功能化离子液体支载的分子筛膜反应器的催化分离耦合特性

The immobilization of ionic liquids has been a hot research topic in recent years, but there is quite a few studies on the integration of ionic liquids and membrane materials. In this project, we have raised a proposal of enough originality to realize the purpose. The proposal is to develop high-performance supported task-specific ionic liquids zeolite membranes reactor in the presence of mordenite zeolite membranes as support material. Task-specific ionic liquids graft well on the surface of zeolite membranes by using chemical grafting method. The research work in this proposal consists of two main parts: 1) to investigate the regulation mechanism on the surface of zeolite membrane from ionic liquids, the interaction between ionic liquids and zeolite membrane microstructure by using several characterization methods, 2) to explore the catalytic activity and permeability performance of zeolite membranes reactor by using cyclohexane ketalization as the probe reaction, finding out the correlations among membrane microstructure, catalytic performance, and permeability, providing the guide for the design of zeolite membranes reactor. It is believed that the successful research on this project may lead to the development of synthesis technique in the ketalization reaction, and also to provide the theoretical basis for revealing several important scientific problems such as the coupling mechanism between ionic liquids catalysis and membrane separation.

离子液体的固载化是当前的研究热点，但将离子液体与膜材料相结合却少见报道。为此，本项目提出"以MOR 型分子筛膜为固定载体，采用功能化离子液体对分子筛膜进行表面接枝，实现离子液体催化与分子筛膜分离相结合"这一创新性思路，研制出高性能的功能化离子液体支载的分子筛膜反应器。研究内容包括：通过先进表征手段认知分子筛膜表面离子液体的调控机制，揭示离子液体与分子筛膜的相互作用；以环己酮和乙二醇的缩酮反应为探针反应，系统探索制备条件对膜反应器的催化活性与分离性能的影响，揭示膜层微结构、催化性能和分离性能三者之间的构效关系，指导离子液体支载的分子筛膜反应器的设计与制备。研究不仅有助于促进现代缩酮合成技术的发展，同时也将为揭示离子液体催化-膜分离耦合机制等重要科学问题提供理论依据。

为实现离子液体催化与分子筛膜分离过程耦合，本项目通过设计合成出硅氧烷基酸功能化离子液体，制备出高分离性能的MOR型分子筛膜，分别以MOR型分子筛和MOR型分子筛膜为载体，采用化学嫁接法对分子筛和分子筛膜实行化学接枝和表面修饰，成功将功能化离子液体均匀负载到分子筛和分子筛膜表面，研制出高催化活性的MOR型分子筛固载硅氧烷基酸性离子液体催化剂（BAIL@MOR）和兼具催化和分离双功能的离子液体支载分子筛膜催化反应器；以环己酮与乙二醇缩酮反应体系为模型反应，研究BAIL@MOR催化合成环己酮乙二醇缩酮反应动力学和膜反应器催化缩酮反应-分离耦合过程，实现了膜催化过程催化速率与分离速率的有效匹配，获得了反应分离一体化制备缩酮的新工艺。项目共发表SCI论文10篇，培养硕士研究生毕业4名、在读3名，较为圆满地完成了项目合同规定的任务。