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Top Catal (2010) 53:714–720

DOI 10.1007/s11244-010-9457-0

ORIGINAL PAPER

Biodiesel: Current Trends and Properties


Gerhard Knothe

Published online: 13 April 2010


Ó GovernmentEmployee: U.S. Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research 2010

Abstract Biodiesel, an alternative to petroleum-derived in the search for additional feedstocks. Among the addi-
diesel fuel, is defined as the mono-alkyl esters of vegetable tional feedstocks are animal fats (for example, beef tallow)
oils and animal fats. Several current issues affecting bio- [4, 5] and used cooking or frying oils [6, 7]. Although these
diesel that are briefly discussed include the role of new feedstocks have more favorable economics due to lower
feedstocks in meeting increased demand for biodiesel and costs, their supply does not suffice to solve the availability
circumventing the food versus fuel issue, biodiesel pro- problem. Besides the issues of supply and economics, in
duction, as well as fuel properties and their improvement. recent years the food versus fuel issue has gained attention,
i.e., that a potential source of food (edible vegetable oil)
Keywords Biodiesel  Fatty esters  Fuel properties  should not be used for fuel purposes due to effects on food
Algae  Genetic modification  Microbiology  prices and land-use change. While this issue is complex, it
Vegetable oils has provided significant incentive to the search for addi-
tional feedstocks not affected by this issue. Some potential
feedstocks of interest in this connection are algae [8–11]
1 Introduction and jatropha [12–14].
Regardless of the feedstock, all biodiesel fuels need to
The search for alternative and renewable sources of energy meet the specifications in standards such as ASTM D6751
to diminish the dependence on fossil fuels has caused fuels [3] and EN 14214 [15]. Also, some of the technical prob-
derived from biological sources to be increasingly scruti- lems such as poor cold flow and oxidative stability prop-
nized and utilized. Biodiesel [1, 2], defined as the mono- erties can affect biodiesel from any feedstock. Therefore,
alkyl esters of vegetable oils or animal fats [3] and derived the issue of fuel composition of biodiesel, i.e. the mono-
from these feedstocks by transesterification, is probably the alkyl esters largely comprising this fuel, is very significant
most commonly used biofuel as a replacement for petro- as technical problems may counteract any solutions to the
leum-derived diesel fuel (petrodiesel). social and economic aspects mentioned above. Therefore,
Commonly biodiesel has been obtained from commod- this article briefly summarizes the need for additional
ity vegetable oils such as soybean, rapeseed (canola), palm, biodiesel feedstocks taking aspects of technical viability as
and sunflower oils. The observations that such oils can expressed by fuel properties into consideration.
replace only a few percent of the petrodiesel market and
that biodiesel from these feedstocks is more expensive than
petrodiesel (unless subsidized in some form) have resulted 2 Discussion

2.1 Sources and Availability


G. Knothe (&)
National Center for Agricultural Utilization Research,
The use of vegetable oils as a source of energy to power
Agricultural Research Service, U.S. Department of Agriculture,
1815 N. University St., Peoria, IL 61604, USA diesel engines is not a new concept. Indeed, it is almost as
e-mail: gerhard.knothe@ars.usda.gov old as the diesel engine itself. At the 1900 World

