ZSM-35/MOR共晶分子筛绿色合成及其二甲醚羰基化催化反应机制研究

多相分子筛催化剂上二甲醚羰基化反应是解决煤基合成气高效转化利用的重要途径。在分子尺度深入了解催化剂结构与活性位之间的构效关系，开发多相易分离催化剂的绿色合成路线，对于目前均相含卤贵金属催化剂的替代具有重要的指导意义。本项目重点考察影响 ZSM-35 催化剂二甲醚羰基化反应活性的关键因素，揭示（8+10）二维孔道结构对羰基化反应的稳定机制，并通过孔道二次化学修饰与调控铝物种分布来提升其反应活性；澄清ZSM-35/MOR共晶分子筛在羰基化反应中的协同作用机理，利用包括原位红外、超极化129Xe在内的多种表征技术阐明两相复合孔道结构、共生晶面及多活性中心在优异羰基化性能中的贡献；由此指明共晶分子筛的合成目标，开发晶种导向ZSM-35/MOR分子筛的无胺绿色合成路线，明确影响产物粒径、形貌及晶面取向的关键因素，通过微结构互补互调为羰基化反应带来特殊催化效果。

Carbonylation reaction of dimethyl ether (DME) with CO using zeolites as catalysts provides an effective way for the utilization of coal-based syngas. New green synthesis routes of zeolite will attract much interest in both academic and industry fields. This proposal focuses on the elucidation of carbonylation reaction mechanism and elemental reaction pathways over ZSM-35/MOR zeolite. Different roles of 8 MR and 10 MR in ZSM-35 will be investigated through the combination of in-situ IR characterization techniques and DFT model calculation. Meanwhile, a clear explanation about the deactivation mechanism will be given. On basis of the above experimental results, effective modification methods and aluminum distribution in-control synthesis will be developped. Besides, ZSM-35/MOR composite zeolites on basis of green synthesis route in the absence of organic template will be provided. Through following the crystallization process using UV-Raman spectra, key influencing factors will be determined which may guide the following in-control synthesis objective. Finally, scale-up production of ZSM-35/MOR via green route is hoped to be realized and applied to the DME carbonylation reaction.