氢气存在下一氧化碳偶联反应的化学和性能(英文)  

CARBON MONOXIDE COUPLING REACTION IN THE PRESENCE OF HYDROGEN

作　　者：孟凡东[1,2] 许根慧[1] 杜葩[1] 郭荣群[3] 

机构地区：[1]天津大学C1化工国家重点实验室 [2]洛阳石化工程公司炼制研究所,河南洛阳471003 [3]洛阳石化工程公司炼制研究所

出　　处：《燃料化学学报》2002年第6期573-576,共4页Journal of Fuel Chemistry and Technology

基　　金：国家"九五"攻关项目 ( 96 5 39 0 1)~~

摘　　要：实验研究了在氢气存在下 ,一氧化碳与亚硝酸乙酯偶联合成草酸二乙酯反应体系在典型操作条件下的化学反应和反应性能 ,结果表明氢气只与反应体系中的亚硝酸乙酯反应生成乙醇。由于氢气与一氧化碳在催化剂表面竞争吸附 ,并且氢的存在打破了生成草酸二乙酯所必需的正常的氧化还原过程 :Pd0 →Pd2 + →Pd0 ,因此氢的引入使一氧化碳转化率及草酸二乙酯选择性下降。此外 ,化学吸附测试结果表明氢气和一氧化碳是在催化剂表面同一活性中心上吸附。The use of carbon monoxide from coal or natural gas to produce dialkyl oxalate is an important research area in C 1 chemical technology. The chemical reactions and performance in the coupling reaction system for synthesis of diethyl oxalate from carbon monoxide and ethyl nitrite were tested in the presence of hydrogen under the typical coupling reaction conditions. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol. The introduction of hydrogen to the reaction system lowered the conversion of carbon monoxide and the selectivity of diethyl oxalate because hydrogen competed with carbon monoxide to adsorb on the surface of the catalyst and interrupted the normal redox process of Pd 0→Pd 2+→Pd 0 necessary for the formation of diethyl oxalate. Also, the chemisorption measurements revealed that hydrogen and carbon monoxide adsorbed on the same active sites of the catalyst.

关 键 词：一氧化碳 偶联反应 草酸二乙酯 氢气 反应性能 亚硝酸乙酯 

分 类 号：O623.624[理学—有机化学]