甲酸辅助Cu-ZnO-Al_(2)O_(3)催化剂制备及其CO_(2)加氢制甲醇性能研究  

Formic acid assisted synthesis of Cu-ZnO-Al_(2)O_(3) catalyst and its performance in CO_(2) hydrogenation to methanol

作　　者：姜秀云 杨文兵 宋昊 马清祥[1] 高新华 李鹏[1] 赵天生[1] JIANG Xiu-yun;YANG Wen-bing;SONG Hao;MA Qing-xiang;GAO Xin-hua;LI Peng;ZHAO Tian-sheng(State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering,College of Chemistry and Chemical Engineering,Ningxia University,Yinchuan 750021,China)

机构地区：[1]宁夏大学化学化工学院省部共建煤炭高效利用与绿色化工国家重点实验室,宁夏银川750021

出　　处：《燃料化学学报（中英文）》2023年第1期120-128,共9页Journal of Fuel Chemistry and Technology

基　　金：国家自然科学基金(22169014,21766027);宁夏自然科学基金(2022AAC03040,2021AAC03108);宁夏大学研究生创新项目(GIP2020053)资助。

摘　　要：采用共沉淀法制备Cu/Zn/Al前驱体,经甲酸处理后N2气氛焙烧得到Cu-ZnO-Al_(2)O_(3)催化剂(CZA)用于CO_(2)加氢制甲醇反应。使用XRD、BET、TG-DSC、SEM、H_(2)-TPR、N_(2)O滴定、XPS-AES、CO_(2)-TPD表征技术对催化剂的物相组成、结构性质以及Cu物种的比表面积、分散度以及价态分布进行分析和讨论。结果表明,甲酸处理调节了催化剂中Cu^(+)与Cu^(0)的比例,同时增加催化剂的中强碱性,并提高甲醇选择性。在W/F(H_(2)/CO_(2)=70/23)=10 g∙h/mol、t=200℃、p=3 MPa反应条件下,使用HCOOH/Cu(物质的量比)=0.8甲酸处理获得的催化剂,CO_(2)转化率6.7%,甲醇选择性达76.3%。The Cu/Zn/Al precursor by coprecipitation was treated with formic acid and then calcined in N2 to obtain Cu-ZnO-Al_(2)O_(3) catalyst(CZA)for the CO_(2) hydrogenation to methanol.XRD,BET,TG-DSC,SEM,H_(2)-TPR,N_(2)O titration,XPS-AES and CO_(2)-TPD characterization techniques were used to analyze the phase composition,structural properties of the catalyst,the Cu specific surface area,the dispersion and valence of the Cu species.The results showed that the formic acid treatment tuned the ratio of Cu^(+)and Cu^(0),increased the number of medium-strong base sites in the catalyst,and raised the selectivity of methanol.Under reaction conditions of W/F(H_(2)/CO_(2)=70/23)=10 g∙h/mol,t=200℃and p=3 MPa,using Cu-ZnO-Al_(2)O_(3) treated under HCOOH/Cu(molar ratio)=0.8,the CO_(2) conversion and the methanol selectivity were 6.7%and 76.3%,respectively.

关 键 词：甲酸处理 Cu-ZnO-Al_(2)O_(3) CO_(2)加氢 甲醇 

分 类 号：O643.36[理学—物理化学]