Y_2O_3掺杂ZrO_2对苯选择加氢制环己烯催化剂Ru-La-B/ZrO_2性能的影响  

Effect of Y_2O_3-Doped ZrO_2 on the Catalytic Performance of Ru-La-B / ZrO_2 for Selective Hydrogenation of Benzene to Cyclohexene

作　　者：孙海杰[1,2] 陈凌霞[2] 李帅辉[1] 张元馨[1] 刘寿长[1] 刘仲毅[1] 任保增[3] 

机构地区：[1]郑州大学化学与分子工程学院,郑州450001 [2]郑州师范学院化学系环境与催化工程研究所,郑州450044 [3]郑州大学化工与能源学院,郑州450001

出　　处：《应用化学》2014年第11期1317-1322,共6页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金资助项目(21273205;U1304204);国家科技型中小企业创新基金(10C26214104505);河南省博士后科研项目资助(2013006)~~

摘　　要：用水热合成法制备了纳米Zr O2和Y2O3掺杂的Zr O2(Zr O2-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/Zr O2性能的影响。结果表明,2种Zr O2具有相同微晶尺寸、织构性质和粒度分布。但Zr O2仅含有单斜相Zr O2,而Zr O2-Y不但含有单斜相Zr O2,还含有一部分四方相Zr O2。Y2O3掺杂影响Zr O2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,Zr O2-Y负载Ru-La-B催化剂活性明显低于Zr O2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Zr O2表面羟基比单斜相少,Zr O2-Y负载Ru-La-B催化剂的亲水性比Zr O2负载的差。环己烯不易从Zr O2-Y负载的催化剂表面脱附。当苯转化率高于52%时,Zr O2-Y负载的催化剂的环己烯选择性低于单斜相Zr O2负载的。Zr O2负载的Ru-La-B催化剂上20 min的环己烯收率达到了52.1%,而Zr O2-Y负载的环己烯收率仅45.2%。纳米单斜相Zr O2较适宜作苯选择加氢制环己烯Ru催化剂的载体。The nano-scale pure ZrO2 and the Y2O3-doped ZrO2 （ZrO2-Y） synthesis method, and investigated have similar crystallite size, texture as supports of Ru-La-B/ZrO2 catalysts property and particle size distribution. ZrO2-Y not only has a monoclinic phase, but also some of the tetragonal were prepared by the hydrothermal It was confirmed that both of them ZrO2 only has a monoclinic phase. 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-seale monoclinie ZrO2 is more suitable support of the catalyst for the selective hydrogenation of benzene to cyclohexene.

关 键 词：苯 选择加氢 环己烯 二氧化锆 氧化钇掺杂 

分 类 号：O643[理学—物理化学]