding the physical/chemical mechanisms that
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affect the operation of the solid catalytic materials and
improve them so that they can catalyze both trans-
esterification and esterification reactions successfully
at mild operational conditions with low deactivation
rates.
Green Diesel
Green diesel is produced from the catalytic hy-
drotreatment (HDT) of VOFD. At typical HDT con-
ditions (300–380◦ C and 30–50 atm), triglycerides are
HDO producing long-chain normal paraffins. These
paraffins have a number of carbon atoms close to
the corresponding range of diesel fuel (C16 –C20 ).
The HDT of triglyceride containing feedstocks oc-
curs via three distinct pathways.105 The first one,
decarboxylation, gives one molecule CO2 per es-
ter bond when the triglyceride is hydrogenated, the
second one, decarbonylation, gives one molecule
of CO and one of water per ester bond, whereas
the third one, hydrodeoxygenation path (HDOP),
gives two molecules of water per ester bond of
triglyceride that undergoes HDT. In Figure 6, these
three paths are shown. In all three cases, assum-
ing that all three ester bonds in each triglyceride
molecule are fully converted, propane is produced,
which can be recovered and used as fuel or in other
processes.
The knowledge of the extent of each of these
three paths, that is, the selectivity of various types of
catalysts, is crucial because both the hydrogen con-
sumption (HCON) and the treatment of produced
gaseous species should be considered. From the three
paths, decarboxylation has the lowest HCON, requir-
ing one mole of hydrogen per ester bond. Decarbony-
lation requires 2 mol of hydrogen per ester bond,
whereas HDOP is the most demanding path needing
4 mol of hydrogen per ester bond. It is obvious that
for an industrial process, HDOP is undesirable and
ways for promoting the other two paths should be
investigated and proposed to make this technology
more attractive.
The industrial application of this technology is
not yet as common as it happens with biodiesel. Only
some major production plants exist with significant
green diesel capacity. UOP and ENI cooperated for
the construction of a green diesel production plant in
Italy, which processes 0.32 million tones per year of
vegetable oils.106 UOP is planning also to construct
a green diesel plant in Louisiana, USA, with a maxi-
mum capacity of 2.68 million tones per year.107 The
most important fact is that nonedible oils and animal
fats will be used as raw material. A European com-
pany, Neste Oil, with its own technology (NExBTL)
built two renewable diesel plants in Rotterdam
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 WIREs Energy and Environment
F I G U R E 6 Hydrogenation of triglyceride via the three proposed reaction pathways.
(Holland) and Singapore with a production capac-
ity of 0.8 million tones per year after the construction
of a plant with 0.17 million tones per year capacity
in Finland.108
Apart from the reactions occurring in the liq-
uid phase, reactions in the gaseous phase may in-
crease HCON. Water gas shift reaction and metha-
nation reactions of CO and CO2 are favored in
these conditions. The first was found to be at equi-
librium at the conventional HDT conditions (310–
350◦ C and 33 atm), whereas CO methanation is prac-
tically irreversible.109
Green diesel has the advantage of being fully
compatible with petro-diesel. It can be used neat or in
blends with diesel and thus no further modifications
need to be done to the diesel engines, as it happens
with biodiesel. Its composition of n-paraffins makes
it a perfect substitute of diesel fuel showing improved
cetane number,110 cetane index,111 and having low
sulfur and nitrogen concentration. Stumborg et al.8
stated that both the properties of the green diesel fuel
were improved compared with the diesel fuel. By us-
ing the green diesel in blends with petro-diesel in a
diesel engine, the emissions were decreased in many
cases. More specific, CO, PM, and THC were de-
creased when green diesel was introduced to the en-
gine, as it happened with biodiesel. But when using
green diesel, NOx emissions also decreased. From an
economic point of view, the infrastructure for its pro-
duction already exists in oil refineries, so capital costs
Volume 3, January/February 2014  2013 John Wiley & Sons, Ltd.
Comparative analysis of biodiesel versus green diesel
are minimized while the use of waste oils makes this
process environmentally friendly.
