活化脂肪醚类C-O官能团的多相催化水解体系探索及高效催化剂的研究

Ethylene Glycol (EG) is an important raw material for polyester synthesis. 2-Methoxyethanol (EG-M) could be prepared selectively via vapor phase carbonylation of Methylal (derivatives of methanol or formaldehyde, DMM) and hydrogenation further. Thus, the development of EG synthesis from EG-M will open up the industrial application for the new C1route of EG synthesis. Based on molecular structure characteristics, ether C-O activation pathway was preferred in the catalytic hydrolysis reaction on lamellar MCM-22 at higher temperature, intends to increase the active site accessibility, improves the protonated complex formation rate, which would promote the catalytic conversion of EG-M. Selective deactivation method of “preoccupied-vapor deposition–regeneration” was conducive to suppress side reactions due to the controllable distribution of acid center, and a breakthrough would achieve on the preparation of high activity catalysts. Combined with the examination of feeds parameters on polarity and common ion effect, and an universal experience method was investigated on the resistance of dissolving loss in the catalytic hydrolysis system. This application is helpful to explore the essence of hydrolysis on ester C-O bond activation, which has common problems in the industrial process of biomass energy utilization, and is also important for clean production in the field of pharmaceutical synthesis.

乙二醇（EG）是聚酯合成的重要原料。甲缩醛（甲醇甲醛衍生物，DMM）经气相羰基化、加氢选择性生成乙二醇单甲醚（EG-M）的多相催化体系研究近期取得新进展，因此，EG-M进一步催化转化制EG，成为乙二醇的DMM合成新路线工业化应用的关键技术。基于分子结构特征分析了脂肪醚C-O活化途径，优选片层状分子筛MCM-22上的高温多相水解路线，拟通过增加活性位可接触性、提高质子化络合物生成速率，促进EG-M催化转化；提出“预占位-气相沉积-再生”的小孔酸中心选择性钝化方法，实现MCM-22分子筛上层间12元环侧口袋和层内10元环孔道酸中心的可控分布，抑制副反应发生，开发高活性的分子筛水解催化剂；并结合溶剂极性、同离子效应等工艺参数考察，总结含水体系中分子筛耐溶解流失的普适性方法。本申请的完成有助于探索脂肪醚C-O键水解活化本质，与生物质能高效利用的工业推进存在共性问题，对医药合成领域的清洁生产意义重大

本项目立足于脂肪醚的多相催化转化研究，对比了多类质子交换试剂下的反应特性，考察了脂肪醚C-O键的多相催化断裂活性；通过同位素O18示踪试验，研究了混合脂肪醚中多类C-O键的优先断裂取向；采用理论计算和实验相结合的方法，验证了端基C-O键水解路径的合理性。优选MCM-22分子筛，进行不同孔道内酸中心的可控修饰——选择性钝化10元环酸中心+强化12元环酸落位，探索了水解体系主、副反应的活性中心分布。研究了高压液相过热水体系中分子筛催化材料的结构特性，基于“同离子效应”，通过料液极性、含硅助剂类型的优化，探索了多相催化材料耐水热流失问题的普适性工艺参数和经验方法。作为醇类大化工产品的新型C1转化路线，优选的乙二醇单甲醚水解过程中，乙二醇单程选择性达85%；料液经预补硅后，加压液相过热水体系中单克分子筛上料液处理通量超过12000ml•gcat。