甲醇制烃类反应机理研究进展

Research Progress on the Reaction Mechanism of Methanol to Hydrocarbons

摘要:

甲醇制烃类（MTH）反应是从非石油路线出发制取各种烃类的重要途径，有着重要的基础研究和工业应用价值，已成为煤基替代能源标志性的研究热点之一。然而，目前对甲醇制烃类反应机理的认知、反应步骤的确认仍存在巨大争论，复杂的反应网络限制了对反应机理的分析和证实，因而减缓了反应过程的反应器设计和工艺开发进程。本文从直接机理和间接机理两个方面，阐述了近年来MTH反应机理研究的主要进展，着重介绍了已被广泛接受的烃池双循环催化机理。MTH烃池机理涉及6个主要的化学过程—烯烃甲基化、烯烃裂解、氢转移、环化、芳烃甲基化和芳烃脱烷基化。系统了解该反应机理为精准设计催化剂的晶体型貌、尺寸和孔道结构、调控酸性位点的分布等提供理论依据，为这种复杂反应催化剂构-效关系的建立奠定基础，这对煤化工发展的产业化进程具有重要意义。

Abstract:

Methanol to hydrocarbon (MTH) reaction is an important way to prepare various hydrocarbons from non-oil routes, which has important basic research and industrial application value, and has become one of the research hotspots of coal-based alternative energy sources. However, there is still much debate about the understanding of the reaction mechanism of methanol-based hydrocarbons and the confirmation of reaction steps. The complex reaction network limited the analysis and verification of the reaction mechanism, thus slowing down the design of the reactor and development process of technology in these reactions. In this review, the main progress of the reaction mechanism of MTH in recent years is summarized from the two aspects: direct mechanism and indirect mechanism. The double-cycle catalytic mechanism of the hydrocarbon pool accepted widely was highlighted. The MTH hydrocarbon pool mechanism involved six major chemical processes: olefin methylation, olefin cracking, hydrogen transfer, cyclization, aromatic methylation and aromatic dealkylation. A systematic understanding of the mechanism of the reaction provides a theoretical basis, with accurately designing crystal shape, size, pore structure of the catalyst, as well as regulating of the distribution of acidic sites, which lays a foundation for the establishment of the catalytic structure-activity relationship of this complex reaction. This is of great significance to the industrialization process of the development of coal chemical industry.