甲醇制烯烃反应工艺、反应机理及其动力学研究进展  

Progresses in reaction processes,mechanism and kinetics of methanol to olefins

作　　者：王有和 吴成成 刘忠文[2] 季生福[1] Wang Youhe;Wu Chengcheng;Liu Zhongwen;Ji Shengfu(State Key Laboratory of Chemical Resource Engineering,Beijing University of Chemical Technology, Beijing 100029,China;Key Laboratory of Applied Surface and Colloid Chemistry,MOE,Shaanxi Normal University,Xi’an 710062,Shaanxi,China)

机构地区：[1]北京化工大学化工资源有效利用国家重点实验室,北京100029 [2]陕西师范大学应用表面与胶体化学教育部重点实验室,陕西西安710119

出　　处：《工业催化》2018年第1期13-21,共9页Industrial Catalysis

基　　金：陕西师范大学应用表面与胶体化学教育部重点实验室开放课题基金项目(2017026)

摘　　要：甲醇制烯烃工艺近年来已成为煤化工领域的研究热点。不同的甲醇制烯烃催化剂将导致不同的反应过程,以SAPO-34为催化剂时,甲醇主要遵循烃池机理,通过快速的平行反应直接生产乙烯和丙烯(MTO)等低碳烯烃;以ZSM-5为催化剂时,甲醇主要遵循双循环机理中的烯烃循环机理,通过甲基化-裂解等多步反应间接生产丙烯(MTP)。这种反应特征的不同也决定着反应器类型和工艺条件的不同:SAPO-34催化剂易失活的特性决定了工业MTO过程通常采用易再生的流化床反应器从甲醇一步生成乙烯和丙烯,而具有良好抗结焦能力的ZSM-5催化剂使得工业MTP过程通常选择易放大的固定床反应器,通过大量烯烃循环与分离逐步获得丙烯。针对SAPO-34催化剂上MTO过程以及ZSM-5催化剂上MTP过程的不同反应情况,综述了近年来甲醇制烯烃代表性的反应工艺、反应机理以及反应动力学等方面的研究进展,并根据其存在的问题提出了相应的发展方向。Methanol to olefins process has recently been a hot research topic in modern coal chemical industry.However,reaction mechanism and kinetic behavior differ greatly in case of different catalysts.Methanol-to-Olefins(MTO)over SAPO-34 catalyst is a direct conversion process following hydrocarbon pool mechanism,with methanol mainly transforming to ethylene and propylene rapidly through parallel reaction steps.On the contrary,Methanol-to-Propene(MTP)over ZSM-5 catalyst is a complex interconversion process and the propene comes mainly from methylation and cracking processes via the alkene cycle of dual-cycle mechanism.Hence,suitable reactors and different operating conditions must be chosen for commercial MTO or MTP processes.Ethene and propene can be produced over easily deactivated SAPO-34 catalyst in the commercial MTO process by one step in fluidized bed reactor,whereas fixed bed reactor is generally applied in the commercial MTP process over ZSM-5 catalyst with better anti-coking capability,and olefins should be separated and recycled for the maximum production of propene.In order to give a comprehensive understanding of methanol transformation over the SAPO-34 and ZSM-5 catalysts,advance in typical commercial reaction processes,mechanism and kinetics research of methanol to olefins(MTO/MTP)process would be reviewed in this paper.According to the existing problems and challenges,the prospective tendencies of methanol to olefins process are also proposed.

关 键 词：化学动力学 甲醇制烯烃 甲醇制丙烯 SAPO-34催化剂 ZSM-5催化剂 反应机理 反应动力学 

分 类 号：O643.12[理学—物理化学] TQ221.21[理学—化学]