Fatty acid methyl ester, production

In this study, we have attempted to evaluate the efficacy of a technique for the production of the methyl ester of rapeseed oil via enzyme-catalyzed transesterifications using tert-butanol, a moderately polar organic solvent. We conducted experiments involving the alteration of several reaction conditions, including reaction temperature, methanol/oil molar ratio, enzyme amount, water content, and reaction time. The selected conditions for biodiesel production were as follows reaction temperature 40 °C, Novozym 435 5% (w/w), methanol/oil molar ratio 3 1, water content 1% (w/w), and 24h of reaction time. Under these reaction conditions, a conversion of approximately 76.1% was achieved. Further studies are currently underway to determine a method by which the cost of fatty acid methyl ester production might be lowered, via the development of enzyme-catalyzed methanolysis protocols involving a continuous bioprocess. 

Palomo JM, Munoz G, Fernandez-Lorente G et al. (2003) Modification of Mucor miehei lipase properties via directed immobilization on different heterofunctional epoxy resins. Hydrolytic resolution of (R,S)-2-butyroyl-2-phenylacetic acid. J Mol Catal B Enzym 21 201-210 Palomo JM, Ortiz C, Fernandez-Lorente G et al. (2005) Lipase-lipase interaction as a new tool to immobilize and modulate the lipase properties. Enzyme Microb Technol 36 447-454 Park EY, Sato M, Kojima S (2006) Fatty acid methyl ester production using Upase-immobilizing silica particles with different particle sizes and different specific surface areas. Enzyme Microb Technol 39(4) 889-896... 

Cao, P., Dube, M. A., Tremblay, A. Y. (2008a). High-purity fatty acid methyl ester production from canola, soybean, palm, and yellow grease lipids by means of a membrane reactor. Biomass Bioenergy, 32, 1028—1036. 

Park, E. Y, M. Sato, and S. Kojumo. 2006. Fatty Acid Methyl Ester Production Using Lipase-Immobilizing Silica Particles with Different Particle Sizes and Different Specific Surface Areas. Enzyme and Microbial Technology 39 889-896. 

Lukic, I., Kesic, Z., et al., 2016. Calcium diglyceroxide synthesized by mechanochemical treatment, its characterization and application as catalyst for fatty acid methyl esters production. Fuel 165, 159—165. 

Proton and NMR were used to characterize a-olefin sulfonates and the intermediate sultones (11). While the spectra of purified fractions were studied, this technique is potentially applicable to the characterization of commercial mixtures. Characterization of sodium a-sulpho fatty acid methyl ester products has also been described (12). A C NMR... 

The C10-C,8 fatty acids and fatty acid methyl esters, important intermediates for the production of surfactants, are almost exclusively produced by hydrolysis or a transesterification reaction of animal or vegetable fats and fatty oils. 

Schmid et al. studied in detail the sulfonation reaction of fatty acid methyl esters with sulfur trioxide [37]. They measured the time dependency of the products formed during ester sulfonation. These measurements together with a mass balance confirmed the existence of an intermediate with two S03 groups in the molecule. To decide the way in which the intermediate is formed the measured time dependency of the products was compared with the complex kinetics of different mechanisms. Only the following two-step mechanism allowed a calculation of the measured data with a variation of the velocity constants in the kinetic differential equations. 

The chemistry of fatty acid methyl ester (FAME) sulfonation is complicated and not yet fully elucidated, but it may be summarized as depicted in the following reaction scheme. The initial reaction between FAME and S03, although fast, is far from instantaneous. Two intermediate products are formed ... 

Transesterification of fat triglycerides is the predominant method for manufacture of mixed fatty acid methyl esters, and direct esterification of fatty acids (FA) is practiced if very selective cuts of product, in general as an intermediate detergent range alcohol, are desired. Methyl cocoate is a mobile, oily liquid above 25 °C with a yellow tint and a characteristic fatty pungent odor. FAME sulfonation to FAMES is technically possible but been rarely applied up to now (1990) (Table 13). 

The organic feedstock suitable for surfactant production (i.e., detergent-grade alkylates, fatty alcohols, ethoxylated fatty alcohols, a-olefins, and fatty acid methyl esters) and the S03/gas are fed concurrently. 

Alkaloids, amines, drugs, fatty acid methyl esters, hydrocarbons, petroleum products, phenols, solvents, waxes, general purposes... 

Biodiesel (fatty acid methyl ester (FAME)) production is based on transesterification of vegetable oils and fats through the addition of methanol (or other alcohols) and a catalyst, giving glycerol as a by-product (which can be used for cosmetics, medicines and food). Oil-seed crops include rapeseeds, sunflower seeds, soy beans and palm oil seeds, from which the oil is extracted chemically or mechanically. Biodiesel can be used in 5%-20% blends with conventional diesel, or even in pure form, which requires slight modifications in the vehicle. 

No-calories fat substitutes, such as sucrose polyesters (Olestra), which are synthesized from sucrose and fatty acid methyl esters, have been widely studied and several snacks fried in this medium are available in the market place. This product has no calories since digestive enzymes are not able to break it down due to structural impairment. A major disadvantage that prevents a wide acceptance of this product is related to the gastrointestinal discomfort that may be caused to some individuals (Dobraszczyk et ah, 2006, p. 104). 

D.G.B. Boocock, in Process for production of fatty acid methyl esters from fatty acid triglycerides , US, 2004. 

