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-catalyzed synthesis of cyclohexanone oxime from cyclohexanone by ammoximation with ammonia and hydrogen peroxide was carried out in a batch plant. Cyclohexane was used as the solvent to introduce a three-phase reaction system. The influences of essential process parameters on ammoximation in the three-phase system were investigated. With high conversion of cyclohexanone and selectivity to oxime (both > 99%) under optimum conditions, the three-phase ammoximation process showed an equal catalytic activity for TS-1 but much more convenient and simpler for the separation of catalyst in comparison to the industrial two-phase system where t-butanol was used as solvent.

摘要： 首次提出了制备己内酰胺的非均相氨肟化-液相重排绿色集成新工艺，并对以环己酮、氨、双氧水为原料，TS-1分子筛为催化剂，环己烷为溶剂的非均相氨肟化反应过程进行了考察。结果表明：相较于现有以叔丁醇为溶剂的均相氨肟化工艺，非均相氨肟化过程简化，操作方便，TS-1活性较高；在适宜的工艺条件下，环己酮转化率及环己酮肟选择性均可大于99%。

关键词: 氨肟化, TS-1分子筛, 环己酮肟, 环己烷, 三相体系