48 Biodiesel

R. C. Prince ExxonMobil Biomedical Sciences, Inc., Annandale, NJ, USA Roger.C.Prince@ExxonMobil.com

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2272 2 Chemical Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2272 3 Scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2273 4 Other Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2273 5 Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2273 6 Environmental Implications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2274 7 Research Needs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2274

K. N. Timmis (ed.), Handbook of Hydrocarbon and Lipid Microbiology, DOI 10.1007/978-3-540-77587-4_165, # Springer-Verlag Berlin Heidelberg, 2010

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1

Biodiesel

Abstract: Biodiesel is the term commonly reserved for the methylesters of the fatty acids in plant or animal triglycerides. The principal biodiesels in commerce today are methyl esters from soybean, oilseed rape and oilpalm, and they are typically blended at low levels (usually 2 or 5%, but up to 20%) with petroleum diesel. The fatty acid methyl esters are readily degraded under aerobic and at least some anaerobic conditions.

Introduction

Biodiesel is a non-petroleum-based diesel fuel, principally saturated, monoenoic and dienoic C16, C18 and/or C22 alkyl (usually methyl) esters, made by transesterication of plant oils. It should not be confused with hydrotreated vegetable and animal oils (Huber et al., 2007), sometimes known as green diesel, which are principally hydrocarbons, but are only beginning to be commercialized (Kalnes et al., 2007; Neste oil, 2008). Biodiesel can be used alone (when it is known as B100), or blended with conventional petroleum diesel (e.g., 5% biodiesel in petroleum diesel is known as B5), in relatively unmodied diesel-engine vehicles, although few manufacturers warrant their engines for fuels containing more biodiesel than B5 (National Biodiesel Board, 2008). Fatty acid methyl esters were probably rst used on a substantial scale in South Africa in the 1970s (Goering, 1981), when the ethyl ester of sunower (Helianthus annuus) oil was investigated as a transportation fuel, but research stopped with the fall of apartheid. Similarly, a palm oil ethylester was used in Belgium and the Belgian Congo prior to its independence, as discussed by Knothe (2001), but this also failed to achieve commercial viability. Recent use began in the 1990s and the name biodiesel was popularized in the US by the Soy Diesel Development Board, now the National Biodiesel Board (Ramadhas et al., 2004). The name has subsequently achieved international acceptance. Like other fuels, there are strict analytical standards that biodiesel must meet in the US and Canada, biodiesel (for blending) must meet ASTM standard D6751, and European Biodiesel must meet EN 14214, etc. Some states and nations mandate a minimum amount of biodiesel in all diesel fuel sold, typically 25%, and the US military often requires B20, at least for terrestrial applications.

Chemical Composition

Biodiesel is a mixture of mono-alkyl esters, and is distinct from the initially harvested triglycerides. It is typically made by transesterication of triglycerides with methanol and an alkaline catalyst to liberate the methyl esters (Ma and Hanna, 1999), although enzymatic options are under investigation (Ranganathan et al., 2008), and may offer environmental benets (Harding et al., 2008). The product is thus sometimes known as FAME (Fatty acid methyl esters) or VOME (Vegetable oil methyl esters). Although the transesterication works on triglycerides of animal or plant origin, virgin or used (e.g., discarded frying oils (Encinar et al., 2005)), production from fresh plant oils dominates the industry. The main source of biodiesel in Europe, the largest producer and consumer is oilseed rape (Brassica napus), while in the US biodiesel is made from soybean (Glycine max) oil. Palm oil (Elaeis guineensis) is the principal source of biodiesel in Malaysia and Thailand. These have subtly different compositions, as shown in > Table 1, but all have substantial unsaturated character on average more than one unsaturated bond per molecule. This property is one of the determinants of the relative instability of biodiesel compared to petroleum diesel (Leung et al., 2006; Knothe, 2007). Proprietary antioxidant mixes are typically added to B100 at 100200 ppm (Knothe, 2007).

