化工进展 ›› 2019, Vol. 38 ›› Issue (10): 4554-4563.DOI: 10.16085/j.issn.1000-6613.2019-0086

• 工业催化 • 上一篇    下一篇

甲醇制烃反应ZSM-5催化剂微孔孔道控制的最新研究进展

王玉杰(),付廷俊(),马哲,邵娟,马倩,李晗,郭宇航,崔丽萍,李忠()   

  1. 太原理工大学煤科学与技术教育部和山西省重点实验室,山西 太原 030024
  • 收稿日期:2019-01-14 出版日期:2019-10-05 发布日期:2019-10-05
  • 通讯作者: 付廷俊,李忠
  • 作者简介:王玉杰(1994—),女,硕士研究生,研究方向为碳一化学。E-mail:994168079@qq.com
  • 基金资助:
    国家重点研发计划(2018YFB0604901);国家自然科学基金(21606160);山西省自然科学基金(201701D221039)

Recent progress on the control of microporous channel for ZSM-5 catalyst in methanol to hydrocarbon

Yujie WANG(),Tingjun FU(),Zhe MA,Juan SHAO,Qian MA,Han LI,Yuhang GUO,Liping CUI,Zhong LI()   

  1. Key Laboratory of Coal Science and Technology,Ministry of Education and Shanxi Province,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China
  • Received:2019-01-14 Online:2019-10-05 Published:2019-10-05
  • Contact: Tingjun FU,Zhong LI

摘要:

甲醇在ZSM-5分子筛催化作用下,定向转化为低碳烯烃、汽油和芳烃等产品,是现代煤化工的重要技术。虽然ZSM-5结构规整有序,酸性强且水热稳定性好,具备优异的择形催化效应,但其孔结构以微孔为主,反应产物不能快速扩散出微孔,易形成积炭,导致催化剂活性降低而快速失活。缩短微孔孔道促进产物扩散成为甲醇定向转化催化剂研究的关键问题。本文总结了近十年来关于ZSM-5微孔孔道控制的最新研究进展,归纳了通过控制其晶粒尺寸、形貌和介孔结构,调控微孔孔道长度,提升反应分子在微孔内扩散性能的方法,特别分析了上述控制因子的关键调控机制;提出对纳米尺度的ZSM-5进一步精准构筑介孔结构,是获得高稳定性催化剂的重要途径;而在控制孔结构的基础上,优化表面酸性,有望提升甲醇制烃反应的产物选择性。本综述期望为甲醇制烃领域研究提供相关理论基础。

关键词: 分子筛, 微孔控制, 晶粒尺寸与形貌, 介孔构建, 甲醇制烃, 稳定性, 选择性

Abstract:

Methanol can be selectively transformed into light olefins, gasoline, aromatics and other products under the catalysis of ZSM-5 zeolite, which is an important technical route of modern coal chemical industry. ZSM-5 zeolite with regular and ordered structure, strong acidity, good hydrothermal stability and excellent shape-selectivity effect is extensively applied in the conversion of methanol to hydrocarbons. However, the product molecules cannot rapidly diffuse out of the microporous channels due to the transition limitation caused by the purely microporous structure of ZSM-5, and tend to form coke, leading to the reduction of catalyst activity and rapid deactivation. Therefore, reducing the length of microporous channels and improving the product diffusion performance become the key issues in the research of catalysts for directional methanol conversion. In this paper, the latest research on the control of microporous channels of ZSM-5 catalysts in the last decade is summarized, and the means of controlling the grain size, morphology and mesoporous structure of ZSM-5 to regulate the length of its microporous channel and improve the diffusion performance of reactive molecules are generalized. Typically, the key regulatory mechanism of the above control factors is analyzed. It is proposed that the further precise construction of mesoporous structure of nano-scale ZSM-5 is an important way to obtain highly stable catalysts in methanol to hydrocarbon(MTH) process. On the basis of controlling the porous structure, the selectivity of methanol to hydrocarbon is expected to be improved by accurately optimizing the surface acidity. This review is expected to provide a theoretical basis for the study of methanol to hydrocarbon.

Key words: zeolite, control of micropores, crystal size and morphology, mesopore fabrication, methanol to hydrocarbon, stability, selectivity

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