铈基复合氧化物负载CuO用于甲醇水蒸气重整制氢  

Cerium-Based Composite Oxide Supported CuO Used for Hydrogen Production From Methanol Steam Reforming

作　　者：高瑞瑞 徐青文 李鹏[1] 李蕊 马清祥[1] 赵天生[1] GAO Ruirui;XU Qingwen;LI Peng;LI Rui;MA Qingxiang;ZHAO Tiansheng(State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering,College of Chemistry and Chemical Engineering,Ningxia University,Yinchuan 750021,China;Testing and Analysis Center,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 [2]宁夏大学测试分析中心,宁夏银川750021

出　　处：《石油学报（石油加工）》2024年第6期1473-1484,共12页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：宁夏自然科学基金项目(2021AAC03108)资助。

摘　　要：甲醇水蒸气重整制氢工艺具有反应温度低、H_(2)选择性高、副产物CO含量低等优点,常与燃料电池联用。CeO_(2)有较好的储放氧功能,但其热稳定性较差。采用共沉淀法将不同过渡金属掺杂在CeO_(2)载体上形成CeMO_(2)(M为Zr,Mn,Fe和Cr)固溶体,后通过沉积-沉淀法负载一定量的CuO,制备出一系列的CuO/CeMO_(2)催化剂。通过XRD、H_(2)-TPR、XPS等表征手段,探究不同过渡金属掺杂对催化剂结构、性质和甲醇水蒸气重整制氢活性的影响。结果表明,掺杂Zr和Mn提高了催化剂的比表面积和Cu分散度,促进了缺陷结构的形成和氧空位的迁移效率,使CuO和CeO_(2)之间的相互作用加强。而Fe和Cr的加入降低了CuO的分散,削弱了Cu-Ce的相互作用,使催化剂的催化性能降低,产生负面影响。其中,CuO/CeZrO_(2)催化活性最佳,在反应温度250℃、水/醇摩尔比1.3和气体体积空速2400 h^(-1)时,甲醇转化率达到90%,产氢速率为95 mL/(g·min)。Methanol steam reforming for hydrogen production(SRM)has the advantages of low reaction temperature,high H_(2) selectivity,and low by-product CO content,and is often used in conjunction with fuel cells.CeO_(2) has a good function of storing and releasing oxygen,and poor thermal stability.Using the coprecipitation method,different transition metals were doped on CeO_(2) support to form CeMO_(2)(M=Zr,Mn,Fe and Cr)solid solution.Then a certain amount of CuO was loaded by the deposition precipitation method to prepare a series of CuO/CeMO_(2) catalysts.The effects of different transition metal doping on the structure,properties,and hydrogen production activity of catalysts for methanol steam reforming was explored by characterization methods such as XRD,H_(2)-TPR,and XPS.The results show that doping Zr and Mn has increased the specific surface area and Cu dispersity of the catalyst,promoted the formation of defect structures and improved the migration efficiency of oxygen vacancies,thus strengthening the interaction between CuO and CeO_(2).The addition of Fe and Cr reduces the dispersion of CuO,weakens the interaction between Cu-Ce,reduces the catalytic performance of the catalyst,and thus has a negative impact.In particular,CuO/CeZrO_(2) has the best catalytic activity.At the reaction temperature of 250℃,water to alcohol molar ratio of 1.3,and GHSV of 2400 h^(-1),the methanol conversion rate reaches 90%,and the hydrogen production rate is 95 mL/(g·min).

关 键 词：过渡金属 甲醇水蒸气重整 氧化铈 固溶体 掺杂 

分 类 号：O643.36[理学—物理化学]