Article(id=1146098721231569140, tenantId=1146029695717560320, journalId=1146031591421210625, issueId=1146500023279260422, articleNumber=null, orderNo=19, doi=10.3981/j.issn.1000-7857.2024.08.00986, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1723392000000, receivedDateStr=2024-08-12, revisedDate=1728403200000, revisedDateStr=2024-10-09, acceptedDate=null, acceptedDateStr=null, onlineDate=1751180828583, onlineDateStr=2025-06-29, pubDate=1744473600000, pubDateStr=2025-04-13, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1747065600000, onlineIssueDateStr=2025-05-13, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=1751180828583, onlineFirstDateStr=2025-06-29, sourceXml=null, magXml=null, createTime=1751180828583, creator=18627231156, updateTime=1774079575307, updator=sys-migrate, issue=Issue{id=1146500023279260422, tenantId=1146029695717560320, journalId=1146031591421210625, year='2025', volume='43', issue='7', pageStart='1', pageEnd='148', issueExtLink='null', onlineDate='null', pubDate='1744473600000', pubDateStr='2025-04-13', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1751276506490, creator='13701087609', updateTime=1774330951331, updator='13041195026', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1243197373556568751, tenantId=1146029695717560320, journalId=1146031591421210625, issueId=1146500023279260422, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1243197373556568752, tenantId=1146029695717560320, journalId=1146031591421210625, issueId=1146500023279260422, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=67, endPage=78, ext={EN=ArticleExt(id=1146098722712158471, articleId=1146098721231569140, tenantId=1146029695717560320, journalId=1146031591421210625, language=EN, title=Development and application status of new hydrogen storage and transportation technologies, columnId=1150494642224591153, journalTitle=Science & Technology Review, columnName=Exclusive, runingTitle=null, highlight=null, articleAbstract=

Various hydrogen storage and transportation technologies emerging at the forefront of research and development, including solid-state metal hydrides, hydrogen-rich organic liquids, methanol-based hydrogen storage, and ammonia-based hydrogen storage, have distinct characteristics and are suited to different application scenarios. This review provides an in-depth analysis of the technical features, current development status, economic costs, and key technological challenges of these novel approaches. Additionally, it explores future development trends and offers a comprehensive assessment of their economic feasibility and potential applications. At present, solid-state hydrogen storage has been demonstrated through certain applications, but large-scale commercialization remains challenging due to high costs and high energy consumption. Organic liquid hydrogen storage offers operational convenience yet is limited by high dehydrogenation temperatures, slow hydrogen release rates, and reliance on precious metal catalysts. Meanwhile, green methanol and green ammonia-based hydrogen storage face challenges related to energy consumption, safety risks, and economic constraints. Given the unique advantage and limitation of each storage and transportation technology, it is crucial to conduct a comprehensive analysis considering factors such as hydrogen storage capacity, transportation distance, safety, carbon emissions, and specific application scenarios to determine the most suitable technological pathway and deployment strategy.

, authors=null, authorsList=Yan ZHANG, Xusheng WANG, Xi LIN, Jiaze YAN, Yujie SUN, Fang JIANG, Jianxin ZOU, authorCompany=null, correspAuthors=Jianxin ZOU, authorNote=null, correspAuthorsNote=null, copyrightStatement=All rights reserved. Unauthorized reproduction is prohibited., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1146098734091305650, articleId=1146098721231569140, tenantId=1146029695717560320, journalId=1146031591421210625, language=CN, title=新型氢储运技术发展及应用现状, columnId=1150494642375586098, journalTitle=科技导报, columnName=特色专题, runingTitle=null, highlight=null, articleAbstract=

重点分析了固态储氢、有机液态储氢、甲醇储氢和氨储氢等多种新型储运氢技术特点、发展现状、经济成本及关键技术瓶颈,探讨了其未来发展方向,并横向对比了不同氢储运技术的经济性水平与应用前景。当前,固态储氢技术已在部分领域实现示范应用,但其大规模产业化仍面临高成本和高能耗等挑战。有机液态储氢技术虽然操作便捷,但受限于脱氢温度高、释氢速率低及对贵金属催化剂的依赖。绿色甲醇和绿氨储氢技术在能耗、安全性和经济性方面仍存在一定制约。不同储运技术各具优势与局限,需要综合考虑氢储运量、运输距离、安全性、碳排放及具体应用场景,以确定最优的技术路径和应用方案。

, authors=

张岩,高级工程师,研究方向为储运氢技术,电子信箱:

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邹建新(通信作者),教授,研究方向为储运氢技术,电子信箱:
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张岩,高级工程师,研究方向为储运氢技术,电子信箱:

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种类 代表化学式 储氢量/% 优势 尘势
合金储氢材料 AB5 LaNi5 1.4 反应所需压力低、吸/放氢速率快、抗杂质性能好 稀土系储氢材料成本较高、循环稳定性较差、且易氧化
AB TiFe 1.9 成本低廉、吸/放氢温度较低 储氢量较低、活化较困难
AB2 TiMn2 2.0 成本低廉、吸/放氢温度较低 储氢量较低、活化较困难
A2B Mg2Ni 3.6 循环稳定性优异、质量较轻 反应活化能较高、吸/放氢动力学速率迟缓
纯金属储氢材料 V 3.8 储氢量较大、吸/放氢速率较快 材料容易氧化、成本较高
Mg 7.6 成本低廉、储氢密度高、材料可逆性能良好 放氢所需温度更高、动力学速率迟缓
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典型储氢金属/合金性能及其优缺点

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种类 代表化学式 储氢量/% 优势 尘势
合金储氢材料 AB5 LaNi5 1.4 反应所需压力低、吸/放氢速率快、抗杂质性能好 稀土系储氢材料成本较高、循环稳定性较差、且易氧化
AB TiFe 1.9 成本低廉、吸/放氢温度较低 储氢量较低、活化较困难
AB2 TiMn2 2.0 成本低廉、吸/放氢温度较低 储氢量较低、活化较困难
A2B Mg2Ni 3.6 循环稳定性优异、质量较轻 反应活化能较高、吸/放氢动力学速率迟缓
纯金属储氢材料 V 3.8 储氢量较大、吸/放氢速率较快 材料容易氧化、成本较高
Mg 7.6 成本低廉、储氢密度高、材料可逆性能良好 放氢所需温度更高、动力学速率迟缓
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项目 氢气 甲醇 氨气
分子式 H2 CH3OH NH3
摩尔质量/(g/mol) 2 32 17
密度/(kg/m3 70.8 791.0 617.0
沸点/℃ -252.87 64.85 -34.00
闪电/℃ -253.00 11.15 132.15
自燃温度/℃ 560 465 654
热值/(MJ/kg) 143.0 20.0 18.6
氢体积分数/% 100.0 17.6 12.5
体积能量密度/(Wh/L) 1305 4600 4325
化学计量空燃比 34.78 6.50 6.14
储存温度 -253 20 20
储存压力 1.01 1.01 11.11
爆炸极限/% 4.0~75.6 6.0~36.0 16.0~25.0
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甲醇、氨、氢物理性质对比

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项目 氢气 甲醇 氨气
分子式 H2 CH3OH NH3
摩尔质量/(g/mol) 2 32 17
密度/(kg/m3 70.8 791.0 617.0
沸点/℃ -252.87 64.85 -34.00
闪电/℃ -253.00 11.15 132.15
自燃温度/℃ 560 465 654
热值/(MJ/kg) 143.0 20.0 18.6
氢体积分数/% 100.0 17.6 12.5
体积能量密度/(Wh/L) 1305 4600 4325
化学计量空燃比 34.78 6.50 6.14
储存温度 -253 20 20
储存压力 1.01 1.01 11.11
爆炸极限/% 4.0~75.6 6.0~36.0 16.0~25.0
), ArticleFig(id=1242143055780851846, tenantId=1146029695717560320, journalId=1146031591421210625, articleId=1146098721231569140, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
储运氢技术 固态储运氢 有机液态储运氢 甲醇储运氢 氨储运氢
氨储运氢 固态储氢在氢能自行车、公交车、氢发电等方面有示范应用,但其距离大规模产业化发展还有一定距离 日本千代田化工建设、德国HT,以及国内武汉氢阳等公司开展了相关应用 现阶段,甲醇的储运技术成熟,可通过卡车、火车、船舶等多种运输方式实现甲醇的运输 氨作为一种全球范围内广泛使用和运输的原料物质,可充分利用当前已有氨工业的技术设施进行未来氢能的广泛运输
技术特点 固态储氢系统体积储氢密度高、储氢压力低,从而降低了其对储氢装置压力等级等关键技术指标的要求 有机液态储氢技术利用有机液态载体与氢气的可逆加氢、脱氢反应实现氢的储存 基于甲醇的储氢技术是将氢气与二氧化碳反应,生成甲醇,来存储与运输氢气 基于氨的储氢技术是将氢气与氮气反应,生成氨,来存储与运输氢气
技术瓶颈 能耗较高、固定成本大 脱氢温度较高、释氢速率较低、氢气提纯难度较大 能耗较高、有一定碳排放、氢气纯化和除一氧化碳杂质气体困难 绿氨技术能耗较高、存在安全风险隐患以及成本较高
发展前景 有望广泛应用于船舶、车载用氢、大规模储能等领域 车载用氢、氢运输、储能等领域 船舶动力、大规模储运氢等领域 船舶动力、大规模储运氢等领域
), ArticleFig(id=1242143055847960711, tenantId=1146029695717560320, journalId=1146031591421210625, articleId=1146098721231569140, language=CN, label=表3, caption=

