Epoxidation of Unsaturated Fatty Acid Methyl Esters in the Presence of SO3H-functional Brφnsted Acidic Ionic Liquid as Catalyst

摘要/Abstract

摘要： The epoxidation of unsaturated fatty acid methyl esters(FAMEs)by peroxyacetic acid generated in situ from hydrogen peroxide and acetic acid was studied in the presence of SO₃H-functional Brnsted acidic ionic liquid (IL)[C₃SO₃HMIM][HSO₄] as catalyst.The effects of hydrogen peroxide/ethylenic unsaturation ratio,acetic acid concentration,IL concentration,recycling of the IL catalyst,and temperature on the conversion to oxirane were studied.The kinetics and thermodynamics of unsaturated FAMEs epoxidation and the kinetics of oxirane cleavage of the epoxidized FAMEs by acetic acid were also studied.The conversion of ethylenic unsaturation group to oxirane, the reaction rate of the conversion to oxirane,and the rate of hydrolysis(oxirane cleavage)were higher by using the IL catalyst.

关键词: in situ epoxidation, kinetics, oxirane cleavage, unsaturated fatty acid methyl esters, Brφnsted acidic ionic liquids

Abstract: The epoxidation of unsaturated fatty acid methyl esters(FAMEs)by peroxyacetic acid generated in situ from hydrogen peroxide and acetic acid was studied in the presence of SO₃H-functional Brnsted acidic ionic liquid (IL)[C₃SO₃HMIM][HSO₄] as catalyst.The effects of hydrogen peroxide/ethylenic unsaturation ratio,acetic acid concentration,IL concentration,recycling of the IL catalyst,and temperature on the conversion to oxirane were studied.The kinetics and thermodynamics of unsaturated FAMEs epoxidation and the kinetics of oxirane cleavage of the epoxidized FAMEs by acetic acid were also studied.The conversion of ethylenic unsaturation group to oxirane, the reaction rate of the conversion to oxirane,and the rate of hydrolysis(oxirane cleavage)were higher by using the IL catalyst.

Key words: in situ epoxidation, kinetics, oxirane cleavage, unsaturated fatty acid methyl esters, Brφnsted acidic ionic liquids

蔡双飞, 王利生. Epoxidation of Unsaturated Fatty Acid Methyl Esters in the Presence of SO₃H-functional Brφnsted Acidic Ionic Liquid as Catalyst[J]. , 2011, 19(1): 57-63.

CAI Shuangfei, WANG Lisheng. Epoxidation of Unsaturated Fatty Acid Methyl Esters in the Presence of SO₃H-functional Brφnsted Acidic Ionic Liquid as Catalyst[J]. , 2011, 19(1): 57-63.

