催化学报

催化学报 ›› 2014, Vol. 35 ›› Issue (1): 134-139.DOI: 10.1016/S1872-2067(12)60735-9

• 研究论文 • 上一篇    下一篇

CuCl2和HY分子筛的表面反应及Cu/Y分子筛的制备及其催化甲醇氧化羰基化

王瑞玉a, 李忠b   

  1. a 中国矿业大学江苏省煤基CO2捕集与地质储存重点实验室, 江苏徐州 221116;
    b 太原理工大学煤科学与技术教育部与山西省重点实验室, 山西太原 030024
  • 收稿日期:2013-07-28 修回日期:2013-10-09 出版日期:2013-12-23 发布日期:2014-01-17
  • 通讯作者: 李忠
  • 基金资助:

    国家自然科学基金（20936003）；中央高校基本科研业务费专项基金（2010QNA11）；中国矿业大学连云港徐圩新区创新创业基金（2011KDGXYJJ06）

Surface reactions of CuCl2 and HY zeolite during the preparation of CuY catalyst for the oxidative carbonylation of methanol

Ruiyu Wanga, Zhong Lib   

  1. a Key Laboratory of Coal-Based CO2 Capture and Geological Storage of Jiangsu Province, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China;
    b Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
  • Received:2013-07-28 Revised:2013-10-09 Online:2013-12-23 Published:2014-01-17
  • Contact: Zhong Li
  • Supported by:

    This work was supported by the National Natural Science Foundation of China (20936003), the Fundamental Research Funds for the Central Universities (China University of Mining and Technology, 2010QNA11), and the Innovation Funds for China University of Mining and Technology and High Tech Insititute of Lianyungang Xuwei new district (2011KDGXYJJ06).

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摘要：

以CuCl2为前驱物与HY分子筛进行固相离子交换制备了Cu/Y催化剂，采用热重方法研究了CuCl2与HY分子筛的表面固相离子交换反应，结合活性测试表明催化剂中高度分散的CuCl和离子交换形式的Cu+物种是甲醇氧化羰基化合成碳酸二甲酯的催化活性中心。X射线光电子能谱表征和元素分析结果表明，活性金属Cu主要以CuCl形式存在于分子筛外表面，而在分子筛笼内则以交换的Cu+和少量吸附的CuCl形式存在。与以CuCl为交换铜源所制催化剂相比，以CuCl2为铜源制备的催化剂Cu含量低，催化活性更高。

关键词: 氯化铜, 固相离子交换, 催化剂, 氧化羰基化, 甲醇, 碳酸二甲酯

Abstract:

A CuI/Y catalyst was prepared for the vapor phase oxidative carbonylation of methanol to dimethyl carbonate (DMC). The surface solid-state interactions of CuCl2 with HY zeolite were studied using thermogravimetry. The surface properties and morphologies of catalyst samples were analyzed by thermogravimetry, X-ray photoelectron spectroscopy, and elemental analysis, and their catalytic performance was assessed in a fixed-bed reactor. Both CuCl and CuCl2 were found to co-exist on the external surface of the catalyst, while ion-exchanged CuΙ along with small amounts of adsorbed CuCl were contained in the internal Y zeolite cage structures. Both the CuCl and CuCl2 were active species during the DMC synthesis. Compared with a conventional CuI/Y catalyst prepared by heating a mixture of CuCl and HY zeolite, the CuI/Y catalyst prepared by heating a mixture of CuCl2 and HY zeolite showed increased catalytic activity for the oxidative carbonylation of methanol, even though it had lower Cu and Cl contents.

Key words: Copper chloride, Solid-state ion exchange, Oxidative carbonylation, Methanol, Dimethyl carbonate