The Ideal Vegetable Oil-Based Biodiesel Composition A Review of Social Economical & Technical Implications

The Ideal Vegetable Oil-based Biodiesel Composition: A Review of
Social, Economical and Technical Implications

S. Pinzi,
I. L. Garcia,
F. J. Lopez-Gimenez,
M. D. Luque de Castro,
G. Dorado,
|
and
M. P. Dorado*
,
Department of Chemical Physics and Applied Thermodynamics, EPS, Edicio Leonardo da Vinci;
Department of Agricultural Engineering, ETSIAM, Edicio Leonardo da Vinci; Department of Analytical
Chemistry, Edicio Marie Curie; and Department Bioqu mica y Biolog a Molecular, Campus Rabanales,
C6-1-E17, UniVersidad de Cordoba, 14071 Cordoba, Spain
ReceiVed December 15, 2008. ReVised Manuscript ReceiVed April 6, 2009
Though a considerable number of publications about biodiesel can be found in literature, several problems
remain unsolved, encompassing economical, social, and technical issues. Thus, the biodiesel industry has come
under attack by some environmental associations, and subsidies for biofuel production have been condemned
by some governments. Yet, biodiesel may represent a truly competitive alternative to diesel fuel, for which
fuel tax exemption and subsidies to energetic crops are needed. Biodiesel must increase its popularity among
social movements and governments to constitute a valid alternative of energy source. In this sense, the use of
nonedible oils to produce biodiesel is proposed in the present review. Moreover, the compromise of
noninterference between land for energetic and food purposes must be addressed. Concerning technical issues,
it is important to consider a transesterication optimization, which is missing or incomplete for too many
vegetable oils already tested. In most cases, a common recipe to produce biodiesel from any raw material has
been adopted, which may not represent the best approach. Such strategy may t multifeedstock biodiesel plant
needs but cannot be accepted for oils converted individually into biodiesel, because biodiesel yield will most
likely fail, increasing costs. Transesterication optimization results depend on the chemical composition of
vegetable oils and fats. Considering sustainable vegetable oils, biodiesel from Calophyllum inophyllum,
Azadirachta indica, Terminalia catappa, Madhuca indica, Pongamia pinnata, and Jatropha curcas oils ts
both current biodiesel standards: European EN 14214 and US ASTM D 6751 02. However, none of them can
be considered to be the ideal alternative that matches all the main important fuel properties that ensure the
best diesel engine behavior. In search of the ideal biodiesel composition, high presence of monounsaturated
fatty acids (as oleic and palmitoleic acids), reduced presence of polyunsaturated acids, and controlled saturated
acids content are recommended. In this sense, C18:1 and C16:1 are the best-tting acids in terms of oxidative
stability and cold weather behavior, among many other properties. Furthermore, genetic engineering is an
invaluable tool to design oils presenting the most suitable fatty acid prole to provide high quality biodiesel.
Finally, most published research related to engine performance and emissions fails in using a standard
methodology, which should be implemented to allow the comparison between tests and biofuels from different
origin. In conclusion, a compromise between social, economical, and technical agents must be reached.
1. Introduction
Nowadays, the depletion of fossil fuel reserves and the
necessity to reduce CO
2
emissions in order to limit global
warming are leading the research on alternative sources of
energy. Among these alternatives are biofuels for internal
combustion engines.
1
In recent years, biofuel research has been directed mainly to
explore plant-based fuels: that is, fatty acid methyl esters
(FAME) of seed oils, and in some cases, fats.
2
FAME, also
known as biodiesel, is environmentally less contaminating,
nontoxic, and biodegradable compared to diesel fuel.
3
The usual
raw materials being exploited commercially to produce biodiesel
consist of edible fatty oils derived from rapeseed, soybean, palm,
sunower, and other plants. However, biodiesel from edible oils
is controversial. Some nongovernmental organizations (NGO)
and social movements (e.g., the Global Forest Coalition, among
others), pinpoint the making of biofuels from edible raw
materials as the main cause of increased global food market
prices. Another claim against the use of biofuels is the depletion
of ecological resources due to the intensive agricultural practices
in the crop cultivation. Although international authorities such
as the Food and Agriculture Organization of the United Nations
(FAO) and the Austrian Biofuels Institute (ABI), among others,
provide gures to demonstrate the small and nonsignicant
aftereffect of biofuels in global economy,
4
the focus must be
* Corresponding author. Phone: +34 957 218332; fax: +34 957 218417;
e-mail: pilar.dorado@uco.es.
Department of Chemical Physics and Applied Thermodynamics.
Department of Agricultural Engineering.
Department of Analytical Chemistry.

|
Department Bioqu mica y Biolog a Molecular.
(1) Luque, R.; Herrero-Davila, L.; Campelo, J. M.; Clark, J. H.; Hidalgo,
J. M.; Luna, D.; Marinas, J. M.; Romero, A. A. Energy EnViron. Sci. 2008,
1, 542564.
(2) Dorado, M. P. In Biofuels Rening and Performance; Nag, A., Ed.;
McGraw Hill Professional: 2008; pp 107-148.
(3) Azam, M.; Waris, A.; Nahar, N. M. Biomass Bioenergy 2005, 29,
293302.
(4) Bergsma, G.; Kampman, B.; Croezen, H.; Sevenster, M. Biofuels
and their global inuence on land aVailability for agriculture and nature;
Delft: CE, 2006.
Energy & Fuels 2009, 23, 23252341 2325
10.1021/ef801098a CCC: $40.75 2009 American Chemical Society
Published on Web 04/29/2009
put on nonedible oils instead of edible ones, to gain social
acceptance of biodiesel.
These arguments are not contradictory to the last annual report
on the state of food and agriculture (2008), where FAO warns
that policies concerning biofuels production should aim at the
equal distribution of benets between rich, developing, and poor
countries.
5
In this way, an increase in biofuels demand could
help the rural development of less-favored countries. The FAO
report concluded that both farm subsidies of biofuels and trade
barriers that create articial markets that benet producers
belonging to the Organization for Economic Co-operation and
Development (OECD) countries at the expense of producers in
developing countries should be removed.
Another main concern in further usage of biodiesel is the
economic viability. Several studies have identied that the price
of feedstock oils is by far one of the most signicant factors
affecting the economic viability of biodiesel manufacturing.
6-8
Approximately 70-95% of the total biodiesel production cost
arises from the raw material.
7
Therefore, to produce a competi-
tive biodiesel, the feedstock price is a key factor that needs to
be taken into consideration.
2
It has been shown that biodiesel quality depends on fatty acid
composition of raw materials (oils or fats). A biodiesel reaction
is depicted in Scheme 1. Among the main fuel specications
related to chemical composition are cetane number; kinematic
viscosity; oxidative stability; cold-ow properties in the form
of cloud point (CP), pour point (PP), and cold-lter plugging
point (CFPP); exhaust emissions; lubricity; and heat of combus-
tion.
9
Other parameters inuenced by fatty acid composition
are conversion rate of FAME and optimal amount of reagents
involved in the transesterication reaction. Those parameters
are also important in terms of economic viability of biodiesel
production.
2
According to these reasons, the use of nonedible, low-cost,
and sustainable feedstocks compatible with a good quality of
biodiesel should become a primary research target for the
scientic community, thus facilitating the acceptance of biodiesel
by both customers and vehicle manufactures. For this reason,
the aim of this work is to provide a review about the main
achievements concerning the inuence of the chemical com-
position of biodiesel on several fuel topics (i.e., fuel properties,
engine performance, etc.), focused on low-cost and nonedible
oils. An approach to the biodiesel ideal chemical composition
is also proposed. The ideal chemical structure of vegetable oils-
based biodiesel, together with some ethical, social, and eco-
nomical considerations is presented. According to the conclu-
sions of these sections, some nonedible low-cost vegetable oils
with high potential to be used to produce biodiesel are
recommended. Because of the limitations of the proposed
vegetable oils, the inuence of free fatty acids (FFA) content
in biodiesel production are discussed, as well as potential
modications by genetic engineering. Finally, a comparative
study concerning the best-tting raw materials to produce
biodiesel is presented.
2. The Ideal Chemical Structure of Biodiesel
The inuence of the chemical structure of fatty acids on
biodiesel quality has been demonstrated.
9-13
In this section, the
optimal fatty acid prole of low-cost and nonedible vegetable
oils, to be considered suitable and sustainable raw materials for
biodiesel production, is discussed. According to this, main fuel
properties are provided and analyzed, as shown in Table 1.
2.1. Iodine Value (IV). This parameter reects total unsat-
uration regardless of the relative proportion of mono-, di-, tri-,
and polyunsaturated compounds. In this sense, several authors
have determined IV as a function to fatty acid prole.
3,14
Results
reveal that a high IV has been linked with low oxidation
stability, causing the formation of various degradation products,
which can negatively affect engine operability by forming
deposits on engine nozzles, piston rings, and piston ring grooves.
The effects of oxidative degradation represent a legitimate
concern in terms of maintaining fuel quality of biodiesel.
15
Biodiesel may oxidize more rapidly than conventional diesel
fuel, particularly when the former is produced from highly
unsaturated sources.
The oxidation rate of biodiesel can be inuenced by many
factors, including temperature and chemical composition. The
inuence of fatty acid composition on biodiesel oxidation rate
is higher than the inuence of environmental conditions such
as air, light, and the presence of metals.
16
Monounsaturated fatty
acid methyl esters (such as C18:1) are considered to be better
than poly unsaturated ones (such as methyl linoleate (C18:2)
and C18:3) in terms of oxidation stability, without any adverse
effect on fuel cold properties.
17
In particular, the number and
position of double bonds in fatty acid esters affect the rate of
oxidation.
18
According to literature, the rates of oxidation have
a relative value of 1 for oleates like methyl esters (ME) and
ethyl esters (EE), 41 for linoleates, and 98 for linolenates. Small
amounts of more highly unsaturated fatty compounds containing
bis-allylic carbons have a signicant strong effect on oxidative
stability. In the case of lubricating oil dilution, highly unsaturated
esters present in engine oil are suspected of forming high-
molecular compounds, which may reduce the lubricating qual-
ity.
19
The IV limit of 120 set by the European biodiesel standard
(EN 14214) excludes several promising oil sources such as
(5) FAO The state of food and agriculture (SOFA) 2008; Food and
Agriculture Organization of the United Nations (FAO): Rome, 2008.
(6) Dorado, M. P.; Cruz, F.; Palomar, J. M.; Lopez, F. J. Renewable
Energy 2006, 31, 12311237.
(7) Krawczyk, T. In International News on Fats, Oils and Related
Materials; American Oil Chemists Society Press: Champaign, IL, 1996;
Vol. 7, p 801.
(8) Zhang, Y.; Dube, M. A.; McLean, D. D.; Kates, M. Bioresour.
Technol. 2003, 90, 229240.