新型氢储运技术对比

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储运氢技术 固态储运氢 有机液态储运氢 甲醇储运氢 氨储运氢
氨储运氢 固态储氢在氢能自行车、公交车、氢发电等方面有示范应用,但其距离大规模产业化发展还有一定距离 日本千代田化工建设、德国HT,以及国内武汉氢阳等公司开展了相关应用 现阶段,甲醇的储运技术成熟,可通过卡车、火车、船舶等多种运输方式实现甲醇的运输 氨作为一种全球范围内广泛使用和运输的原料物质,可充分利用当前已有氨工业的技术设施进行未来氢能的广泛运输
技术特点 固态储氢系统体积储氢密度高、储氢压力低,从而降低了其对储氢装置压力等级等关键技术指标的要求 有机液态储氢技术利用有机液态载体与氢气的可逆加氢、脱氢反应实现氢的储存 基于甲醇的储氢技术是将氢气与二氧化碳反应,生成甲醇,来存储与运输氢气 基于氨的储氢技术是将氢气与氮气反应,生成氨,来存储与运输氢气
技术瓶颈 能耗较高、固定成本大 脱氢温度较高、释氢速率较低、氢气提纯难度较大 能耗较高、有一定碳排放、氢气纯化和除一氧化碳杂质气体困难 绿氨技术能耗较高、存在安全风险隐患以及成本较高
发展前景 有望广泛应用于船舶、车载用氢、大规模储能等领域 车载用氢、氢运输、储能等领域 船舶动力、大规模储运氢等领域 船舶动力、大规模储运氢等领域
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新型氢储运技术发展及应用现状
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张岩 1 , 王旭升 2 , 林羲 2 , 晏嘉泽 1 , 孙玉杰 1 , 姜方 3 , 邹建新 2, *
科技导报 | 特色专题 2025,43(7): 67-78
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科技导报 |特色专题 2025 , 43 (7) : 67 -78
新型氢储运技术发展及应用现状
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张岩1 , 王旭升2, 林羲2, 晏嘉泽1, 孙玉杰1, 姜方3, 邹建新2, *
作者信息
  • 1. 北京国氢中联氢能科技研究院有限公司, 北京 100007
  • 2. 上海市氢科学重点实验室 & 上海交通大学氢科学中心, 上海 200240
  • 3. 上海氢枫能源技术有限公司, 上海 201100
通讯作者:
邹建新(通信作者),教授,研究方向为储运氢技术,电子信箱:
Development and application status of new hydrogen storage and transportation technologies
Yan ZHANG1 , Xusheng WANG2, Xi LIN2, Jiaze YAN1, Yujie SUN1, Fang JIANG3, Jianxin ZOU2, *
Affiliations
  • 1. Beijing Guohydro Zhonglian Hydrogen Energy Technology Research Institute Co. Ltd., Beijing 100007, China
  • 2. Shanghai Key Laboratory of Hydrogen Science & Center of Hydrogen Science, Shanghai Jiao Tong University, Shanghai 200240, China
  • 3. Shanghai Qingfeng Energy Technology Co. Ltd., Shanghai 201100, China
出版时间: 2025-04-13 doi: 10.3981/j.issn.1000-7857.2024.08.00986
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重点分析了固态储氢、有机液态储氢、甲醇储氢和氨储氢等多种新型储运氢技术特点、发展现状、经济成本及关键技术瓶颈,探讨了其未来发展方向,并横向对比了不同氢储运技术的经济性水平与应用前景。当前,固态储氢技术已在部分领域实现示范应用,但其大规模产业化仍面临高成本和高能耗等挑战。有机液态储氢技术虽然操作便捷,但受限于脱氢温度高、释氢速率低及对贵金属催化剂的依赖。绿色甲醇和绿氨储氢技术在能耗、安全性和经济性方面仍存在一定制约。不同储运技术各具优势与局限,需要综合考虑氢储运量、运输距离、安全性、碳排放及具体应用场景,以确定最优的技术路径和应用方案。

新型氢储运技术  /  镁基固态储氢  /  有机液态储氢  /  甲醇储氢  /  氨储氢

Various hydrogen storage and transportation technologies emerging at the forefront of research and development, including solid-state metal hydrides, hydrogen-rich organic liquids, methanol-based hydrogen storage, and ammonia-based hydrogen storage, have distinct characteristics and are suited to different application scenarios. This review provides an in-depth analysis of the technical features, current development status, economic costs, and key technological challenges of these novel approaches. Additionally, it explores future development trends and offers a comprehensive assessment of their economic feasibility and potential applications. At present, solid-state hydrogen storage has been demonstrated through certain applications, but large-scale commercialization remains challenging due to high costs and high energy consumption. Organic liquid hydrogen storage offers operational convenience yet is limited by high dehydrogenation temperatures, slow hydrogen release rates, and reliance on precious metal catalysts. Meanwhile, green methanol and green ammonia-based hydrogen storage face challenges related to energy consumption, safety risks, and economic constraints. Given the unique advantage and limitation of each storage and transportation technology, it is crucial to conduct a comprehensive analysis considering factors such as hydrogen storage capacity, transportation distance, safety, carbon emissions, and specific application scenarios to determine the most suitable technological pathway and deployment strategy.

new hydrogen storage and transportation technology  /  magnesium-based solid-state hydrogen storage  /  liquid organic hydrogen storage  /  methanol hydrogen storage  /  ammonia hydrogen storage
张岩, 王旭升, 林羲, 晏嘉泽, 孙玉杰, 姜方, 邹建新. 新型氢储运技术发展及应用现状. 科技导报, 2025 , 43 (7) : 67 -78 . DOI: 10.3981/j.issn.1000-7857.2024.08.00986
Yan ZHANG, Xusheng WANG, Xi LIN, Jiaze YAN, Yujie SUN, Fang JIANG, Jianxin ZOU. Development and application status of new hydrogen storage and transportation technologies[J]. Science & Technology Review, 2025 , 43 (7) : 67 -78 . DOI: 10.3981/j.issn.1000-7857.2024.08.00986
氢能具有能源和化工原料的双重属性,是实现“双碳”目标、确保国家能源安全、发展低碳能源的重要技术途径,目前主要应用于能源、交通、钢铁冶金、石油化工等领域[12]。随着国家政策的大力支持以及氢能产业技术的快速发展,目前氢能正朝着高效、先进、多元的方向发展,在储能、燃料、化工、钢铁、冶金等领域应用广泛[3]。中国可再生能源丰富,尤其是“三北”地区蕴含大量风、光资源,实现可再生能源向氢能的高效、低成本转化是未来绿色氢能发展的重要方向。但风能和太阳能资源固有的随机性与波动性影响了电力系统的可靠运行与高效输出,减弱了其调峰能力。随着氢能技术及上下游产业链的升级和完善,以及高效储氢技术的引入,基于风、光资源的电解制氢技术成为解决大规模可再生能源利用的关键技术途径。一方面降低了电网弃光、弃风的程度,降低了制氢成本并且提升了电网灵活性;另一方面促进了氢能的灵活应用,实现了氢能在能源、化工、交通等领域的高效利用[45]
随着中国氢能产业技术的大规模发展,制氢和用氢的单一项目早已突破万吨级,而储氢技术依然停留在百吨级水平,这严重制约了氢能的大规模发展。因此,发展先进高效的新型氢储运技术对中国能源转型以及实现“双碳”战略目标至关重要。相比于高压气态和低温液态储氢技术,固态金属储氢技术的储氢材料种类较多,可根据应用场景的不同灵活选择性能不同的储氢材料,使其在加氢站、叉车、应急电源、移动发电等多种应用场景中均能发挥优势[6]。富氢液体储氢技术具有储氢量大、可循环使用、操作便捷等优势,还可利用现有液体燃料的基础设施降低成本,因此在长距离氢储运领域也尤为受到关注[7]。此外,基于氨、甲醇等燃料清洁及化学稳定性等特点,以“绿氢”作为原料所生产的“绿氨”及“绿色甲醇”为实现行业脱碳提供了新的解决路线,因此世界主要发达国家正积极布局并大力推广液氨及液态甲醇技术,鼓励“氢–氨”及氢气与甲醇等技术的融合发展[89]。本研究针对固态储氢、有机液态储氢、绿色甲醇及绿氨在实际应用中的关键技术问题,重点分析了上述新型氢储运技术的发展现状、应用前景、经济性水平及技术瓶颈,并指出不同储氢技术未来发展的方向,为新型氢储运技术的推广提供参考及相关技术指导。
固态储氢技术是指将氢气储存于固态材料的表面或原子间隙中,可通过物理吸附、化学吸附2种机制来实现。物理吸附储氢是通过范德瓦耳斯力将氢气吸附到固态材料表面,氢分子内部H–H键并未发生断裂。例如碳基纳米材料、金属有机骨架(MOFs)、共价有机骨架(COFs)、本征微孔隙聚合物(PIMs)和沸石等材料储氢技术均为物理吸附机制的储氢方式。化学吸附主要通过破坏H–H键,使氢以离子键、金属键以及共价键等形式存在于氢化物及配位氢化物等化合物中,例如金属氢化物储氢、配位氢化物储氢等。物理吸附储氢方式通常具有更快的动力学速率以及良好的可逆性能。而化学吸附通常需要克服化学反应能垒,导致其吸/放氢动力学速率较慢,但其因高储氢效率、高储氢密度、高放氢纯度、操作简单、运输便捷等特性,有望广泛应用于船舶、核电站、氢能工业等领域,是当前最受关注且极具发展潜力的新型氢储运技术。目前,主要的金属/合金氢化物储氢材料见表 1[1011]
目前,金属储氢材料主要有稀土系合金、钛系合金、镁系合金和钒系合金等。图 1比较了不同储氢材料,如镁基材料(Mg)、金属化合物(A2B、AB、AB2、AB5)、可逆复合物(complex)、混合金属间化合物(MIC)、固溶体(SS)等的性能[12]。由图 1[12]可知,复杂金属氢化物储氢材料具有较高的质量储氢密度,但其复杂的合成过程以及较低的可逆循环性能对其工程应用带来严峻挑战。可以看到,镁基储氢材料平均储氢密度最高(框内黑色线条),同时,中国镁资源丰富,产量约占全球的85% 以上。镁系合金由于储氢量高、资源丰富且价格低,有望成为最有大规模发展前景的储氢合金材料[13]。然而,镁基储氢材料因热稳定性较高(放氢焓值Hd=75 kJ/mol H2)、吸/放氢热动力学速率迟缓,大规模应用时容易导致能源系统综合能效过低。因此,为提升其动力学速率并降低热力学稳定性,目前研究重点主要集中通过纳米化和催化剂协同效应以规模化、稳定化开发具有低吸放氢温度和高储氢容量的镁基复合储氢材料,并降低材料成本、延长其使用寿命。
