碳酸盐/高炉矿渣定型复合相变储热材料的制备与性能

doi:10.19799/j.cnki.2095-4239.2022.0385

储能科学与技术 ›› 2022, Vol. 11 ›› Issue (9): 3028-3034.doi: 10.19799/j.cnki.2095-4239.2022.0385

碳酸盐/高炉矿渣定型复合相变储热材料的制备与性能

王君雷¹^,²^,³(), 张第玲¹, 王昆³, 许东东¹^,², 徐祥贵¹, 姚华¹^,², 刘文巍¹^,², 黄云¹^,²^,⁴()

^1.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
^2.中国科学院大学，北京 100049
^3.天津大学内燃机燃烧学国家重点实验室，天津 300072
^4.中国科学院洁净能源创新研究院，辽宁大连 116023

收稿日期:2022-07-11 修回日期:2022-07-23 出版日期:2022-09-05 发布日期:2022-08-30
通讯作者: 黄云 E-mail:jlwang18@ipe.ac.cn;yunhuang@ipe.ac.cn
作者简介:王君雷（1993—），男，博士研究生，研究方向为储热技术，E-mail：jlwang18@ipe.ac.cn；
基金资助:
国家自然科学基金(21975262);中科院清洁能源先导基金(DNL202017);河南省储能材料与过程重点实验室(202102)

Carbonates/blast furnace slag form-stable phase change materials

Junlei WANG¹^,²^,³(), Diling ZHANG¹, Kun WANG³, Dongdong XU¹^,², Xianggui XU¹, Hua YAO¹^,², Wenwei LIU¹^,², Yun HUANG¹^,²^,⁴()

^1.State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^2.University of Chinese Academy of Sciences, Beijing 100049, China
^3.State Key Laboratory of Engines, Tianjin University, Tianjin 300072, China
^4.Dalian National Laboratory for Clean Energy, Dalian 116023, Liaoning, China

Received:2022-07-11 Revised:2022-07-23 Online:2022-09-05 Published:2022-08-30
Contact: Yun HUANG E-mail:jlwang18@ipe.ac.cn;yunhuang@ipe.ac.cn

摘要/Abstract

摘要：

碳酸盐(Na₂CO₃和K₂CO₃)是极具潜力的高温相变材料，高炉矿渣(blast furnace slag，BS)作为基体材料兼具环境和经济效益，但是碳酸盐在高温熔融状态下通常会与高炉矿渣发生反应。为此，本工作发展两步法制备路线以攻克这一问题。首先，使用碳酸盐对高炉矿渣进行改性，得到化学性质稳定的改性矿渣(modified blast furnace slag，MBS)；其次，通过混合烧结法制备碳酸盐/改性矿渣定型复合相变材料(form-stable phase change materials，FSPCMs)。经过冷热循环测试制备的K₂CO₃/KMBS复合相变材料比Na₂CO₃/NMBS的定型效果更优。分析发现，K₂CO₃与KMBS具有良好的化学相容性，随着K₂CO₃含量增加，K₂CO₃/KMBS定型相变材料的潜热逐渐增加，且测试结果与计算一致，在质量比4∶6(40K₂CO₃/60KMBS)时，潜热为94.8 kJ/kg，且热稳定性最好。

关键词: 储热, 碳酸盐, 改性矿渣, 定型复合相变材料

Abstract:

Blast furnace slag (BFS) is a very affordable matrix material, and carbonates (Na₂CO₃ and K₂CO₃) are promising phase change materials for high-temperature applications; however, carbonates react with BFS when it is in the molten state. A two-step approach was created as a result to solve this problem. First, carbonate was used to modify BFS so that it can no longer react with carbonate; second, a hybrid sintering method was used to create form-stable phase change materials (FSPCMs). After thermal cycling, the obtained K₂CO₃/KMBS FSPCMs exhibited better shape preservation than Na₂CO₃/NMBS FSPCMs. Further tests revealed that K₂CO₃ and KMBS were chemically compatible. The measurement was consistent with the calculated value, and the latent heat of K₂CO₃/KMBS FSPCMs gradually increased with the increase in K₂CO₃ content. At the mass ratio of 4∶6 (40K₂CO₃/60KMBS), the latent heat is 94.8 kJ/kg, and the thermal stability is the best.

Key words: thermal energy storage, carbonate, modified blast furnace slag, form-stable composite phase change material

中图分类号:

TK 02

王君雷, 张第玲, 王昆, 许东东, 徐祥贵, 姚华, 刘文巍, 黄云. 碳酸盐/高炉矿渣定型复合相变储热材料的制备与性能[J]. 储能科学与技术, 2022, 11(9): 3028-3034.