(9) Knothe, G. Energy Fuels 2008, 22, 13581364.
(10) Knothe, G. Fuel Process. Technol. 2005, 86, 10591070.
(11) Canakci, M.; Sanli, H. J. Ind. Microbiol. Biotechnol. 2008, 35, 431
441.
(12) Harrington, K. J. Biomass 1986, 9, 117.
(13) Ramos, M. J.; Fernandez, C. M.; Casas, A.; Rodr guez, L.; Perez,
A
. Bioresour. Technol. 2009, 100, 261268.

(14) Schober, S.; Mittelbach, M. Lipid Technol. 2007, 19, 281285.
(15) Dunn, R. O. J. Am. Oil. Chem. Soc. 2002, 79, 915920.
(16) Knothe, G.; Dunn, R. O. J. Am. Oil. Chem. Soc. 2003, 72, 1155
1160.
(17) Imahara, H.; Minami, E.; Saka, S. Fuel 2006, 85, 16661670.
(18) Durrett, T. P.; Benning, C.; Ohlrogge, J. Plant J. 2008, 54 (4),
593607.
(19) Knothe, G. Fuel Process. Technol. 2007, 88, 669677.
Scheme 1. Transesterication Process
2326 Energy & Fuels, Vol. 23, 2009
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ReViews Energy & Fuels, Vol. 23, 2009 2327
sunower and some nonedible low-cost oily crops. In fact,
Schober and Mittelbach state that this limit cannot be argued
as a suitable limit to describe or avoid the initial concerns about
problems resulting from oxidative degradation.
14
They state that
IV itself is not the most suitable parameter to express biofuel
stability, because it cannot weigh the signicant difference in
oxidative stability between mono-, di- and triunsaturated esters.
As a matter of fact, it seems that parameters such as oxidation
stability, linolenic acid ester content, and polyunsaturated esters
content are better indicators of degradation tendencies.
20
2.2. Cetane Number (CN). This parameter gives a measure-
ment of the combustion quality during ignition. It provides
information about the ignition delay (ID) time of a diesel fuel
upon injection into the combustion chamber. Fuels with low
CN tend to cause diesel knocking and show increased gaseous
and particulate exhaust emissions (PM), due to incomplete
combustion.
21
Moreover, excessive engine deposits are reported.
In general, biodiesel has higher CN values than fossil fuel, which
is considered to be a signicant advantage in terms of engine
performance and emissions, allowing biodiesel-fuelled engines
to run more smoothly and with less noise.
22
Long ID times, with low CNsand subsequent poor combus-
tionshave been associated to FAME with highly unsaturated
components such as linoleic (C18:2) and linolenic (C18:3) acid
esters. High CN values have been observed in saturated fatty
acid esters, such as palmitic (C16:0) and stearic (C18:0) acid
esters. Generally, the higher the chain length, the higher the
CN value.
12,23
Also, the more sequential CH
2
groups in the fatty
compound, the higher the CN. Knothe et al.
24
studied the effect
of the structure (branching, unsaturation, and length) of the fatty
acid chain and the alcohol moiety on the CN of biodiesel. Such
authors stated that the level of unsaturation of the fatty acid
chains is the most signicant factor causing lower CN. Also,
results have shown that one saturated, long straight chain in a
fatty ester sufces to provide a high CN.
According to engine exhaust emissions, higher CN is cor-
related with reduced nitrogen oxides (NO
x
),
25
although this may
not always hold for all types of engine technologies.
24
The
connection between the structure of fatty acid esters and exhaust
emissions was investigated by studying enriched fatty acid alkyl
esters as fuel and using different vegetable oil esters with a wide
range of iodine numbers.
26
The NO
x
exhaust emissions report-
edly increase with lower saturation and decreasing chain length,
which can also lead to a connection with the CN of these
compounds.
27
Peterson et al.
28
found that fatty acids with two
double bonds had more effect on increasing NO
x
emissions than
those with one double bond. On the other hand, PM was not
inuenced by chain length, but the higher reductions were found
using methyl laurate and methyl palmitate.
27
Changes in carbon
monoxide (CO) and hydrocarbons (HC) could not be linearly
correlated with unsaturation.
28
2.3. Gross Caloric Value (Higher Heating Value) and
Net Caloric Value (Lower Heating Value). These fuel
properties indicate the suitability of fatty compounds as diesel
fuel. Due to higher oxygen content, FAME exhibit lower heating
values than fossil diesel. So, to achieve adequate engine torque
and power, an increasing of injection volumes is needed.
21
However, this leads to higher specic fuel consumptions.
Caloric value is not included in most fuel standards, but it is
a limiting parameter within the European standard for FAME
used as heating fuels (EN 14213). Freedman and Bagby
29
developed a model to predict heating values from different fatty
acids composition. Generally, the higher the chain length
(number of carbons and hydrogens in FAME molecules), the
higher the heating value.
10
The increase in the ratio of these
elements relative to oxygen also results in a heat content
increase. A decrease in heat content is the result of fewer
hydrogen atoms (i.e., higher unsaturation) in the fuel molecule.
Therefore, from this point of view, oil sources with a high
proportion of long-chain saturated compounds should be selected
for transesterication.
21
2.4. Brake-specic Fuel Consumption. BSFC is the ratio
between mass fuel consumption and brake effective power,
being inversely proportional to break thermal efciency (BTE).
Biodiesel-specic fuel consumption is expected to increase
around 10-20% in relation to diesel fuel, since the loss of
heating value of biodiesel must be compensated with higher
fuel consumption. An indicator of the loss of heating value is
the oxygen content in the fuel.
30
Several researchers found a
correlation between BSFC and oxygen content, concluding that
the increase in BSFC is due to the oxygen enrichment from the
fuel, but not from the air intake.
31,32
2.5. Cold Weather Performance. One of the major prob-
lems associated with the use of biodiesel is poor ow properties
at low temperatures.
10
Partial solidication in cold weather may
cause blockages of fuel lines and lters, leading to fuel starvation
and problems during engine start-up.
21
Provided that long-chain
saturated fatty esters signicantly increase CP and PP, reducing
saturated fatty acid content of vegetable oils can improve cold
temperature ow properties of biodiesel.
To improve cold temperature ow characteristics of biodiesel,
several proposals have been suggested, including winterization,
additives, esterication with branched alcohols, and modication
of oil chemical composition. Several authors have stated that
the cheapest and more effective way to improve the low-
temperature ow properties of biodiesel is the optimization of
fatty acid composition of the raw material.
18,33,34
With this aim,
Imahara et al.
17
developed a prediction model to estimate CP
of biodiesel from various oils/fats, providing a useful tool to
determine optimal fatty acid methyl ester composition. They
observed that CP depends mostly on saturated ester content,
while the effect of unsaturated ester composition could be
negligible.
2.6. Kinematic Viscosity. Fuel viscosity impacts on both
injection and combustion efciency. Higher viscosity leads to
(20) Mittelbach, M. Bioresour. Technol. 1996, 56, 711.
(21) Mittelbach, M.; Remschmidt, C. Biodiesel: The ComprehensiVe
Handbook; Martin Mittelbach: Graz, Austria, 2004.
(22) Knothe, G.; Matheaus, A. C.; Ryan, T. W. Fuel 2003, 82, 971
975.
(23) Klopfenstein, W. J. Am. Oil. Chem. Soc. 1985, 62, 10291031.
(24) Knothe, G.; Matheaus, A. C.; Ryan, T. W. Fuel 2003, 82, 971
975.
(25) Ladommatos, N.; Parsi, M.; Knowles, A. Fuel 1996, 75, 814.
(26) Peterson, C. L.; Taberski, J. S.; Thompson, J. C.; Chase, C. L. Trans.
ASAE 2000, 43, 13711381.
(27) Knothe, G.; Sharp, C. A.; Ryan, T. W. Energy Fuels 2006, 20,
403408.
(28) Peterson, C.; Reece, D. Trans. ASAE 1996, 39, 805816.
(29) Freedman, B.; Bagby, M. O. J. Am. Oil. Chem. Soc. 1989, 66, 1601
1605.
(30) Lapuerta, M.; Armas, O.; Rodr guez-Fernandez, J. Prog. Energy
Combust. Sci. 2008, 34, 198223.
(31) Rakopoulos, Ct. D.; Hountalas, D. T.; Zannis, T. C.; Levendis, Y. A.
SAE Paper 2004-01-2924; 2004.
(32) Graboski, M. S.; Ross, J. D.; McCormick, R. L. SAE Paper 961166;
1996.
(33) Lee, I.; Johnson, L. A.; Hammond, E. G. J. Am. Oil. Chem. Soc.
1996, 73, 631636.
(34) Lee, I.; Johnson, L. A.; Hammond, E. G. J. Am. Oil. Chem. Soc.
1995, 72, 11551160.
(35) Allen, C. A. W.; Watts, K. C.; Ackman, R. G.; Pegg, M. J. Fuel
1999, 78, 13191326.
a higher drag in the injection pump, causing higher pressures
and injection volumes, especially at low engine operating
temperatures. As a direct consequence, the timing for fuel
injection and ignition tends to be slightly advanced for biodiesel,
which might in turn lead to increased NO
x
emissions due to
higher maximum combustion temperatures.
21
Allen et al.
35
developed a method for predicting the kinematic viscosity of
biodiesel from its fatty acid composition. Results showed that
for saturated fatty acid esters, viscosity increased with carbon
number in a curvilinear trend, rather than linear. Indeed, for
unsaturated C18 esters, they observed a nonlinear decrease in
viscosity, while increasing number of double bonds. The most
signicant effect was found for the rst unsaturation. Contami-
nation with small amounts of glycerides signicantly increased
biodiesel viscosity.
35
2.7. Mono-, Di-, and Triglycerides (TG) or Triacylglycer-
ols (TAG) Content. Fuel exceeding the limits of mono-, di-,
and triglycerides dened in the EN 14214 standard may cause
formation of deposits to injector nozzles, pistons, and valves.
Indirect hints at high glycerides contents in biodiesel are
correspondingly increased values for viscosity and carbon
residue.
21
There are only few studies about the inuence of fatty
acid composition of vegetable oils on transesterication yield.
Abreu et al.
36
studied the effect of heterogeneous catalysts and
found that the activity of metal complexes increases for short
chains. It is worthy to highlight that their results indicated that
both the saturation degree and the alkyl-chain length are
determinant factors in the catalytic activity. Stavarache et al.
37
established the relationship between yield of FAME during
ultrasound-assisted transesterication and the composition of
fatty acids from different vegetable oils. In fact, they found that
saturated fatty acids that have a natural preference for rst and
third positions in triglycerides were transesteried mostly at the
beginning of the reaction, while the amount of unsaturated fatty
acids esters increased as the reaction progressed.
38
Warabi et
al.
39
studied the alkyl esterication in supercritical alcohol and
observed that saturated fatty acids, including palmitic and stearic
acids, had slightly lower reactivity than unsaturated fatty acids
(i.e., oleic, linoleic, and linolenic acids).
