DOI: 10.1002/cssc.
200900107
Transforming Triglycerides and Fatty Acids into Biofuels
Siswati Lestari ,[a, b] Pivi Mki-Arvela,[a] Jorge Beltramini,[b] G. Q. Max Lu,[b] and
Dmitry Yu. Murzin*[a]
Fuels derived from biobased materials are attracting attention
for their potential in securing the energy supply and protect-
ing the environment. In this Minireview, we evaluate the use of
biobased sources, particularly fatty acids and triglycerides from
seed oils and animal fats, as fuels. The physical and chemical
properties of these fatty acids and triglycerides are discussed,
including the link to their sources and current availability to
1. Introduction
Economical, social, and environmental demands have driven
research focusing on alternative fuel sources. As reserves of
fossil fuels decline and energy demand from emerging econo-
mies increases, the price of conventional fossil fuels will contin-
ue to rise. Furthermore, the environmental damage caused by
the combustion of fossil fuels is a factor that contributes to
global warming. These emissions add to greenhouse CO2 as
well as being a major source of other air contaminants, includ-
ing SOx, NOx, CO, particulate matter, and volatile organic com-
pounds.[1–3]
These consequences have motivated worldwide research
into developing economic and energy-efficient processes for
the sustainable production of transport fuels and chemicals. In
this context biobased sources, specifically triglycerides and
fatty acids, are sustainable resources with high energy densi-
ties that can be efficiently converted into liquid fuels. In this
Minireview we evaluate the current technology for converting
biobased feedstocks into transportation fuels. Among the alter-
native transportation fuels, bioethanol and biodiesel are widely
known as substitutes for their fossil counterparts, gasoline and
diesel. We limit our discussion to the recent literature on tech-
nologies for bioethanol and biodiesel, which includes further
development towards the next generation of gasoline- and
diesel-like hydrocarbons.
1.1 Historical perspective and background
The idea of using vegetable oil as a transportation fuel is not
new. Many papers have reported the diesel engine tests with
peanut oil, already carried out at the 1900 World Fair in
Paris.[3–6] There were a number of experiments on the use of
vegetable oils as fuels in the early 1940s, particularly among
European nations with tropical colonies because of the interest
in supplying their colonies with energy and industry from their
own resources. In 1937, the Belgian researcher G. Chavanne
from the University of Brussels patented a procedure for the
transformation of vegetable oils. The patent described the re-
ChemSusChem 2009, 2, 1109 – 1119  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
meet fuel demands. The current technologies, also known as
the first-generation ones, for converting triglycerides into fuels
are covered, including conventional methods such as transes-
terification, pyrolysis, cracking, and emulsions. Recent, second-
generation technological developments that lead to more
commercially viable biofuels based on diesel-like hydrocarbons
are also discussed.
action of the vegetable oil with a short-chain alcohol in order
to separate the fatty acid from the glycerol bond.[7] This ap-
pears to be the first attempt at producing biodiesel, with the
reaction referred to as transesterification.
During World War II vegetable oils were used as an emer-
gency fuel when the supply of petroleum was disrupted.[7]
With the steady supply and low price of oil during the post-
war era, the use of vegetable oils as transportation fuel was
not considered. It was not until the oil embargo in 1970s,
when oil supply disrupted and prices increased continuously,
that the use of blend biofuels was reintroduced. Recently, bio-
fuels have become a hot issue among governments, industry,
and academia as a response to uncertain oil prices and supply
shortages. Moreover, the dependency of importer nations on
supply countries has created much tension and uncertainty.
1.2 Environmental concerns
Increased environmental awareness is also a driving force in
the search for an alternative and sustainable renewable energy
supply. The combustion of fossil fuels has been linked to an ac-
celeration of global warming and contributes to acid rain and
smog. Biofuel is carbon-neutral, meaning that the CO/CO2 re-
leased from the combustion of biofuels is derived from the
photosynthesis process. Moreover, biofuels contain no sulfur.
However, biofuels have received recently negative evaluation
as instead of being carbon-neutral, they release higher levels
[a] Dr. S. Lestari , Dr. P. Mki-Arvela, Prof. D. Yu. Murzin
Process Chemistry Centre
bo Akademi University
Turku, 20500 (Finland)
Fax: (+ 35) 82-154-479
E-mail: dmurzin@abo.fi
[b] Dr. S. Lestari , Dr. J. Beltramini, Prof. G. Q. M. Lu
ARC Centre of Excellence for Functional Nanomaterials
University of Queensland
St. Lucia, QLD 4072 (Australia)
1109
 D. Yu. Murzin et al.

of carbon dioxide and affect biodiversity.[8–10] The latter is a Scheme 1. The fatty acids vary in their carbon chains and
result of their production routes. The ethical dilemma of using number of unsaturated chains. When the three fatty acids are
biofuels that compete with food resources has to be taken similar, the product is a simple triglyceride; when they are dif-
into consideration when applying this technology as an alter- ferent, the product is a mixed triglyceride.
native energy source on a large scale. These considerations
have promoted the development of the second- or next-gener-
ation biofuels, which are characterized by the utilization of al-
ternative nonfood sources and lignocelluloses such as grass,
microalgae, agricultural waste products, and low-quality vege-
table oils as well as heavier side products of kraft pulping in-
dustries.