The main disadvantage of green diesel is that
the high concentration of n-paraffins in the final
fuel downgrades the cold flow properties of the fuel.
Simacek and Kubicka112 reported that by hydroc-
racking petroleum vacuum distillate and rapeseed
oil mixtures, the cold flow properties of the pro-
duced organic mixture were significantly improved
[cloud point (CP) = −23◦ C, cold filter plugging
point (CFPP) = −24◦ C]. Another option, though,
could be the isomerization of the final product using
an acid catalyst. Another drawback of green diesel
when it is compared with biodiesel is that the nor-
mal paraffins constituting the green diesel are not
biodegradable.8
The activity and selectivity of the HDO of
triglyceride feedstocks have been studied for a variety
of heterogeneous catalysts. These catalysts are rang-
ing from typical HDT catalysts used in oil refineries
like CoMo or NiMo, to catalysts based on noble met-
als like Pt. The most important catalysts tested and
referred in literature are presented in the following
section.
Catalytic HDO of Model Compounds
For the successful elimination of the oxygen-
containing groups from triglycerides or carboxylic
acids of the vegetable oils, firstly the HDO reaction
mechanisms have been investigated. Oxygen removal
13
Overview
is imperative because it leads to a more stable fuel. So,
the knowledge of how this removal occurs, which pa-
rameters affect it and the way the HDO reaction can
be directed toward the desired result, is more than im-
portant. These parameters are reaction temperature,
water and nitrogen compounds content, and hydro-
gen sulfide when a sulfided catalyst is used.
Oxygen is not present only in carboxylic or
ester bonds but in carbonyl, aldehyde, ketone, and
amide molecules. To best determine all the previously
mentioned points, model compounds have been used
for the study of the HDO reaction. The model com-
pounds, which have been extensively used, are esters
and carboxylic acids. The catalysts tested so far can be
generally classified in two categories. One comprising
the catalysts used for petroleum fractions HDT that
is NiMo/Al2 O3 and CoMo/Al2 O3 , and the other, any
innovative catalytic system with one or two active
metals on porous supports.
Typical Hydrogenation Catalysts
The first category is important because these catalytic
systems will allow cohydroprocessing of feeds consist-
ing of petroleum fractions and vegetable oils and/or
fats avoiding additional investment cost for existing
or new refineries. For this purpose, Senol et al.113
tested the performance of both a NiMo/γ -Al2 O3 and
a CoMo/γ -Al2 O3 catalyst by using two model com-
pounds, methyl hexanoate and methyl heptanoate.
NiMo was proved to be more active, whereas both
catalysts suffered from measurable deactivation. Hy-
drocarbons were formed in all cases but following
different reaction pathways. A reaction scheme was
proposed according to the final measurable products.
In another consecutive communication,114 the effect
of added H2 O and H2 S was estimated. It was found
that water has an important inhibition effect on the
aliphatic ester’s HDO over both catalysts. So, the to-
tal amount of C7 and C6 hydrocarbons decreased,
whereas water content in the feed increased. H2 S was
found to successfully compensate the inhibition of
water for both catalysts. Krause and coworkers115 in-
vestigated the HDO reaction of methyl heptanoate,
heptanol, and heptanoic acid over NiMo/γ -Al2 O3
and CoMo/γ -Al2 O3 catalysts. Again a variety of dif-
ferent oxygenated groups (alcohols, aldehydes, ethers,
and carboxylic acids) were formed as intermediates,
whereas some sulfur-containing compounds led to
catalyst deactivation. Saturated or not, C7 and C6
hydrocarbons were formed through a complex re-
action network. NiMo/γ -Al2 O3 catalyst showed the
highest activity but also the highest HCON. Senol
et al.116 further reported that when H2 S was in-
troduced to maintain catalytic activity, HDO of
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both aromatic and aliphatic compounds was affected.
HDO of aliphatic esters proved to be unaffected by
the presence of H2 S indicating that the two oxy-
genated groups follow different reaction mechanisms.
