Research progress on enhancing hydrate gas storage performance in porous media

doi:10.16085/j.issn.1000-6613.2024-0641

Abstract

Abstract:

Natural gas, hydrogen and other gas energy sources are an important part of the energy transition, and the storage and transportation of gas energy is the key to restricting their development. Hydrate gas storage is a new type of solid-state gas storage method with high economy, environmental protection and high safety, which has great development potential. However, slow growth kinetics and low gas storage efficiency are the main technical problems restricting the industrial application of hydrate gas storage. Focusing on the research of hydrate gas storage technology, this paper summarizes the research history and research progress of porous media (carbon-based materials, metal-organic frameworks, silica sand and metal foams) as hydrate accelerators. The particle size, pore size and arrangement, surface chemical properties, thermal conductivity and water content of porous media, as well as the effects of chemical accelerator on hydrate formation induction time, gas storage rate and gas storage density are summarized. The mechanism of some porous media to promote hydrate formation is described. The advantages and disadvantages of different porous media as hydrate accelerators are compared, and the development trend and current technical bottlenecks of porous media as accelerators are analyzed, so as to provide further analytical basis for the application of porous media as hydrate accelerators. Finally, some suggestions are put forward on the key points and development directions of porous media as accelerators.

Key words: novel solid-state gas storage, gas hydrates, porous media, kinetic intensification

摘要：

天然气、氢气等气体能源是能源转型的重要组成部分，气体能源的储运是制约其发展的关键。水合物法储气是一种经济环保、安全性较高的新型固态储气方式，具有巨大的发展潜力。但生长动力学缓慢、储气效率低是限制水合物储气工业化应用的主要技术难题。文章围绕水合物储气技术研究，总结了多孔介质（碳基类材料、金属有机框架、硅砂以及金属泡沫等）作为水合物促进剂的研究历程与研究进展。归纳了多孔介质的粒径、孔隙大小排布、表面化学性质、热导率、含水量以及与化学促进剂复配使用时对水合物生成的诱导时间、储气速度和储气密度的影响。阐述了部分多孔介质促进水合物生成的机理；对比了不同多孔介质作为水合物促进剂的优缺点；分析了多孔介质作为促进剂的发展趋势和目前的技术瓶颈；为多孔介质作为水合物促进剂的应用提供进一步的分析依据。最后针对多孔介质作为促进剂的重点和发展方向提出建议。

关键词: 新型固态储气, 气体水合物, 多孔介质, 动力学强化

CLC Number:

TE09

ZHEN Xiaofei, YANG Tebo, DONG Ti, QI Yonghao, LIU Jia. Research progress on enhancing hydrate gas storage performance in porous media[J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3413-3431.

甄箫斐, 杨特勃, 董缇, 齐永豪, 刘佳. 多孔介质强化水合物储气性能研究进展[J]. 化工进展, 2025, 44(6): 3413-3431.

Figures/Tables 27

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强化方法	具体操作
物理方法	搅拌^[11]、喷雾^[12]、鼓泡^[13]
物理化学方法
热力学促进剂	四氢呋喃（THF）^[14]、四氢吡喃（THP）、四丁基溴化铵（TBAB）^[15]、环戊烷（CP）^[16]
表面活性剂	十二烷基硫磺钠（SDS）^[17]、季铵盐类（TBAB、TBAF）、生物表面活性剂^[18]
多孔介质	沸石、聚酯氨泡沫（PU）^[19]、石英砂^[20]、有机金属骨架^[21-22]、碳纳米管、泡沫金属

强化方法	具体操作
物理方法	搅拌^[11]、喷雾^[12]、鼓泡^[13]
物理化学方法
热力学促进剂	四氢呋喃（THF）^[14]、四氢吡喃（THP）、四丁基溴化铵（TBAB）^[15]、环戊烷（CP）^[16]
表面活性剂	十二烷基硫磺钠（SDS）^[17]、季铵盐类（TBAB、TBAF）、生物表面活性剂^[18]
多孔介质	沸石、聚酯氨泡沫（PU）^[19]、石英砂^[20]、有机金属骨架^[21-22]、碳纳米管、泡沫金属

孔径大小	诱导时间/min	气体消耗量/mol	储气量/m³∙m^-3	最大生成速率/m³∙m^-3∙min^-1
10PPI	60	0.1670	169.6	18.99
35PPI	48	0.1494	151.8	11.70

孔径大小	诱导时间/min	气体消耗量/mol	储气量/m³∙m^-3	最大生成速率/m³∙m^-3∙min^-1
10PPI	60	0.1670	169.6	18.99
35PPI	48	0.1494	151.8	11.70