石油炼制与化工 ›› 2022, Vol. 53 ›› Issue (10): 42-49.

• 催化剂 • 上一篇    下一篇

不同硅铝比小晶粒ZSM-5分子筛的合成及催化苯/甲醇烷基化反应性能

魏书梅   

  1. 中国石油乌鲁木齐石化公司研究院
  • 收稿日期:2022-02-11 修回日期:2022-05-25 出版日期:2022-10-12 发布日期:2022-09-23
  • 通讯作者: 魏书梅 E-mail:weismws@petrochina.com.cn
  • 作者简介:2022-08-10

SYNTHESIS OF SMALL PARTICLE SIZE ZSM-5 ZEOLITE WITH DIFFERENT Si/Al RATIO AND ITS CATALYTIC ACTIVITY FOR BENZENE/METHANOL ALKYLATION

  • Received:2022-02-11 Revised:2022-05-25 Online:2022-10-12 Published:2022-09-23

摘要: 采用简单的原位水热合成法制备了5种硅铝比的小晶粒多级孔ZSM-5分子筛,对制备的小晶粒多级孔ZSM-5分子筛进行了X射线衍射、NH3程序升温脱附、N2吸附-脱附等表征分析,考察了不同硅铝比的ZSM-5分子筛催化苯/甲醇烷基化反应的性能。结果表明:合成的5种不同硅铝比的ZSM-5分子筛具有多级孔结构,呈现不规则的颗粒状,晶粒尺寸较小,颗粒聚集形成蜂窝状;随着硅铝比升高,分子筛的比表面积和孔体积增大、酸强度减小、酸量降低。在470 ℃、0.5 MPa、质量空速2 h-1、苯/甲醇摩尔比1:1条件下,不同硅铝比ZSM-5分子筛催化苯/甲醇烷基化反应的结果表明:随着分子筛硅铝比升高,苯转化率和二甲苯选择性提高,乙苯选择性降低;当分子筛硅铝比为150、反应时间为72 h时,苯转化率最高为62.92%,二甲苯选择性为37.38%,乙苯选择性为0.81%;该ZSM-5分子筛运行1 200 h后仍具有良好的活性,应用前景较好。

关键词: 硅铝比, 小晶粒, 多级孔, ZSM-5, 烷基化

Abstract: Five kinds of Si/Al ratio ZSM-5 zeolites with small particle size and hierarchical pore were prepared by simple in-situ hydrothermal methods. XRD, N2 adsorption-desorption, NH3-TPD, Py-IR and SEM were used to characterize the prepared ZSM-5. The catalytic performance of ZSM-5 Zeolites with different Si/Al ratio for benzene/methanol alkylation was investigated. The results showed that the ZSM-5 zeolites with different Si/Al ratio had multi-stage pore structure, irregular particle shape, small crystal size and honeycomb shape. Under the conditions of 470 ℃, 0.5 MPa (H2) and space velocity 2 h-1, n(methanol): n(benzene)=1:1, the alkylation of benzene with methanol catalyzed by ZSM-5 zeolites with different Si/Al ratio was studied. The results showed that the conversation of benzene was 62.92%, the selectivity of xylene was 37.38%, and the selectivity of ethylbenzene 0.81% when n(SiO2)/n(Al2O3) was 150 and the reaction time was 72 h. The ZSM-5 still has good activity after 1 200 h operation and has a good application prospect.

Key words: Si/Al ratio, small particle size, hierarchical, ZSM-5, alkylation