CoMo/γ -Al2 O3 indicated higher activity for the HDO
of phenol than NiMo, whereas exactly the opposite
was observed for the HDO of aliphatic esters.
Novel Catalytic Systems
New catalytic systems have also been tested for the
HDO of vegetable oils and production of green diesel
with the aim to achieve better conversions at mild
conditions. Kubickova et al.117 carried out experi-
ments in a semi-batch reactor using a Pd/C catalyst.
This catalyst was reduced in situ at 200◦ C for 2 h,
while a constant flow of hydrogen was maintained.
Stearic acid, ethyl stearate, and tristearine were used
as model compounds and all were converted to the
same final product, which was n-C17 . However, n-
heptadecane was not the only product but various
isomers were also produced. Ethyl stearate produced
n-C17 through stearic acid intermediate but concen-
tration of unsaturated C17 hydrocarbons was higher
than in the case of stearic acid. From its decomposi-
tion, CO, CO2 , C2 H6 , and ethylene were produced.
Further study of the system118 showed that the most
appropriate catalysts for carrying out the stearic acids
HDO reaction are Pd/C and Pt/C. A variety of active
metals (Ni, Mo, Pd, Pt, Ir, Ru, Rh, and Os) and sup-
ports (Al2 O3 , Cr2 O3 , MgO, SiO2 , and activated car-
bon) were evaluated for this reaction. In this study,
all catalysts underwent the same pretreatment pro-
cedure. The HDO reaction was conducted in a semi-
batch system at 300◦ C temperature and 6 bar pressure
giving heptadecane with high activity and selectivity.
Snare et al.119 attempted to estimate the kinetic be-
havior of ethyl stearate’s decarboxylation. Again the
catalyst used was a Pd/C in a semi-batch reactor. A
reaction network of the conversion of ethyl stearate to
hydrocarbons (n-C17 or aromatic C17 ) was presented
and the kinetic modeling of all reactions occurred re-
sulted in the calculation of the corresponding rate
constants. In a later work,120 a variety of model com-
pounds (nonanoic, stearic, behenic, oleic, and ethyl
stearate) was used for the estimation of HDO reac-
tion pathways over a Pd/C catalyst. Several other pa-
rameters affecting the reaction selectivity were studied
such as reaction atmosphere, support acidity, and cat-
alyst quantities. High yields to n-C17 were achieved
under helium atmosphere with stearic acid, whereas
when ethyl stearate was used, high yields were ob-
tained only in the case of the most alkaline Pd/C cata-
lyst. However, the formation of aromatics made this
catalyst less attractive. When hydrogen was
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 WIREs Energy and Environment
F I G U R E 7 Schematic diagram of production of a mixture of diesel and green diesel with neat vegetable oil HDO and gas oil HDS.
introduced to the reaction atmosphere, higher con-
versions were achieved. Moreover, the length of the
molecule under investigation was also an impor-
tant factor and, as expected, the longer the carbon
chain was, the slower the reaction proceeded. Fi-
nally, Madsen et al.121 used a model feed consist-
ing of oleic acid and tripalmitin with molar ratio
of 1:3. The mixture was hydrotreated at 325◦ C at
20 atm pressure in a stirred batch reactor. A 5 wt%
Pt/γ -Al2 O3 catalyst was investigated. Decarboxyla-
tion/decarbonylation paths for both molecules were
highly favored over HDOP. Pd/γ -Al2 O3 and Ni/γ -
Al2 O3 catalysts were also tested with the first show-
ing even higher decarboxylation/decarbonylation se-
lectivity than Pt/γ -Al2 O3 , whereas Ni/γ -Al2 O3 was
less active than Pt/γ -Al2 O3 and showed higher selec-
tivity to HDOP. By and large, oleic acid presented
higher activity than the ester molecule.
