微波法高效合成全结晶ZSM-5分子筛催化剂及其催化性能

doi:10.16085/j.issn.1000-6613.2023-0618

化工进展 ›› 2023, Vol. 42 ›› Issue (7): 3582-3588.DOI: 10.16085/j.issn.1000-6613.2023-0618

微波法高效合成全结晶ZSM-5分子筛催化剂及其催化性能

王达锐(), 孙洪敏, 薛明伟, 王一棪, 刘威, 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国家重点实验室，上海 201208

收稿日期:2023-04-17 修回日期:2023-05-17 出版日期:2023-07-15 发布日期:2023-08-14
通讯作者: 杨为民
作者简介:王达锐（1990—），男，博士，高级工程师，研究方向为工业催化。E-mail：wangdr.sshy@sinopec.com。
基金资助:
材料基因工程关键技术与支撑平台专项(2017YFB0702800)

Efficient synthesis of fully crystalline ZSM-5 zeolite catalyst by microwave method and its catalytic performance

WANG Darui(), SUN Hongmin, XUE Mingwei, WANG Yiyan, LIU Wei, 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:2023-04-17 Revised:2023-05-17 Online:2023-07-15 Published:2023-08-14
Contact: YANG Weimin

摘要/Abstract

摘要：

采用微波法高效合成含有100%活性组分的全结晶ZSM-5分子筛催化剂，并采用X射线衍射、扫描/透射电子显微镜、固体核磁共振、比表面积及孔径分析以及机械强度测试等手段对样品进行综合表征分析。结果表明：采用微波辐射的加热方式，在优化的合成配方条件下，经过8h晶化，ZSM-5分子筛催化剂的相对结晶度已达到100%，其晶体形貌规整、97%铝原子为四配位状态，机械强度高达110N/cm，完全满足工业应用需求。此全结晶ZSM-5分子筛催化剂在接近工业装置的工艺条件下，在苯和乙烯气相烷基化反应中表现出优异的催化性能，其中乙烯转化率接近100%，乙基选择性大于99.6%，关键杂质二甲苯含量仅为450μL/L左右，且长周期稳定性能良好。

关键词: 微波法, 全结晶, 分子筛, 催化剂, 苯, 乙苯

Abstract:

Fully crystalline ZSM-5 zeolite catalyst with 100% active components was efficiently synthesized by the microwave radiation method, and the samples were characterized by X-ray diffraction (XRD), scanning/transmission electron microscopy (SEM and TEM), solid-state nuclear magnetic resonance (NMR), specific surface area and pore size analysis, and mechanical strength measurement. The results showed that the relative crystallinity of the obtained catalyst reached 100% after 8h crystallization under the optimized synthesis condition and heated by microwave irradiation. And the crystal morphology of the obtained ZSM-5 zeolite catalyst was regular and 97% of the aluminum atoms were in tetrahedral coordination. The mechanical strength of the catalyst was as high as 110N/cm, which fully meets the industrial application requirements. Under the process conditions close to the industrial ones, the fully crystalline ZSM-5 catalyst exhibited excellent catalytic performance and long-term stability in the gas-phase alkylation reaction of benzene and ethylene to ethylbenzene. The ethylene conversion rate was about 100% and the ethide selectivity was higher than 99.6%, while the key impurity xylene content was about 450μL/L.

Key words: microwave radiation method, fully crystalline, molecular sieves, catalyst, benzene, ethylbenzene

中图分类号:

O643.36

王达锐, 孙洪敏, 薛明伟, 王一棪, 刘威, 杨为民. 微波法高效合成全结晶ZSM-5分子筛催化剂及其催化性能[J]. 化工进展, 2023, 42(7): 3582-3588.

WANG Darui, SUN Hongmin, XUE Mingwei, WANG Yiyan, LIU Wei, YANG Weimin. Efficient synthesis of fully crystalline ZSM-5 zeolite catalyst by microwave method and its catalytic performance[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3582-3588.

图/表 12

图1 不同模板剂合成材料的XRD谱图

图2 不同晶化温度合成材料的XRD谱图

图3 不同晶化时间合成材料的XRD谱图

图4 不同晶化时间合成材料的相对结晶度

图5 不同晶化时间合成材料的SEM 照片

图6 全结晶ZSM-5分子筛催化剂的TEM照片和数码照片

图7 全结晶ZSM-5分子筛催化剂的N2吸附-脱附等温曲线

图8 全结晶ZSM-5分子筛催化剂的孔径分布曲线

图9 全结晶ZSM-5分子筛催化剂的29Si固体核磁共振谱图

图10 全结晶ZSM-5分子筛催化剂的27Al固体核磁共振谱图

图11 1000h稳定性实验中乙烯转化率和乙基选择性的变化曲线

图12 1000h稳定性实验中二甲苯含量的变化曲线

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微波法高效合成全结晶ZSM-5分子筛催化剂及其催化性能

Efficient synthesis of fully crystalline ZSM-5 zeolite catalyst by microwave method and its catalytic performance

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