催化学报

催化学报 ›› 2009, Vol. 30 ›› Issue (10): 1068-1072.

• 研究论文 • 上一篇    

不同载体负载的Cu2(OH)3Cl催化剂对甲醇氧化羰基化的催化性能

王瑞玉, 李忠, 郑华艳, 谢克昌   

  1. 太原理工大学煤科学与技术教育部山西省重点实验室, 山西太原 030024
  • 收稿日期:2009-10-25 出版日期:2009-10-25 发布日期:2013-06-06

Catalytic Performance of Cu2(OH)3Cl Catalysts Supported on Various Supports for Methanol Oxidative Carbonylation

WANG Ruiyu, LI Zhong*, ZHENG Huayan, XIE Kechang   

  1. Key Laboratory of Coal Science and Technology of Education Ministry and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
  • Received:2009-10-25 Online:2009-10-25 Published:2013-06-06

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966

被引次数

28

摘要： 采用浆液浸渍法制备了不同载体负载的 Cu2(OH)3Cl 催化剂, 考察了催化剂对甲醇氧化羰基化合成碳酸二甲酯 (DMC) 反应的催化性能. 结果表明, 各载体负载的 Cu2(OH)3Cl 催化剂活性均高于传统的负载 CuCl2 催化剂; 以比表面积较大的活性炭 (AC) 为载体的催化剂活性最高. 以 Cu2(OH)3Cl/AC (w(Cu)=18.71%) 为催化剂时, 甲醇转化率、DMC 选择性和 DMC 时空收率可分别达到 6.93%, 67.3% 和 139.1 mg/(g•h); 其催化性能比较稳定, 反应 60 h 后其催化活性略有下降. 通过 CO 程序升温脱附、X 射线衍射、X 射线光电子能谱和扫描电镜等技术对催化剂进行了表征. 结果表明, 在反应过程中催化剂的活性物种 Cu2(OH)3Cl 的晶粒逐渐团聚、长大, 并且转化为 CuCl2 和 CuO; 同时, 新鲜催化剂中唯一的 CuⅡ物种部分转化为 CuI 物种.

关键词: 甲醇, 氧化羰基化, 碳酸二甲酯, 碱式氯化铜, 负载型催化剂, 活性炭

Abstract: Supported Cu2(OH)3Cl catalysts were prepared by the slurry impregnantion method and used in MeOH oxidative carbonylation to dimethyl carbonate (DMC). The catalytic activity of Cu2(OH)3Cl supported on various supports was higher than that of supported CuCl2, and active carbon (AC) was the suitable support because of its larger specific surface area. Cu2(OH)3Cl/AC (w(Cu) = 18.71%) exhibited excellent catalytic performance. MeOH conversion, DMC selectivity, and DMC space time yield were 6.93%, 67.3%, and 139.13 mg/(g·h), respectively, and the catalyst was more stable. The supported catalysts were characterized by CO-temperature programmed desorption, X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy, showing that the higher dispersion of Cu2(OH)3Cl in Cu2(OH)3Cl/AC was getting worse and transformed to CuCl2 and CuO during the reaction, resulting in the decrease of catalytic activity. The unique CuⅡ species in the fresh catalyst transferred into CuI species partially during the reaction.

Key words: methanol, oxidative carbonylation, dimethyl carbonate, copper chloride hydroxide, supported catalyst, active carbon