两类复合无机相变储热材料高温热稳定性和安全性研究

doi:10.11949/0438-1157.20200355

化工学报 ›› 2020, Vol. 71 ›› Issue (S2): 314-320.DOI: 10.11949/0438-1157.20200355

• 材料化学工程与纳米技术 • 上一篇

两类复合无机相变储热材料高温热稳定性和安全性研究

刘亮^1,²(),吴爱枝¹,黄云²,黄剑³

^1.北京市安全生产科学技术研究院，北京 101101
^2.中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190
^3.西安石油大学化学化工学院，陕西西安 710065

收稿日期:2020-04-07 修回日期:2020-06-04 出版日期:2020-11-06 发布日期:2020-11-06
通讯作者: 刘亮
作者简介:刘亮（1982—），男，博士，工程师，liuliang8@126.com
基金资助:
国家重点基础研究发展计划项目(2015BAA01B02);国家自然科学基金项目(91434116);江苏省科学计划项目(BA2016120);陕西省教育厅专项科研计划项目(18JK0609)

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

Liang LIU^1,²(),Aizhi WU¹,Yun HUANG²,Jian HUANG³

^1.Beijing Academy of Safety Science and Technology, Beijing 101101, China
^2.State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^3.College of Chemistry and Chemical Engineering, Xi??an Shiyou University, Xi&#x1001b3 ;an 710065, Shaanxi, China

Received:2020-04-07 Revised:2020-06-04 Online:2020-11-06 Published:2020-11-06
Contact: Liang LIU

摘要/Abstract

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

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

中图分类号:

TK 512

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.

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.

图/表 14

表1 复合无机相变储热材料制备仪器

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

表2 四种典型复合硝酸盐配比

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

图1 四种典型复合硝酸盐配比相变组分的DSC图

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

表3 六种典型复合碳酸盐配比

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

图2 六种典型复合碳酸盐配比相变组分的DSC图

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

表4 两类复合熔融盐类储热材料原材料最佳配比

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

图3 复合硝酸盐类储热材料的热分析-质谱图(Ar气中，NO气体产物)

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

图4 复合硝酸盐类储热材料的热分析-质谱图(Ar气中, NO2气体产物)

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

图5 复合硝酸盐类储热材料的热分析-质谱图(air气中, NO气体产物)

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

图6 复合硝酸盐类储热材料的热分析-质谱图(air气中, NO2气体产物)

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

图7 复合碳酸盐类储热材料的热分析-质谱图(Ar气中, CO气体产物)

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

图8 复合碳酸盐类储热材料的热分析-质谱图(Ar气中, CO2气体产物)

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

图9 复合碳酸盐类储热材料的热分析-质谱图(air气中，CO气体产物)

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

图10 复合碳酸盐类储热材料的热分析-质谱图(air气中, CO2气体产物)