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Exposition in Paris, a diesel engine operated on peanut oil especially for rapeseed (canola) [27]. However, the use of
as reported by Rudolf Diesel, the inventor of the engine soy-based biodiesel was reported to lead to a reduction of
that bears his name, himself [16, 17]. The background was greenhouse gases by 41–57% [28, 29], with algae-based
that the French Government at the time was interested in fuels possibly faring even better [30], but another study
providing its tropical colonies with a local source of energy stating that the total environmental balance is not clear
[16, 17]. The theme of energy independence, especially for [31]. Also, the issue of land-use change appears to be more
the colonies of European countries but also to some extent complex than simple changing of land use for the sake of
in Brazil, China, India and elsewhere, can be observed in producing biofuels. This is exemplified by soybeans, which
numerous literature sources from the 1920s to the late yield about 20% oil as potential source for biodiesel and
1940s concerned with vegetable oils as fuels [18]. A fuel 80% protein, which can be used as animal feed. Thus,
meeting the current definition of biodiesel was also pro- should soybeans indeed be grown for their oil content, an
duced and tested during this time with a Belgian patent excess of soy protein should result, making animal nutri-
dating from 1937 appearing to be the first report on bio- tion and production less expensive with potentially corre-
diesel [19]. Reports from 1942 deal with this subject in sponding effects on consumption of animal products by
more detail, especially the use of ethyl esters of palm oil humans and negating effects of the demand for fuel. Fur-
[20, 21]. The biodiesel discussed in these reports was thermore, a question that has found little to no attention in
produced by acid catalysis. During what may be termed the the literature is if population growth, accompanied by an
‘‘age of petroleum’’, research on alternative and renewable increasing need for food and fuel as well as by increasing
energy sources was largely dormant until the energy crises urbanization, is the major and ultimate driving force for
of the 1970s and early 1980s led to a revival of interest in any land-use change.
this area. The first report of biodiesel from ‘‘modern’’ times In any case, increasing focus is currently being placed
appears to date from 1980 [22, 23]. The conditions for on potential sources of biodiesel that avoid the food versus
base-catalyzed production of biodiesel, which is also the fuel issue (the food versus non-food use of vegetable oils
basis of its commercial production, were established a few appears to exist only for fuels use as no concerns have been
years later [24]. It is important to note that the major reason raised about other non-food products), i.e., inedible oils.
for using biodiesel instead of the neat vegetable oils is its Besides used cooking or frying oils, several sources of
reduced viscosity, which is close to that of petrodiesel. The triacylglycerol-containing materials have achieved promi-
viscosity of vegetable oils, approximately an order of nence in this area, most notably jatropha oil [12–14] and
magnitude higher than that of petrodiesel, can lead to algae [8–11]. Other characteristics of jatropha that are
operational problems such as engine deposits. being promoted in this connection are that it can grow on
Besides extensive research in the area of biodiesel in marginal lands, not competing with other crops, and
recent times, standards for a commercial biodiesel product requires only little maintenance, while in the case of algae,
have been developed around the world. Especially the the potentially high yield per unit of land is being pro-
European standard EN 14214 [15] and the American moted. However, the properties of biodiesel derived from
standard ASTM D6751 [3] have found attention as jatropha may be problematic under some conditions (see
guidelines for standards elsewhere. Emphasis was origi- text below) while problems with algae include growth,
nally placed on commodity oils such as rapeseed (canola), isolation and harvesting as well as overall economics. Even
soybean, palm and sunflower oils for biodiesel production these additional sources will not suffice to replace all pet-
due to their relatively large production volume. On the rodiesel fuel. And besides the economic, social and polit-
other hand, this large production volume is connected to ical issues mentioned above, it must be considered that the
the fact that these oils are largely used for physiological properties of the fuels obtained from the various feedstocks
purposes such as human nutrition and food preparation. ultimately play a significant role if there will be sustained
With the expanding interest in and production of biodiesel, interest in the use of biodiesel from these feedstocks. Thus
some production expansion of these oils was dedicated to the economic and other issues discussed above are inex-
fuel production. This production expansion has raised tricably intertwined with the marketability of a fuel based
concerns about the effect on the price of food, what is on its properties.
termed land-use change (agricultural production for the
sake of producing biofuels on previously virgin land or 2.2 Commercial Biodiesel Production
change of already existing agricultural production from
food to fuel use) and accompanying carbon footprint, Biodiesel production has increased significantly worldwide
which has especially affected palm oil [25, 26], as well as in the last decade. In the United States, estimated biodie-
other issues such as increased use of fertilizer and nitrous sel production increased from 2 million gallons (=7.56
oxides emissions from agricultural production as discussed million liters; approximately 6,700 metric tons) in

