CuCrAl和CuCrZr低温液相合成甲醇催化剂的研究  

Study on CuCrAl and CuCrZr Oxides as Catalysts for Low-Temperature Slurry Phase Methanol Synthesis

作　　者：郝立庆[1] 单绍纯[1] 田瑞芬[1] 丁延伟[2] 陈根发[1] 庄叔贤[1] 

机构地区：[1]中国科学技术大学生物质洁净能源实验室,安徽合肥230026 [2]中国科学技术大学理化分析中心,安徽合肥230026

出　　处：《催化学报》2003年第9期711-715,共5页

基　　金：科技部基础研究专项基金资助重大项目;中国科学院知识创新工程基金资助项目

摘　　要：用络合共沉淀法制备了CuCrAl和CuCrZr复合氧化物液相合成甲醇催化剂 ,其比表面分别达到 119和 116m2 /g .在5 0～ 5 5MPa和 383K条件下 ,分别用间歇式和流动式反应釜考察了催化剂的活性和稳定性 .结果表明 :CuCrAl和CuCrZr的活性均明显高于CuCr;CuCrAl的活性略高于CuCrZr,但甲酸甲酯 (MF)的选择性明显低于CuCrZr;两者在 12h内未见活性明显下降 .甲醇钠在反应过程中部分转化为甲酸钠和NaOH .CuCrAl和CuCrZr有较高的氢解活性可抑制甲醇钠与MF生成甲酸钠 ,从而有较低的甲酸钠浓度 .但是 ,Al2 O3 和ZrO2 的酸性有利于甲醇脱水 ,引起甲醇钠水解生成NaOH .溶剂对CuCr基催化剂的活性和选择性有明显影响 .CuCrAl and CuCrZr composite oxide catalysts, with high surface area of 119 and 116 m 2/g respectively, were prepared by coprecipitation and complex precipitation. The catalytic activity, selectivity and stability of the catalysts for slurry phase methanol synthesis at low temperature were evaluated in a stainless steel autoclave in a semi batch semicontinuous manner at 5 0～5 5 MPa and 383 K. It was found that the activity of CuCrAl and CuCrZr catalysts was much higher than that of CuCr catalyst. The catalytic activity of CuCrAl catalyst was a little higher than that of CuCrZr, but the methyl formate (MF) selectivity of CuCrZr was significantly higher than that of CuCrAl. Both the CuCrAl and CuCrZr catalysts demonstrated high stability. The sodium methoxide was partly converted to sodium formate and NaOH. The higher activity of CuCrAl and CuCrZr catalysts for hydrogenation of MF suppresses the reaction between MF and sodium methoxide to form sodium formate, which increases the catalyst life. However, the acidity of Al 2O 3 and ZrO 2 may benefit the dehydration of methanol to form water to further induce the hydrolysis of sodium methoxide. The influence of solvent on the performance of catalytic system was apparent. The reaction mechanism was also discussed.

关 键 词：甲醇 液相合成 铜 铬 铝 锆 复合氧化物 

分 类 号：O643.3[理学—物理化学]