Junlei WANG, Diling ZHANG, Kun WANG, Dongdong XU, Xianggui XU, Hua YAO, Wenwei LIU, Yun HUANG. Carbonates/blast furnace slag form-stable phase change materials[J]. Energy Storage Science and Technology, 2022, 11(9): 3028-3034.

图/表 11

表1

图1

表2

图2

图3

表3

图4

图5

图6

表4

图7

参考文献 31

1	SHEN Z W, RITTER M. Forecasting volatility of wind power production[J]. Applied Energy, 2016, 176: 295-308.
2	ZHANG H L, BAEYENS J, CÁCERES G, et al. Thermal energy storage: Recent developments and practical aspects[J]. Progress in Energy and Combustion Science, 2016, 53: 1-40.
3	NAZIR H, BATOOL M, BOLIVAR OSORIO F J, et al. Recent developments in phase change materials for energy storage applications: A review[J]. International Journal of Heat and Mass Transfer, 2019, 129: 491-523.
4	ALVA G, LIN Y X, FANG G Y. An overview of thermal energy storage systems[J]. Energy, 2018, 144: 341-378.
5	WU S F, YAN T, KUAI Z H, et al. Thermal conductivity enhancement on phase change materials for thermal energy storage: A review[J]. Energy Storage Materials, 2020, 25: 251-295.
6	ALVA G, LIN Y X, LIU L K, et al. Synthesis, characterization and applications of microencapsulated phase change materials in thermal energy storage: A review[J]. Energy and Buildings, 2017, 144: 276-294.
7	LIN Y X, ALVA G, FANG G Y. Review on thermal performances and applications of thermal energy storage systems with inorganic phase change materials[J]. Energy, 2018, 165: 685-708.
8	JIANG F, ZHANG L L, SHE X H, et al. Skeleton materials for shape-stabilization of high temperature salts based phase change materials: A critical review[J]. Renewable and Sustainable Energy Reviews, 2020, 119: doi: 10.1016/j.rser.2019.109539.
9	FERNÁNDEZ A I, BARRENECHE C, BELUSKO M, et al. Considerations for the use of metal alloys as phase change materials for high temperature applications[J]. Solar Energy Materials and Solar Cells, 2017, 171: 275-281.
10	GE Z W, YE F, CAO H, et al. Carbonate-salt-based composite materials for medium- and high-temperature thermal energy storage[J]. Particuology, 2014, 15: 77-81.
11	LI C, LI Q, CONG L, et al. MgO based composite phase change materials for thermal energy storage: The effects of MgO particle density and size on microstructural characteristics as well as thermophysical and mechanical properties[J]. Applied Energy, 2019, 250: 81-91.
12	桑丽霞, 李锋. 碳酸盐复合蓄热材料的制备及热物性研究[J]. 化工学报, 2018, 69(S1): 129-135.
	SANG L X, LI F. Study on preparation and thermal properties of carbonates composite heat storage materials[J]. CIESC Journal, 2018, 69(S1): 129-135.
13	ACURIO K, CHICO-PROANO A, MARTÍNEZ-GÓMEZ J, et al. Thermal performance enhancement of organic phase change materials using spent diatomite from the palm oil bleaching process as support[J]. Construction and Building Materials, 2018, 192: 633-642.
14	JIANG Z, LENG G H, YE F, et al. Form-stable LiNO₃-NaNO₃-KNO₃-Ca(NO₃)₂/calcium silicate composite phase change material (PCM) for mid-low temperature thermal energy storage[J]. Energy Conversion and Management, 2015, 106: 165-172.
15	ZHANG H Z, SUN S Y, WANG X D, et al. Fabrication of microencapsulated phase change materials based on n-octadecane core and silica shell through interfacial polycondensation[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2011, 389(1/2/3): 104-117.
16	LI Q, LI C, QIAO G, et al. Effects of MgO particle size and density on microstructure development of MgO based composite phase change materials[J]. Energy Procedia, 2019, 158: 4517-4522.