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C18:3 Linolenic 8.6 8.3 0.3 C22:1 Erucic 50.9

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. Table 1 Fatty acid composition of the principal plant oils used to make biodiesel C12:0 Lauric Oilseed rape Soy Palm 0.9 1.3 C14:0 Myristic C16:0 Palmitic 2.7 10.3 43.9 C18:0 Stearic 2.8 4.7 4.9 C18:1 Oleic 21.9 22.5 39.0 C18:2 Linoleic 13.1 54.1 9.5

Processing converts these to the methyl esters in the biodiesel fuel. The top row indicates the number of carbon atoms in the fatty acid (first number) and the number of unsaturated bonds (second number thus C22:1 (erucic acid) has 22 carbons and a single unsaturated bond. All the fatty acids shown here are cis-unsaturated. The second row contains the trivial name of the acid; the trivial name for the fatty acid methyl ester would be methyl laurate for example. Data taken from Allen et al. (1999), but there is considerable plasticity in the oil content of different cultivars (Neff and Byrdwell, 1995). The European standard, EN14214 has a maximal limit for linolenic acid (C18:3) of 12%

Scale

Plant oils, the principal feedstock for biodiesel production, are mainly used for food, and only about 2% (2.2 billion liters) of current global production goes to biodiesel (Johnston and Holloway, 2007). In so doing, biodiesel provides about 0.125% of the diesel fuel used in the world (BP, 2007), USDA (2007) predicts US production rising to 2.7 billion liters in 2011/12, which would use about 23% of US soybean oil production, but provide less than 2% of predicted highway diesel fuel use in the United States. Canada and Argentina are both predicted to increase production of biodiesel to about 220 million liters per year in the next few years, from rapeseed and soybean respectively, with Brazil producing about half that, from soybean (USDA, 2007). The EU has a target of 5.75% of total transportation fuel use coming from biofuels by 2010, with biodiesel (from oil seed rape) accounting for two-thirds of it. Johnston and Holloway (2007) predict an upper limit of 51 billion gallons of biodiesel per year, produced in a total of 119 countries; some 2.9% of current diesel consumption of 1.8 trillion liters per year (BP, 2007). Whether this level can be achieved remains to be seen.

Other Sources

Although soy, rape and palm oils are the principal sources of biodiesel today, many other plant oils have been used on at least an experimental scale (e.g., Ramadhas et al., 2004; Pinto et al., 2005). Sunower was mentioned above, and Jatropha curcas is being planted on a large scale (Achten et al., 2008). Even algae are being considered (Chisti, 2007), although today they are only grown commercially for food and nutraceutical use.

Biodegradation

Biodiesel and mixtures with petroleum diesel are rapidly biodegraded in fresh (Prince et al., et al., 2006), and in activated 2008) and salt (DeMello et al., 2007) water, in soil (Lapinskiene sludge treatment plants (Pasqualinoa et al., 2006; Sendzikiene et al., 2007). The fatty acid

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Biodiesel

methyl esters are degraded at about the same rate as the n-alkanes (typically nC12 to nC24) that are the dominant components of petroleum diesel. Biodiesel is also degraded effectively under and Martinkus, 2007). anaerobic conditions in soil (Lapinskiene Furthermore, it is possible that biodiesel may stimulate the biodegradation of petroleum products. Miller and Mudge (1998) were apparently the rst to suggest that biodiesel might stimulate the biodegradation of other hydrocarbons in contaminated sediment, and Taylor and Jones (2001) showed that biodiesel did indeed stimulate the biodegradation of coal tar polycyclic hydrocarbons in soil, More recently, Pasqualinoa et al. (2006) reported that adding biodiesel to diesel or gasoline synergistically stimulated the mineralization of the petroleum product. Biodiesel also has solubilizing activity when applied to oiled sediments (Pereira and ndez-Alvarez and colleagues (2006, 2007) tested whether biodiesel Mudge, 2004), and Ferna could aid the clean-up of the Prestige spill on Spanish shorelines, but concluded that the benets were small with this very heavy fuel oil.

Environmental Implications

Biodiesel has been shown to be somewhat less toxic than petroleum diesel in acute toxicity tests with daphnia (Daphnia magna) and Rainbow Trout (Oncorhynchus mykiss) (Khan et al., 2007). Combustion of B20 in a diesel engine typically reduces the production of particulate matter, carbon monoxide and hydrocarbon in the exhaust by about 15%, with perhaps a small (0.5%) increase in NOx emissions (McCormick, 2007). A thorough life cycle assessment by Sheehan et al. (1998) concluded that soy biodiesel yields 3.2 units of biodiesel energy for every unit of fossil energy consumed in its life cycle, making it a rather more effective biofuel than ethanol (Hill et al., 2006). As discussed above, however, the scale at which biodiesel can possibly be used makes these benets somewhat tenuous.

Research Needs

The biodegradation of biodiesel under the many different anaerobic conditions (methanogenic, iron-reducing, sulfate-reducing, etc.) is not well characterized.

References
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