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

Chin.J.Chem.Eng. ›› 2012, Vol. 20 ›› Issue (5): 889-894.

• CATALYSIS, KINETICS AND REACTION ENGINEERING • Previous Articles Next Articles

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

LIU Guoqing^1,2, WU Jian², LUO He'an²

1. School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, China;
2. School of Chemical Engineering, Xiangtan University, Xiangtan 411105, China

Received:2011-06-09 Revised:2011-12-15 Online:2012-11-06 Published:2012-10-28
Supported by:
Supported by the National Natural Science Foundation of China and Sinopec (20736009)

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

刘国清^1,2, 吴剑², 罗和安²

1. School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, China;
2. School of Chemical Engineering, Xiangtan University, Xiangtan 411105, China

通讯作者: LUO He'an,E-mail:hluo@xtu.edu.cn
基金资助:
Supported by the National Natural Science Foundation of China and Sinopec (20736009)

Abstract

Abstract: 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); H₂O₂/yclohexanone molar ratio of 1.10; NH₃/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.

Key words: ammoximation, molecular sieve TS-1, cyclohexanone oxime, cyclohexane, three-phase system

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); H₂O₂/yclohexanone molar ratio of 1.10; NH₃/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

LIU Guoqing, WU Jian, LUO He'an. AmmAmmoximation of Cyclohexanone to Cyclohexanone Oxime Catalyzed by Titanium Silicalite-1 Zeolite in Three-phase System^*[J]. Chin.J.Chem.Eng., 2012, 20(5): 889-894.

刘国清, 吴剑, 罗和安. AmmAmmoximation of Cyclohexanone to Cyclohexanone Oxime Catalyzed by Titanium Silicalite-1 Zeolite in Three-phase System^*[J]. Chinese Journal of Chemical Engineering, 2012, 20(5): 889-894.

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

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

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