化工进展 ›› 2021, Vol. 40 ›› Issue (12): 6696-6704.DOI: 10.16085/j.issn.1000-6613.2020-2582

• 工业催化 • 上一篇    下一篇

ZnZr/HZSM-5双功能催化剂在合成气与苯烷基化反应中的催化性能

刘海华1(), 李艳春1(), 丁传敏1, 葛晖2, 李学宽2, 张玮1   

  1. 1.太原理工大学化学化工学院,山西 太原 030024
    2.中国科学院山西煤炭化学研究所,山西 太原 030001
  • 收稿日期:2020-12-30 修回日期:2021-03-16 出版日期:2021-12-05 发布日期:2021-12-21
  • 通讯作者: 李艳春
  • 作者简介:刘海华(1994—)男,硕士研究生,研究方向为合成气制芳烃。E-mail:1909179700@qq.com
  • 基金资助:
    国家自然科学基金(21706178);山西省自然科学基金(201801D221074);中国博士后科学基金(2019M651079)

Catalytic performance of ZnZr/HZSM-5 bifunctional catalyst for the alkylation of syngas with benzene

LIU Haihua1(), LI Yanchun1(), DING Chuanmin1, GE Hui2, LI Xuekuan2, ZHANG Wei1   

  1. 1.College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
    2.Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China
  • Received:2020-12-30 Revised:2021-03-16 Online:2021-12-05 Published:2021-12-21
  • Contact: LI Yanchun

摘要:

将系列锌锆金属氧化物与HZSM-5分子筛耦合制备成双功能复合催化剂,并将其应用于合成气与苯烷基化反应。研究结果表明,ZnO是合成甲醇的主要活性组分,ZrO2的加入能够促进ZnO分散,同时其表面具有的氧空位可促进CO的活化,二者结合方式显著影响反应活性。SEM、XPS、CO-TPD等表征结果表明,ZnO与ZrO2相结合不仅能够提高ZnO的分散度,而且能调控氧化物表面的氧空位浓度,当二者形成固溶体时,锌在氧化锆中的分散度最大,表面氧空位浓度最高,CO吸附量最大,催化活性最高。锌锆结合方式一定时,锌含量是影响催化活性的另一重要因素,n(Zr)/n(Zn)=2的锌锆固溶体与HZSM-5以质量比1∶2耦合表现出最高的催化活性,CO和苯的转化率为34.65%和35.82%时,甲苯和二甲苯的总选择性高达85.24%。

关键词: 苯, 合成气, 烷基化, 双功能催化剂, 氧空位, 甲苯, 二甲苯

Abstract:

Alkylation of benzene with syngas was studied using a bi-functional ZnZr/HZSM-5 catalyst containing zinc oxide (ZnO), zirconium oxide (ZrO2) and HZSM-5 zeolite. The catalyst was carefully characterized and the results showed that ZnO was the main active component for the synthesis of methanol while the addition of ZrO2 not only helped the dispersion of ZnO but also generated large amount of oxygen vacancy that was beneficial to the adsorption and activation of CO. The combination of ZnO and ZrO2 significantly affected the catalytic activity, and the highest ZnO dispersion and oxygen vacancy concentration were obtained when the solid solution (ZnZryOx) was formed. The ZnZr2Ox coupling with HZSM-5 zeolite with the mass ratio of 1∶2 exhibited the best catalytic performance, resulting in benzene conversion of 35.82%, CO conversion of 34.65%, and the total toluene and xylene selectivity of 85.24%.

Key words: benzene, syngas, alkylation, bi-functional catalyst, oxygen vacancy, toluene, xylene

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