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2000–700 million gallons (=2.646 billion liters; approxi- catalyzed transesterification on the remaining material
mately 2.33 million metric tons) in 2008, with the greatest [34]. Besides the desired mono-alkyl esters, glycerol is
production increase occurring in the last few years [32]. In formed as co-product during transesterification. A major
June 2009, production capacity in the United States was advantage of base-catalyzed transesterification is the mild
given as 2.69 billion gallons (approximately 10.17 billion reaction conditions, which for the production of methyl
liters; approximately 8.97 million metric tons) [32]. In esters typically are 1 h at 60–65 °C and ambient pressure,
Europe (EU countries), estimated biodiesel production 1% catalyst and a molar ratio of alcohol to oil of 6:1. The
increased from 1.065 million metric tons in 2002– product is typically washed with water after the reaction
7.715 million metric tons in 2008 [33]. The largest bio- and removal of the glycerol phase. The yield from this
diesel producer in the EU and the world is Germany with transesterification procedure is typically very high, usually
an increase in biodiesel production from 450,000 metric more than 96%, and generally does not depend on the fatty
tons in 2002–2.819 million metric tons in 2008. France as acid profile of the feedstock. When using alcohols other
the second largest biodiesel producer in the EU increased than methanol, some changes to the reaction conditions are
biodiesel production from 366,000 metric tons in 2002– necessary such as higher reaction temperature (around the
1.815 million metric tons in 2008. The third largest pro- boiling point of the alcohol) and other effects may occur
ducer in the EU, Italy, expanded biodiesel production from such as the possible formation of emulsions when pro-
210,000 metric tons in 2002–595,000 metric tons in 2008. ducing ethyl esters. Small amounts of triacylglycerol
Biodiesel production capacity in the EU for 2009 is esti- starting material and mono- and diacylglycerols formed as
mated at 20.909 million metric tons, 5.2 million thereof in intermediates can remain in the finished product as do
Germany, 2.505 million in France, 3.656 million is Spain, traces of glycerol co-product, alcohol and catalyst. These
1.91 million in Italy, and 1.036 million in The Netherlands minor components (impurities) are limited in biodiesel
[33]. Besides these examples, biodiesel production has standards by corresponding specifications. These minor
increased significantly in other countries around the world, components can influence fuel properties.
Brazil and Malaysia being notable examples. Numerous other catalysts and catalytic procedures have
been developed for the synthesis of biodiesel including
2.3 Transesterification heterogeneous catalysis and enzymatic processes, often
under the aspect of permitting lower quality feedstocks to
As mentioned above, base catalysis is the most common be used directly, or using other alcohols without significant
process in the transesterification of an oil or fat with an change of reaction conditions or ease of catalyst separation.
alcohol to give biodiesel (see Fig. 1 for the principle of the Some reviews are [35–56].
transesterification reaction). Bases such as NaOH or KOH
have been commonly applied but alkoxides such as 2.4 Fatty Acid Composition and Fuel Properties
NaOCH3 have the advantage that water formation
according to the reaction XOH ? ROH ? H2O ? ROX Both building blocks of fatty esters, the fatty acid chain and
(X = Na or K, R = alkyl) is not possible. Both water and the alcohol moiety, influence biodiesel fuel properties and
free fatty acids should be kept to a minimum in base-cat- varying either can lead to a change in fuel properties.
alyzed transesterification [24]. As lower quality feedstocks However, the varying fatty acid profiles of the feedstocks
such as used cooking oils have high free fatty acid content, used for biodiesel production are the main parameter cas-
an acid-catalyzed pre-treatment is necessary to reduce the ing changes in biodiesel fuel properties influenced by the
free fatty acid content (thus converting the free fatty acids structure of fatty esters. The properties of biodiesel largely
to alkyl esters) to a level acceptable for carrying out base- influenced by the fatty ester profile are discussed here
briefly.
O

