CeO2复合改性ZSM-5分子筛用于催化甲醇制丙烯研究

硅酸盐通报 ›› 2022, Vol. 41 ›› Issue (7): 2549-2557.

CeO₂复合改性ZSM-5分子筛用于催化甲醇制丙烯研究

杨欣欣^1,2,3, 刘飞^1,2,3, 姚梦琴^1,2,3

1.贵州大学化学与化工学院,贵阳 550025;
2.贵州大学,贵州省绿色化工与清洁能源技术重点实验室,贵阳 550025;
3.贵州大学,贵州省工业废弃物高效利用工程研究中心,贵阳 550025

收稿日期:2022-03-03 修回日期:2022-04-21 出版日期:2022-07-15 发布日期:2022-08-01
通讯作者: 刘飞,博士,教授。E-mail:ce.feiliu@gzu.edu.cn
姚梦琴,博士,讲师。E-mail:mqyao@gzu.edu.cn
作者简介:杨欣欣(1994—),女,硕士研究生。主要从事能源资源催化转化相关的研究。E-mail:2918006366@qq.com
基金资助:
贵州省教育厅创新群体项目(黔教合KY字[2021]010);贵州省百层次创新型人才专项(黔科合平台人才[2016]5655);贵州省科技创新人才团队(黔科合平台人才[2018]5607);贵州省优秀青年科技人才项目(黔科合平台人才[2019]5645);遵义市创新人才团队培养项目(遵义科人才[2020]9)

CeO₂ Composite Modified ZSM-5 Molecular Sieve for Catalyzing Methanol to Propylene

YANG Xinxin^1,2,3, LIU Fei^1,2,3, YAO Mengqin^1,2,3

1. School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, China;
2. Guizhou Key Laboratory for Green Chemical and Clean Energy Technology, Guizhou University, Guiyang 550025, China;
3. Guizhou Engineering Research Center for Efficient Utilization of Industrial Waste, Guizhou University, Guiyang 550025, China

Received:2022-03-03 Revised:2022-04-21 Online:2022-07-15 Published:2022-08-01

摘要/Abstract

摘要： 在甲醇制丙烯(MTP)反应中,ZSM-5分子筛较强的酸性易使甲醇与ZSM-5接触发生氢转移、芳构化等二次反应,堵塞孔道,使得其微孔结构更加不利于分子的扩散,加速催化剂积碳失活,导致丙烯选择性和丙烯/乙烯(P/E)比值下降。因此,本文利用催化活性较高的CeO₂对ZSM-5分子筛进行复合改性以达到有效降低其酸性并增大介孔的目的来提高丙烯选择性和P/E比。通过XRD、NH₃-TPD和N₂吸脱附技术表征,研究了不同ZSM-5硅铝比(摩尔比)、两相质量比(m(CeO₂)/m(ZSM-5))对CeO₂/ZSM-5复合催化剂物化性质的影响。在反应温度480 ℃、重时空速2.6 h^-1、N₂流量100 mL·min^-1、常压纯甲醇进料的条件下,考察了所制备的复合催化剂催化MTP的性能。结果表明,硅铝比为250、m(CeO₂)/m(ZSM-5)为1∶4的复合催化剂比以往研究结果具有更优异的MTP催化性能,甲醇转化率为99.9%,丙烯选择性为42.78%,P/E比为6.3。

关键词: CeO₂, ZSM-5分子筛, 复合改性, 甲醇制丙烯, 酸性, 介孔结构, 丙烯选择性, 丙烯/乙烯比

Abstract: In methanol to propylene (MTP) reaction, due to the strong acidity of ZSM-5 molecular sieve, the secondary reactions such as hydrogen transfer and aromatization between methanol and ZSM-5 are easy to block the pores, making its microporous structure more unfavorable to the diffusion of molecules, accelerating the carbon deposition and deactivation of the catalyst, resulting in the decrease of propylene selectivity and propylene/ethylene (P/E) ratio. Therefore, in this paper, ZSM-5 molecular sieve was modified by CeO₂ with high catalytic activity to effectively reduce its acidity and increase mesoporous, so as to improve propylene selectivity and P/E ratio. The effects of different n(SiO₂)/n(Al₂O₃) and mass ratio of two phases (m(CeO₂)/m(ZSM-5)) on the physicochemical properties of CeO₂/ZSM-5 catalysts were investigated by XRD, XRF, NH₃-TPD and N₂ adsorption and desorption. When the reaction temperature was 480 ℃, the weight hourly space velocity was 2.6 h^-1, the nitrogen flow rate was 100 mL·min^-1, the pressure was atmospheric and pure methanol was fed, and the MTP catalytic performance of the prepared composite catalyst was investigated. The results indicate that the composite catalyst with n(SiO₂)/n(Al₂O₃) of 250 and m(CeO₂)/m(ZSM-5) of 1∶4 exhibits better MTP catalytic performance than the previous research results, with conversion of methanol of 99.9%, selectivity of propylene of 42.78%, and P/E ratio of 6.3.

Key words: compound modification, methanol to propylene, acid, mesoporous structure, selectivity of propylene, propylene/ethylene ratio

中图分类号:

TQ032.4

杨欣欣, 刘飞, 姚梦琴. CeO₂复合改性ZSM-5分子筛用于催化甲醇制丙烯研究[J]. 硅酸盐通报, 2022, 41(7): 2549-2557.

YANG Xinxin, LIU Fei, YAO Mengqin. CeO₂ Composite Modified ZSM-5 Molecular Sieve for Catalyzing Methanol to Propylene[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2022, 41(7): 2549-2557.

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CeO₂复合改性ZSM-5分子筛用于催化甲醇制丙烯研究

CeO₂ Composite Modified ZSM-5 Molecular Sieve for Catalyzing Methanol to Propylene

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