硅酸盐学报

甲烷基固体氧化物燃料电池阳极的催化重整研究进展

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魏康伟 ¹^,² , 晏琳瑶 ² , 郭志国 ² , 杨镳豪 ² , 熊佳烨 ² , 殷顺弦 ² , 凌意瀚 ³

硅酸盐学报 | 综合评述 2024,52(10): 3338-3348

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硅酸盐学报 |综合评述 2024 , 52 (10) : 3338 -3348

甲烷基固体氧化物燃料电池阳极的催化重整研究进展

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魏康伟¹^,², 晏琳瑶², 郭志国², 杨镳豪², 熊佳烨², 殷顺弦², 凌意瀚³

作者信息

^1．稀有金属资源安全高效开采江西省重点实验室，江西赣州 341000

^2．江西理工大学应急管理与安全工程学院，江西赣州 341000

^3．中国矿业大学材料与物理学院，江苏徐州 221116

通讯作者:

凌意瀚（1986—），博士，教授。

作者简介:

魏康伟（1993—），博士，讲师。

Research Progress on Catalytic Reforming of Anodes for Methane-Based Solid Oxide Fuel Cells

Kangwei WEI¹^,², Linyao YAN², Zhiguo GUO², Biaohao YANG², Jiaye XIONG², Shunxian YIN², Yihan LING³

Affiliations

^1.Jiangxi Province Key Laboratory of Safe and Efficient Mining of Rare Metal Resources, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, China

^2.School of Emergency Management and Safety Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, China

^3.School of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China

Corresponding Author:

LING Yihan (1986-), male, Ph.D., Professor. E-mail: lyhyy@mail.ustc.edu.cn

WEI Kangwei (1993-), male, Ph.D., Lecturer. E-mail: 1026807262@qq.com

出版时间: 2024-10-20 doi: 10.14062/j.issn.0454-5648.20240299

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摘要

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基于固体氧化物燃料电池（SOFC）电化学催化重整甲烷是实现我国化石能源清洁利用的有效途径。CH₄的直接催化重整是通过SOFC阳极将CH₄先转化为化学活性更高的合成气（H₂和CO），再进一步被氧化成水和二氧化碳并产出电能的过程。首先，分析了基于SOFC的CH₄重整应用前景及潜在优势，介绍了SOFC的电化学转化工作原理及以CH₄为燃料时积碳形成机理，论述了干、湿、部分氧化3种直接催化重整甲烷方法及存在的主要问题；重点探讨了SOFC阳极抗积碳的几种主要材料，包括修饰后的Ni基和耐碳无镍阳极材料；最后，对甲烷基SOFC高效稳定电化学转化的发展方向进行了展望，为碳基燃料低碳高效利用提供参考，助力以天然气为燃料的SOFC绿色供电商业化发展。

关键词

固体氧化燃料电池 / 催化重整 / 甲烷 / 抗积碳 / 阳极材料

Abstract

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Methane reforming based on solid oxide fuel cell (SOFC) is an effective way to realize clean utilization of fossil energy. The direct internal reforming of CH₄ is a process of converting methane into more chemically active syngas (i.e., H₂ and CO) by SOFC, and then further oxidizing into water and carbon dioxide to produce electricity. The application of CH₄ reforming based on SOFC shows some potential advantages. For instance, the internal reforming of CH₄ on the SOFC anode is an exothermic reaction, which can directly use the heat generated inside and reduce the continuous supply of external energy. And the chemical energy in the fuel is directly converted into electrical energy without going through multiple energy conversion stages, greatly improving the power generation efficiency. The products of SOFC are only H₂O and CO₂, and the water vapor in the tail gas can be condensed to capture high-purity CO₂, achieving zero carbon emissions. In addition, the high-temperature water vapor can also be used for waste heat utilization to achieve multi-level utilization of energy.

However, there is a carbon deposit problem in the case of SOFC using hydrocarbons as a fuel. When hydrocarbon is not fully converted into syngas upstream of SOFC, the fuel is directly introduced into the anode, where the carbon-containing gas is adsorbed, activated and dissociated to form carbon species. Also, O or OH adsorbed on the surface is insufficient, the carbon species diffuses into the catalyst, gradually accumulating and forming carbon deposits. Therefore, the anode pore and the transmission of the anode raw gas and product gas could be blocked, resulting in the failure of SOFC. The severity of which depends on the operating conditions (i.e., temperature, fuel composition and the catalytic performance of the anode material). The existing methods proposed in the literature mainly include that increasing the polarization current to promote the carbon elimination reaction, modifying other metals into the Ni-based anode to form an alloy anode, and adding a catalyst layer on the external surface of the anode. Among them, the addition of catalytic reforming layer on the outer surface of the anode is a recent research hotspot to inhibit carbon deposition. In order to ensure that the added catalyst layer can play an effective role in reforming hydrocarbons, we need to find a suitable catalytic coating to improve the catalyst activity of the reforming reaction. The type of CH₄ reforming reaction depends on the added fuel additives, which can be H₂O, O₂, and CO₂, corresponding to dry reforming of methane, wet reforming of methane and partial oxidative reforming, respectively.

