催化学报

催化学报 ›› 2012, Vol. 33 ›› Issue (12): 1913-1918.DOI: 10.1016/S1872-2067(11)60469-5

• 研究论文 • 上一篇    下一篇

NaBH4 还原制备 Ru-[bmim]BF4 及催化苯选择加氢反应性能

薛伟a, 秦燕飞, 李芳, 王延吉b, 王志苗   

  1. 河北工业大学化工学院, 绿色化工与高效节能河北省重点实验室, 天津 300130
  • 收稿日期:2012-08-20 修回日期:2012-09-17 出版日期:2013-01-18 发布日期:2012-12-18

Preparation of Ru-[bmim]BF4 Catalyst Using NaBH4 as Reducing Agent and Its Performance in Selective Hydrogenation of Benzene

XUE Weia, QIN Yanfei, LI Fang, WANG Yanjib, WANG Zhimiao   

  1. Hebei Provincial Key Lab of Green Chemical Technology and High Efficient Energy Saving, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
  • Received:2012-08-20 Revised:2012-09-17 Online:2013-01-18 Published:2012-12-18

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摘要： 在离子液体 1-丁基-3-甲基咪唑四氟硼酸盐 ([bmim]BF4)-水混合介质中, 以 NaBH4 为还原剂制备了 Ru-[bmim]BF4 催化剂, 并用于苯选择加氢反应. 结果表明, 相对于 N2H4•H2O 还原制备的催化剂, 本催化剂具有明显较高的环己烯选择性, 当苯转化率为 49.5% 时, 环己烯选择性可达 34.1%, 这是由于硼的作用所致. 重复使用时, 由于离子液体的流失, 暴露的 Ru 活性中心增多, 因而苯转化率升高, 但环己烯选择性下降, 同时生成了 ZnOHF. 这是离子液体中 F–与 ZnSO4 反应而得; 并且在离子液体的模板作用下, ZnOHF 沿着 (001) 方向生长, 从而形成了一维棒状形貌.

关键词: 钌, 1-丁基-3-甲基咪唑四氟硼酸盐, 硼氢化钠, 羟基氟化锌, 苯, 选择加氢

Abstract: A Ru-[bmim]BF4 catalyst was prepared in a mixture of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF4) and H2O using NaBH4 as a reducing agent. The Ru-[bmim]BF4 catalyst showed higher selectivity for cyclohexene than a catalyst reduced by N2H4·H2O because of the influence of boron. When Ru-[bmim]BF4 was reused, higher activity and lower selectivity were obtained because the number of Ru active sites increased through leaching of the ionic liquid. The used catalyst also contained ZnOHF formed in the reaction between F– and ZnSO4, which was an additive in the reaction. Under the influence of the ionic liquid as a template, ZnOHF grew along the (001) direction and exhibited rod-like morphology.

Key words: ruthenium, 1-butyl-3-methylimidazolium tetrafluoroborate, sodium borohydride, zinc hydroxyfluoride, benzene, selective hydrogenation