高温储热用MgCl2-NaCl-KCl熔盐的研究进展

doi:10.19799/j.cnki.2095-4239.2024.0855

摘要/Abstract

摘要：

随着化石能源短缺和环境问题加剧，聚光太阳能(concentrated solar power，CSP)技术与热储能技术(thermal energy storage，TES)的结合成为有效利用太阳能的重要途径。熔盐是常见的中高温储热材料，而MgCl₂-NaCl-KCl三元氯化物熔盐凭借其优异的热物理性能、较高的热稳定性和低成本，成为下一代熔盐储能技术(工作温度>700 ℃)中最有前途的材料之一。熔盐的热物理性能，例如熔点、比热容、密度、热导率等，对储热系统的设计和优化具有重要意义。同时，氯化物熔盐对金属材料的强腐蚀性也威胁着整个系统的安全。因此，针对目前MgCl₂-NaCl-KCl熔盐面临着热物理性能参数难获取，对金属的腐蚀性较强等问题，本文对近期的相关研究成果进行了汇总及探讨。首先从实验研究和模拟研究两方面综述了MgCl₂-NaCl-KCl熔盐的热物理性能的确定。随后，基于现有与腐蚀相关的研究成果，介绍了此体系熔盐对常用镍基、铁基合金的腐蚀机理，并从降低熔盐的腐蚀性、提高金属材料的耐蚀性能和腐蚀监测系统三方面综述了目前腐蚀缓解的策略。最后，总结了当前研究现状，并展望了未来发展方向。

关键词: 三元氯化物熔盐, 热能储存, 热物理性能, 腐蚀

Abstract:

With the depletion of fossil fuels and environmental concerns, integrating concentrated solar power (CSP) technology with thermal energy storage (TES) has become essential for efficient solar energy utilization. Molten salts are commonly used as heat storage materials, particularly at medium to high temperatures. Among these, MgCl₂-NaCl-KCl ternary chloride molten salt has been identified as a most promising candidate for next-generation storage systems operating above 700 ℃ thanks to its excellent thermophysical properties, high thermal stability, and low cost. The thermophysical properties of molten salts, such as melting point, specific heat capacity, density, and thermal conductivity, are crucial for the design and optimization of heat storage systems. However, the strong corrosiveness of chloride molten salts towards metallic materials is a major safety concern. To address the current challenges of the MgCl₂-NaCl-KCl molten salt, particularly in obtaining thermophysical property parameters and addressing corrosion issues, recent studies have been reviewed. These studies focus on experimental and simulation approaches to determine the thermophysical properties of the MgCl₂-NaCl-KCl molten salt. Moreover, the corrosion mechanisms affecting common nickel-based and iron-based alloys exposed to this molten salt have been explored based on existing research. Corrosion mitigation strategies are discussed from three aspects: reducing the corrosiveness of the molten salt, improving the corrosion resistance of metallic materials, and implementing corrosion monitoring systems. Finally, the current research status is summarized, and future development directions are proposed.

Key words: ternary chloride molten salts, thermal energy storage, thermophysical properties, corrosion

中图分类号:

TB 34

魏大林, 朱琳, 凌祥, 姜峰. 高温储热用MgCl₂-NaCl-KCl熔盐的研究进展[J]. 储能科学与技术, 2024, 13(12): 4421-4435.

Dalin WEI, Lin ZHU, Xiang LING, Feng JIANG. Research progress of MgCl₂-NaCl-KCl molten salt for high-temperature heat storage[J]. Energy Storage Science and Technology, 2024, 13(12): 4421-4435.

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熔盐及其质量分数/%	熔点/℃	最大工作温度/℃	密度/(g/cm³)	比热容/[kJ/(kg·K)]	价格/(CNY/kg)
KNO₃/NaNO₃(40/60)	240	565	~1.8(400 ℃)	~1.5	3.51~5.61
KNO₃/NaNO₃/NaNO₂(53/7/40)	142	540	~1.8(400 ℃)	1.5	6.31
K₂CO₃/Li₂CO₃/Na₂CO₃(32/35/33)	397	>650	2.0(700 ℃)	1.9(700 ℃)	9.11~17.53
KF/LiF/NaF(59/29/12)	454	>700	2.0(700 ℃)	1.9(700 ℃)	>14.20
KCl/NaCl/ZnCl₂(23.9/7.5/68.6)	204	850	~2.0(600 ℃)	0.8(300~600 ℃)	<7.01
KCl/MgCl₂/NaCl(17.8/68.2/14.0)	380	>800	~1.7(600 ℃)	~1.0(500~800 ℃)	<2.45

Mole content/%	melt temperature/℃	Ref.
40-32.5-27.5	405	[26]
50-20-30	390	[26]

44.3-41.9-13.8	403	[27]
59.5-21.9-18.6	387
52.9-33.7-13.4	388

44.7-25.8-29.4	385	[21]

55-20.5-24.5	387	[28]

46.4-22-31.6	385	[29]

合金	304	310S	316L	C276	Incoloy 800H	Inconel 625	C22
最大腐蚀深度/µm	230	140	130	110	150	45	50
腐蚀速率/(µm/a)	20148	12264	11388	9336	13140	3942	4380

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高温储热用MgCl₂-NaCl-KCl熔盐的研究进展

Research progress of MgCl₂-NaCl-KCl molten salt for high-temperature heat storage

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