中低温吸附式热化学储热研究现状与进展

doi:10.19799/j.cnki.2095-4239.2024.0909

摘要/Abstract

摘要：

热化学储能由于具有储能密度高，热量损失低的优点，特别适合长时热能储存。本文综述了基于吸附反应的热化学储能材料，重点聚焦于中低温段的材料，包括物理吸附材料(如硅胶和沸石)和化学吸附材料(如水合盐)。首先，本文总结了物理吸附材料的优势与不足，分析了这些材料在实际应用中的潜在使用方式。针对水合盐类化学吸附材料，本文介绍了其反应条件、储能密度以及水合特性，并着重讨论了如何通过将水合盐负载于多孔载体来制备复合水合盐材料，以克服水合盐在应用中常见的团聚和潮解问题。本文还回顾了吸附式热化学反应器，对比了固定床、移动床反应器的特点和性能，提出了强化传热传质的办法。本文对热化学反应系统中的开式和闭式系统进行了全面分析，归纳了这两类系统在实际应用中的优缺点，探讨了各类系统在能效与性能方面的表现。此外，本文通过案例阐述了热化学系统的效率和性能，提出了系统设计思路以满足不同应用需求。此外还对热化学储热系统进行了技术经济分析，以评估系统的商业化潜力。最后，本文展望了提升吸附式热化学系统性能和降低成本的未来研究方向。

关键词: 热化学储热, 吸附材料, 水合盐, 反应器, 系统

Abstract:

Thermochemical energy storage (TCES) is particularly suitable for long-term thermal energy storage due to the advantages of high energy storage density and low heat loss. This paper reviews thermochemical energy storage materials based on sorption, focusing on materials in the low to medium temperature range, including physical adsorption materials (e.g. silica gel and zeolite) and chemical sorption materials (e.g. salt hydrate). Firstly, the properties of physical adsorption materials are summarised and their use in applications is analysed. For salt hydrate-based chemical sorption materials, their reaction conditions, energy storage densities and hydration properties are described. Then, the preparation of composite material by loading salt hydrates onto porous supports is introduced and highlighted, aiming to overcome the challenges of agglomeration and deliquescence in practical applications. Meanwhile, the design of thermochemical reactors has been reviewed. The characteristics and performance of fixed bed and moving bed reactors were also compared, and further suggestions for improving heat and mass transfer were discussed. An analysis of open and closed systems was also summarised in terms of advantages and disadvantages. Further discussions on the performance of each type of system including energy efficiency, performance and system design ideas to meet different application requirements are proposed. A techno-economic analysis of thermochemical heat storage is also carried out to assess the commercialisation potential of various systems. Finally, future research directions to improve the performance and reduce the cost of adsorption-based thermochemical systems are outlined.

Key words: thermochemical heat storage, sorption material, salt hydrate, reactor, system

中图分类号:

TK 02

马鸿坤, 纪明希, 丁玉龙. 中低温吸附式热化学储热研究现状与进展[J]. 储能科学与技术, 2024, 13(12): 4436-4451.

Hongkun MA, Mingxi JI, Yulong DING. Current status and advances in the low-to-medium temperature sorption-based thermochemical heat storage[J]. Energy Storage Science and Technology, 2024, 13(12): 4436-4451.

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类别	再生温度/℃	优点	缺点
硅胶	65～100	安全无毒、便宜、吸附性能好	导热性能差
沸石	200～300	稳定性能好、渗透性能好	成本高、热导率低
活性炭	100～150	导热性能好、表面积大	稀释条件有限、热稳定性有限
天然岩石	90～120	孔隙大、稳定性能好	吸附性能有限
磷酸盐	70～95	稳定性能好、吸附性能好	成本高、研究较少
金属有机骨架	90～140	水热稳定性好、吸水性好	合成难、成本高

材料	脱水温度/℃	水合温度/℃	能量密度/(GJ/m³)	主要优缺点
CaCl₂⋅6H₂O	156	32	3.10	成本低；水合湿度非常低
MgCl₂⋅6H₂O	214	40	3.10	成本低；高温脱水时会产生HCl
MgSO₄⋅7H₂O	329	25	2.80	成本低；水合湿度非常高
K₂CO₃⋅1.5H₂O	100	40	1.30	材料稳定；能量密度较低
SrBr₂∙6H₂O	80	30	2.49	脱水水合反应快；成本高
Na₂S∙5H₂O	110	27	2.80	反应温度适宜；可能产生有毒气体H₂S
LaCl₃·7H₂O	158	48	2.41	反应温度适宜；熔点较低

复合材料工作对	制备方法	脱水温度/℃	水合温度/℃	能量密度	循环次数	参考文献
沸石13X/MgCl₂	浸渍法	200	30	1368 J/g	20	[51]
氧化石墨烯气凝胶/MgCl₂	水热和冷冻干燥	—	—	1598 J/g	—	[52]
膨胀石墨/MgSO₄	浸渍法	120	—	718.90 J/g	—	[53]
硅胶/CaCl₂	浸渍法	80	30	1080.51 J/g	10	[54]
活性氧化铝/MgSO₄	浸渍法	200	25～40	395.13 J/g	—	[40]
膨胀石墨/SrBr₂	湿法浸渍法	150	—	约 600 J/g	—	[50]
金属有机框架材料MOF/SrBr₂	湿法浸渍法	80	30	233 kWh/m³	10	[55]
蛭石/LiCl	浸渍法	85	35	1890～2150 J/g	14	[56]
硅胶/MgSO₄	雾化喷涂法	110～130	30～50	603.36 J/g	15	[57]

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