摘要
以硝酸铜为铜源、拟薄水铝石为铝源、柠檬酸为添加剂,以乙酸锰为第三组分部分取代铜,采用球磨法制备了Cu_(0.7)Mn_(0.3)Al_(2.5)三元固溶体尖晶石催化剂;借助XRD、BET、H_(2)-TPR和XPS等表征技术,对Cu_(0.7)Mn_(0.3)Al_(2.5)的晶相结构、织构性质、还原性质及表面阳离子状态及分布进行研究,并在甲醇水蒸气重整制氢(MSR)反应中考察其缓释催化性能。结果表明,与Cu Al_(2.5)、Cu_(0.7)Zn_(0.3)Al_(2.5)相比,Cu_(0.7)Mn_(0.3)Al_(2.5)的晶粒最小,比表面积最大,且晶胞收缩最大,晶胞常数最小;该催化剂呈富铝状态,但表面尖晶石相Cu^(2+)占比更高,H_(2)气氛下还原难度增大,在MSR反应中表现出较好的缓释催化性能;在温度为265℃、n(H_(2)O)/n(CH_(3)OH)=2、质量空速为2.25 h^(-1)的条件下反应40 h,甲醇转化率高达84%。该研究为研发高效铜基缓释催化剂提供了数据参考。
Cu_(0.7)Mn_(0.3)Al_(2.5) ternary solid solution spinel catalysts were prepared by ball milling method using copper nitrate as the copper source,proposed thin alumina as the aluminium source,citric acid as the additive,and manganese acetate as the third component to partially replace copper.With the help of characterisation techniques such as XRD,BET,H_(2)⁃TPR and XPS,the crystalline phase structure,weaving properties,reducing properties and surface cation states and distributions of Cu_(0.7)Mn_(0.3)Al_(2.5) were investigated.The catalytic performance of Cu_(0.7)Mn_(0.3)Al_(2.5) in methanol steam reforming(MSR)for hydrogen production with a sustained release feature was scrutinized,and a comparison was made with CuAl_(2.5) binary spinel and Cu_(0.7)Zn_(0.3)Al_(2.5) ternary spinel catalysts.The results showed that compared with CuAl2.5 and Cu_(0.7)Zn_(0.3)Al_(2.5),the Cu_(0.7)Mn_(0.3)Al_(2.5) exhibited the maximum contraction of the unit cell,resulting in a smaller unit cell constant.The catalyst had smaller crystalline size and higher specific surface area.The catalyst showed an aluminium⁃rich state,but with a higher percentage of Cu in the surface spinel phase,which made the reduction under H_(2) atmosphere more difficult,and exhibited a better slow⁃release catalytic performance in MSR hydrogen production.Under the conditions of a reaction temperature of 265℃,n(H_(2)O)/n(CH_(3)OH)=2,and mass flow rate of 2.25 h^(-1),a stable conversion rate of 84%was achieved for 40 hours.The study provided valuable data reference for the development of efficient copper⁃based sustained⁃release catalysts.
作者
吕昌赫
吴殿卿
张楷文
于东北
张财顺
韩蛟
高志贤
LÜChanghe;WU Dianqing;ZHANG Kaiwen;YU Dongbei;ZHANG Caishun;HAN Jiao;GAO Zhixian(School of Petrochemical Engineering,Liaoning Petrochemical University,Fushun Liaoning 113001,China)
出处
《石油化工高等学校学报》
CAS
2024年第2期50-57,共8页
Journal of Petrochemical Universities
基金
国家自然科学基金项目(22379059)
辽宁省应用基础研究计划项目(2023JH2/101300224)
辽宁省教育厅服务地方项目(LJKFZ20220201)。
关键词
缓释催化
甲醇重整
尖晶石
球磨法
Sustained release
Methanol steam reforming
Spinel
Ball⁃milling method
作者简介
第一作者:吕昌赫(1998⁃),男,硕士研究生,从事催化新材料方面的研究,E⁃mail:396618320@qq.com;通信作者:张财顺(1984⁃),男,博士,讲师,从事催化新材料、氢能方面的研究,E⁃mail:caiszhang@126.com。
