不同载体负载的Cu_2(OH)_3Cl催化剂对甲醇氧化羰基化的催化性能  

Catalytic Performance of Cu_2(OH)_3Cl Catalysts Supported on Various Supports for Methanol Oxidative Carbonylation

作　　者：王瑞玉[1] 李忠[1] 郑华艳[1] 谢克昌[1] 

机构地区：[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

出　　处：《催化学报》2009年第10期1068-1072,共5页

基　　金：国家自然科学基金(20576085);国家重点基础研究发展计划(973计划;2005CB221204)

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139.1mg/(g·h);其催化性能比较稳定,反应60h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.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 Cu^Ⅱ species in the fresh catalyst transferred into Cu^Ⅰ species partially during the reaction.

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 

分 类 号：O643.36[理学—物理化学]