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 pa-rameters 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 sim-pler 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 pa-rameters 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 sim-pler 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