In conclusion, given the antagonistic requirements between
low-temperature ow characteristics and the oxidative stability,
NO
x
emissions, and CN, there is strictly no fatty acid prole
providing a fuel for which all these parameters are optimal.
18
However, various studies have suggested that biodiesel with
high levels of methyl oleate may have excellent, if not optimal,
characteristics with regard to ignition quality, NO
x
emissions,
fuel stability, ow properties at low temperature, and iodine
number according to the standard EN 14214.
10,13
Furthermore,
it is expected that biodiesel with an average of 1.5 double bonds
per molecule will produce an equivalent amount of NO
x
to
conventional diesel fuel.
40
Lastly, given that polyunsaturated
fatty acids have a disproportionably large effect on the auto-
oxidation of biodiesel,
16
it is recommended to avoid their
presence in TG to be used as raw material for biodiesel
production.
3. Considerations about Biodiesel Produced from
Vegetables Oils
3.1. Ethical Issues. The major obstacle for large-scale
adoption of biodiesel from vegetable oils is the production of
sufcient amounts of oilseed crops without signicantly affect-
ing food supply and cost. To reach this goal, researchers and
industry have put a lot of effort proposing and developing
alternative sources to produce biofuels. Although a large
proportion of these efforts are focused on conversion of
lignocellulosic feedstocks to ethanol (second-generation fuels),
some strategies to design new crops to produce biodiesel are
outlined below.
18
It must be noted that there is currently a social
controversy over biofuels produced from energy crops that are
primarily used for feeding purposes. Yet, even in case the
scientic community eventually nds an efcient technology
to produce alcohol from agricultural pruning and forest residues
that denitely will not compete with food, this will provide us
with an insufcient quantity of biofuels. Plantations of trees to
process biomass into alcohol may be needed, leading to the same
social alarm caused by the use of energy crops (rst-generation
fuels) instead of crops for food.
Increased demand for the production of edible oils for feeding
purposes has put limitations on the use of these oils for biodiesel
production. Some voices claim that edible oils are too important
for human feeding to run vehicles.
2
However, the FAO has
calculated that 41.88 million km
2
of land are available for
agriculture, although just 15.06 million km
2
are in use, and only
0.11 million km
2
are used for biofuels production today, which
is no more than 1% of that area. The FAO estimates that in
2030, 0.325 million km
2
will be used for biofuels production,
which is no more than 2% of total agricultural land use.
41
Nevertheless, to avoid the use of edible crops to produce fuel,
and the supposed subsequent increase of food price, nonedible
crops developed in marginal lands could provide a sustainable
option as biodiesel feedstocks. Biodiesel technology should not
cause starvation in underdeveloped countries. In fact, it can have
the opposite effect: it should be focused to help poor and
developing countries to decrease their dependence to fossil oil
imports, thus enhancing their Balance of Payments (BOP) and
general welfare.
However, it is important to mention again that either energy
crops grown in marginal lands or biomass from forests to
produce biofuels cannot nowadays provide the total amount of
fuels required for the current high energy-dependent life.
Therefore, to reduce the impact on climate change and other
related problems including pollution, a change in the consump-
tion habits is strongly recommended.
3.2. Economical Issues. One main concern in further usage
of biodiesel is the economic viability of its production. A few
years ago, biodiesel unit price was 1.5-3.0 times higher than
that of petroleum-derived diesel fuel.
11
But currently, due to
the dramatic increase of crude mineral oil price, cost of biodiesel
is not too far from diesel price (Table 2). Remarkably, in
different countries, biodiesel price has always shown the same
price as diesel fuel, even after the increase of fossil fuels price.
The reason for this linearity is not clear, as other interests seem
to control the market.
(36) Abreu, F. R.; Lima, D. G.; Hamu, E. H.; Wolf, C.; Suarez, P. A. Z.
J. Mol. Catal A: Chem. 2004, 209, 2933.
(37) Stavarache, C.; Vinatoru, M.; Maeda, Y. Ultrason. Sonochem. 2007,
14, 380386.
(38) Richards, A.; Wijesundera, C.; Palmer, M.; Salisbury, P. AOCS
Australian Workshop: Sydney, 2002; p 29.
(39) Warabi, Y.; Kusdiana, D.; Saka, S. Bioresour. Technol. 2004, 91,
283287.
(40) McCormick, R. L.; Graboski, M. S.; Alleman, T. L.; Herring, A. M.;
Tyson, K. S. EnViron. Sci. Technol. 2001, 35, 17421747.
(41) Konandreas, P.; Smithuber, J. Global Biofuel Production Trends
and Possible Implication of Swaziland; Food and Agricultural Organization
of United Nations: 2007.
Manufacturing costs and raw feedstock prices are the main
economic criteria to take into account for biodiesel production
to compete with diesel fuel. Manufacturing costs include direct
costs for oil extraction, reagents, operating supplies, and
manpower, as well as indirect costs related to insurance and
storage. For a complete analysis, xed capital costs involved
in the construction of processing plants and auxiliary facilities,
distribution, and retailing must also be taken into consideration.
6
In this sense, several studies have identied that the price of
feedstocks is by far one of the most signicant factors affecting
the economic viability of biodiesel manufacture.
6-8,42
In fact,
approximately 70-95% of total biodiesel production cost arises
from the cost of the raw material.
42,43
Thus, to produce a
competitive biodiesel, the feedstock price is a factor that needs
to be taken into consideration.
Several authors have found that a key factor to make biodiesel
economically feasible is the application of tax credits.
44,45
To
promote biodiesel consumption, several countries have exempted
biodiesel from their fuel excise tax. According to this, the
European Union (EU) approved the biodiesel tax exemption
program in May 2002 (Art. 21, Finance Law 2001).
2
Despite
this, some European countries, including Germany (considered
one of the fathers of biodiesel), have started removing tax
exemption. On Oct 22, 2008, the German federal government
ratied the law entitled Gesetz zur A
nderung der Forderung

von Biokraftstoffen (Energy Tax Law).
46
According to this,
starting in January 2009, the German government will receive
nine cents on the dollar more per liter of biodiesel (increasing
from 0.18 to 0.21 Euros). Such a tax will increase to more than
65 cents on the dollar in 2012, putting obstacles to the
development of German biofuel reneries, constituting a
stimulus for the importation of cheaper biodiesel. Taxes remove
the price advantage of biodiesel over conventional diesel fuel
and should result in a massive decline in biodiesel output.
A lower-cost biodiesel production can also be achieved by
the optimization of the process. Because biodiesel chemical
properties determine its feasibility as fuel, the optimization of
reaction parameters can be exploited to maximize the yield of
ester, thus achieving a low-cost chemical process and ensuring
appropriate chemical properties to guarantee adequate engine
performance and appropriate exhaust emissions. In this sense,
it is important to characterize the oil (i.e., fatty acid composition,
water content, and other signicant parameters) to determine
the feasibility to convert the oil into biodiesel.
3.3. Ecological, Political, and Agronomical Issues. The
renewed interest in the use of vegetable oils to produce biodiesel
is due to its less polluting and renewable nature, compared to
conventional petroleum-based diesel fuel. Biodiesel could be
benecial for environment, local population job creation,
provision of modern energy carriers to rural communities,
mitigation of human migration, and reduction of CO
2
and sulfur
levels in the atmosphere.
47
Current biodiesel energy originates from the sun, through
photosynthesis of biomass. However, to keep the main benet
of its use (i.e., to be an environmentally friendly energy),
limiting factors such as the extensive use of land, irrigation,
and labor practices (such as fertilizing, weed control, etc.) must
be taken into consideration and reduced to minimal levels.
Implementation of efcient farming practices to preserve soil
fertility and to reduce the use of valuable inputs, such as
fertilizers and water, gain special interest.
The increasing development of biodiesel opens new chal-
lenges to the scientic community, including the production of
renewable energy respecting natural ecosystems. Genetic en-
gineering can nowadays be carried out in a clean, environmen-
tally friendly, and cost-effective way, thus becoming an efcient
approach to achieve such ecological, political, and agronomical
goals, as discussed below. Another way to increase global
vegetable oil production without harming ecosystems is to use
marginal or nonarable wasteland.
18
In addition, the set-aside
rules of the EU Agricultural Policy specify a minimum area of
obligatory set-aside (10% in 2001) of the total arable land, but
also allow up to 50% of the total claimed area to be put into
voluntary set-aside. Nevertheless, an exception has been intro-
duced into the rules for managing set-aside land, allowing
farmers to cultivate crops for nonfood purposes.
48,49
It should
be noted that increasing the set-aside area could lead to erosion
problems, and may have an impact on arable land. Related to
that, in response to the increasingly tight situation on the cereal
market, the EU agriculture ministers recently approved a
Commission proposal to remove the obligatory set-aside rate
for autumn 2007 and spring 2008 sowings. Furthermore, the
abolition of the compulsory set-aside from 2009 onward is part
of the Common Agricultural Policy (CAP) Health Check
proposal, which was adopted by the Commission on 20th May
2008 and it is currently under discussion in the Council, the
European Parliament and other European Institutions.
50
For all these reasons, another approach is the use of nonedible
crops and trees, which have several advantages, such as growing
in arid or less favored regions, requiring very little manpower
and care, having high oil content, being resistant to plagues and
drought, etc. The foliage could be used as manure, giving an
added value to the crop. As an example, most trees and crops
(42) Connemann, J.; Fischer, J. The International Liquid Biofuels
Congress. US National Biodiesel Foundation: Brazil, 1998, p. 15.
(43) Haas, M. J.; McAloon, A. J.; Yee, W. C.; Foglia, T. A. Bioresour.
Technol. 2006, 97, 671678.
(44) Bender, M. Bioresour. Technol. 1999, 70, 8187.
(45) Peterson, C. L. Transactions of the ASAE 1986, 29, 14131422.
(46) Vorblatt Entwurf eines Gesetzes zur A
nderung der Frderung von

Biokraftstoffen. Federal Ministry for the Environment, Nature Conservation
and Nuclear Safety, Oct. 20, 2008; pp 38. (http://www.bmu.de/les/pdfs/
allgemein/application/pdf/entw_foerderung_biokraftstoff.pdf).
(47) Demirbas, A. Energy ConVers. Manage. 2008, 49, 21062116.
(48) Dorado, M. P.; Ballesteros, E.; Lopez, F. J.; Mittelbach, M. Energy
Fuels 2004, 18, 7783.
(49) Graciani, A. L., Amores, A. G., Arnal Almenara, J. M., Chico
Gaetan, J. M., Dorado, M. P. In 1st World Conference and Exhibition on
Biomass for Energy and Industry; James & James (Science Publishers) Ltd.:
London, 2001; pp 1560-1561.
(50) Europa s Press Releases; EU: Brussels, 2008; Vol. IP/08/1069.
