固体氧化物燃料电池用甲醇水蒸气重整反应器研究进展

doi:10.16085/j.issn.1000-6613.2024-0055

化工进展 ›› 2025, Vol. 44 ›› Issue (1): 169-183.DOI: 10.16085/j.issn.1000-6613.2024-0055

固体氧化物燃料电池用甲醇水蒸气重整反应器研究进展

胡洋¹(), 韩传军¹(), 胡强², 李汶颖³, 安全成⁴, 苏洋⁵, 武洪松⁶, 袁果¹

^1.西南石油大学机电工程学院，四川成都 610500
^2.浙江臻泰能源科技有限公司，浙江丽水 323000
^3.清华四川能源互联网研究院，四川成都 610500
^4.中国石油集团川庆钻探工程有限公司钻采工程技术研究院，陕西西安 710018
^5.中国石油长城钻探工程技术研究院，辽宁盘锦 124010
^6.中经云数据存储科技(北京)有限公司，北京 100107

收稿日期:2024-01-08 修回日期:2024-05-14 出版日期:2025-01-15 发布日期:2025-02-13
通讯作者: 韩传军
作者简介:胡洋（1995—），女，博士，研究方向为氢能装备。E-mail：yanghu@swpu.edu.cn。
基金资助:
国家资助博士后研究人员计划(GZC20241424);浙江省重点研发计划(2021C01100);浙江省领军型创新创业团队(2020R02015)

Research progress on methanol steam reforming reactors for SOFC

HU Yang¹(), HAN Chuanjun¹(), HU Qiang², LI Wenying³, AN Quancheng⁴, SU Yang⁵, WU Hongsong⁶, YUAN Guo¹

^1.School of Mechanical Engineering, Southwest Petroleum University, Chengdu 610500, Sichuan, China
^2.Zhejiang Zhentai Energy Technology Company Limited, Lishui 323000, Zhejiang, China
^3.Sichuan Energy Internet Research Institute, Tsinghua University, Chengdu 610500, Sichuan, China
^4.Drilling and Production Engineering Technology Research Institute of CNPC Chuanqing Drilling Engineering Company Limited, Xi’an 710018, Shaanxi, China
^5.China Petroleum Great Wall Drilling Engineering Technology Research Institute, Panjin 124010, Liaoning, China
^6.Zhongjing Cloud Data Storage Technology (Beijing) Company Limited, Beijing 100107, China

Received:2024-01-08 Revised:2024-05-14 Online:2025-01-15 Published:2025-02-13
Contact: HAN Chuanjun

摘要/Abstract

摘要：

固体氧化物燃料电池分布式热电联供技术是建设“清洁、低碳、安全、高效”现代能源体系、提高能源供给、保障能源消费安全的重要途径。氢是固体氧化物燃料电池最主要且最适合的燃料，然而，固体氧化物燃料电池分布式热电联供技术的应用受限于氢储运技术的发展。采用液态甲醇作为储氢载体现场重整制氢，有望在氢源供应问题上实现突破。为研究国内外固体氧化物燃料电池用甲醇水蒸气重整反应器进展，本文概述了氢源供应方式，着重总结了现场重整制氢的核心设备——甲醇水蒸气重整反应器的结构功能和供热方式，分析了影响反应器重整性能的操作参数和结构参数，并介绍了甲醇水蒸气重整反应器与固体氧化物燃料电池集成发电的特点，提出固体氧化物燃料电池用甲醇水蒸气重整反应器未来发展方向包括大功率甲醇水蒸气重整反应器的设计、大功率甲醇水蒸气重整反应器制氢机理及传热传质特性研究，以及采用甲醇水蒸气重整反应器直接为中温固体氧化物燃料电池供氢发电的性能。

关键词: 燃料电池, 化学反应器, 氢, 甲醇水蒸气重整, 分布式热电联供

Abstract:

Distributed cogeneration of heat and electricity using solid oxide fuel cells (SOFC) is an important method in building a “clean, low-carbon, safe, and efficient” modern energy system to improve energy supply and ensure energy consumption security. Hydrogen is the most important and most suitable fuel for SOFC. However, the application of SOFC in distributed cogeneration scenario is limited by the challenges in hydrogen storage and transportation technology, which has high cost and significant safety hazards. Using liquid methanol as a hydrogen storage carrier for on-site reforming to produce hydrogen is expected to achieve a breakthrough in the hydrogen supply of SOFC in distributed cogeneration scenario. In this paper, the progress of methanol steam reforming reactor for SOFC at home and abroad are introduced. The hydrogen source supply mode is outlined. And the structure, function and heating mode of methanol steam reforming reactor, which is the core equipment for on-site hydrogen production through reforming, have been summarized. The operation parameters and structural parameters affecting the reforming performance of the reactor are analyzed. And the characteristics of the integrated system of reactor and SOFC are introduced. The future development directions of methanol steam reforming reactor for SOFC include the design of high-power methanol steam reforming reactor, the study of hydrogen production mechanism and the heat and mass transfer characteristics of high-power methanol steam reforming reactor, and the performance of using methanol steam reforming reactor to directly supply hydrogen for medium temperature solid oxide fuel cells to generate power.

