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

Abstract

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

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

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.

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.

References

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).

[1]	Xiaolin Guo, Zhaoyang Zhang, Pengfei Xing, Shuai Wang, Yibing Guo, Yanxin Zhuang. Kinetic mechanism of copper extraction from methylchlorosilane slurry residue using hydrogen peroxide as oxidant [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 228-234.
[2]	Xun Tao, Fan Zhou, Xinlei Yu, Songling Guo, Yunfei Gao, Lu Ding, Guangsuo Yu, Zhenghua Dai, Fuchen Wang. Effect of carbon dioxide on oxy-fuel combustion of hydrogen sulfide: An experimental and kinetic modeling [J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 105-117.
[3]	Junyang Liu, Luming Wang, Yuhang Bian, Chunshan Li, Zengxi Li, Jie Li. Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor: Experimental and kinetic studies [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 1-10.
[4]	Wei Wang, Romain Lemaire, Ammar Bensakhria, Denis Luart. Thermogravimetric analysis and kinetic modeling of the co-pyrolysis of a bituminous coal and poplar wood [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 53-68.
[5]	Bing Liu, Yingjiao Li, Moses Arowo, Guangwen Chu, Yong Luo, Liangliang Zhang, Haikui Zou, Baochang Sun. Sulfonation of 1, 4-diaminoanthraquinone leuco by chlorosulfonic acid: Kinetics and process intensification [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 163-169.
[6]	Xinyu Liu, Hongliang Sheng, Song He, Chunhua Du, Yuansheng Ma, Chichi Ruan, Chunxiang He, Huaming Dai, Yajun Huang, Yuelei Pan. Insight into pyrolysis of hydrophobic silica aerogels: Kinetics, reaction mechanism and effect on the aerogels [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 266-281.
[7]	Guangyuan Chen, Tong Zhou, Meng Zhang, Zhongxiang Ding, Zhikun Zhou, Yuanhui Ji, Haiying Tang, Changsong Wang. Effects of heavy metal ions Cu²⁺/Pb²⁺/Zn²⁺ on kinetic rate constants of struvite crystallization [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 10-16.
[8]	Shujun Peng, Song Lei, Sisi Wen, Jian Xue, Haihui Wang. A Ruddlesden–Popper oxide as a carbon dioxide tolerant cathode for solid oxide fuel cells that operate at intermediate temperatures [J]. Chinese Journal of Chemical Engineering, 2023, 56(4): 25-32.
[9]	Zhiwei Wang, Yu Zhang, Zhi Zhang, Daowei Zhou, Zhikai Cao, Yong Sha. Investigation on catalytic distillation for ethyl acetate production with different catalytic packing structures [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 63-72.
[10]	Tengjie Wang, Wenkai Li, Xuehui Ge, Ting Qiu, Xiaoda Wang. Kinetics measurement of ethylene-carbonate synthesis via a fast transesterification by microreactors [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 243-250.
[11]	Yingjie Song, Shuqi Zhong, Yingjiao Li, Kun Dong, Yong Luo, Guangwen Chu, Haikui Zou, Baochang Sun. Study on the catalytic degradation of sodium lignosulfonate to aromatic aldehydes over nano-CuO: Process optimization and reaction kinetics [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 300-309.
[12]	Xuan Gao, Zhihui Li, Dongsheng Zhang, Xinqiang Zhao, Yanji Wang. Synthesis and kinetics of 2,5-dicyanofuran in the presence of hydroxylamine ionic liquid salts [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 310-316.
[13]	Kechang Gao, Shengjuan Shao, Zhixing Li, Jiaxin Jing, Weizhou Jiao, Youzhi Liu. Kinetics of the direct reaction between ozone and phenol by high-gravity intensified heterogeneous catalytic ozonation [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 317-323.
[14]	Hongbo Song, Wei Wang, Jiachen Sun, Xianhui Wang, Xianhua Zhang, Sai Chen, Chunlei Pei, Zhi-Jian Zhao. Chemical looping oxidative propane dehydrogenation controlled by oxygen bulk diffusion over FeVO₄ oxygen carrier pellets [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 409-420.
[15]	Kai Zhang, Fangming Xue, Zhiqiang Wang, Xingxing Cheng. Research on prediction model of formation temperature of ammonium bisulfate in air preheater of coal-fired power plant [J]. Chinese Journal of Chemical Engineering, 2022, 48(8): 202-210.

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

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments