催化学报

催化学报 ›› 2013, Vol. 34 ›› Issue (8): 1482-1488.DOI: 10.1016/S1872-2067(12)60637-8

• 研究快讯 • 上一篇    下一篇

串联双釜连续反应装置中Ru-Co-B/ZrO2上苯选择加氢制环己烯

孙海杰a,b, 李帅辉a, 张元馨a, 江厚兵a, 曲良龙c, 刘寿长a, 刘仲毅a   

  1. a 郑州大学化学与分子工程学院, 河南郑州450001;
    b 郑州师范学院化学系, 环境与催化工程研究所, 河南郑州450044;
    c 北京安耐吉能源工程技术有限公司, 北京100190
  • 收稿日期:2013-04-18 修回日期:2013-06-20 出版日期:2013-08-16 发布日期:2013-07-30
  • 通讯作者: 刘仲毅
  • 基金资助:

    国家自然科学基金(21273205); 国家科技型中小企业创新基金(10C26214104505); 中国博士后科学基金(2012M511125); 郑州大学优秀博士论文培育基金.

Selective hydrogenation of benzene to cyclohexene in continuous reaction device with two reaction reactors in serie over Ru-Co-B/ZrO2 catalysts

Haijie Suna,b, Shuaihui Lia, Yuanxin Zhanga, Houbing Jianga, Lianglong Quc, Shouchang Liua, Zhongyi Liua   

  1. a College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China;
    b Institute of Environmental and Catalytic Engineering, Department of Chemistry, Zhengzhou Normal University, Zhengzhou 450044, Henan, China;
    c Beijing Energy Engineering Technologies Co., Ltd, Beijing 100190, China
  • Received:2013-04-18 Revised:2013-06-20 Online:2013-08-16 Published:2013-07-30
  • Supported by:

    This work was supported by the National Natural Science Foundation of China (21273205), the Innovation Found for Technology Based Firms of China (10C26214104505), the China Postdoctoral Science Foundation (2012M511125), and the Scientific Research Foundation of Graduate School of Zhengzhou University.

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摘要： 采用化学还原法制备了苯选择加氢制环己烯催化剂Ru-B/ZrO2,考察了Cr,Mn,Fe,Co,Ni,Cu和Zn等过渡金属的添加对Ru-B/ZrO2催化剂性能的影响.结果表明,这些过渡金属的添加均可提高Ru-B/ZrO2催化剂中的B含量.B的修饰及第二种金属或金属氧化物的集团效应和配位效应导致Ru-B/ZrO2催化剂活性降低和环己烯选择性升高.当Co/Ru原子比为0.06时,Ru-Co-B/ZrO2催化剂上反应25min苯转化率为75.8%时,环己烯选择性和收率分别为82.8%和62.8%.在双釜串联连续反应器中和优化反应条件下,Ru-Co-B/ZrO2催化剂使用419h内苯转化率稳定在40%左右,环己烯选择性和收率分别稳定在73%和30%左右.

关键词: 苯, 选择加氢, 环己烯, 钌, 过渡金属, 硼

Abstract: A Ru-B/ZrO2 catalyst for selective hydrogenation of benzene to cyclohexene was prepared using a chemical reduction method. The effects of transition metals such as Cr, Mn, Fe, Co, Ni, Cu, and Zn on the performance of the Ru-B/ZrO2 catalyst were investigated. It was found that the addition of these transition metals all increased the B content of the Ru-B/ZrO2 catalyst. The modification of B, the ensemble effect, and the ligand effect of the second metal or metal oxide resulted in a decrease in the activity and an increase in the selectivity for cyclohexene of the Ru-B/ZrO2 catalyst. When the atomic ratio of Co/Ru was 0.06, the Ru-Co-B/ZrO2 catalyst gave a selectivity for cyclohexene of 82.8% and a cyclohexene yield of 62.8% at a benzene conversion of 75.8% at 25 min. Moreover, the benzene conversion was stable at around 40%, and the selectivity for cyclohexene and the cyclohexene yields stabilized at around 73% and 30%, respectively, in 419 h under the optimum reaction conditions in a continuous device with two reactors in series.

Key words: Benzene, Selective hydrogenation, Cyclohexene, Ruthenium, Transition metal, Boron