固态储氢系统体积储氢密度高、储氢压力低,从而降低了其对储氢装置压力等级等关键技术指标的要求。但固态储氢系统吸/放氢过程伴随大量的热量释放/吸收,这增加了其对储氢系统导热性能的要求。储氢罐体导热性能取决于床层构型、换热管道布置、换热翅片结构、操作参数等[14]图 2[15]对比了不同床层构型下固态储氢系统的储氢效率及换热效率。结果表明,基于不锈钢固定的金属氢化物填充方式可显著提升储氢罐体整体换热性能、提升其吸/放氢速率,并增加罐体储氢密度,降低操作难度。与图 2(a)~(c)方式相比,图 2(d)方式的布置形式可以将放氢时间分别提升约3%、137% 和61.7%。另外,通过优化床层孔隙率并添加高导热系数材料(如金属颗粒、碳纳米管、石墨烯、硼氮化物等)亦可增强储氢系统换热效果。
在换热结构方面,目前设计的储氢罐体内部有直管换热型、内部螺旋管换热型等,同时包含过滤器、鳍片、金属泡沫、加热管等以强化换热效果[16]图 3[17]比较了不同换热结构下固态储氢系统储氢及导热性能。结果表明换热结构(图 3(e))能节省38% 和31%的储存和释放氢气的时间。进一步,与锥形翅片多管反应器、管束反应器、径向翅片反应器和针翅片反应器等相比,盘式翅片多管反应器可节省约22.1%、50.0%、52.1% 和8.7% 的吸氢时间。事实上,系统最优换热结构受制于床层结构、罐体大小、储氢材料、操作条件等众多参数。
为解决固态储氢系统在工程应用中面临的吸/放氢速率迟缓、换热能效不足等问题,当前,在固态储氢罐换热结构及操作参数等的优化上也有不少研究,主要以增强冷却/加热流体与床层及氢气之间的传热效果为目的[18]。Mostafavi等[19]采用NSGA-Ⅱ算法优化了固态储氢罐的运行参数,基于帕累托最优解获得了全局最优的孔隙率、储罐半径及操作温度,并结合多维偏好线性规划分析方法(LINMAP)提高了固态储氢罐的储氢密度与吸/放氢速率。Aadhithiyan等[20]基于反应曲面法(RSM),结合机理模型,并以储氢密度、吸/放氢时间、换热性能等为目标优化了固态储氢罐反应床层的设计结构,结果表明经床层优化后固态储氢罐吸氢时间减少了16.36%。当前,有关固态储氢系统优化设计与遗传算法、粒子群优化算法等先进算法的适应性机制缺乏,同时相关研究暂未建立系统性的储氢系统优化目标、约束条件、决策变量统一。此外,固态储氢系统传热机理复杂,往往需要通过Ansys、Comsol等计算流体力学(CFD)分析软件进行吸/放氢动力学模拟,大量网格单元划分延长了计算时间,从而给储氢罐体床层构型及运行参数等的全局优化带来挑战。因此,未来可基于神经网络、机器学习等深度学习算法,准确辨识固态储氢系统的吸/放氢过程。
固态储氢系统的成本主要涉及充装设备、固定/移动式固态储氢装置、放气及增压设备以及相关环节的能耗、折旧、人力等。经济性计算范围涵盖从氢气源购买氢气到将氢气按照组分、压力等参数的需求交付给用户,涉及氢气的充装、储氢、运氢、脱氢以及将氢气提纯/加压至用户所需组分和压力等级。以镁基固态储氢为例,储氢材料费用约110元/kg,充氢过程能耗约1 kW·h/kg H2,放氢能耗约13 kW·h/kg H2,镁基储氢成本中较高一环为放氢能耗,当使用氢化工、氢冶金的工业余热蒸汽进行放氢时,可大幅减小释氢过程能耗,从而缩减成本。目前,固态储氢技术暂无大规模应用案例,也无相关国家标准,研究显示,现有固态储氢系统成本约为11000~22000元/kg H2[21],其氢气平准化成本(LCOH)与储氢密度、材料循环寿命、使用年限等参数有关。此外,储氢材料费用和循环次数对LCOH的影响较大,现有气态储氢和液态储氢的设备可服役长达20 a左右。固态储氢中,对比钛基和镁基储氢材料,二者循环寿命均能达到2000~ 3000次以上,但相同储氢量条件下钛基储氢材料较镁基储氢材料成本更高。钛基储氢材料可在室温下吸放氢,所以在低温小量用氢场景中能效较高,而镁基固态储氢材料则在大规模和长距离储运氢中更具成本竞争力。需要说明的是,氢化镁除了热解产氢外,还可以水解释氢,然而水解过程不可逆,需要将生成的氢氧化镁重新再生为氢化镁,能耗很大,但其高能量密度的特性使其适应于燃料电池备用电源、野外电源、无人机等低频使用场景。
目前,固态储氢系统的示范主要以镁基固态储氢和钛锰系储氢材料为主。如国家稀土功能材料创新中心牵头研发的稀土系固态储氢系统示范装置,实现了20 kg级低压固态储氢装置,可应用于用氢企业及加氢站等场景。上海交通大学氢科学中心与氢枫能源共同研发的全球首台吨级镁基固态储运车,车载40尺(1尺=0.333 m)储氢集装箱总重量32.5 t,装载14.4 t储氢合金可实现吨级规模储运氢,储氢系统可在12 h内可吸氢900 kg以上,放氢860 kg,具备常温储运、低压存储等用氢特性,其储氢密度是当前主流20 MPa高压长管拖车的3倍以上,如图 4(a)[22]所示。此外,国外众多高新技术研发机构和公司纷纷致力于推动固态储氢技术向应用端迅速发展。如法国McPhy公司于2014年开发的基于镁基固态储氢的INGRI系统,储氢容量达到750 kg,如图 4(b)[23]所示。澳大利亚Hydrexia公司在2015年开发的镁基储运氢系统,单车储氢容量可达700 kg,可实现氢气的大规模安全存储。美国Ergenic Corp公司设计的La-Ni-Al储氢合金系统可在室温下进行吸脱氢循环,可用于如光电转换、水泵、温度传感器、压缩机以及空调等多种领域。总之,固态储氢系统目前仍然处于示范验证阶段,未来实现固态储氢大规模的应用需要进一步降低系统成本,减小氢化/脱氢环节能耗,提升材料循环寿命。
