Grasas y Aceites, Vol 69, No 2 (2018)

Lipase-catalyzed transesterification of epoxidized soybean oil to prepare epoxy methyl esters


https://doi.org/10.3989/gya.1103172

W. Liu
Lipid Chemistry, College of Food Science and Technology, Henan University of Technology, China
orcid http://orcid.org/0000-0003-1706-1208

F. Duan
Lipid Chemistry, College of Food Science and Technology, Henan University of Technology, China
orcid http://orcid.org/0000-0003-2772-9435

Abstract


Epoxidized soybean oil methyl esters could be efficiently prepared with the transesterification of epoxidized soybean oil (ESBO) with a lower dosage of methanol using lipase Novozym 435 as catalyst. The optimum parameters were as follows: the molar ratio of 5:1 (methanol to ESBO), 5% Novozym 435 as catalyst, at 45 °C for 14 h, with a stirring speed of 600rpm, under which the epoxidized soybean oil methyl esters (ESBOME) could be obtained at a 95.7% yield. During the enzymatic transesterification process, the oxirane oxygen values were kept unchangeable, which indicated that excellent functional group tolerance could be achieved under such mild reaction conditions. In addition, the recyclability of the immobilized enzyme Novozym 435 in this transesterification process was examined and the results showed that the biocatalyst could be reused ten times without losing any reaction activity or selectivity. And the final products of ESBOME were also identified by IR and NMR analysis. The kinetic data obtained followed the Ping-Pong Bi mechanism model (Vmax = 6.132 mol·L-1min-1, Km,S = 0,0001 mol·L-1, Km, A = 796.148 mol·L-1, Ki, A = 0,0004 mol·L-1) with competitive inhibition by methanol.

Keywords


Bio-based products; Epoxidized soybean oil; Epoxy methyl esters; Lipase; Transesterification

Full Text:


HTML PDF XML

References


Ahn K, Kraft S, Sun S. 2011. Chemical pathways of epoxidized and hydroxylated fatty acid methyl esters and triglycerides with phosphoric acid. J. Mater. Chem. 21, 9498-9505. https://doi.org/10.1039/c1jm10921a

Alhassan Y, Kumar N, Bugaje IM. 2015. Catalytic upgrading of waste tire pyrolysis oil via supercritical esterification with deep eutectic solvents (green solvents and catalysts). J. Energy. Inst. 89, 683-693. https://doi.org/10.1016/j.joei.2015.05.003

Almeida VFD, García-Moreno PJ, Guadix A, Guadix EM. 2015. Biodiesel production from mixtures of waste fish oil, palm oil and waste frying oil: Optimization of fuel properties. Fuel Process. Technol. 133, 152-160. https://doi.org/10.1016/j.fuproc.2015.01.041

Armylisas AHN, Hazirah MFS, Yeong SK, Hazimah AH. 2017. Modification of olefinic double bonds of unsaturated fatty acids and other vegetable oil derivatives via epoxidation: A review. Grasas Aceites 68, e174. https://doi.org/10.3989/gya.0684161

Bajaj A, Lohan P, Jha PN, Mehrotra R. 2010. Biodiesel production through lipase catalyzed transesterification: An overview. J. Mol. Catal. B-Enzym. 62, 9-14. https://doi.org/10.1016/j.molcatb.2009.09.018

Biermann U, Friedt W, Lang S, Lühs W.; Machmüller G, Metzger JO, Klaas MR, Shafer HJ, Schneider MP. 2008. Chapter 8. New Syntheses with Oils and Fats as Renewable Raw Materials for the Chemical Industry. Biorefineries-Industrial Processes and Products: Status Quo and Future Directions. 253-289.

Campanella A, Rustoy E, Baldessari A, Baltanás MA. 2010. Lubricants from chemically modified vegetable oils. Biotechnol. Tech. 10, 1245-1254.

Gharat N, Rathod VK. 2013. Ultrasound assisted enzyme catalyzed transesterification of waste cooking oil with dimethyl carbonate. Ultrason. Sonochem. 20, 900-905. https://doi.org/10.1016/j.ultsonch.2012.10.011 PMid:23178034

Guldhe A, Singh B, Mutanda T, Permaul K, Bux F. 2015. Advances in synthesis of biodiesel via enzyme catalysis: Novel and sustainable approaches. Renew. Sustain. Energ. Rev. 41, 1447-1464. https://doi.org/10.1016/j.rser.2014.09.035

Gutiérrez-Arnillas E, Álvarez MS, Deive FJ, Rodríguez A, Sanrom MA. 2016. New horizons in the enzymatic production of biodiesel using neoteric solvents. Renew. Energ. 98, 92-100. https://doi.org/10.1016/j.renene.2016.02.058

Holser RA. 2008. Transesterification of epoxidized soybean oil to prepare epoxy methyl esters. Ind. Crop Prod. 27, 130- 132. https://doi.org/10.1016/j.indcrop.2007.06.001

Hwang HS, Erhan SZ. 2001. Modification of epoxidized soybean oil for lubricant formulations with improved oxidative stability and low pour point. J. Am. Oil Chem. Soc. 78, 1179-1184. https://doi.org/10.1007/s11745-001-0410-0

Ilmi M, Hommes A, Winkelman JGM, Hidayat C, Heeres HJ. 2016. Kinetic studies on the transesterification of sunflower oil with 1-butanol catalyzed by Rhizomucor miehei lipase in a biphasic aqueous-organic system. Biochem. Eng. J. 114, 110-118. https://doi.org/10.1016/j.bej.2016.06.026

Kai T, Mak GL, Wada S, Nakazato T, Takanashi H, Uemura Y. 2014. Production of biodiesel fuel from canola oil with dimethyl carbonate using an active sodium methoxide catalyst prepared by crystallization. Biotechnol. Tech. 163, 360-363.

