全结晶MCM-22分子筛催化剂的制备及其催化性能

doi:10.16085/j.issn.1000-6613.2023-1513

化工进展 ›› 2024, Vol. 43 ›› Issue (1): 285-291.DOI: 10.16085/j.issn.1000-6613.2023-1513

• 专栏：化工过程强化 • 上一篇

全结晶MCM-22分子筛催化剂的制备及其催化性能

王一棪(), 王达锐, 沈震浩, 何俊琳, 孙洪敏, 杨为民()

中石化（上海）石油化工研究院有限公司，绿色化工与工业催化全国重点实验室，上海 201208

收稿日期:2023-08-30 修回日期:2023-10-16 出版日期:2024-01-20 发布日期:2024-02-05
通讯作者: 杨为民
作者简介:王一棪（1992—），女，博士，研究方向为工业催化。E-mail：wangyiyan.sshy@sinopec.com。
基金资助:
材料基因工程关键技术与支撑平台专项项目(2017YFB0702800);上海市科研计划专项项目(22YS1401100)

Preparation and catalytic performance of fully crystalline MCM-22 zeolite catalyst

WANG Yiyan(), WANG Darui, SHEN Zhenhao, HE Junlin, SUN Hongmin, YANG Weimin()

State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Sinopec Shanghai Research Institute of Petrochemical Technology Co. , Ltd. , Shanghai 201208, China

Received:2023-08-30 Revised:2023-10-16 Online:2024-01-20 Published:2024-02-05
Contact: YANG Weimin

摘要/Abstract

摘要：

采用水热晶化法高效合成了全结晶的MCM-22分子筛催化剂，利用X射线衍射、扫描/透射电子显微镜、NH₃-TPD等手段对催化剂的晶体结构、微观形貌、酸性质等进行了综合表征，并考察了催化剂在苯和乙烯液相烷基化制乙苯反应中的催化性能。结果表明，该全结晶MCM-22分子筛催化剂在160℃条件下40h即可完成晶化，相对结晶度达到100%。制得的分子筛为薄片层状结构，由100%活性组分组成。晶化后的催化剂成品仍维持条状形貌，机械强度达到82N/cm，满足工业应用需求。将该全结晶MCM-22分子筛催化剂应用于液相烷基化反应时，在反应温度180℃、反应压力3.5MPa、乙烯质量空速1h^-1、苯与乙烯摩尔比为2.5的条件下运行1000h，催化剂表现出良好的反应活性、选择性和稳定性，乙烯转化率接近100%，乙基选择性约99.84%，重组分含量始终维持在1000μL/L左右。

关键词: 水热, 结晶, 分子筛, 催化剂, 苯

Abstract:

Fully crystalline MCM-22 zeolite catalyst was efficiently synthesized by hydrothermal crystallization method. The crystal structure, micro morphology, and acid property of the as-prepared catalyst were characterized by X-ray diffraction, scanning/transmission electron microscopy (SEM and TEM), NH₃-TPD, and so on. The catalytic performance of the as-prepared catalyst in the liquid-phase alkylation of benzene and ethylene to ethylbenzene was investigated. The results showed that the relative crystallinity of MCM-22 zeolite with ultra-thin layered structure reached 100% after 40h crystallization at 160℃. In addition, the morphology of the catalyst after crystallization remained in strip shape with 100% active component, and the mechanical strength of the catalyst was as high as 82N/cm, which fully met the requirement of industrial application. Under reaction conditions close to industrial process: temperature of 180℃, pressure of 3.5MPa, ethylene weight hourly space velocity (WHSV) of 1h^-1, molar ratio of benzene to ethylene of 2.5, the as-prepared fully crystallized MCM-22 zeolite catalyst showed good catalytic activity, selectivity, and stability. The ethylene conversion and the ethyl selectivity of the catalyst were close to 100% and 99.84%, respectively, and the content of heavy components remained about 1000μL/L within 1000h.

Key words: hydrothermal, crystallization, zeolite, catalyst, benzene

中图分类号:

O643.36

王一棪, 王达锐, 沈震浩, 何俊琳, 孙洪敏, 杨为民. 全结晶MCM-22分子筛催化剂的制备及其催化性能[J]. 化工进展, 2024, 43(1): 285-291.

WANG Yiyan, WANG Darui, SHEN Zhenhao, HE Junlin, SUN Hongmin, YANG Weimin. Preparation and catalytic performance of fully crystalline MCM-22 zeolite catalyst[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 285-291.

图/表 8

图1 不同晶化时间合成催化剂样品的XRD谱图和相对结晶度

图2 全结晶MCM-22分子筛催化剂晶化前和成品的照片

图3 不同晶化时间合成的无黏结剂样品和含黏结剂样品M的扫描电子显微镜照片

图4 不同样品的透射电子显微镜(TEM)照片

图5 全结晶MCM-22分子筛催化剂和含黏结剂样品M的低温氮气吸-脱附等温曲线

图6 全结晶MCM-22分子筛催化剂和含黏结剂样品M的NH3-TPD曲线

图7 1000h稳定性实验中乙烯转化率和乙基选择性的变化曲线

图8 1000h稳定性实验中C12+重组分含量的变化曲线

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全结晶MCM-22分子筛催化剂的制备及其催化性能

Preparation and catalytic performance of fully crystalline MCM-22 zeolite catalyst

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