| Zn4Si2O7(OH)2H2O盐修饰的纳米Ru催化剂催化苯选择加氢制环己烯 |
| Selective Hydrogenation of Benzene to Cyclohexene over Nano-Sized Ru Catalyst Modified by Zn4Si2O7(OH)2H2O Salt |
| 作者 | 单位 | E-mail | | 孙海杰 | 郑州大学化学与分子工程学院, 郑州 450001
郑州师范学院化学化工学院, 环境与催化工程研究所, 郑州 450044 | | | 周小莉 | 河南省固体废物管理中心, 郑州 210036 | | | 赵爱娟 | 郑州师范学院化学化工学院, 环境与催化工程研究所, 郑州 450044 | | | 王臻臻 | 郑州师范学院化学化工学院, 环境与催化工程研究所, 郑州 450044 | | | 刘寿长 | 郑州大学化学与分子工程学院, 郑州 450001 | | | 刘仲毅 | 郑州大学化学与分子工程学院, 郑州 450001 | liuzhongyi@zzu.edu.cn |
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| 摘要: 利用沉淀法制备了纳米Ru催化剂, 在ZnSO4存在下考察了Na2SiO3·9H2O和二乙醇胺作反应修饰剂对Ru催化剂催化苯选择加氢制环己烯性能的影响, 并用X-射线衍射(XRD)、X-射线荧光光谱(XRF)和透射电镜-能量散射谱(TEM-EDS)等物理化学手段对加氢前后Ru催化剂进行了表征。结果表明, 在水溶液中Na2SiO3与ZnSO4可以反应生成Zn4Si2O7(OH)2H2O盐、H2SO4和Na2SO4, 化学吸附在Ru催化剂表面上的Zn4Si2O7(OH)2H2O盐起着提高Ru催化剂环己烯选择性的关键作用。Na2SiO3·9H2O量的增加, 生成的Zn4Si2O7(OH)2H2O盐逐渐增加, Ru催化剂的活性降低, 环己烯选择性逐渐升高。向反应体系中加入二乙醇胺, 它可以中和Na2SiO3与ZnSO4反应生成的硫酸, 使化学平衡向生成更多的Zn4Si2O7(OH)2H2O盐的方向移动, 导致Ru催化剂环己烯选择性增加。当Ru催化剂与ZnSO4·7H2O、Na2SiO3·9H2O和二乙醇胺、分散剂ZrO2的质量比为1.0:24.6:0.4:0.2:5.0时, 2 g Ru催化剂上苯转化73%时环己烯选择性和收率分别为75%和55%, 而且该催化剂体系具有良好的重复使用性和稳定性。 |
| 关键词: 苯 选择加氢 环己烯 钌 反应修饰剂 |
| 基金项目: 国家自然科学基金(No.21273205, U1304204);河南省博士后科研项目(No.2013006)资助项目。 |
| Abstract: A nano-sized Ru catalyst was prepared using the precipitation method. The performance of the catalyst for selective hydrogenation of benzene to cyclohexene with Na2SiO3·9H2O and diethanolamine as modifiers was investigated in the presence of ZnSO4. The catalyst after and before hydrogenation was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), and transmission electron microscopy-energy dispersive spectroscopy (TEM-EDS). The results show that Na2SiO3 in the solution could react with ZnSO4 to form a Zn4Si2O7(OH)2H2O salt, H2SO4 and Na2SO4, and the Zn4Si2O7(OH)2H2O salt chemisorbed on the surface of the Ru catalyst plays a key role in improving the selectivity to cyclohexene of the Ru catalyst. The increased dosage of Na2SiO3·9H2O will result in the increased amount of the formed Zn4Si2O7(OH)2H2O salt, the decreased activity of the Ru catalyst and the increased selectivity to cyclohexene. The diethanolamine added into the slurry could neutralize the H2SO4 formed by reacting Na2SiO3 with ZnSO4. This could shift the chemical equilibrium to the direction of the formation of the Zn4Si2O7(OH)2H2O salt, resulting in the increase of the selectivity to cyclohexene of the Ru catalyst. When the mass ratio of the Ru catalyst, ZnSO4·7H2O, Na2SiO3·9H2O, diethanolamine and the dispersant ZrO2 was at 1.0:24.6:0.4:0.2:5.0, 2 g of the Ru catalyst will give a selectivity to cyclohexene of 75% and a cyclohexene yield of 55% at a benzene conversion of 73%. Moreover, this catalytic system shows a good reusability and an excellent stability. |
| Keywords: benzene selective hydrogenation cyclohexene ruthenium reaction modifier |
| 投稿时间：2015-02-07 修订日期：2015-04-17 |
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| 孙海杰,周小莉,赵爱娟,王臻臻,刘寿长,刘仲毅.Zn4Si2O7(OH)2H2O盐修饰的纳米Ru催化剂催化苯选择加氢制环己烯[J].无机化学学报,2015,31(7):1287-1295. |
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