Catalytic HDO of Vegetable Oils
Considerable efforts have been expended on the HDO
of vegetable oils and animal fats and their derivatives
Volume 3, January/February 2014
Comparative analysis of biodiesel versus green diesel
for the study of the actual problems related with the
production process or with the properties of the final
fuel. Thus, experiments with a variety of vegetable
oils were carried out using mainly typical petro-diesel
hydrodesulfurization (HDS) conditions and catalysts.
Because some problems occurred when neat vegetable
oils were introduced to the reactors, like plugging
or faster catalytic deactivation due to sulfur leaching
from the catalytic particles, coprocessing with various
types of gas oils was investigated, namely the simul-
taneous HDS of gas oil and HDO of vegetable oil. In
Figure 7, a schematic diagram of the common indus-
trial processes involved in production of diesel–green
diesel mixtures is presented using one reactor for the
HDO of the vegetable oils and one for the HDS of the
gas oil. The liquids are blended after catalytic treat-
ment to obtain a final fuel with the desired properties
and composition.
In Figure 8, the coprocessing of vegetable oil–
gas oil mixtures is presented. In this case, one reactor
is used for both HDO and HDS reactions and the
product is ready for use.
 2013 John Wiley & Sons, Ltd. 15
Overview
F I G U R E 8 Coprocessing of vegetable oil and gas oil for the
production of a mixture of diesel and green diesel.
HDO of Neat Vegetable Oils
Classic HDT HDS catalysts such as CoMo and NiMo
on a variety of supports were tested. Simacek et al.122
investigated the HDO reaction of neat rapeseed oil
at various temperatures (260–340◦ C) under 70 atm
pressure in a continuous flow reactor using three dif-
ferent NiMo/γ -Al2 O3 commercial catalysts. The final
liquid product consisted mainly of C17 , C18 hydrocar-
bons, and isomers of the two at reaction temperatures
above 310◦ C, whereas unconverted triglycerides and
FFAs were measured when the reaction temperature
was kept low. It was also found that selectivity of
all three catalysts changed with temperature, namely
n-C17 quantities increased with increasing temper-
ature, whereas n-C18 decreased. This trend shows
that the decarboxylation/decarbonylation pathways
are favored at higher temperatures, whereas deoxy-
genation path is suppressed. This result is in agree-
ment with the findings of Huber et al.123 In this work,
experiments with neat sunflower oil, neat heavy vac-
uum oil (HVO) and blends of sunflower oil and HVO
were carried out. It was proved that the triglycerides
hydrogenation occurs via three paths: decarboxyla-
tion, decarbonylation, and HDOP. The products were
n-alkanes with a carbon number from C16 up to C20 .
Guzman et al.124 tested a NiMo/γ -Al2 O3 catalyst for
the HDO of crude palm oil. In a pressure range from
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40 to 90 atm, the triglycerides can be converted to
high cetane index green diesel. However, when the
pressure was reduced the conversion of palm oil was
not complete and reaction intermediates appeared in
the final product. They also found, by measuring in-
creased concentrations of C18 and C16 , that as re-
action pressure increases, the deoxygenation mecha-
nism (removal of two water molecules) becomes more
prominent at 350◦ C and hydrogen to crude palm oil
ratio 12.5:1. Kubicka and coworkers111 used a com-
mercial NiMo/γ -Al2 O3 catalyst for the HDO reaction
of rapeseed oil. Using the same setup as previously,
green diesel was produced with high concentration
of C17 , C18 , and other n-alkanes and i-alkanes. For
the evaluation of the green diesel properties, mixtures
with mineral diesel were formed. These mixtures (5–
30 wt% in green diesel) met the EU specification EN
590. The major advantage of the fuel was the im-
proved cetane index and number but the cold flow
properties, despite the use of Keroflux 3566 and In-
fineum R 288 flow improvers, were little improved.
Toba et al.125 used a batch reactor to investigate the
catalytic activity of sulfided NiMo, CoMo, and NiW
catalysts. Low-grade waste oils were used for the
production of high quality fuel. The CoMo catalyst
showed observable deactivation, whereas NiMo and
NiW indicated high and stable HDO activity. High
temperature was required (above 300◦ C) for full con-
version of these oils. For the improvement of the fi-
nal fuels cold flow properties, a B2 O3 –Al2 O3 support
was used, which appears to accelerate the formation
of iso-paraffins.
