热稳定性增强的铈改性Cu/SiO_2催化剂及在草酸酯加氢制乙二醇反应中的应用  

Ceria-Modified Cu/SiO_2 Catalyst with Enhanced Thermal Stability and Its Application in Hydrogenation of Dimethyl Oxalate to Ethylene Glycol

作　　者：耿尧辰 赵玉军[1] 王胜平[1] 马新宾[1] 

机构地区：[1]天津大学化工学院绿色合成与转化教育部重点实验室,天津300072

出　　处：《化学工业与工程》2015年第6期1-6 12,12,共7页Chemical Industry and Engineering

基　　金：天津市自然科学基金(13JCZDJC33000);国家自然科学基金(21276186);中国石油科技创新基金(2012D-5006-0503)

摘　　要：采用蒸氨法制备了一系列铈改性的Cu/Si O2催化剂,并对该催化剂在草酸二甲酯(DMO)加氢制乙二醇反应中的催化活性及热稳定性进行了考察。研究发现铈的加入对于催化剂表面铜物种的分布有显著的影响,而Cu+的含量是影响加氢活性的主要因素,铈通过影响催化剂中Cu+的含量而影响催化剂的反应活性。此外,催化剂表征结果表明铈可以提高铜物种与载体间的相互作用,同时4价铈的氧化性阻碍了Cu+的进一步还原,从而使得催化剂表面大部分的Cu+在热冲击以及还原后得以保留。因此,相比于铜硅催化剂,铈改性催化剂(Cu-1.0Ce/Si O2)在草酸酯加氢制乙二醇反应中表现出较强的热稳定性。A series of ceria-modified Cu / Si O2 catalysts were prepared by ammonia evaporation method and their catalytic activity and thermal stability for the hydrogenation of dimethyl oxalate( DMO) to ethylene glycol( EG) were investigated. The cerium had a remarkable influence on the distribution of copper species by two kinds of interaction form and the amount of Cu+was found to be the determining factor for the hydrogenation activity. Moreover,the characterization results suggested that the addition of ceria could enhance the interaction between copper and support,and reserve most of the cuprous species on the catalyst surface upon thermal-shock by hindering the further reduction of Cu+due to the oxidability of Ce4+.Hence,the ceria-modified catalyst( Cu-1.0Ce/SiO2) showed a much better thermal stability than Cefree catalyst in hydrogenation of DMO to EG.

关 键 词：铜基催化剂 铈改性 加氢 草酸二甲酯 热稳定性 

分 类 号：TQ223.162[化学工程—有机化工]