物理化学学报 >> 2014, Vol. 30 >> Issue (6): 1155-1162.doi: 10.3866/PKU.WHXB201401252

催化和表面科学 上一篇    下一篇

以类水滑石为前驱体的Cu/Zn/Al/(Zr)/(Y)催化剂制备及其催化CO2加氢合成甲醇的性能

高鹏1,2, 李枫2, 赵宁2, 王慧1, 魏伟1, 孙予罕2,3   

  1. 1 中国科学院上海高等研究院, 温室气体与环境工程研究中心, 上海201203;
    2 中国科学院山西煤炭化学研究所, 煤转化国家重点实验室, 太原030001;
    3 中国科学院上海高等研究院, 中国科学院低碳转化科学与工程重点实验室, 上海201203
  • 收稿日期:2014-02-10 修回日期:2014-04-01 发布日期:2014-05-26
  • 通讯作者: 赵宁,魏伟 E-mail:zhaoning@sxicc.ac.cn;weiwei@sari.ac.cn
  • 基金资助:

    科技部国家科技支撑计划(2013BAC11B02)和中国科学院战略性先导科技专项(XDA05010109,XDA05010110,XDA05010204)资助项目

Preparation of Cu/Zn/Al/(Zr)/(Y) Catalysts from Hydrotalcite-Like Precursors and Their Catalytic Performance for the Hydrogenation of CO2 to Methanol

GAO Peng1,2, LI Feng2, ZHAO Ning2, WANG Hui1, WEI Wei1, SUN Yu-Han2,3   

  1. 1 Center for Greenhouse Gas and Environmental Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203, P. R. China;
    2 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, P. R. China;
    3 Chinese Academy of Sciences Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203, P. R. China
  • Received:2014-02-10 Revised:2014-04-01 Published:2014-05-26
  • Contact: ZHAO Ning, WEI Wei E-mail:zhaoning@sxicc.ac.cn;weiwei@sari.ac.cn
  • Supported by:

    The project was supported by the National Key Technology Research and Development Program of the Ministry of Science and Technology, China (2013BAC11B02) and Strategic Priority Research Program of the Chinese Academy of Sciences (XDA05010109, XDA05010110, XDA05010204).

摘要:

采用共沉淀法合成了Cu:Zn:Al:Zr:Y 原子比分别为2:1:1:0:0、2:1:0.8:0.2:0、2:1:0.8:0:0.2和2:1:0.8:0.1:0.1 的Cu/Zn/Al/(Zr)/(Y)类水滑石化合物. 将前驱体材料在空气中500 ℃焙烧后得到复合金属氧化物,并将其用于CO2加氢合成甲醇反应. 采用X射线衍射(XRD)、热重(TG)分析、N2吸附、氧化亚氮(N2O)反应吸附、氢气程序升温还原(H2-TPR)和H2/CO2程序升温脱附(H2/CO2-TPD)技术对所制备的样品进行表征. 结果表明,Zr和Y的引入使得催化剂BET 比表面积大幅增加,金属铜的比表面积和分散度均按以下顺序依次增加:Cu/Zn/Al2转化率取决于金属铜的比表面积,甲醇选择性则随强碱位比例的增加而线性增加. 因而,Zr和Y的引入有利于甲醇的合成,Cu/Zn/Al/Zr/Y催化剂上的甲醇收率最高.

关键词: 类水滑石前驱体, 助剂, Cu/Zn/Al催化剂, 二氧化碳加氢, 甲醇

Abstract:

Cu/Zn/Al/(Zr)/(Y) hydrotalcite-like compounds with Cu:Zn:Al:Zr:Y atomic ratios of 2:1:1:0:0, 2:1: 0.8:0.2:0, 2:1:0.8:0:0.2, and 2:1:0.8:0.1:0.1 were prepared using the coprecipitation method. The mixed oxides were then obtained by the calcination of the precursors at 500 ℃ in air, and subsequently evaluated in terms of their catalytic performance for the synthesis of methanol from the hydrogenation of CO2. The asprepared samples were characterized by X-ray diffraction (XRD), thermogravimetric (TG) analysis, N2 adsorption, reactive N2O adsorption, H2 temperature-programmed reduction (H2-TPR), and H2/CO2 temperature-programmed desorption (H2/CO2 TPD) techniques. The results of these analyses showed that the BET specific surface area increased significantly with the introduction of Zr and Y, which was related to the amount of H2O and CO2 evolved from the precursors during calcination. The Cu specific surface area and Cu dispersion properties increased in the order of Cu/Zn/Al2 revealed that the CO2 conversion was dependent on the Cu specific surface area, and the CH3OH selectivity increased linearly as the proportion of strongly basic sites increased. The introduction of Zr and Y therefore favored the production of methanol and the maximum CH3OH yield was obtained over the Cu/Zn/Al/Zr/Y catalyst.

Key words: Hydrotalcite-like precursor, Modifier, Cu/Zn/Al catalyst, CO2 hydrogenation, Methanol

MSC2000: 

  • O643