Except for the classic HDS catalysts, other non-
conventional catalysts have been tested. Nava et al.126
reported that from experiments conducted in a fixed-
bed reactor, in downflow operation, at 250◦ C, and
30 atm pressure, a CoMo catalyst supported on SBA-
16 exhibited the optimum performance in the HDO
of a by-product derived from olive oil production.
Other mesoporous silica supports were also tested
(DMS-1, SBA-15, and HMS). The CoMo catalysts
supported on DMS-1, SBA-15, and SBA-16 showed
a more effective oxygen removal and selectivity to-
ward the desired products (paraffins and alcohols)
than the CoMo supported on HMS. Remarkable was
the finding that all the sulfided CoMo catalysts pre-
sented higher activity than a NiMo catalyst supported
on alumina. Lima et al.127 investigated the pyroly-
sis of soybean, palm, and castor oils in a temper-
ature range from 350 to 400◦ C. They stated that
for the upgrading of pyrolysis products, a HZSM-
5 zeolite was employed at 400◦ C, before condensa-
tion of pyrolysis products. By comparing the treated
and untreated liquid fuels using GC analysis, they
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 WIREs Energy and Environment
deducted that the initial carboxylic acids were con-
verted to hydrocarbons. Apart from HZSM-5 zeolite,
Pt was investigated for improving green diesel quality.
Hancsok et al.128 used a Pt/HZSM-22/Al2 O3 catalyst
for the isomerization of prehydrogenated sunflower
oils. The final fuel fulfilled all the required specifica-
tions EU imposes for diesel fuel, namely high cetane
number (>80), low concentration of sulfur, and good
cold flow properties (CFPP <−20 to −15◦ C). From
the variety of metal loadings (0.25–1.1 wt% Pt), the
one with 0.55% Pt was preferred and tested at sev-
eral conditions (320–330◦ C, 50–60 bar, liquid hourly
space velocity (LHSV) = 2 h−1 , and hydrogen to
hydrocarbons ratio of 300 Nm3 /m3 ). The 30 wt%
blend had 13 units higher cetane number (from 40
increased to 53), whereas the cold flow properties re-
mained similar to those of petro-diesel. In another
work, Kikhtyanin et al.129 studied the simultaneous
HDO and isomerization of sunflower oil by using a bi-
functional Pd/SAPO-31 catalyst. The produced green
diesel had improved cold flow properties. The conver-
sion was full at temperatures 330–350◦ C and weight
hourly space velocity (WHSV) = 0.9–1.2 h−1 . Again it
was found that decarboxylation/decarbonylation se-
lectivity increased with temperature increase. Initial
isomerization activity was very high [the ratio of the i-
(C17 + C18 )/n-(C17 +C18) exceeded 10] but declined
over time. This deactivation was attributed to incom-
plete conversion of intermediate oxygenated products
that blocked the acidic sites of SAPO-31. They also
found that the used catalyst can regain its initial ac-
tivity after heated in air at 450◦ C. Finally, a new
catalytic system was proposed by Yakovlev et al.130
Under mild conditions, a Ni-Cu catalyst was more
active than Ni catalysts in HDO reaction. Rh-, Rh-
Co-, Ni-, and Ni-Cu- were tested as active metals. The
catalytic supports selected were SiO2 , Al2 O3 , ZiO2 ,
CeO2 , and CeO2 -ZrO2 . All catalysts were prepared
by wet impregnation or coprecipitation. HDO was
carried out at isothermal conditions in the tempera-
ture range of 250–400◦ C and total pressure 5–20 atm.
Cu was found to play a bifunctional role. In appeared
to facilitate the nickel oxide reduction at tempera-
tures lower than 300◦ C and prevented methanation
of oxy-organic compounds at elevated temperatures.
All catalysts were not sulfided and so a low sulfur
concentration in liquid feeds used was imperative.
