Abstract
Abundant and easily refined, petroleum has provided high energy density liquid fuels for a century. However, recent price fluctuations, shortages, and concerns over the long term supply and greenhouse gas emissions have encouraged the development of alternatives to petroleum for liquid transportation fuels (Van Gerpen, Shanks et al. 2004). Plant-based fuels include short chain alcohols, now blended with gasoline, and biodiesels, commonly derived from seed oils. Of plant-derived diesel feedstocks, soybeans yield the most of oil by weight, up to 20% (Mushrush, Willauer et al. 2009), and so have become the primary source of biomass-derived diesel in the United States and Brazil (Lin, Cunshan et al. 2011). Worldwide ester biodiesel production reached over 11,000,000 tons per year in 2008 (Emerging Markets 2008). However, soybean oil cannot be burned directly in modern compression ignition vehicle engines as a direct replacement for diesel fuel because of its physical properties that can lead to clogging of the engine fuel line and problems in the fuel injectors, such as: high viscosity, high flash point, high pour point, high cloud point (where the fuel begins to gel), and high density (Peterson, Cook et al. 2001). Industrial production of biodiesel from oil of low fatty-acid content often follows homogeneous base-catalyzed transesterification, a sequential reaction of the parent triglyceride with an alcohol, usually methanol, into methyl ester and glycerol products. The conversion of the triglyceride to esterified fatty acids improves the characteristics of the fuel, allowing its introduction into a standard compression engine without giving rise to serious issues with flow or combustion. Commercially available biodiesel, a product of the transesterification of fats and oils, can also be blended with standard diesel fuel up to a maximum of 20 vol.%. In the laboratory, the fuel characteristics of unreacted soybean oil have also been improved by dilution with petroleum based fuels, or by aerating and formation of microemulsions. However, it is the chemical conversion of the oil to fuel that has been the area of most interest. The topic has been reviewed extensively (Van Gerpen, Shanks et al. 2004), so this aspect will be the focus in this chapter. Important aspects of the chemistry of conversion of oil into diesel fuel remain the same no matter the composition of the triglyceride. Hence, although the focus in this book is on soybean oil, studies on other plant based oils and simulated oils have occasional mention in this chapter. Valuable data can be taken on systems that are simpler than soybean based oils, with fewer or shorter chain components. Sometimes the triglycerides will behave differently under reaction conditions, and when relevant, these have been noted in the text. Although the price of diesel fuel has increased, economical production of biodiesel is a challenge because of (1) the increasing price of soybean oil feedstocks and reagent methanol, (2) a distributed supply of feedstocks that reduces the potential for economies of scale, (3) processing conditions that include pressures and temperatures above ambient, and (4) multiple processing steps needed to reduce contaminant levels to ASTM specification D6751 limits (Vasudevan & Briggs 2008). Much of the cost of biodiesel production is related to the conversion of the oil to the methyl ester and so there has been an emphasis to research improved methods of converting soybean oil to biodiesel. However, most of these studies have taken place at the bench scale, and have not demonstrated a marked improvement in yield or reduced oil-to-methanol ratio in comparison with standard base-catalyzed transesterification. One aspect that has a short term chance of implementation is the improvement of the conversion process by the use of a continuous rather than batch process, with energy savings generated by combined reaction and separation, online analysis, and reagent methanol added by titration as needed to produce ASTM specification grade fuel. By adapting process intensification methods, recycled sources of soybean oil may also be used for diesel production, taking advantage of a lower priced feedstock material. Even if the economics of production are feasible, biodiesel distribution is complicated by thermal stability and degradation over time, and the physical properties of methyl esters make them undesirable for standard compression ignition engines in concentrations greater than 20% in a blend with diesel fuel. Generation of truly fungible fuel from biomass is now being investigated through a variety of routes. However, it is too early to judge which will become the most viable. The promise of soybean-generated biodiesel is that of a truly fungible, thermodynamically and economically viable technology bringing a biomass replacement to a petroleum product.
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