CO气相催化偶联制草酸二乙酯反应中催化剂的失活与再生研究  

Study on Deactivation and Regeneration of Catalyst in CO Gaseous Phase Coupling Reaction to Diethyl Oxalate

作　　者：项铁丽[1] 李振花[1] 房金刚[1] 何琲[1] 王保伟[1] 许根慧[1] 

机构地区：[1]天津大学化工学院一碳化学与化工国家重点实验室,天津300072

出　　处：《石油化工》2003年第4期281-284,共4页Petrochemical Technology

基　　金：国家"九五"科技攻关项目(96-539-01)。

摘　　要：在固定床反应器中,对一氧化碳气相催化偶联合成草酸二乙酯的反应体系进行了人为飞温,两次飞温过程分别为:反应温度从120℃飞温到400～500℃和1000～1200℃,考察飞温后催化剂的活性。对飞温失活催化剂进行再生后,测定了再生催化剂的活性。利用XPS技术对催化剂表面元素进行分析测试,发现第一次催化剂飞温失活的主要原因是催化剂活性组分Pd被氧化所致,而第二次催化剂飞温失活的主要原因是催化剂活性组分Pd被其它元素所覆盖。对第一次失活催化剂再生后,其活性可恢复至原来水平,对第二次失活催化剂再生后,其活性仅恢复到原有催化剂活性的50%。Reaction temperatures of CO gaseous phase coupling reaction to diethyl oxalate, in fixed bed reactor, were artificially runaway twice from the optimum 120 ℃ to 400～500 ℃ and 1000～1200 ℃ respectively. Activity of catalysts after temperature runaway was measured and compared with that operated at optimum reaction temperature of 120 ℃. Temperature runaway led to decrease in catalytic activity. Deactivated catalysts of two cases were further analysed by XPS. The cause of the first deactivation was due to the oxidation of the Pd catalyst component, and that of the second deactivation was due to covering of active Pd by other elements. Catalytic activity of deactivated catalysts after regeneration could be fully recovered from deactivation the in first case, but only 50% of the original could be recovered from deactivation in the second case.

关 键 词：一氧化碳 CO 气相催化 偶联 制备 草酸二乙酯 催化剂 失活 再生 研究 

分 类 号：TQ225.242[化学工程—有机化工] TQ426.94