尽管固态储氢系统在部分领域已有相关示范应用,但其距离大规模产业化发展还有一定距离。研究人员在添加催化剂、纳米化和构建复合储氢体系等方面做了大量努力来提升镁基储氢材料性能,但其产业化发展依然面临如下挑战。首先,现有固态储氢技术尚未实现高质量储氢密度和快速吸/放氢速率的协同兼顾。其次,大规模产业化应用场景下的镁基储氢材料放氢温度较高,高放氢温度使氢化镁脱氢环节能耗较大,进而降低了氢能利用路径的综合能源效率。最后,高性能镁基储氢材料的现有技术制备加工成本高,同时大容量镁基储运氢系统试验成本过高。而镁基储氢技术的成本效益是实现大规模产业化应用的关键因素之一,未来需要进一步降低材料成本、制造工艺成本和系统运行成本,以确保镁基储氢技术的市场竞争力。
有机液态储氢技术(LOHC)利用有机液态载体与氢气的可逆加氢、脱氢反应来实现氢的储存。常见的有机液态载体有苯(BZ)、甲苯(TOL)、萘(NAP)、N-乙基咔唑(NEC)、二苄基甲苯(DBT)、氨(NH3)和甲醇(MET)。优异的有机液态储氢载体需要具备较高的储氢能力(体积储氢密度>56 kg/m3,质量储氢密度>6%[24])、良好的热力学性能(包括熔点、沸点、闪点、燃点、吸放氢活化能等)、容易脱氢和纯化、低成本、可逆性能良好以及毒性弱、环境友好等特点。图 5[25]总结了不同有机液态储氢载体的储氢性能。
在有机储氢载体中,环己烷的质量储氢密度高达7.2%,同时体积储氢密度为55.9 kg/m3,但环己烷具有可燃性,同时沸点较低,这给脱氢过程氢气的提纯与分离带来挑战。甲苯的质量储氢密度同样较高,约6.12%,但甲苯为危险化学品,毒性较高且易燃易爆。十氢化萘的质量储氢密度同样较高,可达7.3%,但其沸点较高,约为185.5℃,这增加了吸/放氢过程中的能耗,从而降低了系统整体的综合能源效率。NEC的储氢密度约为5.8%,氢化/加氢过程多使用铂基催化剂及镍基催化剂,与其他载体相比,NEC脱氢焓变较低(~50 kJ/mol H2),使其能够在较低的温度(170~200℃)下完成催化放氢,但NEC储氢技术未来大规模应用受制于其工业产量(现阶段年产小于10000 t)[2627]。有机液态储氢技术在不破坏载体主体结构的基础上实现氢化和脱氢,吸/放氢反应伴随较大的热能转移。尽管目前苯、甲苯、萘、环己烷等均可作为储氢载体,但现有有机载体吸/放氢催化剂很难兼具高温稳定性和低温高催化活性,未来有机液态储氢技术仍然很大程度上依赖于能否开发兼具高脱氢效率、低脱氢温度,且稳定性好、成本低廉的催化剂。
日本千代田化工建设公司和德国Hydrogenious Technologies(HT)公司为国际领先的有机液体储氢技术公司。日本千代田化工建设公司基于Pt/Al2O3型催化剂的甲基环己烷(MCH)液态储氢载体已实现商业化生产和应用,可连续使用1万h,将Pt颗粒负载在催化剂基体,经硫化后形成的副产物可有效抑制甲烷和苯等中间产物的生成,有效提高储氢效率,转化率超过95%。此外,2017年日本千代田化工建设公司联合三菱商事株式会社、三井物产株式会社、日本邮船株式,成功将甲基环己烷储氢载体应用于远洋氢运输(文莱至日本川崎),年供氢规模突破210 t。德国HT公司致力于研发二苄基甲苯储氢载体,实现小规模储氢载体的灵活装运,脱氢产能达到1.5 t/d,加氢产能达到5 t/d,该公司计划于2025年推出成熟的商业产品。
中国在有机液态储氢载体的研发主要集中在甲苯、二苄甲苯和NEC等载体上,以武汉氢阳能源有限公司、中化学科学技术研究有限公司、南通久格储能科技有限公司、青岛海望氢能科技有限公司、中氢源安(北京)科技有限公司、陕西氢易能源科技有限公司等为代表的有机液体储运氢技术研发单位近年来在实际应用方面取得了实质性进展。2022年2月,中国船舶重工集团公司第七一二研究所成功开发的国内首套120 kW级氢气催化燃烧供热的有机液体供氢装置完成调试,同时完成了其与燃料电池系统的集成匹配。2022年11月,中化学科学技术研究有限公司联合天辰公司成功开发了国内首套甲基环乙烷–甲苯有机液体储氢中试示范装置,规模300 kg H2/d,成功运行时间超过1000 h。2023年7月,中化学(北京)建设投资有限公司联合氢阳公司打造的全球首套常温常压有机液体储氢加注一体化示范项目,产氢规模达400 kg/d,氢气加注压力为12.6 MPa[28]。近年来,有机液态储氢技术在中国发展迅猛,吸引了大量氢能企业的关注与投资。
目前,有机液态储氢技术成熟度较低,远未规模商业化应用,因此现有示范运行项目经济性成本与期望水平相差较大。同时,有机液态储氢技术成本边界涵盖吸氢/放氢设备、催化剂、载体、氢气提纯等环节以及相关路径的能耗成本,储氢价格受用氢区域和应用场景的影响较大。尽管目前关于有机液态储氢成本的研究较多,但不同的研究选择的评判条件、影响因素、系统特征及边界参数不同,因此经济性成本差别较大。如NEC价格约40 €/kg(~43.73 $/kg),二苄基甲苯4 € /kg(~4.37 $/kg),萘0.6 €/kg(~0.66 $/kg),甲苯0.8 €/kg(~0.87 $/kg)[29]。根据美国能源署预测,2030年氢气成本将下降到28元/kg H2(~3.96 $/kg)以下,2050年将进一步下降到23元/kg H2(~3.25 $/kg)以下[30]图 6[31]比较了不同有机液态储氢技术在相同储氢规模下的投资成本,结果表明,在LOHC技术中,换热成本占比最高,其次为反应器开发成本;在NEC和NAP技术中,压缩机成本也不容忽视。
