Methyl ester product

The ruthenium acyloxymethyl complex produced by step 6 of Scheme 1 could, of course, eliminate the methyl ester product, but it also has the possibility of leading to a two-carbon product via alkyl group migration to coordinated CO (eq. 2). 

The process involves reacting the degummed oil with an excess of methyl alcohol in the presence of an alkaline catalyst such as sodium or potassium methoxide, reaction products between sodium or potassium hydroxide and methyl alcohol. The reaction is carried out at approximately 150°F under pressure of 20 psi and continues until trans-esterification is complete. Glycerol, free fatty acids and unreacted methyl alcohol are separated from the methyl ester product. The methyl ester is purified by removal of residual methyl alcohol and any other low-boiling-point compounds before its use as biodiesel fuel. From 7.3 lb of soybean oil, 1 gallon of biodiesel fuel can be produced. See FIGURE 12-5. 

The canola growing countries in Europe, notably, Germany, Austria, and France, but also others, have developed significant methyl ester production capacity and use. 

USA-ASTM standard for 100% pure biodiesel is similar in many respects (146), but it is written for the use of soybean oil as the main starting material. Canola oil for methyl ester production must either be degummed (<20 mg/kg of phosphorus), or in addition, must be alkali refined and bleached, depending on the methyl ester production process requirements (148). 

Figure 4 Gas chromatograph of hydrogenated pyrolysed methyl ester product.

Substrate methyl ester, product acid. Alkyl = Me, Pr, t-Bu, CgH, CgHi,. 

Southern Europe and France use relatively little canola oil. Instead, olive, sunflower and peanut oils predominate. In the case of France, this is somewhat surprising, since this country is a large producer of canola seeds. France uses large amounts of canola oil for biodiesel 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. 

Gutsche, B. Technology of methyl ester production and its application to biofuels. (Technologic der Methylesterherstellung - Anwendung fiir die Biodieselproduktion.) Fett/Lipid 1997, 99, 418-427. 

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... 

Structure Analyses of the Product with a GC Rt of 18 min. The major methyl ester product (Rt 18 min) was purified twice by silica gel TLC. The structure was identified through GC-MS and NMR analysis. The electron impact mass spectrum (EI-MS) obtained from the methyl ester/O-trimethylsilyl ether (OTMSi) of the purified product (Fig. 2) gave a molecular ion of m/z 486 [M]+ (0.2). Typical fragment ions were interpreted as follows 396 [M-TMSiOH]+ (2), 381 [M-CH3-TMSiOH]+ (1), 355 [M-CH3CH2CHOTMSi]+ (2), 289 [M-CH2CH=CH (CH2)7C00CH3]+ (10), 265 [355-TMSiOH]+ (8), 199 [289-... 

Fig.l. Gas chromatograms (GC) of the methyl ester products converted from a-linolenic acid by Clavibacter sp. ALA2. (A) Bioconversion of a-linolenic acid by Clavibacter sp. ALA2. Peak I the product with GC retention time (Rt) of 18 min Peak II the product with GC Rt of 26 min. (B) Incubation of a-linolenic acid with autoclaved C/av/bacfer sp. ALA2. 

Proton and Nuclear Magnetic Resonance Signals and Molecular Assignments for the Methyl Ester Product with Gas Chromatography Retention Time of 18 min... 

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. 

Methyl esters can be prepared with the reagent diazomethane (CH2N2). When reacted with a carboxylic acid, diazomethane becomes protonated and serves as an extremely reactive electrophile since it contains an extremely good leaving group (N2). A rapid and irreversible Sn2 displacement by the carboxyl-ate nucleophile gives the methyl ester product. 

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. 

Even more impressive is Diederich s pyruvate oxidase mimic based on a cyclophane (Fig. 4) in methanol this host can bind an aromatic aldehyde within its cavity, create a covalent intermediate by reaction with its attached thiazolium group, oxidise this tethered intermediate by intramolecular transfer of a hydride-equivalent to the appended flavin, and then release the methyl ester product by solvolysis. Catalytic... 

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... 

---