物理化学学报 >> 2014, Vol. 30 >> Issue (5): 932-942.doi: 10.3866/PKU.WHXB201403212

催化和表面科学 上一篇    下一篇

苯部分加氢制环己烯新型Ru-B/MOF催化剂

谭晓荷1, 周功兵1, 窦镕飞1, 裴燕1, 范康年1, 乔明华1, 孙斌2, 宗保宁2   

  1. 1 上海市分子催化和功能材料重点实验室, 复旦大学化学系, 上海200433;
    2 催化材料与反应工程国家重点实验室, 中国石化石油化工科学研究院, 北京100083
  • 收稿日期:2014-01-24 修回日期:2014-03-21 发布日期:2014-04-25
  • 通讯作者: 乔明华 E-mail:mhqiao@fudan.edu.cn
  • 基金资助:

    国家重点基础研究发展规划项目(973)(2012CB224804),国家自然科学基金(21373055),上海市科委科技基金(08DZ2270500),北京高能所同步辐射实验室开放课题及中石化技术开发课题(S411063)资助

Partial Hydrogenation of Benzene to Cyclohexene over Novel Ru-B/MOF Catalysts

TAN Xiao-He1, ZHOU Gong-Bing1, DOU Rong-Fei1, PEI Yan1, FAN Kang-Nian1, QIAO Ming-Hua1, SUN Bin2, ZONG Bao-Ning2   

  1. 1 Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200433, P. R. China;
    2 State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, China Petroleum & Chemical Corporation, Beijing 100083, P. R. China
  • Received:2014-01-24 Revised:2014-03-21 Published:2014-04-25
  • Contact: QIAO Ming-Hua E-mail:mhqiao@fudan.edu.cn
  • Supported by:

    The project was supported by the National Key Basic Research Program of China (973) (2012CB224804), National Natural Science Foundation of China (21373055), Science and Technology Commission of Shanghai Municipality, China (08DZ2270500), Beijing Synchrotron Radiation Facility, China and the China Petroleum & Chemical Corporation (S411063).

摘要:

制备了多种金属-有机骨架(MOF)材料,采用浸渍-化学还原法制备了非晶态Ru-B/MOF催化剂,考察了它们在苯部分加氢反应中的催化性能. 催化性能评价结果表明,这些催化剂的初始反应速率(r0)顺序为Ru-B/MIL-53(Al)>Ru-B/MIL-53(Al)-NH2>Ru-B/UIO-66(Zr)>Ru-B/UIO-66(Zr)-NH2>Ru-B/MIL-53(Cr)>Ru-B/MIL-101(Cr)>>Ru-B/MIL-100(Fe),环己烯初始选择性(S0)顺序为Ru-B/MIL-53(Al)≈Ru-B/MIL-53(Cr)>Ru-B/UIO-66(Zr)-NH2>Ru-B/MIL-101(Cr)>Ru-B/MIL-53(Al)-NH2>Ru-B/UIO-66(Zr)≈Ru-B/MIL-100(Fe). 催化性能最好的Ru-B/MIL-53(Al)催化剂上的r0S0分别为23 mmol·min-1·g-1和72%. 采用多种手段,对催化性能差异最为显著的Ru-B/MIL-53(Al)和Ru-B/MIL-100(Fe)催化剂的物理化学性质进行了表征. 发现MIL-53(Al)载体能够更好地分散Ru-B纳米粒子,粒子的平均尺寸为3.2 nm,而MIL-100(Fe)载体上Ru-B纳米粒子团聚严重,粒径达46.6 nm. 更小的粒径不仅能够提供更多的活性位,而且也有利于环己烯选择性的提高. 对Ru-B/MIL-53(Al)催化剂的反应条件进行了优化,在180 ℃和5 MPa的H2压力下,环己烯得率可达24%,展示了MOF材料用作苯部分加氢催化剂载体的良好前景.

关键词: 金属有机骨架, 钌, 苯, 环己烯, 部分加氢

Abstract:

A series of metal-organic framework (MOF) materials were synthesized together with the corresponding amorphous Ru-B/MOF catalysts, which were prepared by the impregnation-chemical reduction method. These materials were subsequently evaluated for the first time as catalysts for the partial hydrogenation of benzene to cyclohexene. The results for the initial hydrogenation rate (r0) for the different catalysts followed the trend Ru-B/MIL-53(Al)>Ru-B/MIL-53(Al)-NH2>Ru-B/UIO-66(Zr)>Ru-B/UIO-66(Zr)-NH2>Ru-B/MIL-53(Cr)> Ru-B/MIL-101(Cr)>>Ru-B/MIL-100(Fe), whereas the initial selectivity for cyclohexene (S0) was of the order of Ru-B/MIL-53(Al)≈Ru-B/MIL-53(Cr)>Ru-B/UIO-66(Zr)-NH2>Ru-B/MIL-101(Cr)>Ru-B/MIL-53(Al)-NH2>Ru-B/UIO-66(Zr)≈Ru-B/MIL-100(Fe). The Ru-B/MIL-53(Al) catalyst exhibited the highest r0 and S0 values of 23 mmol·min-1·-1 and 72%, respectively. The characterization results demonstrated that the Ru-B amorphous alloy nanoparticles were highly dispersed on MIL-53(Al) with the average diameter of 3.2 nm. In contrast, the Ru-B nanoparticles on MIL-100(Fe) had an average diameter of 46.6 nm. The smaller Ru-B nanoparticles not only provided more active sites for the hydrogenation to occur, but could also be beneficial in the formation of cyclohexene. The reaction conditions were further optimized for the Ru-B/MIL-53(Al) catalyst. At 180 ℃ under a H2 pressure of 5 MPa, a cyclohexene yield of 24% was obtained, highlighting the potential of MOF materials as catalyst supports for the partial hydrogenation of benzene.

Key words: Metal-organic framework, Ruthenium, Benzene, Cyclohexene, Partial hydrogenation

MSC2000: 

  • O643