Silica Gel Supported Chlorosulfonic Acid Catalyzed Beckmann Rearrangement of Cyclohexanone Oxime in Liquid Phase

Abstract

Abstract The Beckmann rearrangement of cyclohexanone oxime in the liquid phase using fuming sulfuric acid as a catalyst is a traditional method, which brings many problems, such as environmental pollution, corrosion of equipment, and difficulty in treating the by-product ammonium sulfate. This paper designs and prepares a silica gel-supported chlorosulfonic acid solid acid catalyst for the liquid-phase Beckmann rearrangement of cyclohexanone oxime to caprolactam. The factors affecting the preparation of the catalyst and the optimal reaction conditions for Beckmann rearrangement were investigated. It was found that the best catalyst preparation conditions were as follows: mass ratio of silica gel: chlorosulfonic acid of 1:0.2, room temperature, stirring time of 3 hours, solvent dichloromethane, and silica gel mesh size of 100-200 mesh, and best Beckmann rearrangement conditions were as follows: mass ratio of cyclohexanone oxime: catalyst of 1:1, temperature of 140°C, solvent benzonitrile volume of 40 mL/g cyclohexanone oxime, reaction time of 5 hours. Under the above conditions, the conversion of cyclohexanone oxime is 74%, and the selectivity of caprolactam is 40%.