1.3 Government regulations

Scheme 1. Reaction of glycerol and fatty acids to produce triglyceride,
More rigid government regulations for the use of alternative which is a constituent of vegetable oil.
fuels, in order to meet targets from the Kyoto protocol, have
also forced recent activities in using biofuels. For example, the
European Union has set a target of 5.75 % for the percentage Fully saturated triglycerides are solid at room temperature
of total transport fuel sales to come from biofuel by 2010, and are thus difficult to apply as fuels, whereas the use of
which will increase to 10 % in 2020,[11] and furthermore recom- polyunsaturated (i.e., containing several double bonds) acids
mends a constant emission monitoring for non-adapted vehi- leads to excessive carbon deposits in the engine.[16, 17] Table 2
cles. PR China has set a target of 8 % biodiesel usage for 2011, shows common fatty acids found in vegetable oils including
also increasing this target to 15 % by 2020.[12] In addition, bio- their physical and chemical properties.
diesel constituted a share of 7.5 billion gallons (1 gallon = Numerous types of vegetable oils have been identified for
3.785 L) of total transportation fuels in India, with an expected potential use as raw materials for fuel production. Generally,
increase by 20 % in 2017.[13–15] Detailed government regulations several factors such as geography, economy, and climate deter-
for target percentages of biofuel usage are presented in mine which types of oils can be used in the production of bio-
Table 1. fuels. In the USA, corn and soybean oils are used, while in
many European countries rapeseed oils are preferred. Tropical
Table 1. Target of biofuels share in transportation fuels usage per countries are more interested in the abundant palm or coco-
region.[15] nut oils. Other types of vegetable oils such as sunflower, olive,
Region Current Future and castor oils have also been studied.[1] Furthermore, animal
fats and waste cooking oils have been investigated as alterna-
Brazil 25 % ethanol in gasoline by 2007 5 % of biodiesel by 2011
2 % of biodiesel by 2008 tive sources. The fatty acid compositions of vegetable oils used
PR China 8 % of gasoline and diesel by 2011 15 % by 2020 in the production of biofuels are presented in Table 3.
Europe 5.75 % gasoline and diesel by 2010 10 % by 2020 Literature reports have compared the chemical and physical
USA 5 % ethanol in gasoline by 2007 30 % by 2030 properties of unprocessed vegetable oils and conventional
India 7.5 billion gallons by 2012 20 % by 2017
diesel fuels.[3, 20–22] These properties included density, viscosity,
cetane number, carbon residue, heating value, flash point,
pour point, cloud point, acid value, renewability, and energy.
2. Biobased Feedstocks
From the comparison of unprocessed vegetable oils with con-
To date, liquid feedstocks, such as vegetable oils, have been ventional diesel fuels, a number of disadvantages and advan-
the preferred source for converting biobased materials into tages of using vegetable oils as fuel have become apparent.
fuels owing to their higher energy content and easy handling Vegetable oils have many advantages, including ready availa-
for processing in large-scale production. Other alternative sour- bility as liquids, renewability, high heat content, lower sulfur
ces, such as microalgae, cellulose, and waste agricultural sour- content, lower aromatic content, and biodegradability. There
ces, are also available; however, the energy efficiency of col- are some disadvantages to note, including higher viscosity,
lecting these materials and the technology for converting lower volatility, and the high reactivity of unsaturated hydro-
them into high-quality fuels are still to be evaluated and devel- carbon chains.
oped. Although short-term tests using unprocessed vegetable oils
showed promising results, longer tests led to injector choking,
enhanced formation of carbon deposits in combustion cham-
2.1 Vegetable oils
ber, ring sticking, and thickening of engine lubricant due to
Vegetable oils are substances comprising triglycerides derived the higher viscosity of unprocessed vegetable oils.[20] It appears
from plants. Chemically, a triglyceride is the reaction product that although unprocessed vegetable oils have several positive
of one glycerol with three fatty acid molecules, as shown in aspects, their further processing is required to convert these

1110 www.chemsuschem.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2009, 2, 1109 – 1119
Transforming Triglycerides and Fatty Acids into Biofuels

domestic market,[5] which is not

Table 2. Chemical structure of common fatty acids found in vegetable oils.[18]
feasible. However, the necessi-
Trivial name IUPAC name Structure x:y[a] Mr m.p. [8C] b.p. [8C (kPa)] ties for diversification of energy
Saturated sources to secure energy supply
Capric acid Decanoic acid 10:0 172.3 32 239.7 (101.3) as well as increase awareness of
Lauric acid Dodecanoic acid 12:0 200.3 43 20.6 (101.3) environmental issues justifies
Myristic acid Tetradecanoic acid 14:0 228.4 54 298.9 (101.3)
the development of sustainable
Palmitic acid Hexadecanoic acid 16:0 256.4 62 309.0 (68.3)
Stearic acid Octadecanoic acid 18:0 284.5 69 332.6 (68.3) alternative energies.
Arachidic acid Eicosanoic acid 20:0 312.5 75 355.2 (68.3)
Behenic acid Docosanoic acid 22:0 340.6 81 –
Monounsaturated 2.3 Alternative feedstocks
Palmitoleic acid 9-hexadecenoic acid 16:1 254.4 0 –
Oleic acid 9-octadecenoic acid 18:1 282.5 13 334.7 (53.3) As mentioned above, the sensi-
Vaccenic acid 11-octadecenoic acid 18:1 282.5 7 – tive issue of biofuels competing
Gadoleic acid 9-eicosenoic acid 20:1 310.5 25 – with food sources has led to a
Erucic acid 13-docosenoic acid 22:1 338.6 33 –
Polyunsaturated
search for alternative non-edible
Linoleic acid 9,12-octadecadienoic acid 18:2 280.5 9 230.0 (2.1) materials, which can grow in
A-linolenic acid 9,12,15-octadecatrienoic acid 18:3 278.4 17 230.0 (2.3) non-arable land or desertlike
A-Linolenic acid 6,9,12- octadecatrienoic acid 18:3 278.4 – – areas, such as crops including
Arachidonic acid 5,8,11,14-eicosatetraenoic acid 20:4 304.5 50 –
EPA 5,8,11,14,17-eicosapentaenoic acid 20:5 302.4 – –
mahua,[25, 26] karanja,[27–30] polan-
ga,[27, 31] and jatropha.[27, 31–39] In
[a] Number of carbon atoms (x) and number of unsaturated bonds (y).
addition, other-low grade trigly-
cerides and fatty acids such as
used frying oils,[40–42] animal
oils into more compatible forms of fuel suitable for the current
combustion engine.
Table 3. Fatty acid composition in common vegetable oil and fats.[19]

