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Citation: Zhou Gongbing, Wang Hao, Pei Yan, Qiao Minghua, Sun Bin, Zong Baoning. Pore Size Effect of Ru-Zn/ZrO2 Catalyst on Partial Hydrogenation of Benzene to Cyclohexene[J]. Acta Chimica Sinica, ;2017, 75(3): 321-328. doi: 10.6023/A16100569 shu

Pore Size Effect of Ru-Zn/ZrO2 Catalyst on Partial Hydrogenation of Benzene to Cyclohexene

  • a.

    Key Laboratory of Green Synthesis and Applications, College of Chemistry, Chongqing Normal University, Chongqing 401331

  • b.

    Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433

  • c.

    State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, Beijing 100083

  • Corresponding author: Qiao Minghua, mhqiao@fudan.edu.cn Zong Baoning, zongbn.ripp@sinopec.com
  • Received Date: 28 October 2016

    Fund Project: the National Key Research Program of China 2012CB224804the Science & Technology Commission of Chongqing Municipality cstc2016jcyjA0392the National Key Research and Development Project of China 2016YFB0301602the National Natural Science Foundation of China 21373055Beijing Synchrotron Radiation Facility, the Scientific and Technological Research Program of Chongqing Municipal Education Commission KJ1500305Science and Technology Commission of Shanghai Municipality 08DZ2270500

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  • Partial hydrogenation of benzene to cyclohexene is an important industrial process and features exceptional superiority to processes such as dehydration of cyclohexanol, dehydrogenation of cyclohexane, and the Birch reduction in terms of inexpensive feedstock, succinct reaction route and consequently, improved operational simplicity. In this work, the pore size effect on the partial hydrogenation of benzene to cyclohexene over the Ru-Zn/ZrO2 catalysts was studied for the first time. Three ZrO2 supports with the same tetragonal crystallographic form (t-ZrO2) but different pore sizes were synthesized by the precipitation and the solvothermal methods. Using these ZrO2 samples, the Ru-Zn/ZrO2 catalysts were prepared by the deposition-precipitation method followed by reduction in ZnSO4·7H2O aqueous solution. The supports and catalysts were characterized by powder X-ray diffraction (XRD), N2 physisorption, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), CO chemisorption, X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge structure (XANES), temperature-programmed reduction of H2 (H2-TPR), and transmission electron microscopy (TEM). It is identified that the Ru nanoparticles (NPs) on these catalysts had similar size and chemical state. In the partial hydrogenation of benzene to cyclohexene, a pronounced pore size effect of the catalyst was identified. With the increase in the pore size, while the turnover frequency (TOF) of benzene was essentially unchanged, the initial selectivity (S0) to cyclohexene increased steadily. The Ru-Zn/ZrO2(11.7) catalyst with the ZrO2 support having the pore size of 11.7 nm exhibited the highest S0 (88%) and yield (54%) of cyclohexene. On the basis of the characterization results, the similarity in the TOFs of benzene on the Ru-Zn/ZrO2 catalysts with different pore sizes is associated with the identical sizes of the Ru NPs. On the other hand, we tentatively propose that the ZrO2 support with large pore size is beneficial for the out-diffusion of the cyclohexene nano-droplets formed in the pore channels, thus avoiding consecutive hydrogenation to cyclohexane and improving the S0.
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