Available at: http://europa.eu.
Table 2. Price of Biodiesel from Different Raw Materials and
Diesel Fuel
fuel price (USD/t), Sept 2007 price (USD/t), Sept 2008 ref
diesel fuel 733 1017 145
RME (B100)
a
1020-1060 1415 145
SME (B99)
b
850-865 1185 145
PME (B99)
c
780-850 990 145
a
RME: rapeseed oil methyl ester, pure and without additives,
matching EN 14214 standard and typically reaching -10 or -12 C
quoted in USD/MT on a free on board (FOB) Northwest Europe (North
German ports, North France, Benelux and South-East UK) basis.
b
SME:
soybean oil methyl ester, with a minimum of 99% biodiesel (B99),
typically not matching the EN 14214 and reaching a 0/-5 C CFPP,
quoted in USD/MT on a cost, insurance, freight (CIF) ARA with the
6.5% duty paid included (T2).
c
PME: palm oil methyl ester, with a
minimum of 99% biodiesel (B99), typically not matching the EN 14214
and reaching a +11/+15 C CFPP, quoted in USD/MT on a cost,
insurance, freight (CIF) ARA with the 6.5% duty paid included (T2).
mentioned below grow well on wasteland and therefore can
tolerate long periods of drought and dry conditions.
2
4. Nonedible and Low-cost Vegetable Oils with High
Potential to Be Used As Raw Materials to Produce
Biodiesel
In terms of sustainability, provided the previous technical,
ethical, economical, and social considerations, potentially suit-
able vegetable raw materials for biodiesel production are
described below. The selection has been done considering low
input crops and the most promising ones, according to their
properties (Tables 3 and 4).
2
In the following sections,
potentially suitable low-cost vegetable oils for biodiesel produc-
tion are analyzed separately, in terms of fuel properties and their
suitability to be used as alternative diesel fuel. Finally, a
comparison between them facilitates nding out the best tting
low-cost vegetable oil for biodiesel production.
4.1. Jatropha curcas. J. curcas is a perennial plant, native
and widely spread throughout many tropical countries. It grows
readily in poor and stony soil. It is drought- and disease-resistant,
and its oil yields high-quality biodiesel.
51,52
Biodiesel produced
from J. curcas oil meets all the requirements stipulated by the
EU standard EN 14214.
53
However, as J. curcas is still a wild
plant, the initiation of systematic selection and breeding
programs is a prerequisite for sustainable utilization of this plant
for biodiesel production.
54
The FFA content of J. curcas seed oil (JCSO) varies
depending on the quality of the feedstock. Although Sivaprakasam
and Saravanan
55
reached 91% yield on jatropha oil methyl ester
(JOME) using alkaline transesterication and jatropha oil poor
on FFA, Berchman and Hirata
56
developed a technique to
produce biodiesel from crude JCSO containing high levels
(15%) of FFA. Some researchers have proposed the use of
immobilized enzymes, such as those from Chromobacterium
Viscosum, Candida rugosa, and Sus scrofa porcine pancreas as
catalyst.
57,58
In this sense, Modi et al.
59
proposed the use of
propan-2-ol as an acyl acceptor for immobilized Candida
antarctica lipase B. Additionally, Zhu et al.
60
proposed the use
of a heterogeneous solid superbase catalyst (catalyst dosage of
1.5%) and calcium oxide, at 70 C for 2.5 h, with a 9:1
methanol:oil molar ratio to produce biodiesel.
Kumar et al.
61
obtained values of brake thermal efciency
of jatropha oil methyl ester comparable to diesel fuel values,
higher values of CH and CO emissions, but lower values of
NO
x
exhaust emissions.
4.2. Pongamia pinnata (Karanja Seed Oil). This nonedible
oil tree is drought-resistant, tolerant to salinity, moderately frost
hardy, and is commonly found in East Indies, Philippines, and
India.
2
Several scientists have investigated and proposed karanja
oil as a potential source of biodiesel.
3,62-66
Most researchers
have conducted the transesterication of P. pinnata oil by using
methanol and potassium hydroxide.
64,66,67
Due to its high FFA content, some researchers have proposed
the esterication of the FFA with H
2
SO
4
, prior to transesteri-
cation with NaOH.
68
In all cases, karanja oil has shown
promising properties to be used as a raw material to produce
biodiesel, saving large quantities of edible vegetable oils. Diesel
engine performance tests have been carried out with karanja
oil methyl ester (KOME) and its blend with diesel fuel from
20 to 80% by volume (v/v).
65
Results have revealed a reduction
in exhaust emissions together with an increase in torque, brake
power, thermal efciency, and reduction in brake-specic fuel
consumption compared to diesel fuel. Prakash et al.
69
optimized
transesterication of karanja oil using the Taguchi optimization
methodology
70
and carried out performance and emission tests
using diesel fuel and biodiesel blends. Among the blends, 20%
KME showed better performance characteristics compared to
other blends. They observed better BTE, BSFC, and indicated
thermal efciency (ITE). With regard to exhaust emissions, 20%
blend slightly increased the NO
x
due to the higher specic
gravity of the fuel. Both the PM emission and smoke density
were low.
69
4.3. Madhuca indica (Mahua Oil). This is a deciduous tree
that belongs to the family Sapotaceae. It can reach up to 21 m
high. Several approaches to produce biodiesel from this crop
can be found in literature.
2
In this sense, Ghadge and Raheman
have proposed a two-step pretreatment to reduce high FFA
levels. Transesterication was carried out adding 0.25 (v/v)
methanol and 0.7% KOH. Fuel properties were found to be
comparable to those of diesel fuel.
71
Other authors have
proposed different successful alternatives to produce biodiesel
from this species: ethanol and sulfuric acid, and methanol and
sodium hydroxide.
72-74
Excepting water content, the fuel
properties of mahua biodiesel are within the limits specied by
the ASTM D 6751-02 and EN 14214 standards.
71
Besides
caloric value, all other fuel properties of mahua biodiesel were
found to be higher than high-speed diesel fuel.
75
Raheman and Ghadge
75
measured engine performance and
emissions of biodiesel obtained from mahua oil and its blends
with diesel fuel. They observed that BSFC increased while BTE
decreased by increasing the proportion of biodiesel in the blends.
Smoke level and CO were reduced, whereas NO
x
increased with
(51) Becker, K.; Makkar, H. P. S. Lipid Technol. 2008, 20, 104108.
(52) Banapurmath, N. R.; Tewari, P. G.; Hosmath, R. S. Renewable
Energy 2008, 33, 19821988.
(53) Kumar, A.; Sharma, S. Ind. Crops Prod. 2008, 28, 110.
(54) Foidl, N.; Foidl, G.; Sanchez, M.; Mittelbach, M.; Hackel, S.
Bioresour. Technol. 1996, 58, 7782.
(55) Sivaprakasam, S.; Saravanan, C. G. Energy Fuels 2007, 21, 2998
3003.
(56) Berchmans, H. J.; Hirata, S. Bioresour. Technol. 2008, 99, 1716
1721.
(57) Shah, S.; Sharma, S.; Gupta, M. N. Energy Fuels 2004, 18, 154
158.
(58) Shah, S.; Sharma, S.; Gupta, M. N. Indian J. Biochem. Biophys.
2003, 40, 392399.
(59) Modi, M. K.; Reddy, J. R. C.; Rao, B. V. S. K.; Prasad, R. B. N.
(60) Zhu, H.; Wu, Z. B.; Chen, Y. X.; Zhang, P.; Duan, S. J.; Liu, X. H.;
Mao, Z. Q. Chin. J. Catal. 2006, 27, 391396.
(61) Senthil Kumar, M.; Ramesh, A.; Nagalingam, B. Biomass Bioenergy
2003, 25, 309318.
(62) Naik, M.; Meher, L. C.; Naik, S. N.; Das, L. M. Biomass Bioenergy,
2008, 32 (4), 354-357.
(63) Meher, L. C.; Dharmagadda, V. S. S.; Naik, S. N. Bioresour.
Technol. 2006, 97, 13921397.
(64) Meher, L. C.; Naik, S. N.; Das, L. M. J. Sci. Ind. Res. 2004, 63,
913918.
(65) Raheman, H.; Phadatare, A. G. Biomass Bioenergy 2004, 27, 393
397.
(66) Karmee, S. K.; Chadha, A. Bioresour. Technol. 2005, 96, 1425
1429.
(67) Vivek, G. A. K. J. Sci. Ind. Res. 2004, 63, 3947.
(68) De, B. K.; Bhattacharyya, D. K. Lipid Fett 1999, 101, 404406.
(69) Prakash, N.; Arul Jose, A.; Devanesan, M. G.; Viruthagiri, T. Indian
J. Chem. Technol. 2006, 13.
(70) Rao, R. S.; Kumar, G.; Prakasham, R.; Hobbs, S. P. J. Biotechnol.
J. 2008, 3, 510523.
(71) Ghadge, S. V.; Raheman, H. Biomass Bioenergy 2005, 28, 601
605.
(72) Raheman, H.; Ghadge, S. V. Fuel 2007, 86, 25682573.
(73) Ghadge, S. V.; Raheman, H. Bioresour. Technol. 2006, 97, 379
384.
(74) Puhan, S.; Vedaraman, N.; Sankaranarayanan, G.; Ram, B. V. B.
Renewable Energy 2005, 30, 12691278.
(75) Raheman, H.; Ghadge, S. V. Fuel 2008, 87, 26592666.
(76) Nabi, M. N.; Akhter, M. S.; Zaglul Shahadat, M. M. Bioresour.
Technol. 2006, 97, 372378.
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an increase of biodiesel percentage from mahua oil in the blends.
They considered that mahua oil methyl esters were safely
blended with diesel fuel up to 20%, without signicantly
affecting engine performance (BSFC, BTE) and emissions
(smoke, CO, and NO
x
), and thus it was recommended as a
suitable alternative fuel for diesel engines.
4.4. Azadirachta indica (Neem Oil). This large tree grows
in almost all types of soils. It thrives well in arid and semiarid
climate with maximum shade temperature as high as 49 C,
bearing rainfalls as low as 250 mm/year.
3
Nabi et al. have produced biodiesel from neem oil by using
20% methyl alcohol and 0.6% anhydrous NaOH catalyst.
Reaction temperature was kept at 55-60 C. Compared with
conventional diesel fuel, exhaust emissions including smoke and
CO were reduced, whereas NO
x
emissions were increased with
diesel fuel-biodiesel blends, except when the exhaust gas
recirculation (EGR) was applied. According to their results, they
recommended it as an environment-friendly alternative fuel for
diesel engines.
76
4.5. Calophyllum inophyllum (Nagchampa/Polanga Oil).
This tree thrives in xerophytic habitats. It grows best in deep
soil or exposed sea sands. The rainfall requirement is just
750-5000 mm/year.
