甲醇作为甲基化试剂催化体系研究进展  

Research Progress on Catalytic System Using Methanol as Methylating Reagent

作　　者：杨东元 王斌[2] 崔新江[2] 常春然 YANG Dongyuan;WANG Bin;CUI Xinjiang;CHANG Chunran(Shaanxi Key Laboratory of Energy Chemical Process Intensification,School of Chemical Engineering and Technology,Xi′an Jiaotong University,Xi′an 710049,China;Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China;Shaanxi Yanchang Petroleum(Group)Co.,Ltd.,Xi′an 710069,China)

机构地区：[1]西安交通大学化学工程与技术学院陕西省能源化工过程强化重点实验室,陕西西安710049 [2]中国科学院兰州化学物理研究所,甘肃兰州730000 [3]陕西延长石油(集团)有限责任公司,陕西西安710069

出　　处：《石油学报（石油加工）》2023年第6期1442-1452,共11页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(22078257和22038011);甘肃省自然科学基金(21JR7RA096)资助。

摘　　要：甲醇是最小的含有碳氢氧的饱和有机分子,广泛应用于能源、化工以及有机合成等领域。通过氢转移的方法,将甲醇作为甲基化试剂,与胺、醇/酮以及烃类化合物耦合转化制备高值化的甲基化产品,是一项非常有意义的研究工作。氢转移反应过程的机理主要包括:甲醇的催化脱氢制甲醛;甲醛与底物脱水获得不饱和键;不饱和键原位加氢获得最终的产物。总结了近年来甲醇作为甲基化试剂,通过氢转移的方法制备甲基化胺、醇/酮以及烃类化合物催化体系的发展,并重点介绍了基于贵金属与非贵金属的均相和多相反应体系。鉴于反应过程中甲醇催化脱氢和不饱和键加氢对反应活性和选择性的影响这一科学问题,通过配位结构/金属载体的相互作用的调控有可能制备高催化性能均相/多相催化反应体系,且多相非贵金属催化体系具有较好的工业化应用前景。As the smallest saturated organic molecules containing carbon,hydrogen,and oxygen,methanol is widely utilized in energy,chemical industry and organic synthesis.This is a very meaningful study,in which methanol is used as a methylating agent to prepare high-value methylated products through coupling conversion with amines,alcohols/ketones,and hydrocarbon compounds by means of hydrogen transfer.The hydrogen transfer reaction mechanism mainly includes:catalytic dehydrogenation of methanol to formaldehyde,dehydration of formaldehyde and substrate to form unsaturated bonds,and in situ hydrogenation of unsaturated bonds to generate the final product.This paper summarizes the development of catalytic systems for preparing methylated amines,alcohols/ketones,and hydrocarbon compounds through hydrogen transfer using methanol as a methylating agent in recent years,and introduces the homogeneous and heterogeneous reaction systems based on noble and non-noble metals.Considering the effect of methanol catalytic dehydrogenation and unsaturated bond hydrogenation on reactivity and selectivity in the reaction process,it is possible to prepare homogeneous/heterogeneous catalytic reaction systems with high catalytic performance under regulation by the coordination structure and metal carrier interactions,and the heterogeneous non-noble metal catalytic system has a better commercial application prospect.

关 键 词：甲醇 甲基化 胺 醇 烃 

分 类 号：TQ426[化学工程]