现阶段,有机液态储氢技术成熟度较低,包括当前主流甲苯、二苄基甲苯等储氢载体脱氢温度较高、释氢速率较低、氢气提纯难度较大;同时氢化和脱氢过程依赖于贵重金属催化剂,制约了有机液态储氢技术的大规模产业化发展。此外,受制于储氢系统自身热物性条件,当前技术还未能大规模应用。为推动有机液态储氢技术的商业化应用,未来技术发展方向应主要集中在:(1)借助当前油气储运基础设施,进行“氢油”输送,以降低运输成本;(2)开发化学性能更为稳定的储氢载体,包括高沸点、稳定化学结构、挥发性低等;(3)进一步提高储氢密度,且减小氢气提纯难度;(4)储氢载体应该表现出良好的环境适应性。
基于甲醇和氨的储氢技术是将氢气与二氧化碳或氮气发生反应,生成甲醇或氨,来存储与运输氢气。基于甲醇、氨的氢气储运方式与直接运输氢气相比,具有更高的储运氢密度。同时,甲醇和氨(加压)常温下为液态形式且相对稳定,可借助现有技术设施来存储和运输,大幅降低储运成本。另外,甲醇和氨的储运氢方式具有较高的安全性,且操作便捷,有望成为未来氢能技术发展的重要方向之一。甲醇、氨和氢气的基本物理性质如表 2[3233]所示。
甲醇和氨化学性质稳定,是理想的氢气替代燃料。甲醇的储氢质量密度可达12.5%,且甲醇来源广泛、成本低廉、技术成熟度高。另外,还可通过风、光等可再生资源进行绿色甲醇的制取。常温常压下甲醇储氢技术能够以更高的能量密度承载氢气,相较于液化和高压储氢技术更为优越。此外,甲醇储氢技术还可与现有加油站系统耦合使用,无须建设昂贵的加氢站。2021年中国甲醇产能、产量分别为9743.1万t和7765.2万t;2021年中国甲醇消费量8211.41万t,同比增长11.67%[34]。中国作为世界上最大的甲醇生产和消费国,具有巨大的潜力。氨作为一种富氢物质,含氢质量分数为17.6,被视为理想的氢能载体。相较于纯氢,氨更易于长时间储存和长距离运输,尤其在零碳经济中具备重要战略地位。尽管氨储运氢模式有望成为解决氢储运难题的重要方案之一,但目前大多数绿氨直接利用/合成技术仍处于示范论证,完全商业化尚需时日。
传统的甲醇合成工艺主要基于天然气、煤等化石燃料来生产。目前,全球共有90多家甲醇生产工厂,总产能接近1.1亿t[35]。但传统甲醇生产方式伴随大量二氧化碳产生,基于此,绿色甲醇项目吸引了众多投资者的关注,典型绿色甲醇合成过程如图 7[36]所示。绿色甲醇主要以可再生电力制取的氢气和基于二氧化碳封存和捕集技术获取的二氧化碳为原料。现阶段,甲醇的储运技术成熟,可通过卡车、火车、船舶等多种运输方式实现甲醇的运输。一方面,甲醇可以直接作为能源或工业生产的原料,或利用催化重整技术制氢;另一方面,甲醇重整后产生的二氧化碳可通过碳捕集技术回收,再次应用于甲醇生产,实现碳的闭环循环。2012年,冰岛George Olah可再生甲醇工厂成功运行,每年可回收5500 t二氧化碳,合成约4000 t甲醇。2022年,中国科学院大连化学物理研究所在兰州建成集成光伏发电、电解水制氢、二氧化碳加氢合成甲醇一体化的“液态阳光”示范项目,成功实验了千吨级绿色甲醇燃料生产装置的运行。2022年冬奥会上,中国在张家口开展了绿色甲醇作为绿氢载体的示范应用,将甲醇运输至加氢站制备氢气并回收二氧化碳。纯化后的氢气用于燃料电池汽车的氢源,而二氧化碳回收再次作为甲醇制备原料,形成碳循环的闭环[37]。2023年,杭州亚运会开幕式火炬塔燃料采用了基于废碳再生的绿色甲醇循环技术。
氨作为高效的储氢介质,具有高能量密度、清洁无污染、高安全性等特点,能够显著提升储运氢过程的效率。全球绿氨市场预计将以高达90% 的速度高速发展,预计在2030年前将达到54亿美元[38],氨作为一种全球范围内广泛使用和运输的原料物质,可充分利用当前已有氨工业的技术设施进行未来氢能的广泛运输。然而,绿氨技术仍处于起步阶段。与传统氨气合成技术相比,绿氨合成是将电解水制氢技术、空分技术及哈伯法合成氨技术相结合。2021年绿氨市场规模约为0.36亿美元,预计2030年将达到54.8亿美元的市场份额[39]。目前,国内多家企事业单位宣布了多个绿氨项目,自2021年以来,国内陆续有20多个绿氨合成项目宣布立项。2022年,中国天楹股份有限公司与通辽市人民政府、中国投资协会签署战略合作框架协议,总投资达600亿元(~84.75亿美元),计划建成年产5万t绿氢、30万t绿氨的零碳产业园区。吉林省大安市规划拟建成包含700 MW风力发电设施、100 MW光伏发电设施和配套的年产18万t绿氨装置[40]。典型绿氨合成方法及应用前景如图 8所示[41]
