Biodiesel triglycerides transesterification

Starch and fatty acids are the main food constituents of biomass. Sugar is derived from starch by hydrolysis or directly by extraction from sugar cane or beet. Fermentation converts sugars into alcohol that can be directly used as fuel, or in principle can be used as the raw material of a bioreftnery plant for further upgrading. Triglycerides, derived from oil seeds, are used to be converted into biodiesel through transesterification processes (Fig. 1.14). 

Reproduced from Wilson, K., et al., 2008. The application of calcined natural dolomitic rock as a solid base catalyst in triglyceride transesterification for biodiesel synthesis. Green Chemistry, 654—659. Available at http //dx.doi.org/10.1039/b800455b with permission from The Royal Society of Chemistry. 

Biodiesel is a fuel derived from renewable natural resources such as soybean and rapeseed and consists of alkyl esters derived from transesterification of triglycerides with methanol. In spite of all the advantages of biodiesel, such as low emissiotts, biodegradability, non-toxicity, and lubricity, the major hurdle in penetration of biodiesel is its high cost because of the expensive food grade refined vegetable oil feedstock. 

Keywords Triacetin, transesterification, glycerol, triglyceride, biodiesel... 

Most biodiesel is produced today through transesterification of triglycerides of refined edible oils (Scheme 10.1). 

The use of heterogeneous basic catalysts for the transesterification of triglycerides has long been considered the main tool to reduce processing costs in the production of biodiesel, as it would lead to simplified operations and eliminate waste streams. 

The transesterification of triglycerides with methanol is a simple and straightforward process. It is commercially practiced worldwide in the production of FAMEs, which have become popular as a replacement for diesel known as biodiesel . The process consists of three separate equilibrium reactions that can be catalyzed by both acids and bases. (4) The overall process is described in Figure 3. Phase separation of the glycerin is the predominant driving force for this process. 

In homogeneous catalysis, the catalyst is in the same phase as the reactants and products. Here we will concentrate on homogeneous catalysis in the liquid phase. In the classic case, the reactant (also called the substrate) molecules and the catalyst are reacted in a solvent. For example, the transesterification of fatty acid triglycerides with methanol (Figure 1.10) is catalyzed by hydroxide (OH-) ions. This is an important process for making fatty acid methyl esters which are then used as biodiesel. 

Several processes for the production of biodiesel fuel have been developed by acid-, alkali-, and enzyme-catalyzed transesterification reactions (7-10). Transesterification, called alcoholysis, is the displacement of alcohol from an ester by another alcohol in a process similar to hydrolysis. Transesterification is represented by a number of consecutive and reversible reactions. The reaction step is the conversion of triglycerides to diglycerides, followed by the conversion of diglycerides to monoglycerides and of monoglycerides to glyceride at each step (11,12). 

A catalyst-free supercritical methanol method for biodiesel fuel production was proposed with the optimum conditions of 350°C, 20 MPa, a molar ratio of 42 in methanol, and a 4-min treatment period (12-13). This method has been proved to produce a high yield, because of simultaneous reactions of transesterification of triglycerides and methyl esterification of free fatty acids (10). The only shortcoming of this one-step method is that it requires a severe reaction condition compared with the conventional commercial method with acid or alkaline catalyst. Consequently, our method would require a special alloy to cover the high temperature and high pressure of the reaction system. 

The components of biodiesel are vegetable oils composed of glycerol esters of fatty acids. In the process of transesterification, the glycerol components of the triglyceride molecules are exchanged for methanol. The products are fatty-acid methyl esters consisting of straight saturated and unsaturated hydrocarbon chains, as described under chemical processes. 

Older biodiesel processes are essentially batchwise. The oil is submitted to transesterification in a stirred-tank reactor in the presence of a large amount of methanol, and base catalyst, mostly NaOH or KOH. An excess of methanol is necessary chiefly to ensure full solubility of triglyceride and keep the viscosity of the reaction mixture low, but also for shifting the chemical equilibrium. A minimum molar ratio methanoktriglyceride of 6 1 is generally accepted [16, 17, 29], The reaction... 

Fukuda et al. (2001) reported enzymatic transesterification using lipase has become more attractive for biodiesel production, since the glycerol produced as a by-product can easily be recovered and the purification of FAME is simple to accomplish. Lipases shown in Table 9.1 can effectively catalyze the transesterification of triglycerides and the problems mentioned above can be circumvented by using the enzyme. 

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