AmmAmmoximation of Cyclohexanone to Cyclohexanone Oxime Catalyzed by Titanium Silicalite-1 Zeolite in Three-phase System  

三相体系中TS-1分子筛催化环己酮氨肟化制环己酮肟(英文)

作　　者：刘国清 吴剑 罗和安 

机构地区：[1]School of Chemistry and Chemical Engineering,Hunan University of Science and Technology [2]School of Chemical Engineering,Xiangtan University

出　　处：《Chinese Journal of Chemical Engineering》2012年第5期889-894,共6页中国化学工程学报（英文版）

基　　金：Supported by the National Natural Science Foundation of China and Sinopec (20736009)

摘　　要：An innovative green process of producing ε-caprolactam was proposed by integrating ammoximation and Beckmann rearrangement effectively. As a first part of the new process, TS-1 molecular sieve-catalyzed synthesis of cyclohexanone oxime from cyclohexanone, ammonia and hydrogen peroxide was carried out in a batch plant. Cyclohexane was used as the solvent in the three-phase reaction system. The influences of essential process parameters on ammoximation were investigated. Under the reaction conditions as catalyst content of 2.5% (by mass); H 2 O 2 /yclohexanone molar ratio of 1.10; NH 3 /cyclohexanone molar ratio of 2.20; reaction temperature of 343 K; reaction time of 5 h, high conversion of cyclohexanone and selectivity to oxime (both>99%) were obtained. Thus, the three-phase ammoximation process showed equal catalytic activity as TS-1 but much more convenient and simpler for the separation of catalyst in comparison to the industrial two-phase system with t-butanol used as solvent.An innovative green process of producing ε-caprolactam was proposed by integrating ammoximation and Beckmann rearrangement effectively. As a first part of the new process, TS-1 molecular sieve-catalyzed synthesis of cyclohexanone oxime from cyclohexanone, ammonia and hydrogen peroxide was carried out in a batch plant. Cyclohexane was used as the solvent in the three-phase reaction system. The influences of essential process parameters on ammoximation were investigated. Under the reaction conditions as catalyst content of 2.5% （by mass）; H 2 O 2 /yclohexanone molar ratio of 1.10; NH 3 /cyclohexanone molar ratio of 2.20; reaction temperature of 343 K; reaction time of 5 h, high conversion of cyclohexanone and selectivity to oxime （both〉99%） were obtained. Thus, the three-phase ammoximation process showed equal catalytic activity as TS-1 but much more convenient and simpler for the separation of catalyst in comparison to the industrial two-phase system with t-butanol used as solvent.

关 键 词：AMMOXIMATION molecular sieve TS-1 cyclohexanone oxime CYCLOHEXANE three-phase system 

分 类 号：TQ234.2[化学工程—有机化工]