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

参考文献 30

1	Hoshi A, Mills D R, Bittar A, et al. Screening of high melting point phase change materials (PCM) in solar thermal concentrating technology based on CLFR[J]. Solar Energy, 2005, 79(3): 332-339.
2	张寅平, 胡汉平, 孔祥冬. 相变储热-理论与应用[M]. 合肥: 中国科技大学出版社, 1996.
	Zhang Y P, Hu H P, Kong X D. Phase Change Thermal Storage-Theory and Application [M]. Hefei: University of Science and Technology of China Press, 1996.
3	Pielichowska K, Pielichowski K. Phase change materials for thermal energy storage[J]. Progress in Materials Science, 2014, 65(10): 67-123.
4	张贺磊, 方贤德, 赵颖杰. 相变储热材料及技术的研究进展[J]. 材料导报, 2014, 28(13): 26-32.
	Zhang H L, Fang X D, Zhao Y J. Research progress of phase change thermal storage materials and technologies [J]. Materials Review, 2014, 28 (13): 26-32.
5	Jamekhorshid A, Sadrameli S M, Barzin R, et al. Composite of wood-plastic and micro-encapsulated phase change material (MEPCM) used for thermal energy storage[J]. Applied Thermal Engineering, 2016, 112: 82-88.
6	Cheralathan M, Velraj R, Renganarayanan S. Heat transfer and parametric studies of an encapsulated phase change material based cool thermal energy storage system[J]. Journal of Zhejiang University-Science A(Applied Physics & Engineering), 2006, 7(11): 1886-1895.
7	Ho C J, Gao J Y. Preparation and thermophysical properties of nanoparticle-in-paraffin emulsion as phase change material[J]. International Communications in Heat & Mass Transfer, 2009, 36(5): 467-470.
8	何天白, 胡汉杰. 功能高分子与新材料[M]. 北京: 化学工业出版社, 2001.
	He T B, Hu H J. Functional Polymers and New Materials [M]. Beijing: Chemical Industry Press, 2001.
9	杨岳澔, 程晓敏, 李丹, 等. 硬脂酸/改性碳纳米管复合相变储热材料性能[J]. 储能科学与技术, 2019, 8(4): 759-763.
	Yang Y D, Cheng X M, Li D, et al. Properties of stearic acid / modified carbon nanotube composite phase change thermal storage material [J]. Energy Storage Science and Technology, 2019, 8 (4): 759-763.
10	赵耀. 相变材料及梯级系统传热储热特性的理论与实验研究[D]. 上海: 上海交通大学, 2018.
	Zhao Y. Theoretical and experimental study on heat transfer and storage characteristics of phase change materials and cascade systems[D]. Shanghai: Shanghai Jiao Tong University, 2018.
11	Li M, Wu Z, Tan J. Properties of form-stable paraffin/silicon dioxide/expanded graphite phase change composites prepared by sol–gel method[J]. Applied Energy, 2012, 92(2): 456-461.
12	Zhang H, Wang X, Wu D. Silica encapsulation of n-octadecane via sol-gel process: a novel microencapsulated phase-change material with enhanced thermal conductivity and performance[J]. Journal of Colloid & Interface Science, 2010, 343(1): 246-255.
13	Yu S, Wang X, Wu D. Microencapsulation of n-octadecane phase change material with calcium carbonate shell for enhancement of thermal conductivity and serving durability: synthesis, microstructure, and performance evaluation[J]. Applied Energy, 2014, 114(2): 632-643.
14	Sarı A, Alkan C, Karaipekli A. Preparation, characterization and thermal properties of PMMA/ n-heptadecane microcapsules as novel solid-liquid microPCM for thermal energy storage[J]. Applied Energy, 2010, 87(5): 1529-1534.
15	Alkan C, Sarı A, Karaipekli A. Preparation, thermal properties and thermal reliability of microencapsulated n-eicosane as novel phase change material for thermal energy storage[J]. Energy Conversion & Management, 2011, 52(1): 687-692.
16	吕社辉, 郭元强, 陈鸣才, 等. 复合高分子相变材料研究进展[J]. 高分子材料科学与工程, 2004, 20(3): 37-40.
	Lyu S H, Guo Y Q, Chen M C, et al. Research progress of composite polymer phase change materials[J]. Polymer Materials Science and Engineering, 2004, 20(3): 37-40.
17	张东, 康韡, 李凯莉. 复合相变材料研究进展[J]. 功能材料, 2007, 38(12): 1936-1940.
	Zhang D, Kang Y, Li K L. Research progress of composite phase change materials[J]. Functional Materials, 2007, 38(12): 1936-1940.
18	Wang L B, Zhang K L, Pan H L, et al. 2D molybdenum nitride nanosheets as anode materials for improved lithium storage[J]. Nanoscale, 2018, 10(40): 18936-18941.
19	Ortega F, Nicolas C, Gil A, et al. Thermophysical characterization of a by-product from the steel industry to be used as a sustainable and low-cost thermal energy storage material[J]. Energy, 2015, 89: 601-609.
20	Nasef M M, Gürsel S A, Karabelli D, et al. Radiation-grafted materials for energy conversion and energy storage applications[J]. Progress in Polymer Science, 2016, 63: 1-41.
21	Rathod M K, Banerjee J. Experimental investigations on latent heat storage unit using paraffin wax as phase change material[J]. Experimental Heat Transfer, 2014, 27(1/2/3/4/5): 40-55.
22	Sick N, Blug M, Leker J. The influence of raw material prices on the development of hydrogen storage materials: the case of metal hydrides[J]. Journal of the Knowledge Economy, 2014, 5(4): 735-760.
23	Huang X, Alva G, Jia Y T, et al. Morphological characterization and applications of phase change materials in thermal energy storage: a review[J]. Renewable and Sustainable Energy Reviews, 2017, 72: 128-145.
24	Diarce G, Corro-Martínez, E, Quant L, et al. The sodium nitrate–urea binary mixture as a phase change material for medium temperature thermal energy storage(Ⅰ): Determination of the phase diagram and main thermal properties[J]. Solar Energy Materials and Solar Cells, 2016, 157: 1065-1075.
25	Zhang X, Ma J, Chen K. Impact of morphology of conductive agent and anode material on lithium storage properties[J]. Nano-Micro Letters, 2015, 7(4): 360-367.
26	Banu D, Feldman D, Haghighat F, et al. Energy-storing wallbnant: flammability test[J]. Joumal of Materials in Civil Engineerin, 1998, 10(2): 98-105.
27	Zalba B, Marín J M, Cabeza L F, et al. Review on thermal energy storage with phase change: materials, heat transfer analysis andapplications[J]. Applied Thermal Engineering, 2003, 23(3): 251-283.
28	贺万玉, 闫全英. 熔融盐相变储热材料[J]. 材料导报: 纳米与新材料专辑, 2015, (S1): 128-130.
	He W Y, Yan Q Y. Molten salt phase change heat storage material [J]. Materials Review: Nano and New Materials Special, 2015, (S1): 128-130.
29	Jamekhorshid A, Sadrameli S M, Barzin R, et al. Composite of wood-plastic and micro-encapsulated phase change material (MEPCM) used for thermal energy storage[J]. Applied thermal Engineering, 2017, 112: 82-88.
30	Ruiz M L, Lick I D, Ponzi M I, et al. Thermal decomposition of supported lithium nitrate catalysts[J]. Thermochimica Acta, 2010, 499(1): 21-26.

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两类复合无机相变储热材料高温热稳定性和安全性研究

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

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