Knothe, G. 2001. Characterization of esters of fatty acids and dicarboxylic acids with Guerbet alcohols. J. Am. Oil Chem. Soc. 78, 537-540. https://doi.org/10.1007/s11746-001-0299-7

Kwok Q, Acheson B, Turcotte R, Janès A, Marlair G. 2013. Fire and explosion hazards related to the industrial use of potassium and sodium methoxides. J. Hazard. Mater. 250-251, 484-490. https://doi.org/10.1016/j.jhazmat.2013.01.075 PMid:23507308

Lin YC, Hsu KH, Lin JF. 2014. Rapid palm-biodiesel production assisted by a microwave system and sodium methoxide catalyst. Fuel 115, 306-311. https://doi.org/10.1016/j.fuel.2013.07.022

Liu W, Chen J, Liu RL, Bi YL. 2016. Revisiting the Enzymatic Epoxidation of Vegetable Oils by Perfatty Acid: Perbutyric Acid Effect on the Oil with Low Acid Value. J. Am. Oil Chem. Soc. 93, 1479-1486. https://doi.org/10.1007/s11746-016-2897-3

Martini DDS, Braga BA, Samios D. 2009. On the curing of linseed oil epoxidized methyl esters with different cyclic dicarboxylic anhydrides. Polym. 50, 2919-2925. https://doi.org/10.1016/j.polymer.2009.03.058

Mazo P, Rios L. 2013. Carbonation of Epoxidized Soybean Oil Improved by the Addition of Water. J. Am. Oil Chem. Soc. 90, 725-730. https://doi.org/10.1007/s11746-013-2214-3

Mustata F, Nita T, Bicu I. 2014. The curing reaction of epoxidized methyl esters of corn oil with Diels-Alder adducts of resin acids. The kinetic study and thermal characterization of crosslinked products. J. Anal. Appl. Pyrolysis, 108, 254- 264. https://doi.org/10.1016/j.jaap.2014.04.007

Pastore C, Barca E, Moro GD, Lopez A, Mininni G, Mascolo G. 2015. Recoverable and reusable aluminium solvated species used as a homogeneous catalyst for biodiesel production from brown grease. Appl. Catal. A: General. 501, 48-55. https://doi.org/10.1016/j.apcata.2015.04.031

Rosa CD, Morandim MB, Ninow JL, Oliveira D, Treichel H, Oliveira JV. 2009. Continuous lipase-catalyzed production of fatty acid ethyl esters from soybean oil in compressed fluids. Bioresour. Technol. 100, 5818-5826. https://doi.org/10.1016/j.biortech.2009.06.081 PMid:19616937

Sharma BK, Adhvaryu A, Liu ZS, Erhan SZ. 2006. Chemical modification of vegetable oils for lubricant applications. J. Am. Oil Chem. Soc. 83, 129-136. https://doi.org/10.1007/s11746-006-1185-z

Sharma YC, Singh B. 2010. A hybrid feedstock for a very efficient preparation of biodiesel. Fuel Process. Technol. 91, 1267-1273. https://doi.org/10.1016/j.fuproc.2010.04.008

Silitonga AS, Masjuki HH, Hwai OC, Yusaf T, Kusumo F, Mahlia TMI. 2016. Synthesis and optimization of Hevea brasiliensis and Ricinus communis as feedstock for biodiesel production: a comparative study. Ind. Crop. Prod. 85, 274- 286. https://doi.org/10.1016/j.indcrop.2016.03.017

Souza GK, Scheufele FB, Pasa TLB, Arroyo PA, Pereira NC. 2016. Synthesis of ethyl esters from crude macauba oil (Acrocomia aculeata) for biodiesel production. Fuel. 165, 360-366. https://doi.org/10.1016/j.fuel.2015.10.068

Trinh H, Yusup S, Uemura Y. 2018. Optimization and kinetic study of ultrasonic assisted esterification process from rubber seed oil. Bioresour. Technol. 247, 51-57. https://doi.org/10.1016/j.biortech.2017.09.075 PMid:28946094

Ullah K, Ahmad M, Sofia, Qiu FX. 2015. Assessing the experimental investigation of milk thistle oil for biodiesel production using base catalyzed transesterification. Energy 89, 887-895. https://doi.org/10.1016/j.energy.2015.06.028

Wu XD, Zhang XG, Yang SR, Chena Hg, Wang DP. 2000. The study of epoxidized rapeseed oil used as a potential biodegradable lubricant. J. Am. Oil Chem. Soc. 77, 561-563. https://doi.org/10.1007/s11746-000-0089-2

Zhang KP, Lai JQ, Huang ZL, Yang Z. 2011. Penicillium expansum lipase-catalyzed production of biodiesel in ionic liquids. Biotechnol. Tech. 102, 2767-2772.

Zheng Y, Quan J, Ning X, Zhu LM, Jiang B, He ZY. 2009. Lipase-catalyzed transesterification of soybean oil for biodiesel production in tert-amyl alcohol. World J. Microbiol. Biotechnol. 25, 41-46. https://doi.org/10.1007/s11274-008-9858-4




Copyright (c) 2018 Consejo Superior de Investigaciones Científicas (CSIC)

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.


Contact us grasasyaceites@ig.csic.es

Technical support soporte.tecnico.revistas@csic.es