水合物储氢的研究进展

doi:10.16085/j.issn.1000-6613.2022-0321

摘要/Abstract

摘要：

氢作为一种清洁能源，越来越受到人们的重视，氢能利用技术的需求日益迫切。氢能的利用关键挑战在于氢气的储运，促进剂作用下氢气水合物可使氢气在相对温和的温压条件下安全、长期地储存，为储氢提供了一种选择。水合物储氢因其安全环保的特性具有巨大的工业化应用潜力，其目前工业化应用的两个关键问题即为储氢密度与储氢速率。本文首先回顾了氢气水合物的研究历程，阐述了几种常见氢气水合物的相平衡数据，然后归纳了不同晶型氢气水合物的储氢密度，最后总结了物理方法强化与化学方法强化对水合物储氢速率的影响，通过对近年来水合物储氢评估与总结，提出了当前水合物储氢存在的问题与未来研究方向，以期为水合物储气的工业化应用和氢气水合物的研究提供参考。

关键词: 氢能, 气体水合物, 储氢密度, 储氢速率, 清洁能源

Abstract:

Hydrogen as clean energy attracts more and more attention, and the demand for hydrogen energy utilization technology is increasingly urgent. Hydrogen storage and transportation are widely recognized as the key challenge within hydrogen technologies. Hydrates allow safe, long-term storage of hydrogen under relatively mild temperature and pressure conditions, providing an option for hydrogen storage. Hydrogen storage in hydrates has great potential for industrial application due to its safety and environmental protection characteristics, and the two key issues in its current industrial application are hydrogen storage density and hydrogen storage rate. This paper illustrated the research history of hydrogen hydrates, summarized the phase equilibrium data of several common hydrogen hydrates, then concluded the hydrogen storage densities of different hydrogen hydrates, and finally, generalized the effects of physical strengthening and chemical strengthening on hydration. Through the evaluation and summary of the hydrogen storage of hydrates in recent years, the current problems and future research directions of hydrogen storage in hydrates were put forward to provide references for the industrial application of hydrate gas storage and the research of hydrogen hydrate.

Key words: hydrogen energy, gas hydrate, hydrogen storage density, hydrogen storage rate, clean energy

中图分类号:

O643.1

李昊阳, 张炜, 李小森, 徐纯刚. 水合物储氢的研究进展[J]. 化工进展, 2022, 41(12): 6285-6294.

LI Haoyang, ZHANG Wei, LI Xiaosen, XU Chungang. Research process of hydrate-based hydrogen storage[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6285-6294.

图/表 7

参考文献 73

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晶型	孔穴	表述	孔穴数	孔穴直径/Å	配位数	理想表达式
sI	小	5¹²	2	3.95	20	6X·2Y·46H₂O
	大	5¹²6²	6	4.33	24
sII	小	5¹²	16	3.91	20	8X·16Y·136·H₂O
	大	5¹²6⁴	8	4.73	28
sH	小	5¹²	3	3.91	20	1X·3Y·2Z·34H₂O
	中	4³5⁶6³	2	4.06	20
	大	5¹²6⁸	1	5.71	36

晶型	孔穴	表述	孔穴数	孔穴直径/Å	配位数	理想表达式
sI	小	5¹²	2	3.95	20	6X·2Y·46H₂O
	大	5¹²6²	6	4.33	24
sII	小	5¹²	16	3.91	20	8X·16Y·136·H₂O
	大	5¹²6⁴	8	4.73	28
sH	小	5¹²	3	3.91	20	1X·3Y·2Z·34H₂O
	中	4³5⁶6³	2	4.06	20
	大	5¹²6⁸	1	5.71	36

方法	存储条件	理论储氢密度（质量分数）	安全性	文献
高压气态储氢	298K，35～70MPa	5.7%（70MPa）	危险	[16]
低温液化储氢	23K，0.3～0.5MPa	7.6%	危险	[16]
固体材料储氢	413K，0.001MPa	4.0%（MgH₂）	安全	[18]
氢气水合物	280K，300MPa	3.77%~4.97%（H₂/H₂O）	安全	[19]

方法	存储条件	理论储氢密度（质量分数）	安全性	文献
高压气态储氢	298K，35～70MPa	5.7%（70MPa）	危险	[16]
低温液化储氢	23K，0.3～0.5MPa	7.6%	危险	[16]
固体材料储氢	413K，0.001MPa	4.0%（MgH₂）	安全	[18]
氢气水合物	280K，300MPa	3.77%~4.97%（H₂/H₂O）	安全	[19]

文献	体系	促进剂浓度（摩尔分数）	温度 /K	压力 /MPa
Smirnov等^［42］	H₂/H₂O		260	200
			258	100
			178	50
Hashimoto等^［25］	H₂/THF	5.56%	277.5	0.33
			277.6	0.55
			277.8	1.03
			278.0	1.55
			278.2	2.13
			279.2	4.87
			280.1	8.30
			280.8	11.3
			281.4	13.3
	H₂/TBAB	3.6%	285.4	0.18
			285.5	0.70
			285.8	1.19
			286.1	3.27
			286.3	6.05
			286.6	7.93
			287.2	13.4
Du等^［43］	H₂/叔丁胺	5.56%	268.4	9.54
			269.2	12.53
			269.9	15.09
			271.5	20.85
			273.2	26.12
			274.0	29.95
		8.86%	270.4	11.75
			271.3	15.01
			271.8	17.14
			272.6	19.83
			273.1	21.63
			274.0	27.72
Wang等^［44］	H₂/C₃H₈	33%（体积分数）	279.05	1.60
			278.25	1.40
			277.84	1.20
			276.83	1.00
			275.90	0.80
			274.71	0.60
			273.72	0.40