Pd-Fe/α-Al_2O_3催化CO偶联制草酸二乙酯催化剂临氢失活研究  

Study on Deactivation of Pd-Fe/α-Al_2O_3 Catalyst with Hydrogen in CO Coupling to Diethyl Oxalate

作　　者：房金刚[1] 李振花[1] 许根慧[1] 王保伟[1] 宋瑛[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12期1021-1023,共3页Petrochemical Technology

基　　金：国家九五科技攻关项目(96-539-01-01)。

摘　　要：一氧化碳常压气相催化偶联制草酸二乙酯的反应中,由于氢的引入致使偶联反应催化剂Pd-Fe/α-Al2O3失活。研究了不同氢含量条件下催化剂失活以及失活催化剂再生规律,发现催化剂的失活为可逆的,且失活速率随原料气中氢含量的增加而加快。应用X射线光电子能谱、程序升温还原等方法对催化剂中Pd的形态变化进行了分析,发现临氢失活催化剂比反应后催化剂的Pd2+含量要低得多。结果表明,原料气中氢的存在抑制了二价钯的烷氧基中间体Pd(OC2H5)2在催化剂上的产生,从而抑制了草酸二乙酯的生成,导致了催化剂的失活。Pd-Fe/α-Al_2O_3 catalyst was deactivated with introduction of H_2 to gaseous phase reaction of CO coupling to diethyl oxalate(DEO).Study on effect of different H_2 concentration showed that deactivation of catalyst was reversible and rate of deactivation was correspondent to concentration of H_2.XPS and TPR showed that after CO reaction,Pd on catalyst would be partially oxidized to Pd^(2+),but the amount of Pd^(2+) was much less than that in deactivated catalyst.Due formation of Pd^(2+)(OC_2H_5)_2,an intermediate to DEO,was inhibited by H_2,leading to catalyst deactivation.

关 键 词：氢 钯 失活 草酸二乙酯 CO偶联 催化剂 

分 类 号：O643.362[理学—物理化学]