Review on development of magnesium sulfate heptahydrate for thermochemical storage and application

doi:10.16085/j.issn.1000-6613.2021-0828

Abstract

Abstract:

Magnesium sulfate heptahydrate is an inorganic salt hydrate chemical heat storage material with high heat storage density (2.8GJ/m³) and low working temperature (<150℃). The development of high-efficiency thermochemical heat storage materials and heat storage systems based on magnesium sulfate heptahydrate is expected to achieve good energy-saving and emission-reduction application effects in the fields of solar thermal utilization, industrial waste heat recovery, seasonal energy storage and building heating. This article introduces in detail the heat storage principle and basic physical properties of magnesium sulfate heptahydrate. Magnesium sulfate heptahydrate faces the shortcomings such as large mass transfer resistance, limited service life, insufficient heat transfer performance, etc. Therefore, the methods to prepare high-performance composite materials are introduced by modifying magnesium sulfate with zeolite, polymer foam and carbon materials, as well as the performance of the thermal storage unit. The paper points out the future development trend of magnesium sulfate heptahydrate for thermochemical storage and application.

Key words: thermochemical storage material, magnesium sulfate heptahydrate (MgSO₄·7H₂O), composite material, hydrate, zeolite

摘要：

七水硫酸镁是一种具有高储热密度（2.8GJ/m³）、低工作温度（<150℃）的无机盐水合物化学储热材料。开发基于七水硫酸镁的高效热化学储热材料和储热系统，有望在太阳能热利用、工业余热回收、季节性储能、建筑供热等领域取得良好的节能减排应用效果。本文对七水硫酸镁的储热原理、基本物性进行了详细介绍。针对七水硫酸镁在实际应用过程中存在传质阻力大、使用寿命受限、传热性能不足等缺点，文章综述了通过沸石、高分子泡沫、碳材料等改性制备硫酸镁高性能复合材料及储热器的相关研究，并对此材料的未来发展趋势作出评价。

关键词: 化学储热材料, 七水硫酸镁, 复合材料, 水合物, 沸石

CLC Number:

TK02

FU Hanxun, LAN Yuhao, LING Ziye, ZHANG Zhengguo. Review on development of magnesium sulfate heptahydrate for thermochemical storage and application[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 1956-1969.

付涵勋, 兰宇昊, 凌子夜, 张正国. 七水硫酸镁化学储热材料与应用研究进展[J]. 化工进展, 2022, 41(4): 1956-1969.

