Preparation of Cu/ZnO/MCM-41 catalyst with double-solvent impregnation method and catalytic performance in methanol synthesis by CO$_{\textbf{2}}$ hydrogenation

doi:10.12066/j.issn.1007-2861.1903

上海大学学报(自然科学版) ›› 2019, Vol. 25 ›› Issue (1): 109-119.doi: 10.12066/j.issn.1007-2861.1903

"双溶剂"浸渍法制备Cu/ZnO/MCM-41催化剂及其在CO$_{\textbf{2}}$加氢中的催化性能

张辰¹^,², 廖珮懿¹^,², 石志彪²^,³, 孙俭¹(), 王慧²

1. 上海大学环境与化学工程学院, 上海 200444
2. 中国科学院上海高等研究院低碳转化科学与工程重点实验室,上海 201203
3. 上海大学理学院, 上海 200444

收稿日期:2017-04-07 出版日期:2019-02-28 发布日期:2019-02-26
通讯作者: 孙俭 E-mail:sunjkl@shu.edu.cn
基金资助:
上海市科委重点资助项目(14DZ1207602)

Preparation of Cu/ZnO/MCM-41 catalyst with double-solvent impregnation method and catalytic performance in methanol synthesis by CO$_{\textbf{2}}$ hydrogenation

ZHANG Chen¹^,², LIAO Peiyi¹^,², SHI Zhibiao²^,³, SUN Jian¹(), WANG Hui²

1. School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, China
2. Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences,Shanghai 201203, China
3. College of Sciences, Shanghai University, Shanghai 200444,China

Received:2017-04-07 Online:2019-02-28 Published:2019-02-26
Contact: SUN Jian E-mail:sunjkl@shu.edu.cn

摘要/Abstract

摘要：

以"双溶剂"浸渍法制备 Cu/ZnO/MCM-41 催化剂, 考察其在 CO$_{2}$中的催化性能. 结果表明, 浸渍过程中加入适量的乙二醇, 形成"水-乙二醇"双溶剂, 可以促进金属离子进入 MCM-41 载体孔道, 形成较小的金属颗粒并均匀镶嵌在 MCM-41 孔道内. H$_{2}$程序升温还原 (H$_{2}$-temperature program reduction, H$_{2}$-TPR) 具有相对较低的还原温度, 说明还原后催化剂中 Cu 与 ZnO 有较强的相互作用, 并且高度分散. 使用该方法制备的 Cu/ZnO/MCM-41 催化剂在 CO$_{2}$加氢制备甲醇反应中表现出稳定的催化性能. 通过调整负载量控制 Cu 颗粒粒径, 甲醇选择性和产率可达到 64.3% 和 32.8 g$\cdot$(kgcat)$^{-1 }\cdot$h$^{-1}$. 因此, 使用"双溶剂"浸渍法可以促使 MCM-41 载体限制活性组分迁移与烧结, 调控粒径尺寸, 从而得到活性组分高度分散、性能稳定的 CO$_{2}$加氢制备甲醇催化剂.

关键词: "双溶剂"浸渍法, Cu/ZnO/MCM-41, 催化剂, CO$_{2}$加氢, 甲醇

Abstract:

Cu/ZnO/MCM-41 catalyst was prepared via a double-solvent impregnation method, and its catalytic performance of CO$_{2}$ hydrogenation to methanol was investigated. The water-ethylene glycol double solvent formed by adding an appropriate amount of ethylene glycol to the metal nitrate aqueous solution in the impregnation process promoted metal ions into the channels of MCM-41 support, resulting in the formation of metal particles with very small size. Metal particles were uniformly embedded in MCM-41 channels. The relatively low reduction temperature indicated highly dispersed active sites with strong interaction between Cu and ZnO. Cu/ZnO/MCM-41 catalysts prepared with the method had stable catalytic performance in hydrogenation of CO$_{2}$ to methanol. By adjusting loading to control the particle size of Cu, the methanol selectivity and yield could reach 64.3% and 32.8 g$\cdot$(kgcat)$^{-1 }\cdot$h$^{-1}$. Therefore the double-solvent impregnation method can effectively limit migration and sintering of active components with optimized particle size, so as to obtain catalysts with highly dispersed active sites and stable catalytic performance.

Key words: double-solvent impregnation method, Cu/ZnO/MCM-41, catalyst, CO$_{2}$ hydrogenation, methano

中图分类号:

O643.3

张辰, 廖珮懿, 石志彪, 孙俭, 王慧. "双溶剂"浸渍法制备Cu/ZnO/MCM-41催化剂及其在CO$_{\textbf{2}}$加氢中的催化性能[J]. 上海大学学报(自然科学版), 2019, 25(1): 109-119.

ZHANG Chen, LIAO Peiyi, SHI Zhibiao, SUN Jian, WANG Hui. Preparation of Cu/ZnO/MCM-41 catalyst with double-solvent impregnation method and catalytic performance in methanol synthesis by CO$_{\textbf{2}}$ hydrogenation[J]. Journal of Shanghai University（Natural Science Edition）, 2019, 25(1): 109-119.

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"双溶剂"浸渍法制备Cu/ZnO/MCM-41催化剂及其在CO$_{\textbf{2}}$加氢中的催化性能

Preparation of Cu/ZnO/MCM-41 catalyst with double-solvent impregnation method and catalytic performance in methanol synthesis by CO$_{\textbf{2}}$ hydrogenation

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