Abstract
This study investigated the successful enzymatic production of furfuryl oleate and its detailed kinetic study by Michaelis–Menten model. Esterification of oleic acid and furfuryl alcohol by Candida antarctica lipase B (Novozym 435 preparation) in a solvent free system was studied in the present work at 1:1 molar ratio of furfuryl alcohol and oleic acid. About 99 % conversion (on the basis of oleic acid) has been achieved within 6 h at 5 % enzyme concentration. Ping-pong bi-bi mechanism (inhibition phenomenon taken into account) was applied to describe the ratios as a complex kinetic model. The kinetic parameters were determined using MATLAB language programme. The two initial rate constants KA and KB respectively were found out by different progress curves plotted with the help of MATLAB language programme. It was concluded from the results that furfuryl alcohol considerably inhibited the enzymatic reaction while oleic acid had negligible inhibitory effect. It was clearly seen that the initial rate was increased with the increase in the furfuryl alcohol concentration until 2 M/L after which there was a drop in the initial rate depicting the inhibitory effect of furfuryl alcohol. Surprisingly, it has been observed that addition of 0.1 mol of product activated the esterification reaction. Finally, the model was found to be statistically fitting well with the experimental data.
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H.E. Hoydonckx, D.E. De VOs, S.A. Chavan, P.A. Jacobs, Esterification and transesterification of renewable chemicals. Top. Catal. 27, 83–96 (2004)
K. Bélafi-Bakó, A. Dombi, L. Szabó, E. Nagy, Triacylglycerol hydrolysis by lipase in a flat membrane bioreactor. Biotechnol. Technol. 8, 671–672 (1994)
Y. Linko, M. Lämsä, X. Wu, E. Uosukainen, J. Seppälä, P. Linko, Biodegradable products by lipase biocatalysis. J. Biotechnol. 66, 41–50 (1998)
O. Florea, M. Luca, A. Constantinescu, D. Florescu, in Proceedings of the 12th Romanian International Conference on Chemistry and Chemical Engineering, Bucharest, Romania, 2001
A. Zaidi, J.L. Gainer, G. Carta, A. Mrani, T. Kadiri, Y. Belarbi, A. Mir, Development of green composites from furfuryl palmitate. J. Biotechnol. 93, 209–216 (2002)
A. Dossat, D. Combes, A. Marty, Esterification of fatty acids using nylon-immobilized lipase in n-hexane: kinetic parameters and chain-length effects. J. Biotechnol. 97, 117–124 (2002)
D.E. Ponde, V.H. Deshpande, V.J. Bulbule, A. Sudalai, A.S. Gajare, Efficient lipase catalysed production of a lubricant and surfactant formulation using a continuous solvent-free process. J. Org. Chem. 63, 1058–1063 (1988)
P. Kumar, R.K. Pandey, Selective catalytic transesterification, transthiolesterification, and protection of carbonyl compounds over natural kaolinitic clay. Synlett 2, 251–253 (2000)
A. Orita, C. Tanahashi, A. Kakuda, J. Otera, Highly efficient and versatile acylation of alcohols with Bi(OTf)3 as catalyst. Angew. Chem. 39, 2877–2879 (2000)
Y. Nakae, I. Kusaki, T. Sato, Lithium perchlorate catalyzed acetylation of alcohols under mild reaction conditions. Synlett 10, 1584–1585 (2001)
A. Orita, K. Sakamoto, Y. Hamada, A. Mitsutome, Mild and practical acylation of alcohols with esters or acetic anhydride under distannoxane catalysis (J. Otera, Tetrahedran, 1999), pp. 2899–2910
A. Pelter, B. Singaram, The reactions of furfuryl alcohols with maleic anhydride. J. Chem. Soc. Perkin Trans. 1383–1386 (1983).
G.D. Yadav, P.S. Lathi, Synergism between microwave and enzyme catalysis in intensification of reactions and selectivities: transesterification of methyl acetoacetate with alcohols. Biotechnol. Eng. J. 13, 245–252 (2003)
A. Özgülsün, F. Karaosmanoglu, M. Tüter, Esterification reaction of oleic acid with a fusel oil fraction for production of lubricating oil. J. Am. Oil Chem. Soc. 77, 105–110 (2000)
T. Garcia, A. Coteron, M. Martinez, Kinetic modeling of esterification reactions catalyzed by immobilized lipases. J. Aracil. Chem. Eng. Sci. 51, 2841–2846 (1996)
A. Zaida, J.L. Gainer, G. Carta, A. Mrani, T. Kadiri, Y. Belarbi, A. Mir, Esterification of fatty acids using nylon-immobilised lipase in n-hexane: Kinetic parameters and chain-length effects. J. Biotechnol. 93, 209–216 (2002)
A.C. Oliveira, M.F. Rosa, M.R. Aires-Barros, J.M.S. Cabral, Enzymatic esterification of ethanol and oleic acid, A kinetic study. J. Mol. Catal. B-Enzm. 11, 999–1005 (2001)
R. Goddard, J. Bosley, B. Al-Duri, Esterification of oleic acid and ethanol in plug flow (packed bed) reactor under supercritical conditions: investigation of kinetics. J. Supercrit. Fluids 18, 121–130 (2000)
S. Hazarika, P. Goswami, N.N. Dutta, A.K. Hazarika, Ethyl oleate synthesis by porcine pancreatic lipase in organic solvents. Chem. Eng. J. 85, 61–68 (2002)
Nono Industrials, Analytical Methods Handout (Enzyme Process Division, NOVO Industrials, Denmark, 1995)
D. Firestone, R.C. Walker, Official Methods and Recommended Practices of the American Oil Chemists’ Society. American Oil Chemists’ Society. Cd-3a, 63 (1987).
M. Kates, Techniques for separation of lipid mixtures. Techniques Lipidol. North Holland Publishing Company. 442 (1972).
W.W. Cleland, Optimizing coupled enzyme assays. Anal. Biochem. 99, 142–145 (1979)
L. Zhang, L.I. Hellgren, X. Xuebing, Kinetic study of sphingomyelin hydrolysis for ceramide production. J. Mol. Catal. B Enzym. 51, 93–99 (2008)
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Financial support obtained from The Institution of Engineers (India) is gratefully acknowledged by the authors.
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Sengupta, A., Dey, T., Ghosh, M. et al. Enzymatic Synthesis of Furfuryl Alcohol Ester with Oleic Acid by Candida antarctica Lipase B and Its Kinetic Study. J. Inst. Eng. India Ser. E 93, 31–36 (2012). https://doi.org/10.1007/s40034-013-0008-7
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DOI: https://doi.org/10.1007/s40034-013-0008-7