2.2 Availability, market, and demand Oil or fat Myristic Palmitic Stearic Oleic Linoleic
14:0 16:0 18:0 18:1 18:2
The major issue hindering the use of biofeedstocks as a fuel
Cottonseed 0.8–1.5 22–24 2.6–5 19 50–52.5
source is the availability and supply of bioderived materials to Corn – 7–13 2.5–3 30.5–43 39–52
meet current and future energy demands without infringing Canola – 4-5 1–2 55–63 20–31
upon valuable farming land dedicated to growing food. Anoth- Olives – 11 2.2 67 8.9
er critical question is how much land is needed to produce Palm 0.6–2.4 32–46.3 4–6.3 37–53 6–12
Peanut 0.5 6–12.5 2.5–6 37–61 13–41
enough food and fuels. Rapeseed 0.1 5.1 2.1 57.9 24.7
Currently, approximately 81 % of commercial energy de- Safflower – 4.8 2.3–8 73.6–79 11–19
mands are supplied by fossil fuels, which includes 34.3 % oil, Soybean – 2.3–11 2.4–6 22–30.8 49–53
26.0 % coal, and 20.5 % gas. Nuclear energy and hydroelectric Sunflower – 3.5–6.5 1.3–5.6 14–43 44–68.7
Butter 12.8 26.6 8.5 17.0 1.5
power contribute 6.2 % and 2.2 %, respectively, while the re- Lard 1.7 27.9 13.5 46.7 10.2
maining 10.8 % is divided over renewable energy sources such Tallow 3.0 33.0 24.0 36.0 2.0
as biomass (including biofuels), solar, wind, and geothermal
energy.[23] Global energy consumption reached 500 EJ (5 
1020 J) during 1980–2006.[24] Snre analyzed the theoretically
available farming land for growing oils and fats as well as the fats,[43] and tall oils[4, 44, 45] have also been identified as alterna-
estimated amount of energy produced, as follows:[18] tive sources for biofuels. Moreover, the bulk of biomass feed-
stock (i.e., lignocellulose) has been considered as a promising
Theoretically available land: 5  106 km2
candidate for second-generation biofuels.[46–50] Chemically,
Yield of oil crop: 100 000 kg oil per km2 of farming land
lignocellulose consists of linked sugar units in the forms of cel-
Harvest obtained: 1.5  1012 kg per harvest
lulose, starch, and hemicellulose as well as polyphenolic
Energy value per harvest: 52  1018 J (energy value of diesel
lignin.[49] Sugars and oxygen are formed during photosynthesis,
43.3 MJ kg1 and biodiesel yield from plant oil is ca. 80 %)
in which carbon dioxide and water react in the presence of
Therefore, only 11 % of the current total energy demand can sunlight as shown in Scheme 2.
be resupplied by the present farmland and oil crops. This anal- The chemical structure of cellulose is derived from d-glucose
ysis led to the conclusion that although technologies for bio- units through b(1!4)-glycosidic bonds, with a molecular mass
fuel production should be developed, they cannot solely cover more than 106. Hemicellulose is a mixture of various polymer
the total energy demand. Furthermore, it was recently report- monosaccharides such as glucose, mannose, galactose, xylose,
ed that in the USA alone, 61 % of the arable farming land arabinose, and glucuronic acid (Figure 1). In contrast with cel-
would be needed to produce first-generation biofuel for the lulose, hemicellulose has a low molecular mass. The number of

ChemSusChem 2009, 2, 1109 – 1119  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 1111

Scheme 2. Reaction of carbon dioxide and water during photosynthesis to
form sugar and oxygen.
Figure 1. a) Chemical structure of cellulose, and b) main components of
hemicelluloses.
repeating saccharide monomers is ca. 150, compared to the
number in cellulose ranging from 5000 to 10 000. Typically, dry
lignocellulose contains 40–50 wt % cellulose, 25 wt % hemicel-
lulose, and 25 wt % lignin.[48, 49]
3. Technology for Biodiesel Production
(Oxygenated Fuels)
Biodiesel is a term used to describe a fuel comprising mono-
alkyl (mainly methyl) esters of long-chain fatty acids that are
derived from vegetable oils and animal fats.[1, 51, 52] However, an
opinion exists that this term should be used in a broader per-
spective, to describe diesel fuels originating from renewable
raw materials, including products derived from transesterifica-
tion, microemulsion, cracking, and pyrolysis of natural oils and
fats.[53, 54]
3.1 Transesterification
A widely known method to produce biodiesel is via the trans-
esterification reaction (Scheme 3). Triglyceride reacts with a
short-chain alcohol in the presence of either a homogeneous
Scheme 3. Transesterification of triglyceride to produce fatty acid methyl
esters (FAMEs), known as biodiesel.
1112 www.chemsuschem.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
D. Yu. Murzin et al.
or a heterogeneous catalyst to form a mixture of fatty esters
and glycerol.
Methanol is mainly used in commercial biodiesel production,
although some longer alcohols have also been applied, such
as ethanol, butanol, propanol, and amyl alcohol.[16, 48, 52] A su-
percritical alcohol has been reported by some research-
ers.[3, 20, 55–59] Methanol is used most often because of its low
cost and the fact that it is readily available. It can quickly react
with a triglyceride in the presence of an alkaline catalyst, such
as NaOH. Numerous studies have been carried out to identify
the most important parameters in the transesterification reac-
tion, namely, temperature, catalyst type and amount, ratio of
alcohol to reactant, and stirring rate.[6, 60, 61] The ratio of reac-
tants, type of alcohol, and catalyst used as well as tempera-
tures affect the reaction time and conversion efficiency.
3.1.1 Homogeneously catalyzed transesterification
Homogeneous catalysts offer several advantages in liquid
phase reactions because they are robust and form a uniform
mixture with the reactant, eliminating mass transfer limitations
and affording high reaction rates.[62] However, utilization of a
homogeneous catalyst also faces several issues associated with
difficulties in catalyst recovery, disposal of possible toxic waste,
and separation of the desired product. Currently, commercially
available biodiesel is produced mostly by base-catalyzed trans-
esterification, in which either sodium or potassium hydroxide
are employed as active catalysts due to their low cost, availa-
bility, and easy handling. Utilization of homogeneous acid cata-
lysts such as sulfuric acid, phosphoric acid, hydrochloric acid,
and organosulfonic acid is less popular due to the significantly
slower reaction rate compared to the base catalyst counterpart
for a comparable amount of catalyst and similar reaction con-
ditions.[41]
Yield and efficiency conversions of transesterifications are
strongly influenced by the molar ratio between an alcohol and
a reactant. As the reaction is reversible, generally an excess of
alcohol is required to shift the reaction to the product side.
Theoretically, to complete a transesterification reaction, a stoi-
chiometric ratio between alcohol and triglyceride of 3:1 is
needed. However, in practice the ratio needs to be higher to
drive the equilibrium to maximum ester yield. A molar ratio of
6:1 and temperature close to the alcohol boiling point are re-
quired for the complete conversion of triglyceride with 98 %
ester yields. Increasing the molar ratio to larger than 6:1 does
not increase the yield of ester, but instead it causes complica-
tions in ester and glycerol recovery. Ethanolysis of refined soy-
bean oil with sodium and potassium hydroxide has been re-
ported by Kucek et al.[63] The optimum ester yield of 97 wt %
was obtained at 70 8C, with a molar ratio of 12:1 and 0.3 wt %
NaOH. Replacement of 0.3 wt % NaOH by 1.0 wt % KOH under
the same reaction conditions led to a lower ester yield.
The alkali-catalyzed transesterification requires an anhydrous
alcohol together with a feedstock because the presence of
water leads to partial saponification, producing soap. The for-
mation of soap causes catalyst deactivation and decreases the
yield of esters and, thus, needs to be avoided. Another impor-
ChemSusChem 2009, 2, 1109 – 1119
Transforming Triglycerides and Fatty Acids into Biofuels

