生物质热化学转化制备绿氢研究进展

doi:10.16085/j.issn.1000-6613.2024-1899

摘要/Abstract

摘要：

绿色氢能被视为最具潜力的能源之一，其应用对促进能源转型、助力碳减排、推动可持续发展具有重要意义，而清洁、可再生的生物质资源（约35×10⁸t/a）为绿氢的生产提供了一种可持续的原料选择。本文首先从制氢技术/碳排放角度给出了绿氢的界定，并总结了绿氢制备的途径；其次，概述了生物质热化学转化制备绿氢的研究进展，重点围绕热解、气化、化学链技术制备绿氢的反应机理、影响因素和过程强化策略展开讨论，并从效率和成本等角度对比了不同绿氢生产工艺的性能；此外，还讨论了绿氢的分离与纯化工艺。分析结果表明：生物质热化学转化制绿氢成本为1.25~2.20USD/kg，产氢效率为35%~65%，氢产率约为190g/kg。比较几种制氢技术，热解串联重整制氢技术具有工艺简单、产氢速率快的优势；蒸汽气化技术在提升氢气产量和纯度方面具有优势，而化学链转化在负碳高纯氢气的生产方面具有较大的潜力。通过水气变换、酸性气体去除和氢气纯化步骤可获得高纯绿氢。最后，本文讨论了生物质热化学转化制氢的挑战，并从降低原料成本、提高制氢效率和实现CO₂的富集利用三个角度提出了未来发展建议。

关键词: 生物质, 绿氢, 热化学转化, 热解, 气化, 化学链

Abstract:

Green hydrogen is considered one of the most promising energy sources, playing a significant role in promoting energy transition, reducing carbon emissions, and advancing sustainable development. Clean and renewable biomass resources (approximately 3.5×10⁸t/a) provide a sustainable feedstock option for green hydrogen production. This paper first gives the definition of green hydrogen from the hydrogen production technology/ carbon emissions and summarizes the pathways for green hydrogen production. It then reviews the progress of research in the thermochemical conversion of biomass for green hydrogen production, focusing on reaction mechanisms, influencing factors, and process intensification strategies for pyrolysis, gasification, and chemical looping technologies. The performance of different green hydrogen production processes is compared in terms of efficiency, cost, etc. The analysis shows that the cost of producing green hydrogen via biomass thermochemical conversion ranges from 1.25—2.20USD/kg, with a hydrogen production efficiency of 35%—65%, and a hydrogen yield of around 190g/kg. Compared with several hydrogen production technologies, pyrolysis reforming technology exhibits the advantages of simplicity and fast hydrogen production rates, while steam gasification is superior in increasing hydrogen yield and purity. Chemical looping conversion demonstrates significant potential for producing high-purity carbon-negative hydrogen. The separation and purification of green hydrogen are crucial steps in obtaining high-purity hydrogen, achieved through water-gas shift, acid gas removal, and hydrogen purification processes. Finally, the paper discusses the challenges in biomass thermochemical conversion for hydrogen production. It proposes future development suggestions for reducing feedstock costs, improving hydrogen production efficiency, and achieving CO₂ enrichment and utilization.

Key words: biomass, green hydrogen, thermochemistry conversion, pyrolysis, gasification, chemical looping

中图分类号:

TQ 051

孙仲顺, 刘根, 程春昱, 李美昕, 杨宪坛, 吴志强, 杨伯伦. 生物质热化学转化制备绿氢研究进展[J]. 化工进展, 2025, 44(5): 2667-2682.

SUN Zhongshun, LIU Gen, CHENG Chunyu, LI Meixin, YANG Xiantan, WU Zhiqiang, YANG Bolun. Research progress on thermochemical conversion of biomass to green hydrogen[J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2667-2682.

图/表 9

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国家/地区	能量来源	二氧化碳当量阈值	参考文献
印度	生物质能等可再生能源	2kg CO₂/kg H₂	[11]
欧盟	可再生能源/谷电	4.37kg CO₂/kg H₂	[12]
中国	可再生能源	4.9kg CO₂/kg H₂	[13]
美国	使用碳捕集、利用和封存技术的化石燃料，氢载体燃料（甲醇、乙醇等），可再生能源，核能等	生产场所：2kg CO₂/kg H₂ 全生命周期：4kg CO₂/kg H₂	[14]
瑞士	可再生能源	1kg CO₂/kg H₂	[15]
日本	可再生能源/低碳能源	3.4kg CO₂/kg H₂	[16]

