| 孙海杰,朱冰,黄振旭,李永宇,刘寿长,刘仲毅.助剂前体ZnSO4浓度对苯选择加氢制环己烯Ru-Zn催化剂性能的影响[J].分子催化,2016,30(2):105-114 |
| 助剂前体ZnSO4浓度对苯选择加氢制环己烯Ru-Zn催化剂性能的影响 |
| Effect of the concentration of the promoter precursor ZnSO4 on the performance of the Ru-Zn catalyst for selective hydrogenation of benzene to cyclohexene |
| 投稿时间：2016-01-29 修订日期：2016-03-20 |
| DOI： |
| 中文关键词: 苯 选择加氢 环己烯 钌 锌 助剂前体 |
| 英文关键词:benzene selective hydrogenation cyclohexene Ru Zn promoter precursor |
| 基金项目:国家自然科学基金(21273205，U1304204)；河南省科技攻关项目(162102210333)；河南省高校重点科研项目(16A150025) |
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| 中文摘要: |
| 共沉淀法制备了Ru-Zn催化剂，在ZrO2作分散剂下考察了助剂前体ZnSO4浓度对苯选择加氢制环己烯Ru-Zn催化剂性能的影响。并用X-射线衍射(XRD)、X-射线荧光光谱(XRF)、N2-物理吸附、透射电镜(TEM)和X-射线光电子能谱(XPS)等手段对催化剂进行了表征。结果表明，当ZnSO4前体浓度低于0.10 mol/L时，Ru-Zn催化剂中Zn以ZnO形式存在，在加氢过程中ZnO可以与反应修饰剂ZnSO4反应生成(Zn(OH)2)3(ZnSO4)(H2O)3盐。继续增加ZnSO4前体浓度，催化剂中Zn以ZnO和NaZn4(SO4)(Cl)(OH)6•6H2O盐存在，在加氢过程中ZnO和NaZn4(SO4)(Cl)(OH)6•6H2O盐可以与反应修饰剂ZnSO4反应生成(Zn(OH)2)3(ZnSO4)(H2O)5。(Zn(OH)2)3(ZnSO4)(H2O) x (x=3或5)盐的Zn2+可以转移金属Ru的部分电子。因此，随ZnSO4前体浓度的增加，(Zn(OH)2)3(ZnSO4)(H2O) x的量逐渐增加，金属Ru失电子越多，催化剂活性越低，环己烯选择性越高。0.08 mol/L ZnSO4 前体制备Ru-Zn催化剂给出了59.1%的环己烯收率，而且该催化剂具有良好的重复使用性能和稳定性。 |
| 英文摘要: |
| The Ru-Zn catalysts were prepared by a co-precipitation method. The effect of the concentration of the promoter precursor ZnSO4 on the performance of Ru-Zn catalysts for selective hydrogenation of benzene to cyclohexene was investigated with ZrO2 as a dispersant. And the catalysts were characterized by X-ray diffraction (XRD), X-fluorescence (XRF), N2 physisorption, transimission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). It was found that when the concentration of the promoter precursor ZnSO4 was lower than 0.10 mol/L the Zn in the Ru-Zn catalyst were mostly in the form of ZnO, which could react with the reaction modifier ZnSO4 to form a (Zn(OH)2)3(ZnSO4)(H2O)3 salt during the hydrogenation. When the concentration of the promoter precursor ZnSO4 was further increased, the Zn in the catalyst existed in ZnO and a NaZn4(SO4)(Cl)(OH)6•6H2O salt. This salt and ZnO could be converted into a (Zn(OH)2)3(ZnSO4)(H2O)5 salt by reacting with the reaction modifier ZnSO4 during the hydrogenation. The Zn2+ of the (Zn(OH)2)3(ZnSO4)(H2O) x (x=3 or 5) salt could transform some electrons from metallic Ru. Therefore, the higher the concentration of the promoter precursor ZnSO4, the more the (Zn(OH)2)3(ZnSO4)(H2O) x salt formed, and the more electrons metallic Ru lost. And the activity of the Ru-Zn catalysts decreased and the selectivity to cyclohexene increased. The Ru-Zn catalyst prepared with the promoter precursor ZnSO4 of 0.08 mol/L gave a high cyclohexene yield of 59.1%. Moreover, this catalyst exhibited a excellent reusability and a perfect stability. |
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