Figures/Tables 5

References 71

1	KANT K, SHUKLA A, SHARMA A. Advancement in phase change materials for thermal energy storage applications[J]. Solar Energy Materials and Solar Cells, 2017, 172: 82-92.
2	李昭, 李宝让, 陈豪志, 等. 相变储热技术研究进展[J]. 化工进展, 2020, 39(12): 5066-5085.
	LI Zhao, LI Baorang, CHEN Haozhi, et al. State of the art review on phase change thermal energy storage technology[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 5066-5085.
3	冷光辉, 蓝志鹏, 葛志伟, 等. 储热材料研究进展[J]. 储能科学与技术, 2015, 4(2): 119-130.
	LENG G H, LAN Z P, GE Z W, et al. Recent progress in thermal energy storage materials[J]. Energy Storage Science and Technology, 2015, 4(2): 119-130.
4	LI G. Sensible heat thermal storage energy and exergy performance evaluations[J]. Renewable and Sustainable Energy Reviews, 2016, 53: 897-923.
5	CHANDEL S S, AGARWAL T. Review of current state of research on energy storage, toxicity, health hazards and commercialization of phase changing materials[J]. Renewable and Sustainable Energy Reviews, 2017, 67: 581-596.
6	AYDIN D, CASEY S P, RIFFAT S. The latest advancements on thermochemical heat storage systems[J]. Renewable and Sustainable Energy Reviews, 2015, 41: 356-367.
7	李春鸿. 蓄热材料与化学反应[J]. 化学通报, 1983, 46(3): 31-35.
	LI C H. Thermal storage materials and chemical reactions[J]. Chemistry Bulletin, 1983, 46(3): 31-35.
8	ZHANG H, ZHANG L, LI Q, et al. Preparation and characterization of methyl palmitate/palygorskite composite phase change material for thermal energy storage in buildings[J]. Construction and Building Materials, 2019, 226: 212-219.
9	MARANI A, NEHDI M L. Integrating phase change materials in construction materials: critical review[J]. Construction and Building Materials, 2019, 217: 36-49.
10	周四丽, 张正国, 方晓明. 固-固相变储热材料的研究进展[J]. 化工进展, 2021, 40(3): 1371-1383.
	ZHOU SiLi, ZHANG Zhengguo, FANG Xiaoming. Research progress of solid-solid phase change materials for thermal energy storage[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1371-1383.
11	RAMAKRISHNAN S, WANG X, SANJAYAN J, et al. Thermal performance of buildings integrated with phase change materials to reduce heat stress risks during extreme heatwave events[J]. Applied Energy, 2017, 194: 410-421.
12	HARRIES D N, PASKEVICIUS M, SHEPPARD D A, et al. Concentrating solar thermal heat storage using metal hydrides[J]. Proceedings of the IEEE, 2012, 100(2): 539-549.
13	OUSALEH H A, SAIR S, ZAKI A, et al. Double hydrates salt as sustainable thermochemical energy storage materials: evaluation of dehydration behavior and structural phase transition reversibility[J]. Solar Energy, 2020, 201: 846-856.
14	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 H, CHENG X M, LI D, et al. Properties of stearic acid/modified carbon nanotube composite phase change materials[J]. Energy Storage Science and Technology, 2019, 8(4): 759-763.
15	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 the heat transfer and storage characteristics of phase change materials and cascaded systems[D]. Shanghai: Shanghai Jiao Tong University, 2018.
16	李威, 王秋旺, 曾敏. 水合盐基中低温热化学储热材料性能测试及数值研究[J]. 化工学报, 2021, 72(5): 2763-2772, 2330.
	LI W, WANG Q W, ZENG M, et al. Performance test and numerical study of salt hydrate-based thermochemical heat storage materials at middle-low temperature[J]. CIESC Journal, 2021, 72(5): 2763-2772, 2330.
17	徐凯迪, 谢涛, 王升, 等. 太阳能甲烷干重整复杂反应体系的热化学储能特性[J]. 化工进展, 2019, 38(11): 4921-4929.
	XU K D, XIE T, WANG S, et al. Thermochemical energy storage characteristics of complex reaction system for solar methane dry reforming system[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4921-4929.
18	KALLENBERGER P A, BRIELER F J, POSERN K, et al. Magnesium sulfate/polymer composites for seasonal, thermochemical energy storage[J]. Chemie Ingenieur Technik, 2016, 88(3): 384-397.
19	SAKAMOTO Y, YAMAMOTO H. Measurement of thermophysical property of energy storage system (CaCl₂&NH₃ System)[J]. Natural Resources, 2014, 5(12): 687-697.
20	闫霆, 王如竹, 李廷贤. 热化学复合吸附储热循环的理论及实验[J]. 化工学报, 2016, 67(S2): 311-317.
	YAN T, WANG R Z, LI Y X, et al. Theoretical analysis and experiment of thermochemical composite sorption heat storage cycle[J]. CIESC Journal, 2016, 67(S2): 311-317.
21	TRAUSEL F, JONG A J D, CUYPERS R. A review on the properties of salt hydrates for thermochemical storage[J]. Energy Procedia, 2014, 48: 447-452.
22	路丽婷. 七水硫酸镁/十水硫酸钠复合相变储热复合材料的性能分析[D]. 西安: 西北大学, 2018.
