动力学强化水合储氢技术研究进展

doi:10.19799/j.cnki.2095-4239.2022.0358

摘要/Abstract

摘要：

在碳达峰、碳中和的时代背景下，氢能等清洁绿色能源成为能源转型的关键，储氢技术作为氢能从生产到应用的中间桥梁而备受关注。笼型水合物是一种潜在的氢气存储材料，但储氢速率慢、储氢量低制约了水合储氢技术的工业化进程。因此，本文综述了近年来动力学强化水合储氢技术的研究进展，着重介绍了氢气水合物成核、生长动力学机理、提高驱动力、扩大气液接触面积以及改善扩散通道等动力学强化技术，并从储氢速率、储氢密度等方面总结了当前的动力学强化技术，以期促进相关研究的发展。本文指出未来相关工作应在以下几个方面展开：首先，深化氢气水合物的成核、生长和稳定机制研究；其次，寻求高效高驱动力的热力学促进剂，从根本上提高驱动力；最后，高效热力学促进剂与改善氢气水合物的扩散通道相结合，实现高储量和高速率的双重优化。

关键词: 储氢, 笼型水合物, 动力学强化, 储氢速率, 储氢密度

Abstract:

In the era background of carbon dioxide emission peak and carbon neutrality, hydrogen energy was the key to energy transformation as clean and green energy. Therefore, hydrogen storage technology as an intermediate bridge between the production and application of hydrogen energy has attracted much attention. Although clathrate hydrates are potential hydrogen storage materials, the slow hydrogen storage rates and low storage capacity hinder its industrialization. Consequently, this work discussed the progress of the kinetics enhancement technology of hydrogen storage in clathrate hydrates, and the kinetics mechanism of hydrogen hydrate nucleation and growth, including the kinetics enhancement technology of hydrogen hydrate (the driving force, the contact area of the gas-liquid interface, and the diffusion channel). Then, we summarized current kinetics enhancement technology from the aspects of hydrogen storage rates and density to support the development of related research. Notably, this paper emphasizes that corresponding works may be performed in the future. First, to deepen research on nucleation, growth, and the stability mechanism of hydrogen hydrate. Second, to seek high efficiency and high driving force thermodynamic promoters in improving driving forces fundamentally. Finally, to combine high-efficiency thermodynamic promoters and improved diffusion channels in achieving the double optimization of high hydrogen-storage rates and storage capacity.

Key words: hydrogen storage, clathrate hydrate, kinetics, hydrogen storage rate, hydrogen storage capacity

中图分类号:

TQ 03

陈思远, 王燕鸿, 郎雪梅, 樊栓狮. 动力学强化水合储氢技术研究进展[J]. 储能科学与技术, 2022, 11(12): 3787-3799.

Siyuan CHEN, Yanhong WANG, Xuemei LANG, Shuanshi FAN. Review of the kinetics enhancement technology of hydrogen storage in clathrate hydrates[J]. Energy Storage Science and Technology, 2022, 11(12): 3787-3799.

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体系组成	相平衡温度/K	压缩因子z	△H_dis/(kJ/mol)
THF+H₂+H₂O	283.8	1.128	159.23
CP+H₂+H₂O	283.4	1.069	140.68
tert-Butylamine +H₂+H₂O	269.9	1.107	132.06
Acetone+H₂+H₂O	269.9	1.202	159.46
TBAB+H₂+H₂O	286.5	1.112	382.96
TBAF+H₂+H₂O	296.6	1.688	330.34
TBANO₃+H₂+H₂O	284.9	1.192	340.23

客体分子	水合物类型	客体分子直径/Å	客体分子与孔穴的直径比
客体分子	水合物类型	客体分子直径/Å	小孔穴(5¹²)	大孔穴(5¹²6²/5¹²6⁴）
CH₄	sI	4.36	0.855	0.744
C₂H₆	sI	5.5	1.08	0.939
CO₂	sI	5.2	1.02	0.887
C₃H₆	sII	6.4	1.275	0.961
H₂	sII	2.3	0.458	0.345

促进剂(物质的量分数)	温度/K	压力/MPa	样品量	储氢量/%	文献
0.5%THF	255	60	1 g	3.4	Sugahara^[48]
0.58%丙酮	255	74	1 g	3.6	Sugahara^[49]
2.54%TBABh	253	70	1 g	0.5	Shin^[50]
无	140	15～18	2 g	2.7	Kumar^[51]
5.6%呋喃	275.1	41.8	3 g	0.59	Tsuda^[31]
5.6%THT	275.1	41.5	3 g	0.6	Tsuda^[31]
5.56%THF	277.15	66.4	3 g	0.835	Ogata^[29]
1.0%THF	270	13.8	5 g	0.43	Strobel^[52]
5.56%THF	270	57	5 g	0.98	Strobel^[52]
2.71%TBAB	279.5	13.8	5 g	0.214	Strobel^[53]
5.56%THF	265.1	5.0	7.36 g	0.19	Yoshioka^[54]
5.56%THF	266.7	6.5	10 g	0.28	Nagai^[55]
5.6%CP	275.15	18	20 g	0.27	邓灿^[56]
5.6%THF	270	11.6	20 g	0.4	Su^[57]
2.0%THF	278	8.8	190 mL	0.12	Veluswamy^[47]
3.7%TBAB	281.15	16	100 mL	0.046	Treuba^[46]
3.4%TBAF	294.15	13	100 mL	0.024	Treuba^[32]

晶体类型	晶穴类型	理论分子式	储氢速率^①	理论质量储氢密度^②
sI	5¹²5¹²6²	2S∙6L∙46H₂O	—	0.463%
sII	5¹²5¹²6⁴	16S∙8L∙136∙H₂O	11.2～22.3	1.06%
sH	5¹²4³5⁶6³5¹²6⁸	3S∙2M∙1L∙34H₂O	—	1.39%
半笼型	A型/B型	3S∙2M∙2L∙38H₂O	25～38.08	0.362%

添加剂(摩尔分数)	实验压力/MPa	驱动力△P/MPa	R₁/(n/n·h^-1)^①	生成时间t₇₅^②/h	储氢量/%
5.0%THT	15.4	12	0.485	0.38	0.25
5.0%THT	21.4	18	0.7	0.5	0.37
5.0%THT	32.1	28.7	0.94	0.52	0.43
5.0%呋喃	15.5	11.5	0.4	0.45	0.23
5.0%呋喃	23.6	19.6	0.49	0.52	0.44
5.0%呋喃	32.6	28.6	0.79	0.45	0.50
5.0%呋喃	41.8	37.4	1.08	0.14	0.59
5.6%THF	11.4	9.0	0.166	—	0.26
5.6%THF	20.1	17.7	0.38	2.4	0.345
5.6%THF	31.7	29.3	0.78	3.8	0.51
5.6%THF	40.7	38.3	1.22	2.7	0.665
5.6%THF	66.4	64.0	1.48	0.93	0.835