固态研磨-燃烧法制CuO-ZnO-ZrO_2/HZSM-5二甲醚合成催化剂  

Preparation of CuO-ZnO-ZrO_2/HZSM-5 Catalysts for Synthesis of Dimethyl Ether by Solid Grinding-Combustion Method

作　　者：张素娟[1] 吴静[1] 冯小兵 张雅静[1] 李德豹[1] 郑娜[1] 王康军[1] 

机构地区：[1]沈阳化工大学化学工程学院,辽宁沈阳110142 [2]抚顺石化公司催化剂厂,辽宁抚顺113001

出　　处：《分子催化》2013年第5期445-451,共7页Journal of Molecular Catalysis(China)

基　　金：辽宁省科技厅工业攻关项目(No.2007223016);辽宁省教育厅项目(No.L2013161)

摘　　要：以柠檬酸为燃烧剂,采用固态研磨-燃烧法和机械混合法制备了CuO-ZnO-ZrO2/HZSM-5CO2加氢一步合成二甲醚双功能催化剂.采用固定床反应器,在反应温度270℃、压力为3.0 MPa、空速4 200 h-1条件下,考察了催化剂对CO2加氢一步合成二甲醚的反应性能,并采用XRD、BET、H2-TPR、NH3-TPD及XPS对催化剂的结构进行了表征.评价结果表明:随柠檬酸量的增加,二甲醚选择性和收率呈峰形变化趋势;当柠檬酸的量等于化学计量比的100%时,制备的催化剂具有较好的催化性能:CO2单程转化率为24.8%、二甲醚(DME)的选择性和收率分别为35.3%和8.7%.表征结果表明:柠檬酸的量影响催化剂的比表面积、还原性能以及CuO和ZnO的晶粒尺寸等,进而影响催化剂反应性能.Cu-ZnO-ZrO2/HZSM-5 bifunctional catalysts for dimethyl ether synthesis from hydrogenation of COs were prepared by solid grinding-burning and mechanical mixing method. The catalyst performance of the catalyst in the hydrogenation were investigated, at reaction temperature 270 ℃, pressure of 3.0 MPa, space velocity 4 200 h-1 over a fixed-bed reactor. This article focuses on the effects of the amount of citric acid added on the catalyst struc- ture and performance. Experimental results showed that dimethyl ether selectivity and yield first increased and then decreased with the increase of citric acid, the maximum catalytic activity was obtained f~＇om the catalyst prepared with the stoichiometric amount of citric acid. The one way conversion of CO2 was 24.8% , the selectivity and the yield of dimethyl ether were 35.3% and 8.7% respectively. XRD, BET, HE-TPR, NHa-TPD, XPS characteriza- tion results showed that the amount of citric acid added could influence the catalyst surface area, distribution of copper, reduction performance, consequently the catalytic performance was affected by those parameters.

关 键 词：固态研磨-燃烧法 柠檬酸 二甲醚 二氧化碳加氢 CuO—ZnO—ZrO2 HZSM-5 

分 类 号：TQ426[化学工程] O643.32[理学—物理化学]