Parrish (1977) reviewed the research and development of lactose ester-type surfactants carried out by Scholnick and his colleagues (Scholnick et al. 1974, 1975 Scholnick and Linfield 1977). Their initial attempts to form lactose esters followed the same transesterification procedures that had been used with sucrose (a fatty acid methyl ester in N,N-dimethylformamide with potassium carbonate as the catalyst). Their successful approach was the reaction of lactose in N-methyl-2-pyrrolidone as the solvent with fatty acid chlorides, resulting in yields of 88 to 95% for esters of lauric, myristic, palmitic, stearic, oleic, and tallow fatty acids. The principal product was the monoester, which is important for detergent use, since diesters and higher esters of lactose are not water soluble. 

BASIC PROTOCOL I PREPARATION OF FATTY ACID METHYL ESTERS FROM LIPID SAMPLES CATALYZED WITH BORON TRIFLUORIDE IN METHANOL In this method, lipid samples are first saponified with an excess of NaOH in methanol. Liberated fatty acids are then methylated in the presence of BF3 in methanol. The resulting fatty acid methyl esters (FAMEs) are extracted with an organic solvent (isooctane or hexane), and then sealed in GC sample vials for analysis. Because of the acidic condition and high temperature (100°C) used in the process, isomerization will occur to those fatty acids containing conjugated dienes, such as in dairy and ruminant meat products, that contain conjugated linoleic acids (CLA). If CLA isomers are of interest in the analysis, Basic Protocol 2 or the Alternate Protocol should be used instead. Based on experience, this method underestimates the amount of the naturally occurring cis-9, trans-11 CLA isomer by -10%. The formulas for the chemical reactions involved in this protocol are outlined in Equation D1.2.1 Saponification RCOO-R + NaOH, RCOO-Na + R -OH v 100°C DC Esterification RCOO-Na + CH,OH r 3 v RCOO-CH, + NaOH ioo°c ... 

Precoated silica gel plates (silica gel 60) were purchased from Scientific Products. Bio-Sil A (200 - 400 Mesh) was obtained from Bio-Rad Laboratories. Fatty acid methyl esters, sphingosine and dihydrosphingosine were products of Supelco, Inc. as were 10% DEGS-PS, 3% SP-2340 and 3% OV-17 (all on Supelcoport support). N-acetyl and N-glycolyl neuraminic acid, DEAE-Sephadex A50 and neuraminidase type IX were obtained from Sigma Company. Ganglio-side standards from human brain and neutral glycosphingolipid standards from bovine erythrocytes were prepared in this laboratory. 

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. 

Fatty acid methyl esters (FAMEs) show large potential applications as diesel substitutes, also known as biodiesel fuel. Biodiesel fuel as renewable energy is an alternative that can reduce energy dependence on petroleum as well as air pollution. Several processes for the production of biodiesel fuel have been developed. Transesterification processes under alkali catalysis with short-chain alcohols give high yields of methyl esters in short reaction times. We investigated transesterification of rapeseed oil to produce the FAMEs. Experimental reaction conditions were molar ratio of oil to alcohol, concentration of catalyst, type of catalyst, reaction time, and temperature. The conversion ratio of rapeseed oil was enhanced by the alcohohoil mixing ratio and the reaction temperature. 

Biodiesel fuel was prepared by a two-step reaction hydrolysis and methyl esterification. Hydrolysis was carried out at a subcritical state of water to obtain fatty acids from triglycerides of rapeseed oil, while the methyl esterification of the hydrolyzed products of triglycerides was treated near the supercritical methanol condition to achieve fatty acid methyl esters. Consequently, the two-step preparation was found to convert rapeseed oil to fatty acid methyl esters in considerably shorter reaction time and milder reaction condition than the direct supercritical methanol treatment. The optimum reaction condition in this two-step preparation was 270°C and 20 min for hydrolysis and methyl esterification, respectively. Variables affecting the yields in hydrolysis and methyl esterification are discussed. 

Figure 4.1 GC/MS analysis of methyl esters prepared from a whole cell lipid extract of the YEpOLEX-PDesat-TnD11Z-transformed ole1 strain of Saccharomyces cerevisiae (A) total ion spectrum of fatty acid methyl esters resolved by capillary GLC (B) mass spectrum of the degradation products of the DMDS adduct of Z11 -16 Me in A. The diagnostic m/z values of the DMDS adduct of Z11-16 Me are labeled. (Reproduced with permission from Knipple et al., 1998. 1998 by The National Academy of Sciences.)...

The production of a,m-diesters from fatty esters can be realized via their SM as already explained, but it can also be performed by CM with methyl acrylate. The bulk CM of several unsaturated fatty acid methyl esters containing double bonds in different positions with methyl acrylate was studied by Rybak and Meier (Scheme 6) [43], C4 and C5 displayed very good activities with high conversions and CM selectivities. Among them, C5 showed the best performance for both methyl oleate (97% conversion, 92% selectivity, with 0.2 mol%) and methyl 10-undecenoate (99% conversion, 99% selectivity, with 0.1 mol%). The same conditions were successfully applied to methyl erucate and methyl petroselinate. The reaction conditions were further optimized, also considering the effect of 1,4-benzoquinone as additive for the reduction of double-bond isomerization [39], The CM of methyl 10-undecenoate and methyl acrylate worked with full conversions and high selectivity if five- to tenfold excess of methyl acrylate is used. Furthermore, using a 1 1 ratio between both reactants led, after optimization of the reaction... 

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. 

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