参考文献

1 Gunstone, F.D., Padley, F.B., Lipid Technologies and Applications, Marcel Dekker, NewYork, 759-769 (1997).
2 Petrovic, Z.S., Zlatanic, A., Lava, C.C., Sinadinovic-Fiser, S., “Epoxidation of soybean oil in toluene with peroxoacetic and peroxoformic acids-kinetics and side reactions”, Eur. J. Lipid Sci. Technol.,104 (5), 293-299 (2002).
3 Musante, R.L., Grau, R.J., Ba1tanás, M.A., “Kinetics of liquid phase reactions catalyzed by acidic resins: The formation of peracetic acid for vegetable oil epoxidation”, Appl. Catal. A., 197 (1), 165-173 (2000).
4 Kirk, R.E., Othmer, D.F., Mark, H.F., Standen, A., Kirk-Othmer Encyclopedia of Chemical Technology, Wiley-VCH, New York (1965).
5 Goud, V.V., Patwardhan, A.V., Dinda, S., Pradhan, N.C., “Kinetics of epoxidation of Jatropha oil with peroxyacetic and peroxyformic acid catalysed by acidic ion exchange resin”, Chem. Eng. Sci., 62 (15),4065-4076 (2007).
6 Goud, V.V., Patwardhan, A.V., Pradhan, N.C., “Kinetics of in situ epoxidation of natural unsaturated triglycerides catalyzed by acidic ion exchange resin”, Ind. Eng. Chem. Res., 46 (10), 3078-3085 (2007).
7 Welton, T., “Room temperature ionic liquids. Solvents for synthesis and catalysis”, Chem. Rev., 99 (8), 2071-2083 (1999).
8 Hu, Y.Q., Wang, J.Y., Zhao, R.H., Liu, Y.M., Liu, R.J., Li, Y.D., “Catalytic oxidation of cyclohexane over ZSM-5 catalyst in N-alkyl-N-methylimidazolium ionic liquids”, Chin. J. Chem. Eng.,17 (3), 407-411 (2009).
9 Sun, A.J., Nie, Y., Li, C.X., Wang, Z.H., “Preparation of butyl chloride from butanol and hydrochloric acid using ionic liquids as catalyst”, Chin. J. Chem. Eng., 16 (1), 151-154 (2008).
10 Tian, L., Cao, F.H., Fang, D.Y., Guo, S.Z., “Alkylation of toluene with 1,3-pentadiene over [bupy]BF₄-A1Cl₃ ionic liquid catalyst”, Chin. J. Chem. Eng., 15 (5), 680-682 (2007).
11 Zhao, Y.W., Long, J.X., Deng, F.G., Liu, X.F., Li, Z., Xia, C.G., Peng, J.J., “Catalytic amounts of Brφnsted acidic ionic liquids promoted esterification: Study of acidity-activity relationship”, Catal. Commun.,10 (5), 732-736 (2009).
12 Cai, S.F., Wang, L.S., Yan, G.Q., Li, Y., “Solubilities of 1-methyl-3(3-sulfopropyl)-imidazolium hydrogen sulfate in selected solvents”, Chin. J. Chem. Eng., 18 (6), 1008-1012 (2010).
13 Han, M.H., Yi, W.L., Wu, Q., Liu, Y., Hong, Y.C., Wang, D.Z., “Preparation of biodiesel from waste oils catalyzed by a Br nsted acidic ionic liquid”, Bioresour. Technol., 100 (7), 2308-2310 (2009).
14 Jiang, D., Wang, Y.Y., Tu, M., Dai, L.Y., “The alcoholysis of acetonitrile prompted by Br nsted acidic ionic liquid [HSO3 -pmim]HSO4 ”, Chin. Chem. Lett., 19 (8), 889-892 (2008).
15 Shen, J.H., Wang, H., Liu, H.C., Sun, Y., Liu, A.M., “Br nsted acidic ionic liquids as dual catalyst and solvent for environmentally friendly synthesis of chalcones”, J. Mol. Catal. A: Chem., 280 (1-2), 24-28 (2008).
16 Fang, D., Shi, Q.R., Cheng, J., Gong, K., Liu, Z.L., “Regioselective mononitration of aromatic compounds using Br nsted acidic ionic liquids as recoverable catalysts”. Appl. Catal. A. Gen., 345 (2), 158-163 (2008).
17 Yang, Q.W., Wei, Z.J., Xing, H.B., Ren, Q.L., “Br nsted acidic ionic liquids as novel catalysts for the hydrolyzation of soybean isoflavone glycosides”, Catal. Commun., 9 (6), 1307-1311 (2008).
18 Zaher, F.A., El-Mallah, M.H., El-Hefnawy, M.A., “Kinetics of oxirane cleavage in epoxidised soybean oil”, J. Am. Oil. Chem. Soc.,66 (5), 698-700 (1989).
19 Chinese Standard GB 1677-2008. Determination of the epoxy value of plasticizers. General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China & Standardization Administration, Beijing, China (2008).
20 Dinda, S., Patwardhan, A.V., Goud, V.V., Pradhan, N.C., “Epoxidation of cottonseed oil by aqueous hydrogen peroxide catalysed by liquid inorganic acids”, Bioresour. Technol., 99 (9), 3737-3744 (2008).
21 Okieimen, F.E., Bakare, O.I., Okieimen, C.O., “Studies on the epoxidation of rubber seed oil”, Ind. Crop. Pro., 15 (2), 139-144 (2002).
22 Rangarajan, B., Havey, A., Grulke, E.A., Culnan, P.D., “Kinetic parameters of a two-phase model for in situ epoxidation of soybean oil”, J. Am. Oil. Chem. Soc., 72 (10), 1161-1169 (1995).
23 Jankovi, M., Sinadinovi -Fi er, S., Lamshoeft, M., “Liquid-liquid equilibrium constant for acetic acid in an epoxidized soybean oil-acetic acid-water system”, J. Am. Oil. Chem. Soc., 87 (5), 591-600 (2010).
24 Gan, L.H., Goh, S.H., Ooi, K.S., “Kinetic studies of epoxidation and oxirane cleavage of palm olein methyl esters”, J. Am. Oil. Chem. Soc., 69 (4), 347-351 (1992).
25 Goud, V.V., Patwardhan, A.V., Pradhan, N.C., “Studies on the epoxidation of mahua oil (Madhumica Indica) by hydrogen peroxide”, Bioresour. Technol., 97 (12), 1365-1371 (2006).
26 Campanella, A., Baltanás, M.A., “Degradation of the oxirane ring of epoxidized vegetable oils in liquid-liquid heterogeneous reaction systems”, Chem. Eng. J., 118 (3), 141-152 (2006).

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Epoxidation of Unsaturated Fatty Acid Methyl Esters in the Presence of SO₃H-functional Brφnsted Acidic Ionic Liquid as Catalyst

Epoxidation of Unsaturated Fatty Acid Methyl Esters in the Presence of SO₃H-functional Brφnsted Acidic Ionic Liquid as Catalyst

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