CH2-O-C-R CH2-OH 2.5 Cetane Number and Combustion


O O
Catalyst The cetane number (CN) is a dimensionless descriptor
CH-O-C-R + 3 R OH 3 R -O-C-R + CH-OH
related to the ignition delay time a fuel experiences upon
O
injection into the combustion chamber of a diesel engine.
CH2-O-C-R CH2-OH The higher the CN, the shorter the ignition delay time and
vice versa. A cetane scale using hydrocarbons has been
Triacylglycerol Alcohol Alkyl ester Glycerol
established with hexadecane being the high CN reference
(Vegetable oil) (Biodiesel)
compound (CN = 100). The CN is included in biodiesel
Fig. 1 Principle of the transesterification reaction standards with prescribed minimum values of 47 (ASTM

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D6751) and 51 (EN 14214). The CN of fatty esters oxidative stability and vice versa, although a number of
increases with increasing saturation and increasing chain other factors influence oxidative stability considerably.
length [57, 58]. Accordingly, the CN of esters of palmitic Factors promoting oxidation are the presence of air, light,
and stearic acids is [80 [56], the CN of methyl oleate is in elevated temperatures and presence of extraneous materi-
the range of 55–58, that of esters of linoleic acid around 40 als. Oxidative stability is addressed in biodiesel standards
and that of esters of linolenic acid around 25. Thus bio- by the EN 14112 standard (so-called ‘‘Rancimat’’), which
diesel fuels with high amounts of saturated fatty acids tend prescribes a minimum induction time of 3 h (ASTM
to have higher CN while fuels with high amounts of D6751) or 6 h (EN 14214) for a sample subjected to its
polyunsaturated fatty acid chains tend to have lower CN. conditions. The European biodiesel standard contains some
Increasing CN to a certain level (around 60) has been specifications that are also related to oxidative stability,
brought into connection with decreasing NOx exhaust namely the iodine value, which is a problematic inclusion
emissions [59]. Effects of compound structure on regulated [64], content of linolenic esters and content of esters with
exhaust emissions (besides NOx, these are particulate more than three double bonds.
matter, hydrocarbons and carbon monoxide) similar to the
effect on CN have been observed [60, 61]. The CN of soy 2.8 Cold Flow
methyl esters is in the range of 48–52 and that of rapeseed
(canola) methyl esters slightly higher in the range of The low-temperature properties of biodiesel are also
52–55, with biodiesel fuels derived from highly saturated influenced by the properties of the individual components.
feedstocks displaying even higher CN. The melting points of fatty esters generally increase with
chain length (although chains with odd numbers of carbons
2.6 Viscosity have slightly lower melting points that the preceding even-
numbered chain) and increasing saturation. Thus mixtures
Viscosity, in the form of kinematic viscosity, is specified in such as biodiesel exhibit melting ranges, which is reflected
biodiesel standards with the ranges being 1.9–6.0 mm2/s in the specifications used in biodiesel standards. The cloud
(ASTM D6751) and 3.5–5.0 mm2/s (EN 14214). Since point (CP) is the temperature at which the first solids
viscosity increases with decreasing temperature, handling appear in a fuel but the fuel can still flow, although these
of fuels at lower temperatures is facilitated by lower vis- solids can lead to fuel filter plugging [65]. The pour point
cosity. The viscosity of a fatty ester increases with (PP), usually a few degrees below the cloud point, is the
increasing chain length and increasing saturation [62]. temperature at which the fuel can no longer be freely
However, only cis double bonds cause a noticeable poured. Several other methods exist for determining the
reduction of viscosity as esters with trans double bonds low-temperature properties of biodiesel, which are the cold
display viscosity similar to their saturated counterparts filter plugging point (CFPP) and low-temperature flow test
[62]. Typical values for kinematic viscosity are around (LTFT) [65]. The cloud point and CFPP are included in
4.0–4.1 mm2/s for soy methyl esters and 4.4 mm2/s for biodiesel standards but are ‘‘soft’’ specifications, the CP in
rapeseed (canola) methyl esters. ASTM D6751 requiring a report and the CFPP in EN
14214 varying with time of year and geographic location.
2.7 Oxidative Stability Typical values for the CP of soy-based methyl esters are
approximately 0 °C and -3 °C for rapeseed (canola)-
The presence of double bonds in the chains of unsaturated derived methyl esters, while methyl esters fuels with high
esters contained in biodiesel is the structural cause why contents of saturated fatty acid chains (palm oil-, waste
biodiesel is susceptible to autoxidation, i.e., reaction with cooking oil-, animal fat-derived) can have CP of around
oxygen in air. The allylic CH2 positions in the fatty acid 15 °C or even slightly higher. That alternative feedstocks
chains are those susceptible to oxidation with the bis-allylic as discussed above do not necessarily address the issue of
positions in polyunsaturated fatty acids, such as linoleic fuel properties is shown jatropha-derived biodiesel which
acid and linolenic acid being even more prone to autoxi- has a higher content of saturated fatty esters than soybean
dation. Thus, the autoxidation of unsaturated fatty com- oil [12] and thus poorer low temperature properties. Esters
pounds proceeds with different rates depending on the derived from ethanol, iso-propanol or other branched
number and position of double bonds. The species formed alcohols tend to have lower CP.
during the oxidation process cause the fuel to eventually
deteriorate. Relative rates of oxidation given in the litera- 2.9 Lubricity
ture [63, references therein] are 1 for oleates (methyl, ethyl
esters), 41 for linoleates, and 98 for linolenates. Thus, The advent of low-sulfur petrodiesel fuels and, more
biodiesel fuels with higher unsaturation tend to have lower recently, ultra-low sulfur diesel fuels (ULSD) as required

