柠檬酸辅助固相研磨法制备铜基催化剂及在CO_2加氢合成甲醇反应中的性能研究  

Preparation of Cu-based Catalyst by Solid-phase Grinding Method with Citric Acid Assisting and Performance Research in Methanol Synthesis Reaction from CO_2 Hydrogenation

作　　者：吕鹏[1,2,3] 徐钉[3] 申东明[3] 韩冰[3] 盖希坤[1,2,3] 邢闯[1,2,3] 刘赫扬[1,2,3] 吕成学[1,2,3] 杨瑞芹[1,2,3] 

机构地区：[1]浙江省农产品化学与生物加工技术重点实验室,浙江杭州310023 [2]浙江省农业生物资源生化制造协同创新中心,浙江杭州310023 [3]浙江科技学院生物与化学工程学院,浙江杭州310023

出　　处：《分子催化》2017年第2期141-151,共11页Journal of Molecular Catalysis(China)

基　　金：国家自然科学基金项目(21528302);国家国际科技合作专项项目(2014DFE90040);浙江省自然科学基金青年基金(LQ16B060002;LY14B030004)~~

摘　　要：通过柠檬酸辅助固相研磨法制备铜基催化剂,采用XRD、TPR、TG-DSC、SEM、BET、TEM、XPS、CO_2-TPD等手段对催化剂性能进行表征.结果表明室温固相研磨的前驱体在惰性气体N_2中焙烧使体系中的CuO绝大部分被原位还原成Cu^0,不需外加H_2还原,直接制得了C/I-Cu/ZnO催化剂,催化剂具有中孔.利用高压固定床连续反应装置对催化剂活性进行了评价,结果表明,柠檬酸用量、前驱体焙烧温度、焙烧升温速率等条件对催化剂活性产生影响,当C_6H_8O_7/(Cu+Zn)摩尔比为1.2/1并Cu/Zn摩尔比1/1,前驱体在N_2中以3 K·min^(-1)升温速率于623 K焙烧3 h,制得的C/I-Cu/ZnO催化剂比表面积最大,Cu^0粒径最小,在CO_2加氢合成甲醇反应中表现出最佳的活性,CO_2转化率、甲醇选择性和产率分别达到了28.28%、74.29%和21.01%.与外加H_2还原的C/H-Cu/ZnO催化剂相比,原位还原C/I-Cu/ZnO催化剂比表面积较大,Cu^0的粒径较小,活性较高.The Cu-based catalyst was direct prepared by a solid state grinding method with citric acid assisting. The catalysts were characterized by the means of XRD, TPR, TG-DSC, SEM, BET, TEM, XPS, CO2-TPD etc. The results showed that when the precursor obtained by solid state grinding at room temperature was calcined in N2 inert atmosphere, the C/I-Cu/ZnO catalyst with mesoporous structure was obtained directly since most of CuO had been reduced in-situ to Cu0 without further H2 reduction. The catalyst activity was tested by using high pressure fixed bed continuous reaction device. The results showed that the catalyst activity was affected by the citric acid amount, pre- cursor calcination temperature and calcination heating rate. When C6H8O7/（Cu＋Zn） molar ratio was 1.2/1 （Cu/ Zn = 1/1, molar ratio）, the precursor was calcined in N2 atmosphere at 623 K for 3 h with calcination heating rate of 3 K · min-1 , the C/I-Cu/ZnO catalyst was obtained with the maximum surface area and smallest particle size of Cu0. This catalyst showed the best catalytic activity in the methanol synthesis reaction from CO2 hydrogenation, and the CO2 conversion, the selectivity and yield of methanol up to 28.28% , 74.29% and 21.01% , respectively. The in-situ reduction C/I-Cu/ZnO catalyst showed a large surface area, small Cu0 particle size and high catalytic activi- ty compared with the traditional catalyst reduced by additional H2.

关 键 词：柠檬酸 固相研磨 Cu/ZnO CO2加氢 甲醇 

分 类 号：O643.32[理学—物理化学]