制备方法对Al2O3-CeO2物化性质及CO2加氢制甲醇催化性能的影响

人工晶体学报 ›› 2021, Vol. 50 ›› Issue (9): 1745-1755.

制备方法对Al₂O₃-CeO₂物化性质及CO₂加氢制甲醇催化性能的影响

范兴其^1,2,3, 姚梦琴^1,2,3, 刘飞^1,2,3, 王晓丹^1,2,3, 曹建新^1,2,3

1.贵州大学化学与化工学院,贵阳 550025;
2.贵州大学,贵州省绿色化工与清洁能源技术重点实验室,贵阳 550025;
3.贵州大学,贵州省工业废弃物高效利用工程研究中心,贵阳 550025

收稿日期:2021-04-27 出版日期:2021-09-15 发布日期:2021-10-15
通讯作者: 刘飞,教授。E-mail:ce.feiliu@gzu.edu.cn;曹建新,教授。E-mail:jxcao@gzu.edu.cn
作者简介:范兴其(1994—),男,贵州省人,硕士研究生。E-mail:1129285194@qq.com
基金资助:
贵州省教育厅创新群体项目(黔教合KY字[2021]010);贵州省百层次创新型人才专项(黔科合平台人才[2026]5655);贵州省科技创新人才团队(黔科合平台人才[2018]5607);贵州省优秀青年科技人才项目(黔科合平台人才[2019]5645);遵义市创新人才团队培养项目(遵义科人才[2020]9)

Effect of Preparation Methods on Physicochemical Properties of Al₂O₃-CeO₂ and Its Catalytic Performance of CO₂ Hydrogenation to Methanol

FAN Xingqi^1,2,3, YAO Mengqin^1,2,3, LIU Fei^1,2,3, WANG Xiaodan^1,2,3, CAO Jianxin^1,2,3

1. School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, China;
2. Guizhou Key Laboratory for Green Chemical and Clean Energy Technology, Guizhou University, Guiyang 550025, China;
3. Guizhou Engineering Research Center for Efficient Utilization of Industrial Waste, Guizhou University, Guiyang 550025, China

Received:2021-04-27 Online:2021-09-15 Published:2021-10-15

摘要/Abstract

摘要： 复合氧化物界面性质与CO₂加氢制甲醇反应的催化性能有着重要的关系。本文对比考察了物理共混法、浸渍法、传统共沉淀法和微流控连续共沉淀法对Al₂O₃-CeO₂复合氧化物界面性质和催化性能的影响。浸渍作用尽管使Al₂O₃/CeO₂界面产生了一定的结构性质调变,但贫瘠的氧空位缺陷导致催化反应效率低。共沉淀样品中固溶结构的存在增强了Al₂O₃/CeO₂界面的相互作用,增大了电子结合能,形成的大量氧空位缺陷有利于CO₂活化转化。而微流控连续共沉淀法合成样品因具有更小的晶粒尺寸、均匀的复合相结构和丰富的氧空位缺陷,表现出更为优异的催化性能。在原料气配比为V(H₂)∶V(CO₂)∶V(N₂)=72∶24∶4,反应温度为320 ℃,反应压力为3 MPa,体积空速为9 000 mL·g^-1·h^-1的条件下,Al₂O₃-CeO₂复合氧化物的CO₂转化率、甲醇选择性及甲醇时空产率分别达到15.3%,86.4%和0.076 g·mL^-1·h^-1。

关键词: Al₂O₃-CeO₂复合氧化物, 微流控连续共沉淀法, 氧空位, CO₂加氢, 甲醇

Abstract: The interfacial properties of the composite oxides have a significant relationship with the catalytic performance of CO₂ hydrogenation to methanol. Accordingly, the effects of various preparation methods including physical blending, impregnation, traditional co-precipitation and microfluidic continuous co-precipitation on the interfacial property and catalytic performance of Al₂O₃-CeO₂ composite oxides were investigated. Although the impregnation effect can moderately tune the interface properties of Al₂O₃/CeO₂, the insufficient oxygen vacancy defects resulted in inferior catalytic performance. The solid solution structure of co-precipitation sample enhanced the interfacial interaction of Al₂O₃/CeO₂ and the binding energy of the electron, forming sufficient oxygen vacancy defects to activate CO₂. The sample prepared by the microfluidic continuous co-precipitation has the excellent catalytic performance due to its smaller grain size, uniform composite structure and sufficient oxygen vacancy defects. Under the conditions of V(H₂)∶V(CO₂)∶V(N₂)=72∶24∶4, reaction temperature 320 ℃, reaction pressure 3 MPa and space velocity 9 000 mL·g^-1·h^-1, the CO₂ conversion, methanol selectivity and methanol space-time yield of the Al₂O₃-CeO₂ composite oxide can reach 15.3%, 86.4%, and 0.076 g·mL^-1·h^-1, respectively.

Key words: Al₂O₃-CeO₂ composite oxide, microfluidic continuous co-precipitation, oxygen vacancy, CO₂ hydrogenation, methanol

中图分类号:

X701

范兴其, 姚梦琴, 刘飞, 王晓丹, 曹建新. 制备方法对Al₂O₃-CeO₂物化性质及CO₂加氢制甲醇催化性能的影响[J]. 人工晶体学报, 2021, 50(9): 1745-1755.

FAN Xingqi, YAO Mengqin, LIU Fei, WANG Xiaodan, CAO Jianxin. Effect of Preparation Methods on Physicochemical Properties of Al₂O₃-CeO₂ and Its Catalytic Performance of CO₂ Hydrogenation to Methanol[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(9): 1745-1755.

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制备方法对Al₂O₃-CeO₂物化性质及CO₂加氢制甲醇催化性能的影响

Effect of Preparation Methods on Physicochemical Properties of Al₂O₃-CeO₂ and Its Catalytic Performance of CO₂ Hydrogenation to Methanol

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