催化学报

催化学报 ›› 2010, Vol. 31 ›› Issue (6): 683-688.

• 研究论文 • 上一篇    下一篇

CuCl/SiO2-TiO2 催化剂的结构及其催化甲醇氧化羰基化反应性能

李忠, 刘树森, 任军, 牛燕燕, 郑华艳, 赵强, 崔丽萍   

  1. 太原理工大学煤科学与技术教育部和山西省重点实验室, 山西太原 030024
  • 收稿日期:2010-06-25 出版日期:2010-06-25 发布日期:2013-12-05

Structure of CuCl/SiO2-TiO2 Catalyst and Its Catalytic Properties for Oxidative Carbonylation of Methanol

LI Zhong, LIU Shusen, REN Jun*, NIU Yanyan, ZHENG Huayan, ZHAO Qiang, CUI Liping   

  1. Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
  • Received:2010-06-25 Online:2010-06-25 Published:2013-12-05

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995

被引次数

46

摘要： 在微波辐射条件下, 将 CuCl 快速分散到载体表面制得 CuCl/SiO2-TiO2 催化剂, 利用 X 射线衍射、透射电镜、N2 吸附-脱附、热重、H2 程序升温还原和 CO 程序升温脱附对催化剂进行了表征. 结果表明, 微波辐射制备的催化剂中 CuCl 和载体发生了强相互作用, 比传统加热制备的催化剂中形成更多的易还原铜物种, 吸附 CO 的能力更强. 在甲醇液相氧化羰基化反应中, 微波辐射制备的催化剂上甲醇转化率为 11.7%, 碳酸二甲酯选择性达 96.5%, 高于相同条件下传统加热制备催化剂的活性.

关键词: 微波辐射, 氯化亚铜, 二氧化硅, 二氧化钛, 负载型催化剂, 甲醇, 氧化羰基化, 碳酸二甲酯

Abstract: Microwave heating for a mixture of CuCl and SiO2-TiO2 support was used to prepare a CuCl/SiO2-TiO2 catalyst with high dispersion of CuCl on the support surface in a short time. X-ray diffraction, transmission electron microscopy, N2 adsorption-desorption, thermal gravimetric analysis, H2 temperature-programmed reduction, and CO temperature-programmed desorption were carried out to examine the bulk and surface properties of the CuCl/SiO2-TiO2 catalyst. The characterization results showed that in the CuCl/SiO2-TiO2 catalyst prepared by microwave heating, a great amount of CuCl particles strongly attached to the SiO2-TiO2 support as compared with that prepared by con-ventional heating, resulting in a lower reduction temperature of copper species and a stronger adsorption to CO. Microwave heating also caused that the mass loss temperature of part CuCl was higher than 1 200 oC, which could be attributed to the formation of a strong Cu–O coordinate bond between CuCl and the SiO2-TiO2 support. Catalytic test results showed that the CuCl/SiO2-TiO2 catalyst prepared by mi-crowave heating exhibited methanol conversion of 11.7% and dimethyl carbonate selectivity of 96.5%, higher than that prepared by conven-tional heating in liquid-phase oxidative carbonylation of methanol.

Key words: microwave irradiation, cuprous chloride, silicon dioxide, titanium dioxide, supported catalyst, methanol, oxidative carbonylation, dimethyl carbonate