Research progress of SSZ-13 and SAPO-34 zeolites for methanol to olefins

doi:10.16085/j.issn.1000-6613.2017.01.021

Abstract

Abstract: SSZ-13 and SAPO-34 are excellent zeolites for the catalyzation of MTO(methanol to olefins,MTO). From the respects of acidity,coke deposition,hydrocarbon pool species and the MTO reaction pathway,the differences of acid strength and acid site density between SSZ-13 and SAPO-34 and their effects on catalytic performance in MTO process are discussed. The catalyzation mechanism and the deactivation mechanism of SSZ-13 and SAPO-34 are also reviewed. It is found that although SSZ-13 and SAPO-34 have the same CHA framework topology,the acidity of SSZ-13 is stronger than that of SAPO-34,which is more favorable to produce carbonium ions. Compared with the paring mechanism,the side-chain methylation mechanism is more predominant and the methylation rate for SSZ-13 is approximately 3 orders of magnitude higher than that for SAPO-34. There are also some differences in the rate and nature of coke formation,which are influenced greatly by temperature. Therefore,from the perspective of the catalysts,controlling the acid strength and acid site density reasonably,developing a new type of structure that can prevent catalyst deactivation and preparing a typical catalyst of high yield of ethylene or propylene will be the future trend of research. Regarding the reaction mechanism,for SSZ-13 and SAPO-34,the formation of active intermediate compounds, their further transformation and the evolution of active species to coke species should be further studied. In addition,direct observation of the carbonium ions of high reactivity during the reaction of MTO is a great challenge.

Key words: SSZ-13, SAPO-34, molecular sieves, methanol to olefins(MTO)

摘要： SSZ-13和SAPO-34是性能优异的甲醇制烯烃（methanol to olefins，MTO）催化剂。本文从酸性、积炭、烃池物种及其反应途径等方面介绍了SSZ-13和SAPO-34的酸强度和酸中心密度的差异及其对MTO反应催化性能的影响，综述了SSZ-13和SAPO-34在MTO中的催化反应机理和失活机理的研究进展。总结显示，尽管SSZ-13和SAPO-34都是CHA型拓扑结构，但SSZ-13的酸性强于SAPO-34，更有利于碳正离子的生成；与修边机理相比，侧链烷基化机理是更主要的反应途径，且SSZ-13的甲基化速率比SAPO-34高3个数量级；SSZ-13和SAPO-34的积炭速率和积炭物种存在差异，积炭行为受温度影响较大。从催化剂的角度，指出合理调控酸强度和酸中心密度、研制出能够抑制反应失活的催化剂结构、发展高产乙烯或者丙烯的特色MTO催化剂是以后的研究方向；从反应机理的角度，认为SSZ-13和SAPO-34在MTO反应中活性中间体的形成以及转化途径、活性物种到积炭物种的演变有待进一步研究。此外，如何在MTO反应过程中观察到高活性的反应中间体是今后研究的难点。

关键词: SSZ-13, SAPO-34, 分子筛, 甲醇制烯烃

CLC Number:

O643.36

ZHAO Fei, LI Yuan, ZHANG Yan, TAN Xiaoyao. Research progress of SSZ-13 and SAPO-34 zeolites for methanol to olefins[J]. Chemical Industry and Engineering Progree, 2017, 36(01): 166-173.

赵飞, 李渊, 张岩, 谭小耀. 对比SSZ-13和SAPO-34分子筛在甲醇制烯烃中的研究进展[J]. 化工进展, 2017, 36(01): 166-173.

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