3
Polanga oil contains 24.96% saturated and
72.65% unsaturated acids.
77
Saturated fatty acid alkyl esters
increase cloud point, cetane number, and stability. The free fatty
acid content of unrened ltered nagchampa oil was found to
be 22%, with an acid value of 44 mg KOH/g.
78
Sahoo et al.
78
obtained a comparatively higher ash point
than petroleum diesel fuel for nagchampa oil methyl ester
(NOME), indicating better safety conditions during storage. All
characterization tests of biodiesel demonstrated that the most
important properties are very close to those of diesel fuel. The
performance of diesel engines was slightly better in terms of
BTE, BSFC, smoke opacity, and exhaust emissions including
NO
x
for the entire range of operations.
78
4.6. HeWea brasiliensis (Rubber Seed Oil). This rubber tree
originates from the Amazon rain forest (Brazil). Although there
are variations in the oil content from different countries, the
average oil yield is 40%
2
and contains 17-20% saturated and
77-82% unsaturated fatty acids.
79
To check its feasibility as a
source to produce biodiesel, several studies have been under-
taken. Ikwuagwu et al.
79
prepared methyl esters of rubber seed
oil using excess of methanol (6 M), containing 1% NaOH as a
catalyst. The biofuel properties showed similar values compared
to those of diesel fuel, with the exception of the oxidative
stability. Ramadhas et al.
80
performed a prior acid-catalyzed
esterication to reduce the high FFA content, followed by an
alkaline esterication. The lower blends of biodiesel with diesel
fuel increased BTE and reduced both BSFC and exhaust
emissions.
80,81
4.7. Brassica carinata (Ethiopian Mustard Oil). This is an
adequate oil-bearing crop that is well-adapted to marginal
regions. It is drought-resistant and grows in arid regions.
Ethiopian mustard presents up to 6% saturated hydrocarbon
chains. B. carinata oil from wild species presents high erucic
acid content (which is toxic), although cultivars with low erucic
acid are used as food by Ethiopians.
B. carinata adapts better and is more productive in adverse
conditions than B. napus., offering the possibility of exploiting
the Mediterranean marginal areas for energetic purposes.
82
(77) Hemavathy, J.; Prabhakar, J. V. J. Am. Oil. Chem. Soc. 1990, 67,
955957.
(78) Sahoo, P. K.; Das, L. M.; Babu, M. K. G.; Naik, S. N. Fuel 2006,
86, 448454.
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Dorado et al.
48
described a low-cost transesterication process
of B. carinata oil and found negative effects of singular fatty
acids (e.g., erucic acid) in the alkali-catalyzed transesterication.
Cardone et al.
83
found that B. carinata biodiesel produces lower
levels of particulate matter but higher levels of NO
x
concentra-
tions with respect to diesel fuel. The soluble organic fraction
of biodiesel particulate suggested that the carcinogenic potential
is lower than that of petroleum diesel.
83
4.8. Camelina satiWa (Gold-of-pleasure Oil/False Flax).
Budin et al.
84
studied the composition of C. satiVa oil and
concluded that this low-input crop presents food and nonfood
exploitation potential. The oil yield from this species is similar
to that of the spring rapeseed; however, lower fertilizer and
pesticide requirements lead to a substantial cost reduction,
85
being a more environmentally friendly crop. Since production
cost of C. satiVa is relatively low compared to many other oil
crops, including rapeseed, corn, and soybean, it is an attractive
potential crop for biofuels. The free fatty acid content of raw
C. satiVa oil is 3.1% (acid value equals to 6.0), whereas rened
oil presents a value around 0.05% (acid value is 0.1). The iodine
value (152-157), far exceeds the limits of all biodiesel
standards, due to very high level of polyunsaturated fatty acids
in the C. satiVa oil (Table 3). However, the high iodine value
of the C. satiVa oil methyl esters does not seem to lead to a
rapid deterioration of lubricating oil.
86
Frohlich and Rice
86
have investigated the production of
methyl esters from C. satiVa oil. Biodiesel was prepared by
means of a single-stage esterication using methanol and KOH.
They compared two methods of transesterication developed
by Freedman et al.
87
and by Maurer.
88
Steinke et al.
89
developed both alkali and lipase-catalyzed
alcoholeysis of C. satiVa oil. Frohlich and Rice
86
tested biodiesel
from this species in two light transport vehicles. Fuel consump-
tion and general vehicle operation resulted to be similar to those
observed using rapeseed oil methyl esters. Fuel-specic proper-
ties of Camelina satiVa oil methyl esters are largely within
specication, though low-temperature behavior could be a
problem under certain weather conditions.
4.9. Asclepias syriaca (Milkweed Oil). The common milk-
weed is native from the North East and North Central of the
United States of America, where it grows on roadsides and
undisturbed habitat.
90
The seed contains 20-25% (dry weight)
of triglycerides, composed of over 90% unsaturated fatty acids
with nearly 50% of linoleic acid and less than 2% of linolenic
acid (Table 3).
91
On the basis of the fatty acid prole, the oil is
expected to provide an alternative source to biodiesel production.
Milkweed oil contains more than 6% of palmitoleic acid, which
is usually found in smaller amounts in vegetable oils. This is a
very interesting fact, because methyl palmitoleate is a strong
candidate to enhance fuel properties, besides methyl oleate.
9
Holser and OKuru
92
analyzed fuel properties of both methyl
and ethyl esters of milkweed seed oil. Milkweed biodiesel
exhibits pour and cloud point values that may suggest an
improved cold weather performance. Highly unsaturated ester
structures (e.g., linolenate) oxidize more rapidly than saturated
ester structures, leading to fuel degradation, reducing its quality.
4.10. Terminalia catappa. This tree is popularly known in
Brazil as castanhola. It has been studied by Dos Santos et
al.
93
The tree is tolerant to strong winds, salt spray, and
moderately high salinity in the root zone. It grows principally
in freely drained, well-aerated, sandy soils. The oil can be
obtained from the kernels of the fruit, with yields around 49%
w/w.
94
Castanhola oil fatty acid composition is similar to that of the
conventional edible oils. Dos Santos et al.
93
compared basic
and acid catalysis and observed that basic catalysts are more
efcient than acid ones. In the presence of basic catalysts, an
average yield of FAME of ca. 93% was obtained. Although
the fruit is edible, the kernel is nonedible and is considered a
waste. However, it might also be used to produce biodiesel,
giving added value to this crop.
4.11. Ricinus communis (Castor Oil). This plant is native
from Central Africa, being cultivated in many hot climates. The
oil contains up to 90% of ricinoleic acid, which is not suitable
for nutritional purposes due to its laxative effect. The hydroxy-
carboxylic acid is responsible for the extremely high viscosity
of castor oilsalmost a hundred times the value observed in other
fatty materials.
21
Transesterication reactions from this oil have been carried
out mainly by using both ethanol and NaOH, as well as through
enzymatic methanolysis.
95,96
Several authors have studied the
inuence of catalyst on biodiesel yield from castor oil. Results
showed that the most efcient transesterication of castor oil
was achieved in the presence of sodium methoxide and acid
catalysts.
97
The viscosity of castor oil-based biodiesel is extremely high
at low temperatures, and the melting point of methyl ricinoleate
is close to 0 C. Furthermore, the cetane number of methyl
ricinoleate, and therefore neat castor oil biodiesel, do not meet
the minimum requirements for biodiesel standard specications.
The oxidative stability of methyl ricinoleate is signicantly lower
than that of its nonhydroxylated counterpart (methyl oleate),
and is even lower compared to methyl linoleate.
9
To recommend
this biodiesel as an alternative to diesel fuel, more research is
needed.
4.12. Cuphea ssp. (Cuphea). This genus includes species
such as C. carthagenensis, C. painteri, C. ignea, C. Viscosissima,
and C. llaVea. Cuphea grows in temperate and subtropical
(79) Ikwuagwu, O. E.; Ononogbu, I. C.; Njoku, O. U. Ind. Crops Prod.
2000, 12, 5762.
(80) Ramadhas, A. S.; Jayaraj, S.; Muraleedharan, C. Fuel 2005, 84,
335340.
(81) Ramadhas, A. S.; Muraleedharan, C.; Jayaraj, S. Renewable Energy
2005, 30, 17891800.
(82) Cardone, M.; Mazzoncini, M.; Menini, S.; Rocco, V.; Senatore,
A.; Seggiani, M.; Vitolo, S. Biomass Bioenergy 2003, 25, 623636.
(83) Cardone, M.; Prati, M. V.; Rocco, V.; Seggiani, M.; Senatore, A.;
Vitolo, S. EnViron. Sci. Technol. 2002, 36, 46564662.
(84) Budin, J. T.; Breene, W. M.; Putnam, D. H. J. Am. Oil. Chem.
Soc. 1995, 72, 309315.
(85) Downey, R. K. J. Am. Oil. Chem. Soc. 1971, 48, 718722.
(86) Frohlich, A.; Rice, B. Ind. Crops Prod. 2005, 21, 2531.
(87) Freedman, B.; Pryde, E. H.; Mounts, T. L. J. Am. Oil. Chem. Soc.
1984, 61, 16381643.
(88) Maurer, K. Landtechnik 1991, 46, 604608.
(89) Steinke, G.; Schonwiese, S.; Mukherjee, K. D. JAOCS 2000, 77,
367371.
(90) Holser, R. A. Ind. Crops Prod. 2003, 18, 133138.
(91) Adams, R. P.; Balandrin, M. F.; Martineau, J. R. Biomass 1984, 4,
81104.
(92) Holser, R. A.; Harry-OKuru, R. Fuel 2006, 85, 21062110.
(93) Dos Santos, I. C. F.; de Carvalho, S. H. V.; Solleti, J. I.; Ferreira
de La Salles, W.; Teixeira da Silva de La Salles, K.; Meneghetti, S. M. P.
(94) Abdullah, A. H.; Anelli, G. RiVista di Agricoltura Subtropicale e
Tropicale 1980, 74, 245247.
(95) De Oliveira, D.; Di Luccio, M.; Faccio, M.; Dalla Rosa, C.; Bender,
J. P.; Lipke, N.; Amroginski, C.; Dariva, C.; Oliveira, J. V. Appl. Biochem.
Biotechnol. 2005, 122.
(96) Fagundes, F. F.; Garcia, R. B.; Costa, M.; Borges, M. R.
J. Biotechnol. 2005, 118, 166169.
(97) Meneghetti, S. M. P.; Meneghetti, M. R.; Wolf, C. R.; Silva, E. C.;
Lima, G. E. S.; Silva, L. L.; Serra, T. M.; Cauduro, F.; de Oliveira, L. G.
Energy Fuels 2006, 20, 22622265.
climates. The seeds of these plants contain around 30-36% oil.
98
Fatty acid composition of the oil comprises major quantities of
caprylic acid (73% in C. painter and 3% in C. ignea), capric
acid (18% in C. carthagenensis, 24% in C. painteri, 87% in C.
ignea, and 83-86% in C. llaVea), and lauric acid (57% in C.
carthagenensis).