HDO of Vegetable Oil–Gas Oil Blends
Coprocessing of neat vegetable oils and fats and their
derivatives with various gas oils has been studied be-
cause of the great interest of existing refineries on
this process. One reason was that when neat veg-
Volume 3, January/February 2014  2013 John Wiley & Sons, Ltd.
Comparative analysis of biodiesel versus green diesel
etable oils introduced to the catalytic reactors at high
LHSVs, waxes were formed by the HDT of neat veg-
etable oils and fats that caused reactor plugging.123
Another reason is the possible use of existing infras-
tructure in refineries for the simultaneous HDS and
HDO. Thus, a number of researchers have focused
their efforts on the investigation of the coprocessing
of the industrially widely used catalysts NiMo/Al2 O3
and CoMo/Al2 O3 . Simacek and Kubicka112 reported
that the diesel fuel produced from the hydrocrack-
ing of mixtures of a petroleum vacuum distillate with
5 wt% rapeseed oil can substitute directly diesel fuel.
Its worse cold flow properties were improved by par-
tial isomerization of n-C17 and n-C18 molecules de-
rived from the rapeseed oil HDO. Huber et al.123
found that in simultaneous HDT of sunflower oil and
HVO, the HDS reaction was significantly lower than
the HDO of triglycerides on a NiMo/γ -Al2 O3 catalyst
but the presence of sunflower oil did not inhibit the
HDS reaction in any case. On the contrary, this dilu-
tion increased the yield of straight chain alkanes from
the sunflower oil. Bezergianni et al.131 investigated the
hydrocracking of HVO–vegetable oil mixtures for the
production of biofuels. Three different commercial
catalysts were tested. Results have shown that a pre-
treatment of the HVO was imperative because HVO–
sunflower oil mixtures had poor oil conversion and
heteroatom (S and N) removal, whereas an increase
in sunflower oil portion in the feed mixture increased
hydrocracking activity. From the three different cat-
alytic systems, the one with tendency to produce more
naptha exhibited both the highest conversion (65%)
and highest selectivity to naptha (50%). Remarkable
was the fact that in any case, 95% of the sunflower oil
was converted to useful hydrocarbons for various uses
(naptha, diesel, and gasoline). Except hydrocracking
of vegetable oils, the catalytic hydroprocessing of the
latter was studied. Sebos et al.110 conducted exper-
iments with cottonseed oil in petro-diesel mixtures.
The diesel was prehydrodelsulfurized. A commercial
CoMo/γ -Al2 O3 was used at typical HDS conditions
(305–345◦ C, 30 bar, and 5 h−1 < WHSV < 25 h−1 )
and it was found that full conversion of triglycerides
occurred. A simple kinetic model was proposed for
scale-up. Templis et al.132 studied the HDS ability of
the same CoMo catalyst when neat heavy gas oil with
2.5, 5, and 10 wt% refined palm oil was fed to the re-
actor. They found that the HDS activity of the CoMo
catalyst reduced when palm oil was added in the feed
up to 5 wt% but it remained constant for more than
5 wt% palm oil in gas oil. Moreover, an attempt to
estimate the effect of the vegetable oil presence in
the feed on the HCON was made. A kinetic model
was applied for both HDS and HCON reactions. In a
17
Overview
following work, Vonortas et al.109 found the same
trend when the deep-HDS of gas oil–palm oil mixtures
were studied, namely the HDS reaction rate decreased
initially but for 5 wt% or more palm oil it remained
constant. To estimate the HDO reaction selectivity
gas samples were obtained and treated accordingly. It
was indicated that methanation of CO and water–gas
shift reaction occurred in the gaseous phase. The first
led to CH4 formation, whereas the latter was found to
be at equilibrium. It was concluded that HDOP was
preferred by the 38% of the total ester bonds, whereas
the remaining 62% followed the other two pathways.
