双功能催化剂构筑及催化环己烷温和条件下一步制备己内酰胺的研究

本项目针对现有己内酰胺生产工艺复杂、能耗物耗高、环境污染严重等问题开展基础研究。设计和制备具有活化烷烃和重排活性的双功能催化剂，使用廉价易得的亚硝酸钠作为亚硝化试剂，实现温和条件下环己烷一步亚硝化制备己内酰胺；通过考察催化剂的催化性能，结合催化剂的表征研究催化剂微观结构、表面酸性等结构参数与催化性能之间的"构-效"关系，得到较高活性及选择性的亚硝化催化剂；深入研究催化剂催化活性中心状态，考察催化反应机理；研究过渡金属负载型催化剂的失活机理，解决过渡金属催化剂在反应体系中的溶脱及失活等问题，达到催化剂的回收与循环利用的目的。本项目的研究成果对简化己内酰胺生产工艺、降低能耗和成本等方面具有较高的工业应用价值，对人们研究烷烃亚硝化反应制备酰胺类物质具有重要的指导意义。

This project aims at to solve the drawbacks in the present caprolatam synthesis processes, such as complex routes, high energy and material consumptions and serious environment pollution. The novel bifunctional catalysts with both alkane activation and rearrangement functions will be designed, prepared and used in ε-caprolactam synthesis from one step nitrosation of cyclohexane and sodium nitrite, which is a cheap and available nitrosation reagent. The structural parameters and surface acidity of catalysts will be characterized and the catalytic properties will be investigated. By combining the results of catalytic performances and the catalysts characterizations, the relationship between the structural parameters and the catalytic properties will be studied to obtain the high active and selective catalyst in cyclohexane nitrosation. The status of the active sites on catalysts will be in-depth studied and propose the possible catalytic mechanism in the reaction. The deactivation mechanism of the catalyst will be studied to solve the leaching and inactivation of the supported transition metal catalysts in the reaction system and achieve to recover and recycle the catalysts. This novel strategy proposed in this project have a very high industrial application value in the green production of ε-caprolactam and offer a potential guiding in the reaction of alkane nitrosation to form corresponding amide.