99
The correlation analysis between fatty acid
composition of cuphea oil and environmental crop factors as
latitude, elevation, and temperature have been studied by
Ghebretinsae et al.
100
They observed that environmental factors
contribute signicantly, and in particular, with respect to the
ratio of lauric/capric and lauric/myristic acids.
Genetically modied oil of C. Viscosissima presents relatively
low viscosity, enhancing its performance as an alternative to
diesel fuel.
101
Also, the atomization properties suggest better
fuel performance, owing to the presence of short-chain triglyc-
erides, compared to traditional vegetable oils comprising
predominantly long-chain triglycerides.
102
4.13. Cynara spp. This genus includes species such as C.
humilis (thistle), C. cardunculus (cardoon), and C. scolymus
(artichokes). Although the leaf stalks of these species can be
eaten, they are considered weed in many countries. The ower
buds and stems of this genus can also be used for food purposes.
The oil to produce biodiesel is extracted from the nonedible
seeds, therefore not competing with food markets and increasing
the value and protability of the plant. Moreover, this genus
presents a high degree of rusticity, is resistant to plagues, dry
conditions, and frost, is highly efcient in the use of water and
nutrients, and has reduced agrochemical needs.
The low inputs management required, the advantages of
increasing biodiversity by including C. cardunculus in agro-
ecological systems, and its adaptability to native Mediterranean
regions make this crop a potentially optimum alternative for a
sustainable agriculture in those regions.
103
The lignocellulosic biomass of cardoon can be used as a solid
biofuel, and seed-oil can be derived to biodiesel production,
making its cost lower compared to that of sunower oil.
104
Encinar et al. transesteried C. cardunculus oil by using
methanol and several catalysts (sodium hydroxide, potassium
hydroxide, and sodium methoxide) to produce biodiesel.
105,106
C. cardunculus methyl esters provide a signicant reduction in
particulate emissions, mainly due to reduced soot and sulfate
formation.
107
5. The Shortcomings of High FFA Content in Oils to
Biodiesel Production
Several nonedible feedstocks exhibit high level of FFA, as
can be seen in Table 3. This represents a key problem during
common alkaline transesterication. Alkaline catalyst reacts with
FFA and produces soap (saponication reaction), reducing the
biodiesel yield, and preventing the separation of esters, glycerol,
and washing water. Soap formation also increases the viscosity
and leads to gel formation.
87,108-111
In general, the use of alkaline
catalysts in transesterication reactions is not recommended in
feedstock with FFA contents above 0.5%.
108,112,113
Homogeneous mineral acids (i.e., H
2
SO
4
) have been used as
catalysts for raw materials with high FFA content. During the
esterication step (usually called pretreatment), the acid
catalyst converts the FFA into esters. Triglycerides are then
converted into FAME via transesterication with alkaline
catalyst. During pretreatment, the main factor to monitor is water
formation, due to its inhibiting effects in the transesterication.
11
Di Serio et al.
114
showed the possibility to perform a
simultaneous esterication and transesterication, using low
concentrations of homogeneous Lewis acid catalysts (e.g.,
carboxylic acids of given metals). However, this process has
also some associated problems related to the need of separating
catalysts from products by downstream purication.
Demirbas
115
proposed a supercritical transesterication pro-
cess as an alternative method to the previous two-steps catalyzed
process. The advantages of the supercritical process are that
catalysts are not required, both esterication and transesteri-
cation reactions happen simultaneously, and the methodology
is neither sensitive to FFA nor water. Nevertheless, the
supercritical process requires a high molar alcohol/feedstock
ratio (around 40-42:1), involving high-energy consumption
(with high reaction pressures, around 35-40 MPa, and reaction
temperatures generally higher than 300 C). Side reactions
including thermal decomposition and dehydrogenation of un-
saturated fatty acid methyl esters may occur in case reaction
parameters values exceed the optimal levels.
110,116
Recent studies using heterogeneous catalysts (e.g., acidic and
basic solid resins immobilized lipases) have been reported. These
catalysts allow the use of different feedstocks, requiring lower
investment costs and less downstream process equipment, as
compared to supercritical processes. Marchetti et al.
117
carried
out a conceptual design of these alternative production plants
with a techno-economical analysis and concluded that the
supercritical approach is not an economically feasible alternative,
due to its high operating costs.
Heterogeneous catalysts have some advantages, since they
can be easily separated from the reaction products, and reaction
conditions can be less intensive than those required under
supercritical conditions.
118
Most research on the use of heterogeneous catalysts has been
focused on solid base catalysts.
118,119
Solid acid catalysts have
been largely ignored for biodiesel synthesis, due to lower
reaction rates and undesired side reactions found for homoge-
neous mineral acids.
119
Nevertheless, since acid catalysts can
(98) Kaliangilee, I.; Grabe, D. F. J. Seed Technol. 1988, 12, 107113.
(99) Graham, S. A. CRC Crit. ReV. Food Sci. Nutr. 1989, 28, 139173.
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Ind. Crops Prod. 2008, 27, 279287.
(101) Geller, D. P.; Goodrum, J. W.; Knapp, S. J. Ind. Crops Prod.
1999, 9, 8591.
(102) Geller, D. P.; Goodrum, J. W.; Siesel, E. A. Trans. ASAE 2003,
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(103) Raccuia, S. A.; Melilli, M. G. Field Crop Res. 2007, 101, 187
197.
(104) Fernandez, J.; Curt, M. D.; Aguado, P. L. Ind. Crops Prod. 2006,
24, 222229.
(105) Encinar, J. M.; Gonzalez, J. F.; Rodriguez, J. J.; Tejedor, A. Energy
Fuels 2002, 16, 443450.
(106) Encinar, J. M.; Gonzalez, J. F.; Sabio, E.; Ramiro, M. J. Ind. Eng.
Chem. Res. 1999, 38, 29272931.
(107) Lapuerta, M.; Armas, O.; Ballesteros, R.; Fernandez, J. Fuel 2005,
84, 773780.
(108) Canakci, M.; Gerpen, J. V. Trans. ASAE 2001, 44, 14291436.
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(110) Ma, F. R.; Hanna, M. A. Bioresour. Technol. 1999, 70, 115.
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Lohrlein, H. P.; Krause, R. Trans. ASAE 2002, 45, 525529.
(112) Ma, F.; Clements, L. D.; Hanna, M. A. Trans. ASAE 1998, 41.
(113) Dorado, M. P.; Ballesteros, E.; Arnal, J. M.; Gomez, J.; Gimenez,
F. J. L. Energy Fuels 2003, 17, 15601565.
(114) Di Serio, M.; Tesser, R.; Dimiccoli, M.; Cammarota, F.; Nastasi,
M.; Santacesaria, E. J. Mol. Catal A: Chem. 2005, 239, 111115.
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(116) He, H.; Wang, T.; Zhu, S. Fuel 2007, 86.
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Liu, Y.; Lopez, D. E. Catalysis 2006, 19, 4184.
simultaneously carry out the esterication and transesterication,
they could help in the processing low-cost feedstocks involving
nonedible oils with high content of FFA, thereby lowering
overall production costs.
43
Currently, there are extensive reports about enzyme-mediated
alcoholysis for biodiesel production. These processes are
classied into immobilized lipase,
120
whole cell catalyst,
121
and
liquid lipase-mediated alcoholeysis for biodiesel production.
122
Lipase enzymes from microorganisms such as Mucor miehei,
Rhizopus oryzae, Candida antarctica, and Pseudomonas cepacia
have shown suitability to be used for biodiesel production. They
catalyze both transesterication of TG and esterication of FFA
in one step. Enzymatic reactions are carried out at moderate
temperatures, providing high ester yields. This method cannot
be currently used in industry owing to high enzyme costs and
the problems related to its deactivation caused by feed impuri-
ties.
118
According to literature, lipase cost reduction constitutes
the major issue for lipase-mediated alcoholysis for biodiesel
industrialization. Generally speaking, there are two strategies
to reduce lipase cost. One method involves the development of
new lipases, fermentation optimization, and downstream pro-
cessing improvements. Another way is to improve/extend the
operational life of the lipase, which can be achieved through
enzyme immobilization.
122
Lipase-catalyzed transesterication of three nonedible oils
(jatropha, karanja, and putranjiva) has been carried out by
Haldar.
123
This author obtained the maximum yield using 3:1
methanol-to-oil molar ratio, at 40 C during 8 h. Shah et al.
57
used three different lipases (from Chromobacterium Viscosum,
Candida rugosa, and Sus scrofa porcine pancreas) in the solvent-
free transesterication of jatropha oil. Only the lipase im-
mobilized from C. Viscosum on Celite-545 provided an appre-
ciable yield (71%).
6. Genetic Modications to Optimize Biodiesel Fuel
Properties
Living beings can be improved by traditional Mendelian
approaches (e.g., classical agriculture and farming). Yet, there
are currently powerful molecular tools that can assist breeders
to improve species, breeds and cultivars in a quicker and more
efcient way. Besides, the use of molecular biology methodolo-
gies in general, and genetic engineering in particular, allows
genetic manipulations to produce transgenics that are not
possible with the Mendelian crosses, due to species-specic
sexual barriers. Genetic engineering techniques include the use
of site-directed mutagenesis, gene promoters, transcription
factors, antisense RNA, RNA interference (RNAi), etc. Durrett
et al.
18
discussed the ways in which molecular biology could
address some of the major issues related to biodiesel. The main
concerns focus on the increase of oil content in oilseed plants
and the improvement of the fatty acid prole to enhance the
fuel properties of biodiesel. Both targets are discussed in this
section.
6.1. Increasing Oil Content in Oilseed Plants. Viable
strategies to increase oil content in seeds have been developed,
although additional work is needed. In addition, research at an
early stage has also suggested several paths to produce oil in
vegetative tissue rather than in seeds. Durrett et al.
18
proposed
to combine these approaches to develop high-yield energy crops.
Moreover, genetic engineering allows the dwarng of the
stalks for easier harvesting, as well as to increase the harvest
index (seed yield divided by biomass). Although the genes
controlling dwarsm have an unknown function, many genes
that control height are known.
124
Genetic engineering has been
used to produce cuphea cultivars with reduced seed shattering
and increased seed oil.
125,126
6.2. Improving Fatty Acid Prole. Genetic modication of
fatty acid composition offers a method to address most fuel
property issues simultaneously. For example, the presence of
some metabolites (e.g., methyl palmitoleate and esters of
decanoic acid) could be increased. Both are strong candidates
to improve fuel properties, besides methyl oleate.
9
Provided that oils for both food and biodiesel markets need
raw material showing similar properties, that is, high monoun-
saturated fatty acids content, plant breeding to improve biodiesel
quality has been based until recently on goals and techniques
developed by oilseed breeders targeting edible oils markets.