17	GUILLOT S, FAIK A, RAKHMATULLIN A, et al. Corrosion effects between molten salts and thermal storage material for concentrated solar power plants[J]. Applied Energy, 2012, 94: 174-181.
18	MOTTE F, FALCOZ Q, VERON E, et al. Compatibility tests between Solar Salt and thermal storage ceramics from inorganic industrial wastes[J]. Applied Energy, 2015, 155: 14-22.
19	WANG T Y, ZHANG T Y, XU G Z, et al. A new low-cost high-temperature shape-stable phase change material based on coal fly ash and K₂CO₃[J]. Solar Energy Materials and Solar Cells, 2020, 206: doi:10.1016/j.solmat.2019.110328.
20	QIU F, SONG S K, LI D N, et al. Experimental investigation on improvement of latent heat and thermal conductivity of shape-stable phase-change materials using modified fly ash[J]. Journal of Cleaner Production, 2020, 246: doi:10.1016/j.jclepro.2019.118952.
21	RAM V V, SINGHAL R, PARAMESHWARAN R. Energy efficient pumpable cement concrete with nanomaterials embedded PCM for passive cooling application in buildings[J]. Materials Today: Proceedings, 2020, 28: 1054-1063.
22	ROSTAMI J, KHANDEL O, SEDIGHARDEKANI R, et al. Enhanced workability, durability, and thermal properties of cement-based composites with aerogel and paraffin coated recycled aggregates[J]. Journal of Cleaner Production, 2021, 297: doi:10.1016/j.jclepro. 2021.126518.
23	TAYEB A M. Use of some industrial wastes as energy storage media[J]. Energy Conversion and Management, 1996, 37(2): 127-133.
24	王燕, 黄云, 姚华, 等. 太阳盐/钢渣定型复合相变储热材料的制备与性能研究[J]. 过程工程学报, 2021, 21(3): 332-340.
	WANG Y, HUANG Y, YAO H, et al. Fabrication and characterization of form-stable solar salt/steel slag composite phase change material for thermal energy storage[J]. The Chinese Journal of Process Engineering, 2021, 21(3): 332-340.
25	ZHANG Y B, LIU J C, SU Z J, et al. Preparation of low-temperature composite phase change materials (C-PCMs) from modified blast furnace slag (MBFS)[J]. Construction and Building Materials, 2020, 238: doi:10.1016/j.conbuildmat.2019.117717.
26	张浩, 杨刚, 龙红明. 改性钢渣基相变微粉的制备与性能[J]. 过程工程学报, 2017, 17(6): 1304-1309.
	ZHANG H, YANG G, LONG H M. Preparation and performance of modified steel slag-based phase change powders[J]. The Chinese Journal of Process Engineering, 2017, 17(6): 1304-1309.
27	方圆, 吴旻, 唐刚. 改性钢渣基相变储能型丁苯橡胶的制备及其性能研究[J]. 硅酸盐通报, 2018, 37(11): 3669-3673, 3683.
	FANG Y, WU M, TANG G. Preparation of modified steel slag-based phase change energy storage styrene butadiene rubber and its properties[J]. Bulletin of the Chinese Ceramic Society, 2018, 37(11): 3669-3673, 3683.
28	MEMON S A, LO T Y, BARBHUIYA S A, et al. Development of form-stable composite phase change material by incorporation of dodecyl alcohol into ground granulated blast furnace slag[J]. Energy and Buildings, 2013, 62: 360-367.
29	ZHANG Y B, LIU J C, SU Z J, et al. Utilizing blast furnace slags (BFS) to prepare high-temperature composite phase change materials (C-PCMs)[J]. Construction and Building Materials, 2018, 177: 184-191.
30	WANG J L, WANG Y, HUANG Y. Synthesis and characterization of form-stable carbonate/steel slag composite materials for thermal energy storage[J]. Journal of Energy Storage, 2022, 52: doi:10.1016/j.est.2022.104708.
31	GROEN J C, PEFFER L A A, PÉREZ-RAMı́REZ J. Pore size determination in modified micro-and mesoporous materials. Pitfalls and limitations in gas adsorption data analysis[J]. Microporous and Mesoporous Materials, 2003, 60(1/2/3): 1-17.