tant consideration when applying a homogeneous base cata- cled and re-used for long periods, providing an opportunity
lyst in transesterification is the purity of the feedstock. Only a for a large-scale continuous process. Many heterogeneous cat-
refined and pretreated animal fat with a low concentration of alysts that are based on both acid[62, 66–68] and alkaline[69–74] solid
free fatty acids (FFAs) can be used in base-catalyzed transes- catalysts have recently been proposed in the literature.
terification. FFAs can react with a base catalyst, leading to Heterogeneously catalyzed transesterification over three cat-
saponification as shown in Scheme 4. Ideally, the FFA content alysts with different basicity, namely Al2O3, Na/g-Al2O3, and Na/
of the feedstock used in a homogeneous base-catalyzed trans- NaOH/g-Al2O3, has been studied in Ref. [69]. The most active
esterification should not exceed 0.5 wt %.[64, 65] heterogeneous catalyst was found to be Na/NaOH/g-Al2O3,
which had the highest basic strength. Activity comparison with
a homogeneous NaOH catalyst showed that the homogeneous
NaOH gave a 20 % higher ester yield (in mol %) using a metha-
nol to oil ratio of 6:1 at the optimum reaction temperature of
60 8C compared to the heterogeneous catalysts. The higher
ester yield in homogeneously catalyzed transesterification
compared to the heterogeneous one can be explained by two
reasons. Firstly, methanol and oil are immiscible. In the homo-
geneous system, the catalyst NaOH acted as a solvent, making
Scheme 4. Reaction scheme for formation of soap. a) Hydrolysis of ester the reactants miscible. When NaOH was added to the reac-
over a base catalyst forming FFAs, and b) FFAs reacting with a base catalyst tants, small bubbles were formed and the transesterification
to produce soap. reaction took place on the interface of the reactants. In the
heterogeneous system, however, the reactants were separated
Using refined oils with a low FFA content in base-catalyzed in two phases and thus a slow reaction rate in the beginning
transesterification causes the high production costs of biodie- of the reaction was achieved. Therefore, an appropriate co-sol-
sel because of the high cost of the feedstock, which is around vent had to be added to overcome the mixing problems. In
60 % to 75 % of the total production costs.[66] Utilization of a this case n-hexane was found to be the most effective co-sol-
lower-grade feedstock such as grease, beef tallow, and used vent, improving the ester yield by 10 %. Furthermore, the mass
frying oils from the food industry may reduce production transfer limitation due to problems of mixing the two reactants
costs, but on the other hand this requires processing of feeds also contributed to the lower ester yield in the heterogeneous-
with a high content of FFAs. In this case, a homogeneous acid ly catalyzed transesterification. As mentioned above, the stoi-
catalyst is usually applied at the pretreatment stage of lower- chiometric ratio of methanol to oil was 3:1 and under opti-
grade feedstocks to reduce the FFA content. Therefore, an inte- mized conditions a 6:1 molar ratio was used for the homoge-
grated process comprising acid-catalyzed pre-esterification of neous catalyst system. However, as mass transfer limitations
FFAs followed by base-catalyzed transesterification of triglycer- persist in the heterogeneous system, introducing an excess of
ide is the preferred way of dealing with lower-quality feed- alcohol is required to shift the reaction to the product side.
stocks. A comparison between base- and acid-catalyzed reac- When increasing the molar ratio of methanol/oil to 9:1, an op-
tions is given in Table 4. timum biodiesel yield of 94 % was achieved for the heteroge-
neous catalyst. This high yield is distinguished from the value
optimized for the homogenous
Table 4. Comparison between base- and acid-catalyzed reactions for transesterification/esterification. catalyst. Moreover, increasing
molar ratio more than 9:1 gave
Parameter Base homogeneous catalyst Acid homogeneous catalyst
no significant effect on the
Feedstock compatibility More sensitive to feedstock impur- May apply for feedstock with high FFA content product yield.[69]
ity, generally requires less than
0.5 wt % of FFA
Hydrotalcite materials, of a
Alcohol impurity Requires anhydrous alcohol Less sensitive to water content in alcohol general formula of [M2+(1x)
Operating conditions: Reaction temperature range from Requires higher temperature and pressure at a M3+x(OH)2]x+(Ax/n)2(ny)H2O, are
temperature, pressure, oil/ RT to 80 8C (above alcohol boiling comparable amount of catalyst compared to another class of interesting solid
alcohol ratio point) alkaline process. Higher alcohol/oil ratio,
slower reaction rate
base catalysts for the transesteri-
Product quality, yield Typically, 98 % ester yields ach- Lower ester yield produced for a comparable fication reaction, in which acid/
ieved at complete conversion amount of catalyst base properties of the materials
Recovery process Requires separation step Poisoning, often causing corrosion can be easily controlled by vary-
ing their composition. The struc-
ture of hydrotalcites is based on
the layered double hydroxide
3.1.2 Heterogeneously catalyzed transesterification
(LDH) of brucite such as (Mg(OH)2) containing octahedrally co-
An efficient heterogeneous catalyst would provide economic ordinated M2+ and M3+ cations. The Mg–Al calcined hydrotal-
benefits as, unlike homogeneous catalysts, it does not require cite has shown high catalytic activity in transesterification reac-
a separation procedure. In most cases, catalysts can be recy- tions.[75–80] A patent by Corma et al. claimed the possibility to

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 D. Yu. Murzin et al.