国家/地区	能量来源	二氧化碳当量阈值	参考文献
印度	生物质能等可再生能源	2kg CO₂/kg H₂	[11]
欧盟	可再生能源/谷电	4.37kg CO₂/kg H₂	[12]
中国	可再生能源	4.9kg CO₂/kg H₂	[13]
美国	使用碳捕集、利用和封存技术的化石燃料，氢载体燃料（甲醇、乙醇等），可再生能源，核能等	生产场所：2kg CO₂/kg H₂ 全生命周期：4kg CO₂/kg H₂	[14]
瑞士	可再生能源	1kg CO₂/kg H₂	[15]
日本	可再生能源/低碳能源	3.4kg CO₂/kg H₂	[16]

载氧体类型	原料	制备方法	操作类型	反应器类型	操作条件	循环次数	氢气产率/mmol·g^-1
NiO/Al₂O₃^[41]	CH₄	湿浸渍	BCLR	固定床反应器	重整温度650℃ 再生温度：800℃	20	38.6
NiFe₂O₄^[43]	CO、H₂、CO₂	溶胶凝胶	BCLHP	固定床反应器	重整温度850℃	20	24.8
Ni/Al₂O₃^[44]	富水生物油馏分	湿浸渍	BCLR	固定床反应器	重整温度700℃ 汽/碳：3.2	11	67.5
Fe₂O₃+10%KNO₃^[45]	CO	湿浸渍	BCLHP	流化床反应器	重整温度900℃	10	3.1
60%Fe₂O₃/Al₂O₃^[46]	CO	溶胶凝胶	BCLHP	固定床反应器	重整温度900℃	20	20.4
Fe₂O₃@SBA-15^[47]	C₇H₈	湿浸渍	BCLR	固定床反应器	重整温度850℃	10	13.3
Co_0.5Fe_0.5O_2-_y^[48]	CH₄	共沉淀	BCLR	固定床反应器	重整温度850℃	10	5.4

载氧体类型	原料	制备方法	操作类型	反应器类型	操作条件	循环次数	氢气产率/mmol·g^-1
NiO/Al₂O₃^[41]	CH₄	湿浸渍	BCLR	固定床反应器	重整温度650℃ 再生温度：800℃	20	38.6
NiFe₂O₄^[43]	CO、H₂、CO₂	溶胶凝胶	BCLHP	固定床反应器	重整温度850℃	20	24.8
Ni/Al₂O₃^[44]	富水生物油馏分	湿浸渍	BCLR	固定床反应器	重整温度700℃ 汽/碳：3.2	11	67.5
Fe₂O₃+10%KNO₃^[45]	CO	湿浸渍	BCLHP	流化床反应器	重整温度900℃	10	3.1
60%Fe₂O₃/Al₂O₃^[46]	CO	溶胶凝胶	BCLHP	固定床反应器	重整温度900℃	20	20.4
Fe₂O₃@SBA-15^[47]	C₇H₈	湿浸渍	BCLR	固定床反应器	重整温度850℃	10	13.3
Co_0.5Fe_0.5O_2-_y^[48]	CH₄	共沉淀	BCLR	固定床反应器	重整温度850℃	10	5.4

制氢工艺	价格/USD·kg^-1	效率/%	碳排放/kg CO₂·kg^-1H₂	优点	挑战	文献
热解重整	1.3~2.2	35~65	0.25~18.7	不需要氧气，工艺简单，产氢速率快	形成焦油、制氢效率低	[86]
蒸汽气化	1.7	35~50	0.3~8.6	降低合成气中的焦油含量	形成焦油、催化剂烧结和失活	[87]
蒸汽重整	2.3~4	46.2~51.7	管道天然气：7.6 液化天然气：9.3 生物甲烷：<6.1	技术成熟，可大规模生产氢气	制氢效率不高，催化剂易结焦失活	[88]
化学链重整	3.5~4.7	—	0.9~2.2	工艺流程短、设备简单、负碳排放、可生产纯氢	载氧体和反应器的匹配；载氧体抗磨损性能、成本和活性的兼顾	[89]
暗发酵	1.0~2.7	60~80	0	方法简单，无需光，CO₂中性，多种废物均可用作原料	H₂产率低，技术发展水平低，需要巨大体积的反应器，生产密度低，需要对原料进行预处理	[90]
光解	2.8	1~5	0	消耗CO₂，产生O₂作为副产品，在温和条件下工作	氢气产量低、需要阳光、需要大型反应器、氧气敏感，材料成本高	[86]