样品	30Na₂CO₃/70NMBS	40Na₂CO₃/60NMBS	50Na₂CO₃/50NMBS	40K₂CO₃/60KMBS	50K₂CO₃/50KMBS	60K₂CO₃/40KMBS
碳酸盐质量分数/%	30	40	50	40	50	60
改性矿渣质量分数/%	70	60	50	60	50	40
外观形貌	形貌完整	形貌完整	形貌完整	形貌完整	形貌完整	形貌完整

项目	30Na₂CO₃/70NMBS	40K₂CO₃/60KMBS	50K₂CO₃/50KMBS	60K₂CO₃/40KMBS
循环次数	—	30	30	30
外观形貌	变形泄漏	形貌完整	轻微变形	变形泄漏

样品	熔化/凝固过程
样品	起始温度T_s/℃	终止温度T_e/℃	潜热△H/(kJ/kg)
K₂CO₃	887.8/883.7	895.4/877.9	212.0/205.6
60K₂CO₃/40KMBS	885.9/884.7	895.7/874.4	138.8/132.2
50K₂CO₃/50KMBS	884.6/884.2	894.1/875	123.3/116.0
40K₂CO₃/60KMBS	882.9/883.4	892.5/873.2	94.8/90.2

[1]	姜竹, 邹博杨, 丛琳, 谢春萍, 李传, 谯耕, 赵彦琦, 聂彬剑, 张童童, 葛志伟, 马鸿坤, 金翼, 李永亮, 丁玉龙. 储热技术研究进展与展望[J]. 储能科学与技术, 2022, 11(9): 2746-2771.
[2]	尹浩, 唐志伟, 王昊, 金翼, 丁玉龙. 基于高密度复合相变储热材料电热锅炉的分时配比供热系统[J]. 储能科学与技术, 2022, 11(9): 3003-3010.
[3]	李泓, 张强. 蓄势赋能谋发展，勇毅笃行谱新篇[J]. 储能科学与技术, 2022, 11(9): 2691-2701.
[4]	李仲博, 汉京晓, 王成成, 杨慧, 杨娜, 尹少武, 王立, 童莉葛, 唐志伟, 丁玉龙. 热化学反应器放热过程模拟及参数影响规律[J]. 储能科学与技术, 2022, 11(7): 2133-2140.
[5]	杨娜, 王成成, 杨慧, 胡志昊, 童莉葛, 李仲博, 王立, 丁玉龙, 李娜. 基于热化学反应的硅胶非等温动力学计算及储热性能分析[J]. 储能科学与技术, 2022, 11(5): 1331-1338.
[6]	郝金鹏, 杜迎春, 伍弘, 和琨, 汪垒. 侧壁面正弦加热条件下电场强化固液相变研究[J]. 储能科学与技术, 2022, 11(5): 1446-1454.
[7]	周新宇, 栾道成, 胡志华, 凌俊华, 文科林, 刘浪, 阴志铭, 米书恒, 王正云. 含碳二元系相变储热材料储热性能分析选择[J]. 储能科学与技术, 2022, 11(4): 1175-1183.
[8]	李钰颖, 魏雯珍, 李琦, 吴玉庭. 可用于低中温热能储存的四元硝酸盐/埃洛石/石墨定型复合材料的制备与研究[J]. 储能科学与技术, 2022, 11(3): 1044-1051.
[9]	郭云琪, 盛楠, 朱春宇, 饶中浩. 基于模板法制备氧化铝纤维及其石蜡复合相变材料热性能[J]. 储能科学与技术, 2022, 11(2): 511-520.
[10]	王青萌, 刘志, 程晓敏, 程千驹, 吕泽安. In元素对Sn-Bi-Zn传热储热合金高温容器相容性的影响[J]. 储能科学与技术, 2022, 11(1): 9-18.
[11]	张诗钽, 楚帅, 葛维春, 李音璇, 刘闯. 大规模弃风与储热协调调控评估方法[J]. 储能科学与技术, 2022, 11(1): 283-290.
[12]	徐钿昕, 田希坤, 闫君, 叶强, 赵长颖. TiO₂改性的CaCO₃热化学储热的反应性能[J]. 储能科学与技术, 2022, 11(1): 1-8.
[13]	张显荣, 徐玉杰, 杨立军, 李乐璇, 陈海生, 周学志. 多类型火电-储热耦合系统性能分析与比较[J]. 储能科学与技术, 2021, 10(5): 1565-1578.
[14]	韩翔宇, 王亮, 葛志伟, 凌浩恕, 林曦鹏, 陈海生, 彭珑. Co₃O₄/CoO氧化还原反应储/释热动力学特性[J]. 储能科学与技术, 2021, 10(5): 1701-1708.
[15]	鲁博辉, 师志成, 张永学, 赵泓宇, 王梓熙. 石蜡/Fe₃O₄纳米颗粒复合相变材料在管壳式储热单元中的储/放热性能研究[J]. 储能科学与技术, 2021, 10(5): 1709-1719.

碳酸盐/高炉矿渣定型复合相变储热材料的制备与性能

Carbonates/blast furnace slag form-stable phase change materials

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 31

相关文章 15

编辑推荐

Metrics

本文评价