use calcined hydrotalcites and magnesium oxides in promoting
transesterification of triglyceride with monoalcohol.[77] A com-
mercial calcined hydrotalcite was tested in the transesterifica-
tion of rapeseed oil at 60 8C with very poor results, mostly due
to a mild reaction temperature.
On the contrary, Cantrell et al. successfully used a Mg–Al hy-
drotalcite catalyst in promoting the transesterification of glyc-
erol tributyrate with methanol.[78] Mg–Al hydrotalcite has also
been applied in processing cheaper raw materials that are usu-
ally characterized as a waste, such as frying oils, low-quality
acid vegetable oils or high-water-content oils, and waste
animal fats.[80] The experiments were performed at 200 8C, with
an initial methanol to oil ratio of 6:1 and 1 wt % of catalyst.
Within 3 h of reaction, 99 % conversion of triglyceride (given in
wt %) to biodiesel was achieved while the FFA content de-
creased considerably to 1 wt %, which makes the application
of this material promising.
To make the process even more ecologically friendly, a cata-
lyst prepared from naturally available feedstocks would be pre-
ferred. A sulfonated carbon catalyst made from natural resour-
ces such as sugars, starch, or cellulose is one alternative that
could replace the homogeneous sulfuric acid catalyst in the
esterification reaction.[81] The carbon catalyst was prepared by
incomplete carbonization of sugar material at 400 8C for 15 h
followed by its sulfonation with concentrated H2SO4 at 150 8C
for another 15 h. The activity of this catalyst in the esterifica-
tion of vegetable oils was reported to be more than half that
of a liquid sulfuric acid catalyst, which is much higher than any
activity achieved by other conventional solid catalysts.
Utilization of basic resins in the esterification of free fatty
acids has been studied by Marchetti et al.[82] Two different
resins, namely Dowex monosphere 550 A and Dowex upcore
Mono A-625, which have different basic strengths were em-
ployed in the esterification of sunflower oil. These materials
are strongly basic (type I) commercial anion exchange resins in
the form of hydroxide with monodispersed bed size to provide
high efficiency and capacity for fixed-bed applications.[83] The
esterification reaction was carried out at 45 8C using an alco-
hol/oil molar ratio of 6:1. The results showed that the first
resin catalyst, with a higher basic strength, exhibited both a
higher conversion and reaction rate compared to the latter
resin. Utilization of a basic resin in the esterification of FFA
offers the advantage that no additional separation steps are re-
quired compared to homogeneous basic catalysts. In addition,
the byproduct glycerol has a higher purity of 95 wt %, com-
pared to 65 wt % of purity in the case of a homogeneous cata-
lyst. However, the application of this resin catalyst in the trans-
esterification reaction gave a significantly slower reaction rate,
requiring a much higher alcohol/oil molar ratio. An overview of
catalysts and conditions used for biodiesel production is dis-
played in Table 5.
4. Cracking of Biofeedstock
There are major drawbacks associated with the transesterifica-
tion reaction, including its high sensitivity to feedstock purity,
its requirement for an efficient catalyst to avoid saponification,
and the complexity of the separation stage. These drawbacks
demand an alternative technology that can overcome these
issues. Catalytic cracking or pyrolysis is one alternative method
that could be applied in upgrading bioderived feedstock to
fuels.[88, 89] This technology is widely established in the petrole-
um industry and is used to break down high-molecular-mass
components into fragments of lower molecular mass in the
presence of a catalyst and at a high temperature.[90]
Catalytic cracking of palm oil over various zeolite catalysts
has been intensively investigated.[91] The experiments were
performed in a fixed-bed microreactor operated at atmospher-
ic pressure, at a reaction temperature range of 350 to 450 8C
using a weight hourly space velocity WHSV of 1 to 4 h1. Three
types of zeolites, namely HZSM-5, zeolite b, and ultrastable Y
(USY) zeolite with different pore sizes were utilized to study
the effect of reaction temperature and WHSV on the conver-
sion of palm oil and yields of gasoline. Among three zeolites
used in the catalytic tests, HZSM-5 with a pore size of 0.56 
0.5 nm was reported as the most active catalyst, giving the
highest conversion of 99 % and a maximum gasoline yield of
28 % (both defined in wt %) at 350 8C and a low WHSV of 1 h1.
In comparison, zeolite b and USY zeolite gave at the same re-
action conditions conversions of 82 % and 53 %, respectively;

Table 5. Selected optimum reaction conditions for esterification and transesterification of triglyceride to biodiesel.

Catalyst Optimum reaction conditions[a] Product Yield [%] Ref.

[b]
Na/NaOH/g-Al2O3 T = 60 8C; MR = 9:1; 1 g of catalyst; t = 2 h; co-solvent n-hexane FAME 97 [69]
MgAl-hydrotalcite T = 60 8C; MR = 30:1; 0.05 g calcined catalyst; t = 3 h; co-solvent n-hexane Methyl butanoate 74.8[b] [78]
C-SO3H made from sugar catalyst T = 80 8C; MR = 10:1 FAME – [81]
NaOH T = 70 8C; MR = 12:1; 0.3 wt % catalyst; t = 1 h FAME 97.2[c] [63]
KOH T = 70 8C; MR 12:1; 1.0 wt % catalyst; t = 1 h FAME 95.6[c] [63]
Basic resin T = 55 8C; MR = 6:1; 2.3 wt % catalyst; t = 1.5 h FAME 85[c] conversion [82]
WO3/ZrO2 T = 75 8C; MR = 19.4:1; 0.2 g catalyst per 1 mL oil; t = 1 h FAME 83[d] [84]
CoII ions adsorbed in chitosan T = 70 8C; MR = 6:1; 2 wt % catalyst; t = 3 h FAME 94[e] [85]
MgAl-CO3/hydrotalcite T = 200 8C; MR = 6:1; 1 wt % catalyst; t = 3 h FAME 99[c] [80]
AlCl3 T = 110 8C; MR = 24:1; 5 wt % catalyst; t = 18 h; co-solvent THF FAME 98[c] conversion [86]
ZnCl3 T = 110 8C; MR = 60:1; 5 wt % catalyst; t = 24 h; co-solvent THF FAME 83[c] conversion [86]
KOH T = 60 8C; MR = 12:1; 2 wt % catalyst; t = 2 h FAME 95[f] [87]

[a] Molar ratio of alcohol to vegetable oil (MR). [b] mol %. [c] wt %. [d] Method was used for converting free fatty acids (mol %) in vegetable oils to FAME
before the main biodiesel production process. [e] Unit percentage not specified. [f] vol %.