They produced oils primarily composed of monounsaturated
oleic acid, together with some saturated acids, and as little of
the oxidation-prone linolenic acid as possible. Breeders have
been adopting both transgenic (including antisense RNA and
RNAi) and nontransgenic approaches for the generation of high-
oleate germplasm.
127
6.2.1. Transgenic Approaches. The high percentage of poly-
unsaturated fatty acids makes Camelina satiVa and HeVea
brasiliensis, among many other nonedible oils, more susceptible
to oxidation, thus being undesirable for fuel production and other
industrial applications. To improve the oxidative stability of
biodiesel some efforts have been carried out. Although a
traditional approach recommends the addition of antioxidants
to the fuel, a transgenic strategy consists on reducing the content
of unsaturated (particularly polyunsaturated) fatty acids present
in the input oil. An increased understanding of the pathways
involved in the synthesis of tocopherols and tocotrienols (natural
antioxidants present in plants) has provided transgenic strategies
to manipulate the levels of these antioxidants in soybeans and
other crops.
128,129
Such alterations could therefore be incorpo-
rated when developing oil crops for biodiesel.
Lu and Kang
130
developed an in planta method to generate
transgenic C. satiVa plants with less content of polyunsaturated
fatty acids. They demonstrated that C. satiVa is very susceptible
to Agrobacterium-mediated transformation by oral dipping
along with vacuum inltration. As visual selection marker, a
uorescent protein (DsRed) was used. A genetic improvement
of agronomic characters of C. satiVa oil, including the oilseed
fatty acid prole, has been carried out. New clones present less
content of polyunsaturated fatty acids and increased content of
monounsaturated acids.
In contrast to the dominating unsaturated C18 fatty acid,
medium-chain fatty acids (MCFA) are nearly absent in the oil
of traditional raw materials to produce biodiesel (soybean seeds,
sunower seeds, canola seeds, etc.). Modication of the
chemical composition in nonedible oils to higher contents of
C8-C14 fatty acids would provide new possibilities for oleo-
(120) Caballero, V.; Bautista, F. M.; Campelo, J. M.; Luna, D.; Marinas,
J. M.; Romero, A. A.; Hidalgo, J. M.; Luque, R.; Macario, A.; Giordano,
G. Process Biochem. 2009, 44, 334342.
(121) Li, W.; Du, W.; Liu, D. H. J. Mol. Catal., B 2007, 45, 122127.
(122) Du, W.; Li, W.; Sun, T.; Chen, X.; Liu, D. Appl. Microbiol.
Biotechnol. 2008, 79, 331337.
(123) Haldar, S. K.; Nag, A. Open Chem. Eng. J. 2008, 2, 7983.
(124) Gressel, J. Plant Sci. 2008, 174, 246263.
(125) Knapp, S. J.; Crane, J. M. Crop Sci. 2000, 40, 299300.
(126) Knapp, S. J.; Crane, J. M. Crop Sci. 2000, 40, 301301.
(127) Murphy, D. J. Eur. J. Lipid Sci. Technol. 2007, 109, 296306.
(128) Cahoon, E. B.; Hall, S. E.; Ripp, K. G.; Ganzke, T. S.; Hitz, W. D.;
Coughlan, S. J. Nat. Biotechnol. 2003, 21, 10821087.
(129) Karunanandaa, B.; Qi, Q. G.; Hao, M. Metab. Eng. 2005, 7, 384
400.
(130) Lu, C.; Kang, J. Plant Cell Rep. 2007, 27, 273278.
chemical usages. The esters of decanoic acid appear to be the
most suitable saturated shorter-chain esters to produce biodiesel
from fatty acids (esters of lauric acid present too high melting
point, whereas esters of octanoic acid exhibit too low cetane
number).
9
For this purpose, the genes responsible for the
accumulation of MCFA in cuphea oil have been transferred to
a target oil crop. The best result showed up to 7.9% of C10.
131
Unfortunately, the low yield of novel fatty acids in transgenic
Figure 1. Inuence of fatty acid prole of vegetable oils to produce biofuels on cetane number and oxidative stability.
Figure 2. Iodine value of methyl esters from different vegetable oils.
Figure 3. Kinematic viscosity of methyl esters from different vegetable oils.
Figure 4. Cetane number of methyl esters from different vegetable oils.
plants is a common problem and is one of the main reasons
that limit the widespread production of unusual fatty acids using
such approach.
18
It is clear that more basic and applied research
is needed to decipher the molecular basis underlying the plant
metabolism and physiology.
The direct use of cuphea oil as fuel was studied considering
that viscosity increases with the number of acyl carbons, and
decreases with the presence of double bonds.
35
Thus, low
molecular-weight triglycerides have lower viscosities than those
typically found in conventional plant oils. Low-molecular-weight
TAG, from tributyrin (4:0) to tricaprin (10:0), are predicted to
have better fuel atomization characteristics than conventional
TAG.
102
Seed oil with higher levels of tricaproin (6:0) and
tricaprylin from a mutant of Cuphea Viscosissima had a coking
index comparable to that of No. 2 diesel fuel.
101
However, one
of the main problems derived from the direct use of low-
molecular-weight triacylglycerols is the poor cold-temperature
ow properties.
Gressel
124
indicated that several nonedible oilseed plants could
be converted to efcient biofuel crops by rendering them less
toxic, using transgenic approaches. This author emphasized the
importance of both a control of toxic wild crops and genetic
engineering in the release of toxic compounds in nonedible
oilseed crops. To use the byproduct cake generated in the
process for animal feeding, the omission of curcin
132
and phorbol
ester from Jatropha curcas seeds,
133
the release of ricin from
castor oil, and the exclusion of cytotoxic compounds from
Pongamia pinnata and Calophyllum inophyllum are some goals
of transgenic modication for biodiesel production.
6.2.2. Mixed Approaches. Velasco et al.
134
studied the
inheritance of increased oleic acid concentration in a high-erucic
acid Ethiopian mustard mutant oil developed through mutagen-
esis. They found that the monogenic inheritance of increasingly
higher oleic acid levels in the high-erucic acid line could
facilitate the transfer of this trait to zero-erucic acid Ethiopian
mustard germplasm.
Recent isolation of a natural mutant of castor bean with high
oleic acid and low ricinoleic acid concentration diversies the
potential uses of castor oil.
135
Nevertheless, genetic engineering
of castor through silencing the fatty hydroxylase gene (respon-
sible for the conversion of oleic to ricinoleic acid) leads to
accumulation of high levels of oleic acid that would be of
interest to the biodiesel market.
135,136
Fatty acid composition of nonedible oils could be altered to
some extent through interspecic hybridization. However, a
more targeted approach would be to silence -9 or -12
desaturase genes to increase the accumulation of stearic or oleic
acids, respectively.
137
In summary, genetic engineering techniques can be used to
modulate (blocking, reducing, or enhancing) the gene expression
of selected genes and thus their downstream processing (translation
to peptides/proteins). Nevertheless, it should be taken into account
that once the gene expression of a particular gene is altered by
genetic engineering (which may block some metabolic pathways),
the cell may show altered regulatory behaviors, trying to compen-
sate the physiological alteration. This may represent the reduced
or increased synthesis of other metabolites in the metabolomic
(131) Stoll, C.; Luhs, W.; Zarhloul, M. K.; Brummel, M.; Spener, F.;
W., F. Eur. J. Lipid Sci. Technol. 2008, 108, 277286.
(132) Lin, J.; Li, Y.-X.; Zhou, X.-W.; Tang, K.-X.; Chen, F. Mitochon-
drial DNA 2003, 14, 311317.
(133) Makkar, H. P. S.; Aderibigbe, A. O.; Becker, K. Food Chem. 1998,
62, 207215.
(134) Velasco, L.; Fernandez-Martinez, J. M.; De Haro, A. Crop Sci.
2003, 43, 106109.
(135) Rojas-Barros, P.; de Haro, A.; Munoz, J.; Fernandez-Martinez, J.
Crop Sci. 2004, 44, 7680.
(136) Sujatha, M.; Reddy, T. P.; Mahasi, M. J. Biotechnol. AdVances
2008, 26, 424435.
(137) Liu, Q.; Singh, S. P.; Green, A. G. Plant Physiol. 2002, 129, 1732
1743.
(138) Banapurmath, N. R.; Tewari, P. G.; Hosmath, R. S. Renewable
Energy 2008, 33, 20072018.
(139) Vicente, G.; Martinez, M.; Aracil, J. Energy Fuels 2006, 20, 394
398.
(140) In Proceedings of the VI World renewable energy congress.
Korbitz, W., Ed., Brighton, UK, July 1, 2000; Permagon: Amsterdam,
Netherlands, pp 1258-1261.
Figure 5. Gross heat of combustion of methyl esters from different vegetable oils and its comparison to diesel fuel.
network. Thus, caution should be exercised when predicting the
phenotypic effects of genetic engineering approaches.
7. The Ideal Raw Materials to Produce Biodiesel: A
Comparative Study
Although studies about nonedible oils to produce biodiesel
can be found in the literature, comparative studies between them
are missing. Tables 3 and 4 show the most important fuel quality
parameters considering biodiesel from different raw materials.
Several authors have used different methodologies to analyze
properties, as well as different transesterication conditions, thus
making difcult the comparisons between results.
Banapurmath et al.
138
carried out comparative analysis of BTE
and exhaust emissions (HC, CO, and NO
x
) of a diesel engine
fueled with sesame, karanja, and jatropha oil methyl esters.
Results showed that BTE decreased with the use of biodiesel
from jatropha oil. Azam et al.
3
carried out an exhaustive study
about the fatty acid composition of 75 vegetable oils, proposing
mathematical calculation of CN, IV, and saponication value
of each oil. Results showed that oil methyl esters of 26 out of
the 75 (including Azadirachta indica, Calophyllum inophyllum,
Jatropha curcas and Pongamia pinnata) were suitable to be
used as biodiesel. Also, these biofuels meet the major specica-
tions of biodiesel standards on USA, Germany, and Europe.
However, a comparative study concerning biodiesel optimization
and engine performance of those oils was missing.
Vicente et al.
139
carried out a comparative study between
different raw materials (i.e., sunower, rapeseed, high- and low-
erucic Ethiopian mustard, and waste olive oils), all of them
suitable for biodiesel production in Spain. The FFA content of
these vegetable oils varied from 0.02 to 6.47% and were
transesteried with methanol using potassium hydroxide as
catalyst. Viscosity, peroxide value, and acid value were within
the EU biodiesel specications.
The optimization of most potential feedstock is either missing
or incomplete. In most cases, only some parameters have been
taken into consideration and optimized, not taking into account
all involved parameters.
90,92,93
Without a complete optimization
under methodologically homogeneous optimization process, a
comparison between different FAME yields depicted in Table
3 is not enough to provide as much useful information as it
could otherwise. Moreover, following an appropriate optimiza-
tion process, higher values of FAME yield could be expected.
