液态有机储氢技术研究现状与展望

doi:10.16085/j.issn.1000-6613.2023-0515

摘要/Abstract

摘要：

随着构建绿色氢能社会愿景的提出，氢能的需求量将会大规模增长，氢能的储运就成为了制约产业规模化发展的瓶颈。液态有机储氢技术在氢能大规模储存和长距离运输上具有成本低、安全性高等传统高压储氢无法比拟的优势，由于这项技术目前仍处于发展初期，国内相关的报道较少。本文综述了芳香烃类和氮杂环芳香烃类等主要的液态有机储氢材料，并对其储氢性能、优势、存在问题及发展现状展开了分析；阐述了液态有机储氢技术中加氢和脱氢过程所涉及的各种金属催化剂的性能。基于目前的研究，对液态有机储氢技术在未来氢能规模化应用方面的发展前景进行了展望，同时指出液态有机储氢技术在诸多氢能应用领域的可行性及其极高的经济价值。但是若要实现大规模应用，则需选择更优的有机储氢材料，开发高选择性、高催化活性及低成本的新型催化剂，进一步优化加氢和脱氢技术。

关键词: 液态有机储氢, 储氢材料, 芳香烃类, 氮杂环芳香烃类, 催化剂, 加氢, 脱氢, 氢

Abstract:

As the vision of building a green hydrogen society, the demand for hydrogen energy will grow massively on a large scale as well, but the storage and transportation will also be the bottleneck that restricts the scale of the industrial development. Liquid organic hydrogen carries (LOHCs) have advantages over conventional high-pressure hydrogen storage methods in terms of low cost and safety for the large-scale storage and long-distance transportation of hydrogen energy. However, this technology is still at the early stage of development, and the related reports are limited. This paper reviews the main liquid organic hydrogen materials, aromatic such as aromatic hydrocarbons and aza-aromatic hydrocarbons, and analyses their hydrogen storage properties, advantages, problems and development status. Furthermore, various metal catalysts involved in hydrogenation and dehydrogenation processes are described. Finally, based on the current research, the prospects for liquid organic hydrogen storage technology are presented and the feasibility of liquid organic hydrogen storage technology in various fields and its high economic values are pointed out. However, for large-scale application, it's necessary to select the optimal liquid organic hydrogen materials, develop new catalysts with high selectivity, high catalytic activity and low cost, and further optimize hydrogenation and dehydrogenation technologies.

Key words: liquid organic hydrogen carriers, hydrogen storage material, aromatic hydrocarbons, aza-aromatic hydrocarbons, catalyst, hydrogenation, dehydrogenation, hydrogen

中图分类号:

TK91

刘若璐, 汤海波, 何翡翡, 罗凤盈, 王金鸽, 杨娜, 李洪伟, 张锐明. 液态有机储氢技术研究现状与展望[J]. 化工进展, 2024, 43(4): 1731-1741.

LIU Ruolu, TANG Haibo, HE Feifei, LUO Fengying, WANG Jinge, YANG Na, LI Hongwei, ZHANG Ruiming. Recent research and prospect of liquid organic hydrogen carries technology[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 1731-1741.

图/表 14

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序号	名称	质量储氢密度/%	体积储氢密度/kg·m^-3	熔点/℃	沸点/℃	脱氢焓/kJ·mol^-1
1	咔唑	6.7	87	48.12	355	48.12
2	N-甲基咔唑	6.2	—	89	337.8	49.1
3	N-乙基咔唑	5.8	54.0	68	348	50.6
4	N-乙酰咔唑	6.32	63.83	77	315.5	—
5	N-苯甲酰咔唑	6.92	68.92	101	391.2	—
6	N-苯基咔唑	6.94	67.11	70	415.3	57.7

序号	名称	质量储氢密度/%	体积储氢密度/kg·m^-3	熔点/℃	沸点/℃	脱氢焓/kJ·mol^-1
1	咔唑	6.7	87	48.12	355	48.12
2	N-甲基咔唑	6.2	—	89	337.8	49.1
3	N-乙基咔唑	5.8	54.0	68	348	50.6
4	N-乙酰咔唑	6.32	63.83	77	315.5	—
5	N-苯甲酰咔唑	6.92	68.92	101	391.2	—
6	N-苯基咔唑	6.94	67.11	70	415.3	57.7

序号	名称	质量储氢密度/%	体积储氢密度/kg·m^-3	熔点/℃	沸点/℃	脱氢焓/kJ·mol^-1
1	吲哚	6.4	56	53	253	53.6
2	N-甲基吲哚	5.76	59.1	<-20	239	—
3	2-甲基吲哚	5.76	—	57	273	51.7
4	N-乙基吲哚	5.23	—	-17.8	253.5	—
5	1,2-二甲基吲哚	5.23	—	55	260.5	—

序号	名称	质量储氢密度/%	体积储氢密度/kg·m^-3	熔点/℃	沸点/℃	脱氢焓/kJ·mol^-1
1	吲哚	6.4	56	53	253	53.6
2	N-甲基吲哚	5.76	59.1	<-20	239	—
3	2-甲基吲哚	5.76	—	57	273	51.7
4	N-乙基吲哚	5.23	—	-17.8	253.5	—
5	1,2-二甲基吲哚	5.23	—	55	260.5	—

序号	催化剂	反应物	完全加氢产物	温度/℃	压力/MPa	时间/h	转换率/%	选择性/%	参考文献
1	5% Ru/Al₂O₃	1-甲基吲哚	8H-1-甲基吲哚	130	6	—	100	100	[18]
2	5% Ru/Al₂O₃	2-甲基吲哚	8H-2-甲基吲哚	170	7	0.5	>99	>99	[19]
3	5% Ru/Al₂O₃	1-乙基吲哚	8H-1-乙基吲哚	190	9	1.33	100	100	[20]
4	5% Ru/Al₂O₃	1-乙基吲哚	8H-1-乙基吲哚	160	9	4	100	100	[20]
5	4.6% Ru/Al₂O₃	N-乙基咔唑	12H-N-乙基咔唑	130	7	10	—	100	[15]
6	1.3% Ru/YH3	N-乙基咔唑	12H-N-乙基咔唑	130	7	10	—	100	[15]
7	1.3% Ru/YH3	2-甲基吲哚	8H-2-甲基吲哚	130	7	10	100	100	[15]
8	0.62% Ru^0.2	喹啉	十氢喹啉	60	2	24	100	—	[30]
9	3% Pt/ Al₂O₃-P-O₂	二苄基甲苯	18H-二苄基甲苯	140	4	0.5	>99	—	[31]
10	1% Pt/WO₃-500	萘	十氢化萘	70	3	1	100	100	[11]
11	2% Ir3	喹啉	1,2,3,4-四氢喹啉	80	0.1	17	99	98	[32]
12	Ru-Ni/C	2-萘酚	5,6,7,8-四氢-2-萘酚	90	4	3	100	71.08	[33]
13	1% Pt-WO₃/α-Al₂O₃	萘	十氢化萘	70	3	1	100	100	[34]
14	1% Pd-Rh/γ-Al₂O₃	N-乙基咔唑	12H-N-乙基咔唑	160	6	1	100	100	[35]
15	Ru-Pd/Al₂O₃	N-丙基咔唑	12H-N-丙基咔唑	150	7	7	>99	>99	[36]