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by regulations in the United States, Europe and elsewhere, differently fatty acid profiles. An approach taking fuel
has led to failure of engine parts such as fuel injectors and properties but also the economic and political consider-
pumps as they are lubricated by the fuel itself. The poor ations briefly addressed in the present article has been
lubricity of low-sulfur petrodiesel fuels requires additiza- discussed [78]. Algae can be modified to increase lipid
tion or blending with another fuel of sufficient lubricity to production [79, 80]. The fatty acid profiles of various algal
regain lubricity [66]. Biodiesel, which has inherently high species have been reported [10]. The fatty acid profile of
lubricity, restores lubricity to such low-lubricity diesel the algae can apparently be tailored depending on various
fuels at blend levels of about 2% and higher [67, references parameters employed for their cultivation. Recently,
therein]. Lubricity is not specified in biodiesel standards microbiological approaches to biodiesel fuels with modi-
but is one of the major technical advantages of biodiesel. fied fatty ester profiles have been reported and that do not
use classical lipid feedstocks, using carbohydrates instead
2.10 Minor Constituents [81–84].
In conclusion, current research activities regarding bio-
Minor constituents can have significant effects on biodiesel diesel emphasize several areas. These include new feed-
properties as briefly summarized here. An example is the stock development, improvement of biodiesel properties,
mono- and diacylglycerols of saturated fatty acids and biodiesel production as well as others (for example,
increasing the cloud point of methyl soyate in concentra- exhaust emissions) not discussed here. These issues can be
tions as low as 0.1% [68]. On the other hand, monona- strongly intertwined.
cylglycerols (and free fatty acids) possess excellent
lubricity and are likely to a large part responsible for the Disclaimer Product names are necessary to report factually on
available data; however, the USDA neither guarantees nor warrants
lubricity of low-level blends of biodiesel with petrodiesel the standard of the product, and the use of the name by USDA implies
[67]. As another example, recently sterol glucosides (SG), no approval of the product to the exclusion of others that may also be
which have high melting points ([240 °C) and limited suitable.
solubility in biodiesel, have been identified as a cause of
precipitates forming when storing biodiesel in the cold or
sometimes even at ambient temperature [69–71]. Minor References
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