1114 www.chemsuschem.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2009, 2, 1109 – 1119
Transforming Triglycerides and Fatty Acids into Biofuels
and selectivities to gasoline of 22 % and 7 %, respectively. Typi-
cally, the product distribution in the catalytic cracking of palm
oil over HZSM-5 was as follows: 1.0 % residual oil, 7.5 % aque-
ous phase, 6.1 % coke, 41.8 % gas, and 43.6 % organic liquid
products. The maximum gasoline yield over HZSM-5 catalyst
indicated a high shape selectivity of the catalyst, whereas USY
zeolite gave a high selectivity to kerosene and diesel-range hy-
drocarbons.
Since in the previous study the selectivity to gaseous prod-
ucts was higher compared to the desired liquid products,[91]
catalysts with larger pore sizes were applied. Mesoporous ma-
terials of MCM-41 type,[92, 93] as well as a composite catalyst
combining microstructured zeolite and mesoporous MCM-
41,[94] were tested as catalysts in the cracking of palm oil.
MCM-41 showed a high conversion and high selectivity to the
formation of linear hydrocarbons at 450 8C. The composite cat-
alyst with the combined properties of HZSM-5 and MCM-41
gave a palm oil conversion of 80 to 100 %, with the yield of
the gasoline fraction ranging from 38 to 47 % calculated on a
wt % basis.
Recently, Li et al. explored the production of biofuels from
cottonseed oil by fixed-fluidized-bed catalytic cracking.[95] The
work was focused on optimization of the operation conditions
using process design and statistical modeling of response sur-
face methodology (RSM) for production of the gasoline frac-
tion ( 205 8C) and light fuel ( 360 8C). An optimum reaction
temperature of 426.2 8C, a catalyst/oil ratio of 7.8 g g1, and a
residence time of 50.2 s were reported for a maximum yield of
light oil of 65.6 wt %, a gasoline fraction of 33.7 wt %, and a
minimum gas yield of 11.6 wt %. The yields of light fuel and of
the gasoline fraction were significantly higher than those re-
ported previously at comparable reaction parameters.[96]
The main product of the cracking reactions is a mixture of
hydrocarbons and oxygenated compounds, such as carboxylic
acids, ketones, and aldehydes as well as water and gaseous
products. The presence of oxygenated compounds could com-
plicate their application as fuels because of the challenges in
storage and distribution as well as during combustion in an in-
ternal engine. Furthermore, during the catalytic cracking of
vegetable oils at high temperatures, shorter hydrocarbons rep-
resenting gasoline instead of diesel were formed. Even if the
process was optimized, the selectivity for the diesel fraction
was lower than for the gaseous product. In addition, gasoline
products from the catalytic cracking of vegetable oils contain a
significant amount of aromatic components. Although aromat-
ic compounds are beneficial in terms of increasing the octane
number, their use is strictly regulated and their limits have re-
cently been made more strict, for example, through action
EN228 in Europe.[48] Clearly, the drawbacks in catalytic cracking
call for improved methods to produce fuels from bioderived
feedstocks more selectively, which will provide opportunities
for application in large-scale production.
5. Pyrolysis to produce Bio-Oils
Pyrolysis of wood/biomass for bio-oil has the potential to con-
tribute to the high global demand of liquid fuels.[97] Pyrolysis is
ChemSusChem 2009, 2, 1109 – 1119  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
the thermal decomposition of materials in the absence of
oxygen or when significantly less oxygen is present than the
amount required for complete combustion. When this process
is applied to a biomass feed, the product is a dark brown, free-
flowing organic liquid comprising highly oxygenated com-
pounds, and is known as bio-oil. Various feeds of forest and ag-
ricultural biomass waste can be used in the production of bio-
oil, including bagasse, rice hulls, rice straw, peanut hulls,
switchgrass, wheat straw, and wood. Branca et al. have sum-
marized a large number of reactions that occur during bio-oil
production,[98] including hydrolysis, dehydration, isomerization,
dehydrogenation, aromatization, retro-condensation, and
coking. Therefore, the chemical composition of bio-oil is diffi-
cult to determine because it depends on many variables in-
cluding feedstock composition and reaction conditions during
pyrolysis as well as storage time, temperature, and exposure to
air during storage. More than 400 organic compounds have
been found in bio-oil, such as acids, esters, alcohols, ketones,
sugars, furans, phenols, guaiacols, and syringols.[49, 97, 99, 100]
The major problems hindering the utilization of bio-oil as
fuels are poor volatility, high viscosity, coking, corrosiveness,
and cold-flow problems. To date no quality standards have
been set for bio-oil production. Commercially, bio-oils are used
as boiler fuels for stationary power, heat production, and
chemical production. Direct utilization of bio-oils as transporta-
tion fuels, such as in diesel engines, exhibits many challenges
dealing with difficult ignition owing to their low heating value
and high water content, corrosiveness, and coking. Therefore,
bio-oil must be upgraded before use in diesel engine.
6. Hydrotreating
Several literature[101–104] and company[105] reports have ad-
dressed the potential of hydrotreating processes to improve
previous technology (pyrolysis) in upgrading bioderived feed-
stocks, specifically triglycerides and fatty acids with high con-
versions and high yields to hydrocarbon middle distillates,
which are suitable as alternative diesel fuels. Hydrotreating is
usually used in a petroleum refinery to remove sulfur, nitrogen,
and metals from petroleum-derived feedstocks, including
heavy or vacuum gas oil, by introducing high pressure hydro-
gen gas (99 % v/v) into the reactor. Conventional hydrotreating
catalysts containing sulfided mixes oxides such as NiMo, NiW,
and CoMo can be used in the process. Application of this pro-
cess for upgrading vegetable oils involves three main path-
ways, 1) hydrogenation of double bonds in the alkyl chain of
fatty acids, 2) decarboxylation and decarbonylation, and 3) hy-
drodeoxygenation (or dehydration/hydrogenation) to produce
alkanes.[104]
The pioneering work in this respect, leading to commerciali-
zation, was done by Neste Oil.[105] Following the footsteps of
Neste, UOP/Eni Ecofining technology approaches the hydro-
processing route of biologically derived feedstocks in a similar
way through removal of oxygen from the triglyceride mole-
cules by a catalytic reaction with hydrogen, which involves de-
carboxylation and hydrodeoxygenation producing aliphatic hy-
drocarbons.[106–107] Three carbon backbones in the triglyceride
www.chemsuschem.org 1115

