Research on high temperature thermal stability and safety of two types of composite inorganic phase change thermal storage materials

doi:10.11949/0438-1157.20200355

Abstract

Abstract:

In this paper, nitrate (KNO₃, NaNO₃) and carbonate (Li₂CO₃, K₂CO₃, Na₂CO₃ and CaCO₃), which are composite inorganic phase change thermal storage materials suitable for industrial thermal storage, non-toxic and less corrosive, are used as phase change components, respectively. The thermal properties (melting point, latent heat) of 4 different ratios of nitrate phase change components and 6 different ratios of carbonate phase change components were studied, and a distribution ratio of molten salt phase change components was selected respectively. Using the principle of porous carrier adsorption, two types of composite molten salt thermal storage materials with the best ratio were prepared. The ease of decomposition of the thermal storage materials in different media atmospheres (Ar and air) was analyzed. TG-DSC-MS tested high temperature thermal decomposition products show that the composite nitrate thermal storage materials have stable physical and chemical properties and good safety when storing thermal at medium temperature (300℃), but they are easy to decompose NO and high temperature (500℃) or higher. NO₂ and air atmosphere are more likely to generate toxic gases, and composite carbonate thermal storage materials are more likely to generate CO in air than Ar, which affects the safety of the thermal storage process.

Key words: nitrate, carbonate, thermal storage material, thermal decomposition

摘要：

以适合工业储热的复合无机相变储热材料硝酸盐（KNO₃、NaNO₃）和碳酸盐（Li₂CO₃、K₂CO₃、Na₂CO₃和CaCO₃）为相变组分，研究了4种不同配比硝酸盐相变组分和6种不同配比碳酸盐相变组分的热性能（熔点、潜热）差异，分别优选出一种熔融盐相变组分配比。利用多孔载体吸附原理，制备出两种最佳配比的复合熔融盐类储热材料，分析了储热材料在不同介质气氛中（Ar和air）分解难易程度，TG-DSC-MS联用测试的高温热分解产物表明，复合硝酸盐类储热材料在中温（300℃）储热时，物理化学性能稳定，安全性较好，但在高温（500℃以上）时易分解成NO和NO₂，且air气氛中更易生成有毒气体；而复合碳酸盐类储热材料在air中比在Ar中更易生成CO而影响储热过程中的安全性。

关键词: 硝酸盐, 碳酸盐, 储热材料, 热分解

CLC Number:

TK 512

Liang LIU, Aizhi WU, Yun HUANG, Jian HUANG. Research on high temperature thermal stability and safety of two types of composite inorganic phase change thermal storage materials[J]. CIESC Journal, 2020, 71(S2): 314-320.

刘亮, 吴爱枝, 黄云, 黄剑. 两类复合无机相变储热材料高温热稳定性和安全性研究[J]. 化工学报, 2020, 71(S2): 314-320.

Figures/Tables 14

Table 1 Preparation instruments of composite inorganic phase change thermal storage materials

型号及名称	厂家	用途
HC-07040玛瑙研钵	北京中镜科仪技术有限公司	原材料研磨
JH-50700067标准过目筛	新乡金禾机械有限公司	原材料粒径筛选
DZF-6050真空干燥箱	上海一恒科技有限公司	原材料烘干
XS-204 电子天平	METTLER TOLEDO	原材料称量
FYD-40-A电动手动台式压片机	北京鑫骉腾达仪器设备有限公司	压片
SK-G08165真空/气氛管式电炉	天津中环电炉股份有限公司	烧结

Table 2 Proportion of four typical compound nitrates

配比编号	KNO₃∶NaNO₃比例
1	6∶4
2	4∶6
3	1∶0
4	0∶1

Fig.1 DSC diagram of four typical compound nitrate phase change components

Table 3 Proportion of six typical composite carbonates

配比编号	Li₂CO₃∶K₂CO₃∶Na₂CO₃∶CaCO₃比例
1	1∶0∶0∶0
2	1∶0∶1∶0
3	2∶6.5∶1.7∶1
4	2∶6.5∶2∶1
5	2∶6.5∶2.5∶1
6	1.5∶6.5∶2.5∶1

Fig.2 DSC diagram of six typical composite carbonate phase transition components

Table 4 Optimum ratio of raw materials for two types of composite molten salt thermal storage materials

储热材料类别	原材料	组分配比
硝酸盐类	硝酸钠∶二氧化硅∶石墨	7∶3∶1
碳酸盐类	碳酸钠∶碳酸锂∶氧化镁∶石墨	3∶3∶4∶1

Fig.3 Thermal analysis-mass spectrometry diagram of composite nitrate thermal storage material (in Ar, NO gas product)

Fig.4 Thermal analysis-mass spectrometry diagram of composite nitrate thermal storage material (in Ar,NO2 gas product)

Fig.5 Thermal analysis-mass spectrometry diagram of composite nitrate thermal storage material (in air, NO gas product)

Fig.6 Thermal analysis-mass spectrometry diagram of composite nitrate thermal storage material (in air, NO2 gas product)

Fig.7 Thermal analysis-mass spectrometry diagram of composite carbonate thermal storage material (in Ar, CO gas product)

Fig.8 Thermal analysis-mass spectrometry diagram of composite carbonate heat storage material (in Ar, product of CO2 gas)

Fig.9 Thermal analysis-mass spectrometry diagram of composite carbonate thermal storage material (in air, CO gas product)

Fig.10 Thermal analysis-mass spectrometry diagram of composite carbonate thermal storage material (in air, CO2 gas product)

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