石油炼制与化工 ›› 2025, Vol. 56 ›› Issue (6): 20-27.

• 催化剂 • 上一篇    下一篇

Mg/Co浸渍MCM-22分子筛催化联苯与环己烷烷基化反应

张子杨1,2,罗明生1,2   

  1. 1.北京石油化工学院新材料与化工学院

    2.燃料清洁化及高效催化减排技术北京市重点实验室

  • 收稿日期:2024-05-23 修回日期:2024-06-20 出版日期:2025-06-12 发布日期:2025-05-30
  • 通讯作者: 张子杨 E-mail:2110298475@qq.com

ALKYLATION OF BIPHENYL WITH CYCLOHEXENE OVER Mg/Co IMPREGNATED MCM-22 ZEOLITE

  • Received:2024-05-23 Revised:2024-06-20 Online:2025-06-12 Published:2025-05-30

摘要: 以MCM-22分子筛催化联苯与环己烯反应合成4,4'-二环己基联苯(4,4'-DCBP)和4-环己基联苯(4-CBP)。采用普通浸渍法制备了Mg或Co改性的MCM-22分子筛,对比了以柠檬酸进行络合浸渍与普通浸渍的差异,通过X射线衍射、N2吸附-脱附、NH3程序升温脱附、扫描电子显微镜等方法对样品进行了表征,在n(联苯):n(环己烯)=1﹕1.5、初始压力0.5 MPa、反应温度230℃、反应时间200 min条件下进行催化性能评价。结果表明:两种浸渍方式均降低了分子筛的结晶度、比表面积、酸量及酸强度;络合浸渍能够有效避免金属进入分子筛孔道,从而减轻Mg在较高负载量下对孔道的堵塞,但负载量(w)在4%及4%以上时络合浸渍Co引起了分子筛表面金属氧化物的过量覆盖。采用普通浸渍方式负载质量分数4%的Co制备的4Co MCM-22分子筛表现出最佳催化性能,获得了56.5%的联苯转化率,67.2%的目标产物选择性及38.0%的目标产物收率。

关键词: 联苯烷基化, MCM-22分子筛, 金属氧化物改性, 络合浸渍

Abstract: 4,4'-dicyclohexyl biphenyl (4,4'-DCBP) and 4-cyclohexylbiphenyl (4-CBP) were synthesized by MCM-22 zeolite catalyzed reaction between biphenyl and cyclohexene. The MCM-22 zeolite modified by Mg or Co was prepared by ordinary impregnation method, the difference between complexed impregnation with citric acid and common impregnation was compared, and the samples were characterized by XRD, BET, NH3-TPD and SEM, and the catalytic performance was evaluated under the conditions of n(biphenyl):n(cyclohexene)=1:1.5, an initial pressureof 0.5 MPa,a reaction temperature of 230°C, and areaction time of200 min. The results showed that the two impregnation methods reduced the crystallinity, specific surface area, acid content and acid strength of zeolite. Complexation impregnation can effectively prevent metals from entering the molecular sieve pores, thereby reducing the blockage of the pores by Mg under higher loads, but complexing impregnationof Co at 4% and more than 4% loading causes excessive coverage of metal oxides on the surface of molecular sieves. The 4Co MCM-22 zeolite prepared by 4% ofCo by common impregnation showed the best catalytic performance, and obtained a biphenyl conversion rate of 56.5%, a target product selectivity of 67.2% and a target product yield of 38.0%.

Key words: biphenyl alkylation, MCM-22 zeolite, metal oxide modification, complexation impregnation