绿色甲醇和绿氨生产、运输过程的成本主要涵盖基础建设、电力价格、运输工具及场景需求。对绿色甲醇来说,其成本受二氧化碳封存捕集技术及绿氢生产技术的影响较大。目前,制氢技术主要碱性电解槽制氢(AEC)、质子交换膜电解槽制氢(PEM)、固体氧化物电解槽制氢(SOEC)。碱性电解槽因性能稳定成为当前主流制氢技术。SOEC电解效率较高,可达80%,但目前成本较高且电解槽性能易衰退。当前绿氢的价格受制于可再生能源发电成本及电解槽的成本,受地域因素影响较大,约为4~6 $/kg H2,为蓝氢或灰氢的2~3倍[42]。二氧化碳捕集封存技术的成本当前约为10~50 $/t CO2,绿色甲醇价格为800~1600 $/t,随着未来原料成本的降低以及相关技术的进步,成本可进一步降低至220~560 $/t[43]。对于绿氨来说,成本主要涵盖空气分离,绿氢制取以及氨气合成,其中绿氢制取的成本占比约90%以上。目前氨气的成本预计为720~1400 $/t,随着未来技术的进步以及原料价格的降低,预计2050年氨的成本将有可能降低至310~ 610 $/t[43]
目前,甲醇储氢技术的重点主要集中在3个方面。一是甲醇重整和利用过程会产生大量二氧化碳排放。二是甲醇重整过程能耗较大,开发兼具高活性和高稳定性的催化剂是未来进一步发展的方向。三是甲醇利用过程中副产物一氧化碳的纯化过程复杂。同样,氨气裂解过程温度较高,约为500℃,裂解过程伴随大量能量消耗,从而降低了能源系统的综合效率。因此,未来需要重点发展低温低压合成氨和安全低温氨分解催化剂及反应器技术。此外,氨具有更高的毒性、腐蚀性,导致其安全保障成本较高,而目前绿氢的高制取成本也使得绿色甲醇和绿氨制取的成本较高。
不同储运氢技术的特点对比见表 3。此外,图 9比较了不同储氢技术储运环节的经济性水平。首先,管道运输液氢对运输半径的敏感性较弱,在运输半径较长下经济性程度占优,但液氢运输温度较低,容易液化。与之相反的是,高压气态储氢对运输半径的敏感性极强,当前主流的高压储氢运输半径约为150 km,当运输半径进一步扩大后高压气态储氢并不是较为理想的氢气运输方式。另外,镁基固态储氢在中长距离运输规模下的经济性程度占优。目前,有机液体储氢较镁基固态储运氢、氨储运氢、甲醇储运氢发展较慢,横向比较难度较大。综合比较固态、氨、甲醇储运,经济性镁基固态储氢相对较好,甲醇储运经济性稍优于氨储氢技术,但考虑到甲醇可带来二氧化碳的排放,未来碳税市场成型后,经济性可能会较氨储运差。考虑到运输氨为危险化学品,未来大规模运输时,氨气泄露隐患需要更加关注。此外,图 10[44]对比了各种储运氢技术的体积和质量储氢密度。气态储运氢技术的储氢密度较低,而轻金属基固态储氢是非常有前景的储氢技术,可以同时实现高的质量和体积储氢密度。
本研究重点分析了新型的固态储运氢、有机液态储运氢、绿色甲醇储运氢以及绿氨储运氢技术的特点、发展现状、经济成本及关键技术瓶颈,指出了新型储运氢技术的发展方向,横向对比了多种储运氢技术的经济性水平及应用前景,具体结论如下。
1)尽管固态储氢系统在部分氢能领域已有相关示范应用,但其距离大规模产业化应用还有一定距离。现有研究在添加催化剂、纳米化和构建复合储氢体系等方面提升了镁基储氢材料性能,但其产业化发展依然面临高成本、高能耗等诸多关键挑战。
2)有机液态储氢技术优势是液体的操作相对简单,主要问题包括有机液态储氢载体脱氢温度较高、释氢速率较低,氢气需提纯,同时氢化和脱氢过程依赖于贵重金属催化剂,一定程度制约了有机液态储氢技术的大规模产业化发展,需要在有机液体本身和催化剂上进一步研发。
3)绿色甲醇技术面临的关键技术瓶颈主要有制备和放氢能耗较高、绿氢成本高、应用端有二氧化碳排放及氢气纯化和除一氧化碳困难等技术挑战;而绿氨技术面临的挑战有能耗较高、存在安全风险隐患以及成本较高等关键挑战。
4)综合比较镁基固态储氢、有机液体储运氢、氨、甲醇储运氢技术来看,各种技术均有利弊,需要对不同的氢储运量、运送距离、安全性、碳排放、应用场景等做出综合分析,从而找到合适的路径与应用方案。
  • 国家自然科学基金项目(52401386)
  • 中国氢能联盟2023政研项目(CHA2023RP003)
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2025年第43卷第7期
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doi: 10.3981/j.issn.1000-7857.2024.08.00986
  • 接收时间:2024-08-12
  • 首发时间:2025-06-29
  • 出版时间:2025-04-13
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  • 收稿日期:2024-08-12
  • 修回日期:2024-10-09
基金
国家自然科学基金项目(52401386)
中国氢能联盟2023政研项目(CHA2023RP003)
作者信息
    1. 北京国氢中联氢能科技研究院有限公司, 北京 100007
    2. 上海市氢科学重点实验室 & 上海交通大学氢科学中心, 上海 200240
    3. 上海氢枫能源技术有限公司, 上海 201100

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邹建新(通信作者),教授,研究方向为储运氢技术,电子信箱:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

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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