are converted to propane, and they can be easily recovered as
a valuable coproduct. The oxygen content in the triglyceride is
released either as carbon monoxide or carbon dioxide, togeth-
er with the formation of water. The main products, n-aliphatic
hydrocarbons of the corresponding fatty acids, are identified
as green diesel, to be distinguished from the conventional oxy-
genated biodiesel. The chemical reaction is illustrated below:
catalyst
Triglyceride þ H2 ƒƒƒ! green diesel þ H2 O=COx þ C3 H8 ð2Þ
Hydrotreating of pure vegetable oil in comparison with a
mixture of vegetable oil and heavy vacuum oil (HVO) was in-
vestigated in showing the possibility of processing this
method in the same reactor within a petroleum refinery.[103]
Final work concluded that vegetable oils and a mixture of veg-
etable oils and HVO can be converted into liquid alkanes using
a conventional hydrotreating catalyst, NiMo/Al2O3, which con-
tained 3.9 wt % NiO and 18 wt % MoO3. This catalyst was pre-
sulfided with H2S/H2. This method opens the possibility to
apply the process in existing petroleum refineries, thus elimi-
nating the additional capital costs of building new infrastruc-
ture. The liquid product has a relatively simple composition
compared with the products obtained in the catalytic cracking,
mostly comprising n-alkanes in the range of n-C15 to n-C18 to-
gether with, in some cases, a small amount of free carboxylic
acids. Hydroprocessing of pure sunflower oil at 350 8C gave
100 % conversion with 71 % yield to straight-chain C15–C18 alka-
nes corresponding to 75 % of the maximum theoretical yield
(given on a molar carbon basis). At higher reaction tempera-
tures the selectivity decreased owing to enhanced formation
of cracking products. Moreover, when using a mixture of vege-
table oil with HVO, for example 5 wt % sunflower oil–95 %
HVO, a higher yield of straight-chain alkanes was achieved.
Furthermore, it was concluded that the hydrodesulfurization
rate was not affected by the addition of sunflower oil and,
thus, hydrotreating of sun flower oil and hydrodesulfurization
probably occurred on different catalytic sites. Because the feed
vegetable oil did not contain sulfur, it was pointed out that
part of the sulfur could leach out from the catalyst and there
would be a need to add sulfur to the feed.
Coprocessing with the existing refinery reactor was initially
preferred in the hydroprocessing of vegetable oil. However,
further studies have indicated some problems due to the pres-
ence of trace metal contaminants in the vegetable oil, such as
phosphorous, sodium, potassium, and calcium. Furthermore,
the presence of water and carbon oxide affected the catalyst
lifetime and caused problems in the separation of carbon
oxides from the recycle gas. Considering all these potential
issues, the refinery seems to favor the construction of a dedi-
cated or stand-alone unit that is optimized for vegetable oil
processing because of the unique nature of the feedstock.[15]
Hydroprocessing has advantages in terms of the flexibility of
feedstock, because the process can utilize low-quality feeds
such as grease, used frying oils, animal fats, or tall oils from
the kraft pulping industry. The separation stage of the byprod-
ucts is not as complex as in the transesterification reaction.
The main product, which consists mostly of paraffinic hydro-
1116 www.chemsuschem.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
D. Yu. Murzin et al.
carbons, is superior for application in combustion engines. The
improved method and the several advantages offered by this
process have attracted interest to apply this technology to a
large scale biorefinery. For example, Neste Oil has completed
the construction of a biorefinery unit based on hydroprocess-
ing of vegetable oil in Porvoo, Finland.[105] The unit has a ca-
pacity of 170 kt a1. The fuel produced from this refinery,
known as NexBTL, is free from sulfur, nitrogen, oxygen, and ar-
omatics and has a very high cetane number. Furthermore, the
product fulfils the requirements set by the European diesel
fuel standard (EN590) and it demonstrates appropriate fuel
properties in the automotive and engine industries, according
to the World Wide Fuel Charter (WWFC) Category 4 Fuel Speci-
fication. A second unit is under construction. Furthermore, Eni
collaborated with UOP to build a refinery based on the hydro-
treating process in Livorno, Italy, with a capacity of
6500 bbl a1, commercial production is expected in 2009.[107]
7. Deoxygenation
The main challenge in developing biofuels is the removal of
molecular oxygen, which is present in significant amounts in
biobased materials compared to petroleum-derived diesel,
which consists only of carbon and hydrogen. Considering the
sensitive issue of biofuel production competing with food
sources, as well as rigid environmental regulations, there are at
least three parameters required in developing the next genera-
tion of biofuels: 1) optimization of nonfood raw material sour-
ces, 2) production of non-oxygenated or diesel-like hydrocar-
bons, and 3) minimization of the emissions of greenhouse
gases (GHGs) in the complete lifecycle compared to existing
biofuels.[102]
A novel technology for converting bioderived feedstocks
based on the deoxygenation reaction has been recently devel-
oped.[108–113] The advantage of this new technology is that no
hydrogen is required in the process compared to the hydro-
treating process, thus eliminating the additional cost of hydro-
gen. Initially, stearic acid, ethyl stearate, and tristearin, which
represent model compounds of triglycerides, have been tested
in the deoxygenation reaction over a commercial catalyst with
palladium supported on carbon.[108] Using a semibatch reactor
at a reaction temperature of 300 8C under 17 bar of 5 vol % H2
in argon, stearic acid was completely converted at high selec-
tivities (95 mol %) to linear C17 hydrocarbons (n-heptadecane
and n-heptedecene), which corresponds to the direct decar-
boxylation of stearic acid. Additionally, other aromatic C17 hy-
drocarbon products were also identified. Compared with hy-
drotreating process, catalytic deoxygenation gave higher selec-
tivity to desirable straight alkanes in the diesel fuel range.
Studies of the effect of hydrogen pressure revealed that a low
partial pressure of hydrogen was beneficial in increasing the
turnover frequency (TOF) and final conversion, compared to
pure hydrogen or an inert reaction atmosphere. The presence
of hydrogen also diminished the consecutive aromatization,
which is undesirable because aromatics are unsuitable as
diesel constituents and they accelerate catalyst deactivation. It
should be noted that catalytic deoxygenation gives a higher
ChemSusChem 2009, 2, 1109 – 1119
Transforming Triglycerides and Fatty Acids into Biofuels
selectivity than hydrotreating. When ethyl stearate was utilized
as a feedstock, it was observed that stearic acid was an inter-
mediate that subsequently decarboxylated to n-heptadecane.
The same trend of the dependency on the reaction atmos-
phere as previously mentioned for stearic acid deoxygenation
was also found in ethyl stearate deoxygenation. The calculated
activation energy based on the initial reaction rates in the tem-
perature range 300 to 360 8C was 57 kJ mol1. Analogous to
the other reactants, tristearin showed the same trend as in de-
oxygenation of stearic acid and ethyl stearate.[108, 110] Further
comprehensive studies performed by Snre et al. revealed the
proposed plausible reaction path for the production of linear
hydrocarbons from fatty acids via direct deoxygenation,[110] as
illustrated in Scheme 5.
Based on the above schemes, there are several pathways for
the production of straight chain hydrocarbons. Fatty acids of
vegetable oils can be directly decarboxylated or decarbonylat-
ed. Direct decarboxylation removes the carboxyl group by re-
leasing carbon dioxide and paraffinic hydrocarbon, while direct
decarbonylation produces an olefinic hydrocarbon via removal
of the carboxyl group by forming carbon monoxide and water,
as illustrated by Reactions I and II, respectively. Additionally,
fatty acids can be deoxygenated by adding hydrogen; in this
case the production of linear hydrocarbon can occur via direct
hydrogenation or indirect decarboxylation, as illustrated by Re-
actions III and IV, respectively.
In addition to liquid-phase reactions, there are number of
gas-phase reactions that involve production of CO, CO2, hydro-
gen, and water during decarboxylation/decarbonylation, spe-
cifically methanation and the water-gas-shift reaction accord-
ing to Scheme 5. Thermodynamic data for both gas and liquid-
phase reactions are provided at 300 8C.[110]
A series of metals supported on different supports was eval-
uated during deoxygenation of stearic acid at constant tem-
perature and pressure, 300 8C, and 6 bar, respectively. The ther-
mal or noncatalytic deoxygenation showed that less than 5 %
of stearic acid was converted within 6 h of reaction under the
same reaction conditions as applied in the catalytic tests. Cata-
lyst screening revealed that commercial catalysts with palladi-
Scheme 5. Thermodynamic data for the liquid and gas phase reactions during catalytic deoxygenation of fatty acids.
ChemSusChem 2009, 2, 1109 – 1119  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
um or platinum supported on carbon were the most promising
catalysts with the highest reaction rate of 1.9 mmol s1 gmetal1.
Moreover, all of the palladium and platinum on carbon cata-
lysts achieved over 90 % selectivity (in mol %) towards the de-
oxygenation products (n-heptadecane, 1-heptadecene, and the
sum of other C17 products) within 6 h of reaction. The results
of metal catalyst testing on similar supports by normalizing
the results with metal content revealed the following order:
Pd > Pt > Ni > Rh > Ir > Ru > Os.[110]
Deoxygenation of unsaturated renewables, such as oleic
acid, methyl oleate, and linoleic acids also leads to saturated
diesel-fuel-range hydrocarbons. The reaction occurs initially via
hydrogenation of double bonds and subsequent deoxygena-
tion of the corresponding saturated feed. Comparison of the
deoxygenation activity was performed for semibatch and con-
tinuous modes at similar reaction conditions, showing a one
order of magnitude higher productivity in semibatch opera-
tion, which was attributed to mass transfer limitations in the
tubular fixed-bed reactor.[113] Furthermore, a better perfor-
mance was observed in a semibatch reactor compared to a
batch reactor due to the use of a flowing purging gas in the
former reactor, thus flushing the formed gaseous products, CO
and CO2, away from the reactor.[108]
Studies of deoxygenation reactions were performed using
palladium supported on the synthetic mesoporous carbon Sib-
unit.[114–116] Sibunit is a class of porous carbon–carbon compo-
site materials combining advantages of graphite (chemical sta-
bility and electric conductivity) and activated carbon (high spe-
cific surface area and adsorption capacity).[117–119] Catalytic de-
oxygenation of technical-grade stearic acid containing a mix-
ture of 59 % palmitic acid and 40 % strearic acid was
demonstrated over 4 wt % Pd/C(Sibunit) at 300 8C under 17 bar
of 5 vol % H2 in argon. The main products in the catalytic deox-
ygenation of saturated C16 and C18 acids were aliphatic hydro-
carbons containing one carbon less than the corresponding
acids. Additionally it was found that the reaction rates of differ-
ent reactants were independent of the carbon chain length of
its fatty acids, which is in agreement with results reported else-
where.[116]
www.chemsuschem.org 1117

