γ-Al2O3 负载的Ni、Fe、Cu对介质阻挡放电等离子体转化CO2/CH4的影响

doi:10.16085/j.issn.1000-6613.2024-0208

化工进展 ›› 2024, Vol. 43 ›› Issue (5): 2705-2713.DOI: 10.16085/j.issn.1000-6613.2024-0208

• 催化与材料技术 • 上一篇

γ-Al₂O₃负载的Ni、Fe、Cu对介质阻挡放电等离子体转化CO₂/CH₄的影响

冯勇强(), 王洁茹, 王超娴, 李芳, 苏婉婷, 孙宇, 赵彬然()

西北大学化工学院，碳氢资源清洁利用国际科技合作基地, 陕北能源先进化工利用技术教育部工程研究中心，陕西省洁净煤转化工程技术研究中心，陕北能源化工产业发展协同创新中心，陕西西安 710127

收稿日期:2024-01-19 修回日期:2024-03-24 出版日期:2024-05-15 发布日期:2024-06-15
通讯作者: 赵彬然
作者简介:冯勇强（1996—），男，硕士研究生，研究方向为等离子体催化CH₄/CO₂重整。E-mail：yongqiangf@stumail.nwu.edu.cn。
基金资助:
陕西省重点研发计划(2020ZDLGY11-06)

Influence of Ni, Fe, and Cu loaded on γ-Al₂O₃ in CO₂/CH₄ conversion via dielectric barrier discharge plasma

FENG Yongqiang(), WANG Jieru, WANG Chaoxian, LI Fang, SU Wanting, SUN Yu, ZHAO Binran()

International Science & Technology Cooperation Base of MOST for Clean Utilization of Hydrocarbon Resources, Chemical Engineering Research Center of the Ministry of Education for Advanced Use Technology of Shanbei Energy, Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Collaborative Innovation Center for Development of Energy and Chemical Industry in Northern Shaanxi, School of Chemical Engineering, Northwest University, Xi’an 710127, Shaanxi, China

Received:2024-01-19 Revised:2024-03-24 Online:2024-05-15 Published:2024-06-15
Contact: ZHAO Binran

摘要/Abstract

摘要：

二氧化碳和甲烷是大气中主要的温室气体，两者的高效资源化利用有助于实现双碳目标。等离子体催化CH₄/CO₂气液两相均有产物，但存在产物组成复杂、选择性低的问题。等离子体与催化剂结合可以有效提高目标产物选择性，本文采用微燃烧法将活性金属负载在载体γ-Al₂O₃上，与等离子体结合催化转化CH₄/CO₂。负载金属后催化剂氧空位比例的改变增强催化剂表面碱性，进而提高CO₂转化率。负载金属后弱酸比例增加，有利于合成液相产物，其中Lewis酸有利于合成醇类产物，而Brønsted酸促进了乙酸合成。金属催化剂装填增强了介质阻挡放电功率，转移更多电荷，提升了反应能量效率。通过催化剂结构对产物选择性的影响规律研究，有利于针对等离子体催化进行催化剂的理性设计。

关键词: 等离子体, 催化剂, 介质阻挡放电, 二氧化碳, 甲烷

Abstract:

Carbon dioxide and methane are the main greenhouse gases, and their conversion and utilization could contribute to the realization of “dual carbon” target. CH₄/CO₂ conversion via plasma method gets both gas and liquid products, giving the target product low selectivity. Plasma combined with catalysts can effectively improve the selectivity of target product. In this work, active metals of Ni, Fe, and Cu are loaded on γ-Al₂O₃ by micro-combustion method, and their reaction performance for CH₄/CO₂ conversion is significantly improved in combination with plasma. Metal loading changes the oxygen vacancy ratio of the catalyst and strengths the intensity of basic sites, which boosts CO₂ conversion. The weak acid of the metal catalyst enhances the liquid product selectivity, such as Lewis acid benefits the conversion to alcohol products, while Brønsted acid promotes the generation of acetic acid. Metal catalysts enhance the dielectric barrier discharge power, transfer more charge and increase the reaction energy efficiency. This study reveals the influence of catalyst structure on product selectivity and is conducive to the rational design of catalysts for plasma catalysis.

Key words: plasma, catalyst, dielectric barrier discharge, carbon dioxide, methane

中图分类号:

O646.9

冯勇强, 王洁茹, 王超娴, 李芳, 苏婉婷, 孙宇, 赵彬然. γ-Al₂O₃负载的Ni、Fe、Cu对介质阻挡放电等离子体转化CO₂/CH₄的影响[J]. 化工进展, 2024, 43(5): 2705-2713.

FENG Yongqiang, WANG Jieru, WANG Chaoxian, LI Fang, SU Wanting, SUN Yu, ZHAO Binran. Influence of Ni, Fe, and Cu loaded on γ-Al₂O₃ in CO₂/CH₄ conversion via dielectric barrier discharge plasma[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2705-2713.

图/表 12

图1 DBD（电压100V，电流0.5A）结合不同催化剂催化CO2、CH4转化率

图2 DBD（电压100V，电流0.5A）结合不同催化剂催化CO2、CH4的气体产物选择性

图3 DBD（电压100V，电流0.5A）结合不同催化剂催化CO2、CH4的液相产物选择性

图4 金属催化剂与载体的XRD谱图

图5 金属催化剂O 1s 轨道XPS谱图和氧空位比例与CO2转化率

图6 金属催化剂与载体CO2-TPD谱图

图7 金属催化剂与载体NH3-TPD谱图和弱酸比例与液相选择性关系

图8 金属催化剂Py-FTIR谱图

图9 金属催化剂不同酸性位点比例与产物分布

图10 DBD（电压100V，电流0.5A）结合不同催化剂催化CO2、CH4电压电流信号

图11 DBD（电压100V，电流0.5A）结合不同催化剂催化CO2、CH4放电功率和Lissajous图

图12 DBD（电压100V，电流0.5A）结合不同催化剂催化CO2、CH4能量效率

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γ-Al₂O₃负载的Ni、Fe、Cu对介质阻挡放电等离子体转化CO₂/CH₄的影响

Influence of Ni, Fe, and Cu loaded on γ-Al₂O₃ in CO₂/CH₄ conversion via dielectric barrier discharge plasma

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