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Cu-Mn-Al三元尖晶石催化甲醇重整反应特性OACSTPCD

Characteristics of Methanol Steam Reforming Catalyzed by Cu-Mn-Al Ternary Spinel

中文摘要英文摘要

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Cu0.7Mn0.3Al2.5 三元固溶体尖晶石催化剂;借助XRD、BET、H2-TPR和XPS等表征技术,对Cu0.7Mn0.3Al2.5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CuAl2.5、Cu0.7Zn0.3Al2.5 相比,Cu0.7Mn0.3Al2.5 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Cu2+占比更高,H2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(H2O)/n(CH3OH)=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.

Cu0.7Mn0.3Al2.5 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,H2-TPR and XPS,the crystalline phase structure,weaving properties,reducing properties and surface cation states and distributions of Cu0.7Mn0.3Al2.5 were investigated.The catalytic performance of Cu0.7Mn0.3Al2.5 in methanol steam reforming(MSR)for hydrogen production with a sustained release feature was scrutinized,and a comparison was made with CuAl2.5 binary spinel and Cu0.7Zn0.3Al2.5 ternary spinel catalysts.The results showed that compared with CuAl2.5 and Cu0.7Zn0.3Al2.5,the Cu0.7Mn0.3Al2.5 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 H2 atmosphere more difficult,and exhibited a better slow-release catalytic performance in MSR hydrogen production.Under the conditions of a reaction temperature of 265 °C,n(H2O)/n(CH3OH)=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.

吕昌赫;吴殿卿;张楷文;于东北;张财顺;韩蛟;高志贤

辽宁石油化工大学 石油化工学院,辽宁 抚顺 113001

化学工程

缓释催化甲醇重整尖晶石球磨法

Sustained releaseMethanol steam reformingSpinelBall-milling method

《石油化工高等学校学报》 2024 (002)

50-57 / 8

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).

10.12422/j.issn.1006-396X.2024.02.007

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