化学学报 ›› 2012, Vol. 70 ›› Issue (08): 1021-1027.DOI: 10.6023/A1110173 上一篇    下一篇

研究论文

不同取代度纤维素苯甲酸酯负载钌纳米簇催化苯加氢反应

王丽娟a, 张爱清a, 李琳a, 刘汉范a,b, 刘书正a   

  1. a 中南民族大学 催化材料科学湖北省暨国家民委-教育部共建重点实验室 武汉 430074;
    b 中国科学院化学研究所 高分子物理与化学国家重点实验室 北京 100080
  • 收稿日期:2011-10-17 修回日期:2012-01-20 出版日期:2012-04-28 发布日期:2012-01-20
  • 通讯作者: 张爱清 E-mail:aiqingzhang_2000@sina.com
  • 基金资助:

    国家自然科学基金(No. 20774108)资助项目.

Cellulose Benzoyl Ester with Different Substitution Degree Supported Ru Nano-clusters Catalyst for Benzene Hydrogenation

Wang Lijuana, Zhang Aiqinga, Li Lina, Liu Hanfana,b, Liu Shuzhenga   

  1. a Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission and Ministry of Education, College of Chemistry and Materials Science, South-Central University for Nationalities, Wuhan 430074, China;
    b State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China
  • Received:2011-10-17 Revised:2012-01-20 Online:2012-04-28 Published:2012-01-20
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 20774108).

以纤维素为原料、苯甲酰氯为酯化剂的条件下合成了纤维素苯甲酸酯(CB), 通过控制苯甲酰氯的量得到了不同取代度的CB, 且不同取代度的CB 在苯、环己烯和环己烷中的溶胀度不同. 将CB 与正丁醇还原得到的单分散Ru 纳米簇进行杂化后得到Ru/CB 杂化膜, 并将其用于催化苯选择加氢反应. 利用傅立叶转换红外光谱仪, X-射线光电子能谱,X-射线衍射和透射电子显微镜对不同取代度的CB 和杂化膜的结构与性能进行了表征. 研究发现, 杂化膜的溶胀度是影响苯的转化率和环己烯选择性的重要因素. 活性评价结果表明, 苯的转化率随着取代度的增大而增大, 最高为2.8%;环己烯的选择性随取代度的增大而减小, 最高为53.4%.

关键词: 钌纳米簇, 纤维素苯甲酸酯, 苯, 环己烯, 溶胀

Cellulose benzoyl ester (CB) was synthesized from cellulose and benzoyl chloride. Different substitution degree CBs were obtained by controlling the amount of benzoyl chloride, and the resulting CBs have different swelling degree in benzene, cyclohexene and cyclohexane. Hybrid membrane, which was used for the selective hydrogenation, was prepared by supporting Ru nano-clusters (obtained by refluxing reduction of RuCl3 with n-butyl alcohol) into CB. CBs and the hybrid membranes were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and transmission electron microscope (TEM), etc. Research results demonstrated that swelling behavior acts as a crucial factor to the selectivity of cyclohexene. Active evaluation results indicated that the conversion of benzene (highest, 2.8%) increased while the selectivity of cyclohexene (highest, 53.4%) decreased with the increasing of CBs substitution degree.

Key words: Ru nano-cluster, cellulose benzoyl ester, benzene, cyclohexene, swelling