The origin for catalyst deactivation during the deoxygena-
tion of fatty acids and their derivatives has reported to be
both coking and poisoning by CO and CO2.[120] Furthermore, it
was observed that the use of lower-boiling-point solvents,
such as decane and mesitylene, slightly enhanced the catalyst
stability.[120] The catalyst regeneration has not been investigat-
ed until now, but the stable performance of the continuous
deoxygenation of neat stearic acid over a mesoporous Pd sup-
ported on Sibunit was recently demonstrated.[121]
8. Summary
Biofuels have a potential to be used as an alternative energy
source. Furthermore, increasing environmental concerns sur-
rounding fossil-derived fuels are also a driving force for the de-
velopment of more sustainable renewable fuels. As a result,
governmental guidelines have been set to regulate and target
the share of biofuels in transportation fuels usage for the near
future.
Bioderived materials, such as triglycerides and fatty acids,
are potential feedstocks for producing biofuels owing to their
high energy content. The production of the first generation of
biofuels, mainly commercialized via transesterification, utilizes
food-based raw materials for the production of conventional
biodiesel, an oxygenated fuel. The drawbacks of biodiesel, that
is, inferior fuel properties compared to its fossil-fuel counter-
part along with issues in processing, have called for the devel-
opment of the next generation of biofuels, which is character-
ized by at least two criteria: 1) production of diesel-like hydro-
carbon fuels (non-oxygenated biofuels), and 2) utilization of
non-dedicated food sources.
Technological development for the production of the
second generation of biofuels includes cracking, pyrolysis, hy-
drotreating, and deoxygenation reactions leading to diesel-like
hydrocarbons that give similar or superior properties in com-
parison with transportation fuels derived from fossil feed-
stocks. Furthermore, the improved processes and methods in
recent developments allow the use of low-quality feedstocks
and relatively simple separation, thus opening the possibility
for large-scale applications.
Acknowledgements
Research facilities and travel funding provided by the ARC Centre
of Excellence for Functional Nanomaterials at the University of
Queensland, Brisbane, Australia is greatly acknowledged. S.L. also
acknowledges a travel grant provided by Johan Gadolin Scholar-
ship of Process Chemistry Centre, bo Akademi University, Turku,
Finland. This work is part of activities at the bo Akademi Pro-
cess Chemistry Centre of Excellence Programmes (2000–2011) fi-
nanced by the Academy of Finland.
Keywords: biomass · cracking · fatty acids · sustainable
chemistry · transesterification
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