In all three works,109, 110, 132 catalyst deactivation was
typical like in any HDS process. Walendziewski et
al.133 studied the HDO over a NiMo/γ -Al2 O3 cata-
lyst of two mixtures, 10 and 20 wt% rape oil in light
gas oil. Three temperatures were selected (320, 350,
and 380◦ C), two different pressures (30 and 50 atm),
LHSV = 2 h−1 , while hydrogen to liquid feed ratio
was kept at 500 Nm3 /m3 . Several physicochemical pa-
rameters of the obtained fuel were evaluated. Among
them, cloud and melting points had undesirably in-
creased values, whereas flash point was decreased. A
catalyst with mild hydrocracking and isomerization
activities was suggested to be the best selection for
the production of a diesel-like fuel.
Overview
Green diesel appears as a promising biofuel derived
from vegetable oil and fats with some important ad-
vantages. They are mainly its full compatibility with
petro-diesel, its high cetane number, its high stability
and the low emissions when used in diesel engines.
The coprocessing of gas oil–VOFD in existing hy-
drotreaters and infrastructure saves installation cost
in running oil refineries. Moreover, an important ad-
vantage is that all VOFD can be used for green diesel
production without significant catalyst deactivation.
The major drawback is that for the production of
such a biofuel, typical hydrogenation conditions are
required that are severe as compared with the ones
used in biodiesel production. To greatly improve the
process economics, research should focus on reduc-
ing the HCON by altering the selectivity of the HDO
reaction and leading it to the desired pathway. Thus,
apart from the study of commonly used catalysts, light
should be shed on new catalytic systems based on
noble metals and novel porous supports, which will
be able to catalyze the VOFD with optimum HCON
and at milder conditions. Another point for future
research is the target to simultaneously catalyze the
HDO reaction and the partial isomerization of long-
18  2013 John Wiley & Sons, Ltd.
wires.wiley.com/wene
chain paraffin’s produced to improve the poor cold
flow properties of green diesel allowing, thus, its use
as a neat biofuel.
CONCLUSIONS
Biodiesel and green diesel can be produced from veg-
etable oils and fats of low and high acidity. The two
fuels are environmentally friendly compared with the
petro-diesel, have very low sulfur content, and their
use in diesel engines produces very low PM, THC, and
CO emissions. Green diesel molecules do not contain
oxygen, which makes this biofuel very stable over
time.
The production of biodiesel is simpler, requires
lower capital investment but it increases as the acidity
of the feeds increases. The FFAs in the feed oils must
be pretreated and converted to ester molecules before
transesterification otherwise they produce soaps when
the classical acid or basic homogenous catalysis is ap-
plied. This problem can be resolved by using active
and stable solid catalysts operating at mild conditions.
In parallel, the use of solid catalysts allows the pro-
duction of clean glycerine. The enzymatic routes pro-
posed for biodiesel production appear to exhibit the
same as the solid catalysts merits but they appear to be
more expensive and sensitive to feed quality. Because
of the relative simplicity of the biodiesel production
processes, biodiesel appears to be a very attractive so-
lution for small and remote units for production of
renewable fuels.
The production of green diesel requires higher
capital cost and more severe operating conditions in
general. The presence of FFAs in the reactor feed ap-
pears to have a minor effect on the reactor perfor-
mance. The green diesel consists of straight alkanes
and thus it cannot be easily used as a neat biofuel.
However, its mixtures with diesel up to 20 wt% ap-
pear to have excellent properties as fuels for diesel en-
gines. The great advantage of the green oil production
processes based on the HDT of the vegetable oils and
fats is that they can be incorporated in conventional
refineries, either existing or new, using the same cata-
lysts as those used for HDT and hydrodesulfurization.
Another advantage of the green diesel production as
compared with that of biodiesel is that propane is
produced as by product instead of glycerin. For the
production of green diesel, hydrogen is consumed and
its cost affects the production cost of this biofuel. Be-
cause of higher capital cost of the production units
and the relatively severe operating conditions, green
diesel production should not be recommended for low
capacity units.
Volume 3, January/February 2014
 WIREs Energy and Environment Comparative analysis of biodiesel versus green diesel

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