Al_(2)O_(3)前驱体对Cu/ZnO/Al_(2)O_(3)催化甲醇重整制氢性能的影响  

Hydrogen production via steam reforming of methanol on Cu/ZnO/Al_(2)O_(3)catalysts:Effects of Al_(2)O_(3)precursors

作　　者：黄敏 薄其飞 李娟[1,2] 乔靖萱 袁善良 张彪 陈洪林[1] 蒋毅[1] HUANG Min;BO Qifei;LI Juan;QIAO Jingxuan;YUAN Shanliang;ZHANG Biao;CHEN Honglin;JIANG Yi(National Engineering Laboratory for VOCs Pollution Control Material&Technology(Chengdu),Chengdu Institute of Organic Chemistry,Chinese Academy of Sciences,Chengdu 610041,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院成都有机化学研究所挥发性有机物污染控制材料与技术国家工程实验室(成都),四川成都610041 [2]中国科学院大学,北京100049

出　　处：《燃料化学学报（中英文）》2024年第10期1443-1452,共10页Journal of Fuel Chemistry and Technology

基　　金：四川省科技成果转移转化示范项目(2021ZHCG0019);基础科研计划项目(WDZC202202);2023年中国科学院“西部学者”项目资助。

摘　　要：采用共沉淀法制备了一系列Cu/ZnO/Al_(2)O_(3)催化剂,通过XRD、BET、H_(2)-TPR、N_(2)O化学吸附、XPS表征技术,研究了Al_(2)O_(3)前驱体对催化剂结构的影响,同时对其在甲醇重整制氢中的性能进行了考察。结果表明,当Al^(3+)与Cu^(2+)、Zn^(2+)同时共沉淀时,Al^(3+)对碱式碳酸盐中Cu^(2+)-Zn^(2+)部分取代生成类水滑石结构,增强了Zn-Al之间的相互作用。相反,在Cu^(2+)、Zn^(2+)完成共沉淀后,引入Al_(2)O_(3)前驱体对消除Al^(3+)对碱式碳酸盐中Cu-Zn取代的不良影响具有积极作用,有利于促进Cu-ZnO间的相互作用、CuO物种的分散和催化剂的还原,进一步促进表面Cu的分散,有利于其活性的提升。其中,以拟薄水铝石为铝源制备的催化剂呈现出优异的活性。在水醇物质的量比为1.2,反应温度为493 K的条件下,甲醇转化率可达94.8%,H_(2)时空收率可达97.5 mol/(kg·h),并且连续运行25 h其活性仍保持相对稳定。在反应条件下,经过723 K的10 h热处理后,该催化剂的活性损失率仅为5.37%。A series of Cu/ZnO/Al_(2)O_(3)catalysts were prepared by co-precipitation method.This research focuses on investigating the influence of different Al_(2)O_(3)precursors on the catalyst structure through thorough structural characterization techniques.Additionally,the catalytic performance of these catalysts in methanol reforming for hydrogen production was systematically evaluated.The results indicate that the simultaneous co-precipitation of Al^(3+)with Cu^(2+)and Zn^(2+)leads to partial substitution of Cu-Zn in the basic carbonates by Al^(3+).This substitution forms a hydrotalcite-like structure and strengthens Zn-Al interactions.On the contrary,after the co-precipitation of Cu^(2+)and Zn^(2+),introducing the Al_(2)O_(3)precursor has a positive effect on eliminating the adverse effects of Al^(3+)on Cu-Zn substitution in basic carbonates.This process promotes the Cu-ZnO interaction,facilitates the dispersion of CuO species,and enhances the reducibility of catalysts.It also improves the dispersion of Cu on the surface,and ultimately enhanced the catalytic activity.Notably,the catalyst prepared using pseudo-boehmite as the Al_(2)O_(3)precursor exhibited the highest activity.Under the conditions of a H_(2)O/CH3OH molar ratio of 1.2 and a reaction temperature of 493 K,methanol conversion reached 94.8%,and the H_(2)space-time yield was 97.5 mol/(kg·h).The catalyst activity remained relatively stable after continuous operation for 25 h.Even after being heat-treated at 723 K for 10 h,the activity loss of the catalyst was only 5.37%.

关 键 词：Al_(2)O_(3)前驱体 Cu/ZnO/Al_(2)O_(3)催化剂 甲醇水蒸气重整 热稳定性 

分 类 号：TQ426[化学工程]