Transesterification biodiesel production

Schwarz et al. [85] studied the efficiency of different microstructured mixers followed by microchannels and their influence on the space time for obtaining high product yields. With increasing mass transfer performance of the micromixer and decreasing channel diameter of the microchannel reactors, shorter reaction times of several minutes at lower reaction temperatures compared to conventional batch reactor were obtained. Similar observations are reported for the synthesis of biodiesel in capillary microreactors [86] and in zigzag microchannels [87]. 

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In this communication a study of the catalytic behavior of the immobilized Rhizomucor miehei lipase in the transesterification reaction to biodiesel production has been reported. The main drawbacks associated to the current biodiesel production by basic homogeneous catalysis could be overcome by using immobilized lipases. Immobilization by adsorption and entrapment have been used as methods to prepare the heterogeneous biocatalyst. Zeolites and related materials have been used as inorganic lipase supports. To promote the enzyme adsorption, the surface of the supports have been functionalized by synthesis procedures or by post-treatments. While, the enzyme entrapping procedure has been carried out by sol-gel method in order to obtain the biocatalyst protected by a mesoporous matrix and to reduce its leaching after several catalytic uses. 

Animal fats or plant oils can pass on to the final biodiesel product particular characteristics derived from their differences in composition. For instance, if biodiesel is produced from the transesterification of a representative vegetable... 

Figure 7 depicts a simplified block flow diagram (BFD) for a typical biodiesel production process using base catalysis. In the first step, methanol and catalyst (NaOH) are mixed with the aim to create the active methoxide ions (Figure 4, step 1(b)). Then, the oil and the methanol-catalyst solution are transferred to the main reactor where the transesterification reaction occurs. Once the reaction has finished, two distinct phases are formed with the less dense (top) phase containing the ester products and unreacted oil as well as some residual methanol, glycerol, and catalyst. The denser (bottom) layer is mainly composed of glycerin and methanol, but ester residues as well as most of the catalyst, water, and soap can also be found in this layer. 

Generally, alkali-catalyzed transesterification is performed near the boiling point of the alcohol, but several researchers have reported high conversion yield at room temperature (8,14). Low reaction temperature was desirable, since reaction temperature was closely related to the energy cost of the biodiesel production process. 

Reaction temperature and time were significant operating parameters, which are closely related to the energy costs, of the biodiesel production process. Figure 7 shows the effect of reaction time on the transesterification of rapeseed oil at a catalyst concentration of 1%, molar ratio of 1 6, and 60°C. Within 5 min, the reaction was rapid. Rapeseed oil was converted to above 85% within 5 min and reached equilibrium state after about 10 min. Several researchers reported that the conversion of vegetable oils to FAME was achieved above 80% within 5 min with a sufficient molar ratio (8,11). For a reaction time of 60 min, linoleic acid methyl ester was produced at a low conversion rate, whereas oleic and linolenic methyl ester were rapidly produced. 

Biodiesel was prepared in various supercritical alcohol treatments with methanol, ethanol, 1-propanol, 1-butanol, or 1-octanol to study transesterification of rapeseed oil and alkyl esterification of fatty acid at temperatures of 300 and 350°C. The results showed that in transesterification, the reactivity was greatly correlated to the alcohol the longer the alkyl chain of alcohol, the longer the reaction treatment. In alkyl esterification of fatty acids, the conversion did not depend on the alcohol type because they had a similar reactivity. Therefore, the selection of alcohol in biodiesel production should be based on consideration of its performance of properties and economics. 

Meher, L.C., Vidya Sagar, D., Naik, S.N., Technical aspects of biodiesel production by transesterification, Renew. Sustain. Energy Rev., 10, 248-268, 2006 Minami, E., Saka, S., Kinetics of hydrolysis and methyl esterification for biodiesel production in two-step supercritical methanol process. Fuel, 85, 2479-2483, 2006... 

Fatty acids are obtained by fat splitting using water (hydrolysis), methanol (metha-nolysis), and base (saponification) of amines (aminolysis). Splitting with water or methanol can be considered transesterification because glycerol is liberated. The methanolysis is the reaction taking place in biodiesel production as the resulting product is called fatty acid methyl ester. 

In the past, glycerol was produced mainly from propene via allyl chloride and epi-chlorohydrin, a process developed by I. G. Farben and in operation since 1943. Today, glycerol is obtained almost completely as a coproduct in oleochemistry (fat splitting) and biodiesel production (transesterification) with 110 kg crude glycerol or 100 kg pure glycerol per ton of biodiesel [37]. With the rise in biodiesel production, the availability increased while the price decreased drastically by approximately 66% within 15 years in the United States [38]. 

Du, W., Xu, Y., and Liu, D. 2003. Lipase-catalyzed transesterification of soya bean oil for biodiesel production during continuous batch operation. Biotechnol. Appl. Biochem.,38,103-106. 

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. 

Li, L., Du, W., Liu, D., Wang, L., and Li, Z. 2006. Lipase-catalyzed transesterification of rapeseed oils for biodiesel production with a novel organic solvent as the reaction medium. /. Mol. Catal. B Enzym., 43, 58-62. 

The optimization of biodiesel production by transesterification of sunflower oil was studied (122). The best combination of process parameters was found to be three stoichiometric doses of methanol, 0.28% w/w of KOH, and 70°C temperamre. Several reports have been published on the properties of biodiesel manufactured with different fatty materials and on their performance in compression ignition engines, including information about sunflower oil and its esters (30, 31, 41, 123). Table 19 shows major properties of sunflower oil and its methyl esters. The physicochemical characteristics of these esters meet the norm specifications of different countries, even with improvements of some properties, such as the cetane number. 

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