Synthesis of ε-Caprolactone by Oxidation of Cyclohexanone with Monoperoxysuccinic Acid

doi:10.1016/S1004-9541(13)60643-6

Abstract

Abstract: In the absence of catalyst, 70% hydrogen peroxide was used to oxidize succinic anhydride to solid monoperoxysuccinic acid (PSA). Then PSA was applied to synthesis of ε-caprolactone (ε-CL) by oxidation of cyclohexanone in the heterogeneous system. In order to achieve material recycle, solid precipitated in the process of synthesizing ε-CL was dehydrated via reactive distillation followed by recrystallization to prepare succinic anhydride, which was characterized by IR (infrared spectra) and ¹HNMR (¹H nuclear magnetic resonance). Effects of molar ratio of PSA to cyclohexanone, acetic acid dosage, reaction temperature, reaction time on conversion of cyclohexanone, yield and selectivity of ε-CL were investigated respectively. The results indicated that conversion of cyclohexanone, yield and selectivity of ε-CL were upto 98.1%, 97.5% and 99.4% respectively under the optimal conditions. In addition, in the process of synthesizing succinic anhydride, the optimal yield of succinic anhydride reached 67.4%.

Key words: monoperoxysuccinic acid, cyclohexanone, &, epsilon, -caprolactone, reactive distillation, recrystallization

摘要： In the absence of catalyst, 70% hydrogen peroxide was used to oxidize succinic anhydride to solid monoperoxysuccinic acid (PSA). Then PSA was applied to synthesis of ε-caprolactone (ε-CL) by oxidation of cyclohexanone in the heterogeneous system. In order to achieve material recycle, solid precipitated in the process of synthesizing ε-CL was dehydrated via reactive distillation followed by recrystallization to prepare succinic anhydride, which was characterized by IR (infrared spectra) and ¹HNMR (¹H nuclear magnetic resonance). Effects of molar ratio of PSA to cyclohexanone, acetic acid dosage, reaction temperature, reaction time on conversion of cyclohexanone, yield and selectivity of ε-CL were investigated respectively. The results indicated that conversion of cyclohexanone, yield and selectivity of ε-CL were upto 98.1%, 97.5% and 99.4% respectively under the optimal conditions. In addition, in the process of synthesizing succinic anhydride, the optimal yield of succinic anhydride reached 67.4%.

关键词: monoperoxysuccinic acid, cyclohexanone, &, epsilon, -caprolactone, reactive distillation, recrystallization

CHEN Jian, ZHAO Xiaoshuang, ZHANG Guangxu, CHEN Bo, CAI Weiquan. Synthesis of ε-Caprolactone by Oxidation of Cyclohexanone with Monoperoxysuccinic Acid[J]. Chin.J.Chem.Eng., 2013, 21(12): 1404-1409.

陈建, 赵小双, 张光旭, 陈波, 蔡卫权. Synthesis of ε-Caprolactone by Oxidation of Cyclohexanone with Monoperoxysuccinic Acid[J]. Chinese Journal of Chemical Engineering, 2013, 21(12): 1404-1409.

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