Y2O3掺杂ZrO2对苯选择加氢制环己烯催化剂Ru-La-B/ZrO2性能的影响

doi:10.3724/SP.J.1095.2014.40022

摘要/Abstract

摘要： 用水热合成法制备了纳米ZrO2和Y2O3掺杂的ZrO2(ZrO2-Y)，并考察了它们作载体对苯选择加氢制环己烯催化剂Ru-La-B/ZrO2性能的影响。结果表明，2种ZrO2具有相同微晶尺寸、织构性质和粒度分布。但ZrO2仅含有单斜相ZrO2，而ZrO2-Y不但含有单斜相ZrO2，还含有一部分四方相ZrO2。 Y2O3掺杂影响ZrO2的组成和物相，进而影响用其制备催化剂的组成和物相。掺杂的Y2O3可以占据一部分不适宜苯加氢生成环己烯的活性位。因此，ZrO2-Y负载Ru-La-B催化剂活性明显低于ZrO2负载的，在低苯转化率下环己烯选择性前者比后者高。由于四方相ZrO2表面羟基比单斜相少，ZrO2-Y负载Ru-La-B催化剂的亲水性比ZrO2负载的差。环己烯不易从ZrO2-Y负载的催化剂表面脱附。当苯转化率高于52%时，ZrO2-Y负载的催化剂的环己烯选择性低于单斜相ZrO2负载的。 ZrO2负载的Ru-La-B催化剂上20 min的环己烯收率达到了52.1%，而ZrO2-Y负载的环己烯收率仅45.2%。纳米单斜相ZrO2较适宜作苯选择加氢制环己烯Ru催化剂的载体。

关键词: 苯, 选择加氢, 环己烯, 二氧化锆, 氧化钇掺杂

Abstract: The nano-scale pure ZrO2 and the Y2O3-doped ZrO2(ZrO2-Y) were prepared by the hydrothermal synthesis method, and investigated as supports of Ru-La-B/ZrO2 catalysts. It was confirmed that both of them have similar crystallite size, texture property and particle size distribution. ZrO2 only has a monoclinic phase. ZrO2-Y not only has a monoclinic phase, but also some of the tetragonal phase. Y2O3 doping can affect the composition and the phase structure of ZrO2. The Y2O3 doping can cover some of the active sites which are unsuitable for the formation of cyclohexene. Thus the activity of the catalyst supported on ZrO2-Y is lower than that of catalyst supported on ZrO2, and the selectivity to cyclohexene of the former is higher than that of the latter at low benzene conversion. The Ru-La-B catalysts supported on ZrO2-Y has a poorer hydrophilicity than that supported on ZrO2 due to the lower content of the surface hydroxyl groups on the tetragonal phase of ZrO2-Y. It is difficult for cyclohexne to be desorbed from the surface of the catalyst with ZrO2-Y as supports. Thus the selectivity to cyclohexene of the catalyst supported on ZrO2-Y is lower than that supported on ZrO2 when the benzene conversion exceeds 52.0%. A cyclohexene yield of 52.1% is achieved on the Ru-La-B catalysts supported on ZrO2 at 20 min, however, only 45.2% is obtained on that supported on ZrO2-Y. Therefore, the nano-scale monoclinic ZrO2 is more suitable support of the catalyst for the selective hydrogenation of benzene to cyclohexene.

Key words: benzene, selective hydrogenation, cyclohexene,ZrO2, Y2O3 doping

中图分类号:

O643

孙海杰, 陈凌霞, 李帅辉, 张元馨, 刘寿长, 刘仲毅, 任保增. Y₂O₃掺杂ZrO₂对苯选择加氢制环己烯催化剂Ru-La-B/ZrO₂性能的影响[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.40022.

SUN Haijie1,2, CHEN Lingxia2, LI Shuaihui1, ZHANG Yuanxin1, LIU Shouchang1, LIU Zhongyi1*, REN Baozeng3. Effect of Y₂O₃-Doped ZrO₂ on the Catalytic Performance of Ru-La-B/ZrO₂ for Selective Hydrogenation of Benzene to Cyclohexene[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.40022.

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Y₂O₃掺杂ZrO₂对苯选择加氢制环己烯催化剂Ru-La-B/ZrO₂性能的影响

Effect of Y₂O₃-Doped ZrO₂ on the Catalytic Performance of Ru-La-B/ZrO₂ for Selective Hydrogenation of Benzene to Cyclohexene

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