Besides, carbon deposition on SOFC can be suppressed by optimizing the anode material. Four typical carbon resistant anode materials are summarized. Doped precious metals form bimetallic alloys on Ni-based catalysts, which produce synergistic effect and form small and highly dispersed metal particles, inhibiting the growth of Ni particles and carbon deposition. CeO₂-modified Ni-based anodes can promote oxygen mobility and capture massive active oxygen ions to enhance the flow of charge and accelerate the removal of carbon deposited on Ni surface. The Ni-based anodes modified with Ba oxides exhibit excellent WSC and have a high CO₂ adsorption capacity, promoting carbon removal. Ni-free anode materials are considered as alternatives to Ni due to their excellent electrical conductivity and low activity in catalyzing C-C bond formation. However, their limited catalytic activity restricts their commercial application.

Summary and prospects

The power generation of reforming CH₄ based on SOFC has great advantages in energy conversion efficiency, material flexibility and environmental protection. However, it faces some problems such as carbon accumulation and poor stability in practical application. At present, four typical anti-carbon anode materials, such as Ni-based anode doped with precious metals, CeO₂, barium oxide and Ni-free anode, can effectively improve the anti-carbon stability. Although these materials show a good carbon resistance, they have some problems such as high cost of precious metals, easy sintering of cerium oxide, poor chemical stability of barium oxide and low catalytic activity of Ni-free anode. Improving SOFC operating conditions and optimizing anode materials (i.e., modification of existing catalysts, design of anode microstructure and eforming catalysts) are the keys to achieving the efficient and stable reforming of methane. The development of anode catalysts with low cost, high chemical and mechanical stability, anti-coking and high catalytic activity is an urgent need for sustainably converting carbon-based fuels by SOFC. In addition, the internal anode elementary reactions involved in the process of SOFC reforming methane are complex and mostly exothermic reactions, accompanied by a large amount of heat generation, so it is also necessary to conduct electrochemical and thermodynamic coupling studies, combined with cogeneration technology to further improve energy conversion efficiency. In summary, it is still necessary for the commercial development of green power generation by CH₄-based SOFC to investigate the influence mechanism of CH₄-based SOFC reforming reaction, anode catalyst material optimization, and develop new research directions.

Key words

solid oxide fuel cell / catalytic reforming / methane / anti-carbon / anode materials

引用本文

魏康伟, 晏琳瑶, 郭志国, 杨镳豪, 熊佳烨, 殷顺弦, 凌意瀚. 甲烷基固体氧化物燃料电池阳极的催化重整研究进展. 硅酸盐学报, 2024 , 52 (10) : 3338 -3348 . DOI: 10.14062/j.issn.0454-5648.20240299

Kangwei WEI, Linyao YAN, Zhiguo GUO, Biaohao YANG, Jiaye XIONG, Shunxian YIN, Yihan LING. Research Progress on Catalytic Reforming of Anodes for Methane-Based Solid Oxide Fuel Cells[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (10) : 3338 -3348 . DOI: 10.14062/j.issn.0454-5648.20240299

基金

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江西省自然科学基金-青年项目(20224BAB214039)
江西省教育厅科技项目(GJJ2200867)
江西理工大学博士科研启动基金项目(205200100639)
江西理工大学大学生创新创业训练资助项目(S202310407107)

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2024年第52卷第10期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240299

接收时间：2024-04-23
首发时间：2026-10-22
出版时间：2024-10-20

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收稿日期：2024-04-23
修回日期：2024-05-16

基金

江西省自然科学基金-青年项目(20224BAB214039)

江西省教育厅科技项目(GJJ2200867)

江西理工大学博士科研启动基金项目(205200100639)

江西理工大学大学生创新创业训练资助项目(S202310407107)

作者信息

^1．稀有金属资源安全高效开采江西省重点实验室，江西赣州 341000

^2．江西理工大学应急管理与安全工程学院，江西赣州 341000

^3．中国矿业大学材料与物理学院，江苏徐州 221116

通讯作者:

凌意瀚（1986—），博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240299

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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