Key words: fuel cell, chemical reactors, hydrogen, methanol steam reforming, distributed cogeneration technology

中图分类号:

TQ05

胡洋, 韩传军, 胡强, 李汶颖, 安全成, 苏洋, 武洪松, 袁果. 固体氧化物燃料电池用甲醇水蒸气重整反应器研究进展[J]. 化工进展, 2025, 44(1): 169-183.

HU Yang, HAN Chuanjun, HU Qiang, LI Wenying, AN Quancheng, SU Yang, WU Hongsong, YUAN Guo. Research progress on methanol steam reforming reactors for SOFC[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 169-183.

图/表 15

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储氢技术	运输工具	压力 /MPa	体积储氢密度 /kg·m^-3	储运成本 /CNY·kg^-1	能耗 /kW·h·kg^-1
气态储氢
高压气态储氢	长管拖车	20	14.5	2.02	1.0～1.3
高压气态储氢	管道	1～4	3.2	0.3	0.2
液态储氢
低温液态储氢	槽罐车	0.6	64	12.25	15
有机液态储氢	槽罐车	常压	40～50	15	—
固态储氢
金属储氢	货车	4	50	—	10-13.3

储氢技术	运输工具	压力 /MPa	体积储氢密度 /kg·m^-3	储运成本 /CNY·kg^-1	能耗 /kW·h·kg^-1
气态储氢
高压气态储氢	长管拖车	20	14.5	2.02	1.0～1.3
高压气态储氢	管道	1～4	3.2	0.3	0.2
液态储氢
低温液态储氢	槽罐车	0.6	64	12.25	15
有机液态储氢	槽罐车	常压	40～50	15	—
固态储氢
金属储氢	货车	4	50	—	10-13.3

原料种类	储存条件	燃料处理方式	富氢气体成分	理论氢气体积分数	特点
天然气^[18]	250atm	部分氧化≥1123K，放热；水蒸气重整973~1273K，吸热；二氧化碳重整≥913K^[22]，吸热	H₂、CH₄、CO、CO₂、O₂	50%～75%	反应过程中易发生爆炸事故
甲醇^[19]	常温常压	甲醇水蒸气重整473～553K，吸热；甲醇部分氧化重整制氢423～573K，放热；甲醇自热重整反应423～573K，吸放热平衡	H₂、H₂O、CO、CO₂、CH₃OH	40%～75%	催化剂长期使用稳定性较差，产物中CO浓度较高
汽油^[20]	常温常压	汽油蒸气重整1073K，吸热	H₂、CO₂、CO、CH₄、烃类	70%左右	烃类成分多，S易导致催化剂中毒
氨	-240K，1atm；293K，10atm	氨分解制氢673K^[21]，吸热	NH₃、N₂、H₂	75%	需增加分离过程，清除NH₃、N₂^[23]

原料种类	储存条件	燃料处理方式	富氢气体成分	理论氢气体积分数	特点
天然气^[18]	250atm	部分氧化≥1123K，放热；水蒸气重整973~1273K，吸热；二氧化碳重整≥913K^[22]，吸热	H₂、CH₄、CO、CO₂、O₂	50%～75%	反应过程中易发生爆炸事故
甲醇^[19]	常温常压	甲醇水蒸气重整473～553K，吸热；甲醇部分氧化重整制氢423～573K，放热；甲醇自热重整反应423～573K，吸放热平衡	H₂、H₂O、CO、CO₂、CH₃OH	40%～75%	催化剂长期使用稳定性较差，产物中CO浓度较高
汽油^[20]	常温常压	汽油蒸气重整1073K，吸热	H₂、CO₂、CO、CH₄、烃类	70%左右	烃类成分多，S易导致催化剂中毒
氨	-240K，1atm；293K，10atm	氨分解制氢673K^[21]，吸热	NH₃、N₂、H₂	75%	需增加分离过程，清除NH₃、N₂^[23]

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固体氧化物燃料电池用甲醇水蒸气重整反应器研究进展

Research progress on methanol steam reforming reactors for SOFC

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