As showed in Table 3, 12 vegetable oils have been proposed
as raw materials to produce biodiesel. However, the transes-
terication optimization has been carried out only for ve of
them, and in two cases only the catalyst amount was optimized.
To determine the best working conditions and to save resources,
optimization must be carried out for each raw material,
separately. In fact, many authors produce and test biodiesel
considering the optimization procedures developed by other
works, as a generic recipe. This could be acceptable in a
multifeedstock plant, where the target is to produce biodiesel
from different raw materials, without involving dramatic changes
in the working conditions. However, a previous customized
optimization, considering each oil individually, is strongly
recommended. This could help to both increase the knowledge
about the process and nd out the most suitable conditions in
case a multifeedstock is selected.
140
The optimization of the combination of several variables can
be accomplished in a reasonable time using an effective design
of experiments. The use of a screening process followed by a
multifactorial design or a surface response represents a powerful
solution that involves the following advantages: (1) more
information per experiment than unplanned approaches; (2)
reduced number and cost of experiments; (3) calculation of the
interactions among experimental factors within the range studied,
with better process understanding; and (4) easier determination
of the operational conditions for scale-up processes. The
screening process is one of the most powerful techniques of
design of experiments. With a small number of experimental
runs it is possible to select the most important factors that have
a signicant effect on response variable (in case of biodiesel
optimization should be the yield of the transesterication
reaction). The most common screening experiment techniques
are Taguchi and Plackett-Burman.
73
The inuence of fatty acid composition of different nonedible
oils, in terms of CN and oxidative stability, is shown in Figure
1. The most suitable fatty acid composition should contain high
percentage of monounsaturated fatty acids (as oleic and palmi-
toleic acids)
9,13
and minimum amounts of polyunsaturated acids
(such as linolenic acid). Likewise, cautious balanced ratios
between saturated and C18:2 are highly recommended.
Camelina satiVa oil, low erucic Brassica carinata oil and
HeVea brasiliensis seed oils exhibit less suitable fatty acid
proles for biodiesel production when compared to others, due
to their high percentage of polyunsaturated fatty acids (Figure
1 and Table 3). Also, it can be seen from Table 3 that they
exceed the IV value and the linolenic acid limit established by
the European biodiesel standard EN 14214. Figure 2 shows the
comparison of IV from different vegetable oils, according to
EN 14214. Indeed, methyl esters from Asclepias syriaca oil
shows the highest IV, due to its high content of linoleic acid.
Despite this, such fatty acid content is low. Biodiesel from
soybean oil also exceeds the IV limit established by the EN
14214, as depicted in Figure 2.
Due to the crucial importance of viscosity in engine perfor-
mance, Table 4 and Figure 3 show viscosity values from
different FAME samples. Only a few low-cost oils exceed
maximum values of kinematic viscosity established in the EN
14214, but none of them exceed the ASTM D 6751 limit.
Surprisingly, methyl esters from HeVea brasiliensis oil, which
presents a high unsaturated fatty acid content, also shows a high
viscosity value (see Tables 3 and 4).
81
This could be due to the
formation of high molecular-weight compounds from polyun-
saturated fatty acids.
14
However, Brassica carinata (high and
low erucic acid) does not show the same trend, providing similar
average of mono- and polyunsaturated compounds.
83,113
As mentioned for transesterication optimization studies, there
is also a lack of information related to engine performance and
(141) Krisnangkura, K. J. Am. Oil. Chem. Soc. 1986, 73, 471474.
(142) Knothe, G.; Steidley, K. R. Fuel 2005, 84, 10591065.
(143) Demirbas, A. Energy Sources 2003, 25, 721728.
(144) Demirbas, A. Energy ConVers. Manage. 2000, 41, 16091614.
(145) Biodesel Report. Kingsman S. A.; Maillard, X., Ed.; Lausanne:
Switzerland Kingsman: Paris, 2007. (http://www.kingsman.com/images/
SampleRpts/Biodiesel/070919WeeklyBiodieselReport.pdf).
(146) Om Tapanes, N. C.; Gomes Aranda, D. A.; de Mesquita Carneiro,
J. W.; Ceva Antunes, O. A. Fuel 2008, 87, 22862295.
(147) Eevera, T.; Rajendran, K.; Saradha, S. Renewable Energy 2009,
34, 762765.
(148) Bernardo, A.; Howard-Hildige, R.; OConnell, A.; Nichol, R.;
Ryan, J.; Rice, B.; Roche, E.; Leahy, J. J. Ind. Crops Prod. 2003, 17, 191
197.
(149) Curt, M. D.; Sanchez, G.; Fernandez, J. Biomass Bioenergy 2002,
23, 3346.
(150) Agarwal, D.; Agarwal, A. K. Appl. Therm. Eng. 2007, 27, 2314
2323.
(151) Sarin, R.; Sharma, M.; Sinharay, S.; Malhotra, R. K. Fuel 2007,
86, 13651371.
exhaust emissions using different biofuels and their blends with
diesel fuel. Moreover, there is a remarkable difference in the
technical procedures. Some reports do not present their results
referred to standard conditions, thus preventing the comparison
with different engines and places (atmospheric conditions,
latitude, altitude, fuels, etc.). Table 4 summarizes engine
performance and emissions using 100% biodiesel from different
raw materials. Due to the correlation between BSFC and the
heating values,
21,30
it should be expected that FAME with similar
heating values depict similar BSFC and BTE values. According
to Table 4 and Figure 5, a discrepancy between BSFC obtained
for Pongamia pinnata, Madhuca indica, and Brassica carinata
methyl esters (that exhibit an increased BSFC compared to diesel
fuel in the range of 8%, 26% and 13%, respectively) and their
gross heat of combustion (around 36000 kJ/kg in every case)
can be found. This incongruity conrms the difculty of the
comparisons of the results achieved from different engine tests
carried out using a wide range of diesel engines of different
sizes and types, under different working conditions, and remarks
the necessity to establish standard condition for engine tests.
On the basis of these partial results, it is only possible to
state that Calophyllum inophyllum, Brassica carinata (low
erucic) and Azadirachta indica methyl esters may show better
engine performances in terms of BTE and BSFC, due to their
high heating values (Figure 5), as compared to the other
sustainable FAME. However, engine tests for Azadirachta indica
are missing.
Figures 2-Figures 5 show the comparison between FAME
from vegetable oils (with a great potential for a sustainable
production of biodiesel) and other conventional biodiesel (e.g.,
rapeseed oil methyl ester and soybean oil methyl ester). It should
be noticed that mostly all of these raw materials satisfy the
biodiesel ASTM standard. However, only six biodiesel from
sustainable vegetable oils (Calophyllum inophyllum, Termi-
nalia catappa, Azadirachta indica, Madhuca indica, Pongamia
pinnata and Jatropha curcas) are under European standard
limits. According to Figure 5, they have a high heat of
combustion (even higher than the outspread soybean oil methyl
ester, and above 36 000 kJ/kg). C. inophyllum and A. indica oil
methyl esters provide the highest caloric values (Figure 5).
The fatty acid prole of the previously mentioned six vegetable
oils (Figure 1) show similar composition for C. inophyllum, T.
catappa, A. indica, and M. indica oils (40% of unsaturated fatty
acids and 40% of monounsaturated fatty acids), whereas P.
pinnata and J. curcas oils have about 20% of saturation and
between 40 and 70% of monounsaturated acids. According to
Table 4, these two vegetable oils exhibit better low-temperature
ow properties than other oils with higher level of saturation.
Among them, J. curcas oil shows lower oxidation stability than
P. pinnata oil, due to its higher content of di- and poly-
unsaturated fatty acids (Figure 1). C. inophyllum, P. pinnata,
and J. curcas oils show high FFA content (22, 8.3, and 15%,
respectively), whereas the latter exhibits different values,
depending on the quality of the feedstock. High FFA content
represents the most important drawback for an economically
sustainable implementation of biodiesel.
8. Conclusions
Since Rudolf Diesel ran his engine on peanut oil in 1900,
research about biofuels for diesel engines has experienced
signicant growth, mainly during the last decades. Different oils
and fats have been transesteried and tested in diesel engines.
However, some basic and crucial issues related to this topic
remain to be addressed:
(1) There is a correlation between fatty acids composition
and transesterication optimization results. However, a consid-
erable number of papers have used a common recipe, most likely
decreasing transesterication yield and increasing costs, depend-
ing on the raw material. In too many cases, when optimization
has been carried out, not all involved parameters have been taken
into consideration.
(2) When biodiesel performance and emissions have been
tested, a lack in the use of a standard methodology has been
observed. This makes the comparison between different biofuels
difcult.
(3) Among the studied low-cost vegetable oils, biodiesel from
Calophyllum inophyllum, Azadirachta indica, Terminalia cat-
appa, Madhuca indica, Pongamia pinnata, and Jatropha curcas
oils t both the EN 14214 and the US ASTM D 6751-02
standards. Despite that none of them is considered to be the
ideal biodiesel that ensures a perfect diesel engine behavior,
biodiesel from P. pinnata and J. curcas oils are more suitable
to be used under cold climates when compared to the others.
(4) In search of the ideal biodiesel composition, high presence
of monounsaturated fatty acids (as oleic and palmitoleic acids),
reduced presence of polyunsaturated acids, and controlled
saturated acids content are strongly recommended features.
C18:1 and C16:1 are the best-tting acids in terms of oxidative
stability and cold weather behavior. Genetic engineering and
transgenesis should focus on the exclusion of undesirable fatty
acids, through reducing or blocking the gene expression of the
corresponding coding genes. That can be coupled with the
enhancement of the expression of desirable target genes, leading
to the generation of the appropriate fatty acids.
(5) Biodiesel production has been questioned lately by some
social organizations and political actions, which may represent
some serious misrepresentations. Even if most of such anti-
biodiesel arguments are invalid, some warranties must be
provided. Among the conditions that could increase biodiesel
popularity are the use of nonedible raw materials and the
compromise of noninterference with lands for food crops. Only
by providing a socially accepted alternative energy could
biodiesel eventually be considered a transitional energy, until
more appropriate renewable energies such as nuclear fusion are
developed.
Acknowledgment. Authors gratefully acknowledge support for
this research from the Spanish Ministry of Education and Science
(ENE2007-65490/ALT) and from Junta de Andaluc a, Spain
(Grupo PAI TEP 169, BIOSAHE). Special thanks are given to Mr.
Christian Schellert (Fachgebiet Agrartechnik, University of Kassel,
Germany) for excellent assistance.
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The Ideal Vegetable Oil-based Biodiesel Composition: A Review of

Social, Economical and Technical Implications

Department of Chemical Physics and Applied Thermodynamics.

Department of Agricultural Engineering.

Department of Analytical Chemistry.

. Bioresour. Technol. 2009, 100, 261268.

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