	LU L T. Performance analysis of composite phase change heat storage composite material of sodium heptahydrate/sodium sulfate[D]. Xi’an: Northwest University, 2018.
23	CLARK R J, MEHRABADI A, FARID M. State of the art on salt hydrate thermochemical energy storage systems for use in building applications[J]. Journal of Energy Storage, 2020, 27:101145.
24	PRIETO C, COOPER P, FERNÁNDEZ A I, et al. Review of technology: thermochemical energy storage for concentrated solar power plants[J]. Renewable and Sustainable Energy Reviews, 2016, 60: 72-84.
25	吴礼定, 曾波. 钾肥副产镁资源制备氢氧化镁的生产技术[J]. 盐业与化工, 2012, 41(6): 26-30.
	WU L D, ZENG B. Technology of Mg(OH)₂ preparation using magnesium resource from the byproduct of potassium fertilizer production[J]. Journal of Salt and Chemical Industry, 2012, 41(6): 26-30.
26	侯殿保, 杨海云, 陈育刚, 等. 硫酸盐型盐湖盐田泻利盐矿硫酸镁浸取结晶工艺条件研究[J]. 盐湖研究, 2020, 28(2): 71-78.
	HOU D B, YANG H Y, CHEN Y G, et al. Study on the leaching and crystallization conditions of magnesium sulfate leaching from EPS mine of sulfate salt lake.[J]. Journal of Salt Lake Research,2020, 28(2): 71-78.
27	郑绵平, 侯献华. 青海盐湖资源综合利用与可持续发展战略[J]. 科技导报, 2017, 35 (12): 11-13.
	ZHENG M P, HOU X H. Comprehensive utilization and sustainable development strategy of Qinghai salt lake resources[J]. Science&Technology Review, 2017, 35 (12): 11-13.
28	李龙. 青海盐湖镁资源利用概述[J]. 广东化工, 2011, 38(9): 85-86.
	LI L. Magnesium resources and utilization of Qinghai salt lake[J]. Guangdong Chemical Industry, 2011, 38(9): 85-86.
29	ESSEN V M VAN, ZONDAG H A, GORES J C, et al. Characterization of MgSO₄ hydrate for thermochemical seasonal heat storage[J]. Journal of Solar Energy Engineering, 2009, 131(4): 041014.
30	SCAPINO L, ZONDAG H A, BAEL J V, et al. Sorption heat storage for long-term low-temperature applications: a review on the advancements at material and prototype scale[J]. Applied Energy, 2017, 190: 920-948.
31	HONGOIS S, KUZNIK F, STEVENS P, et al. Development and characterisation of a new MgSO₄-zeolite composite for long-term thermal energy storage[J]. Solar Energy Materials and Solar Cells, 2011, 95(7): 1831-1837.
32	DONKERS P A J, BECKERT S, PEL L, et al. Water transport in MgSO₄·7H₂O during dehydration in view of thermal storage[J]. The Journal of Physical Chemistry C, 2015, 119(52): 28711-28720.
33	OKHRIMENKO L, FAVERGEON L, JOHANNES K, et al. Thermodynamic study of MgSO₄·H₂O system dehydration at low pressure in view of heat storage[J]. Thermochimica Acta, 2017, 656: 135-143.
34	MÜLLER D, KNOLL C, GRAVOGL G, et al. Medium-temperature thermochemical energy storage with transition metal ammoniates: a systematic material comparison[J]. Applied Energy, 2021, 285: 116470.
35	POSERN K, OSBURG A. Determination of the heat storage performance of thermochemical heat storage materials based on SrCl₂ and MgSO₄ [J]. Journal of Thermal Analysis and Calorimetry, 2018, 131(3): 2769-2773.
36	GULATI S, TABASSUM Z, SCHWINGENSCHLOGL U, et al. Molecular dynamics simulation of dehydration of salt hydrates (MgSO₄·7H₂O and ZnSO₄·7H₂O)[J]. Materials Today: Proceedings, 2020, 28: 1013-1017.
37	AL-ABBASI O, ABDELKEFI A, GHOMMEM M. Modeling and assessment of a thermochemical energy storage using salt hydrates[J]. International Journal of Energy Research, 2017, 41(14): 2149-2161.
38	VOORT I M V D. Characterization of a thermochemical storage material[D]. Eindhoven: Eindhoven University of Technology, 2007.
39	FERCHAUD C C. Experimental study of salt hydrates for thermochemical seasonal heat storage[D]. Eindhoven: Eindhoven University of Technology, 2016.
40	HAMEER S, NIEKERK J L V. A review of large-scale electrical energy storage[J]. International Journal of Energy Research, 2015, 39(9): 1179-1195.
41	KYRIAKOPOULOS G L, ARABATZIS G. Electrical energy storage systems in electricity generation: energy policies, innovative technologies, and regulatory regimes[J]. Renewable & Sustainable Energy Reviews, 2016, 56: 1044-1067.
42	KHARBANDA J S, YADAV S K, SONI V, et al. Modeling of heat transfer and fluid flow in epsom salt (MgSO₄·7H₂O) dissociation for thermochemical energy storage[J]. Journal of Energy Storage, 2020, 31: 101712.
43	BALASUBRAMANIAN G, GHOMMEM M, HAJJ M R, et al. Modeling of thermochemical energy storage by salt hydrates[J]. International Journal of Heat and Mass Transfer, 2010, 53(25): 5700-5706.
44	N'TSOUKPOE K E, HUI L, NOLWENN L P, et al. A review on long-term sorption solar energy storage[J]. Renewable & Sustainable Energy Reviews, 2009, 13(9): 2385-2396.
45	POSERN K, LINNOW K, NIERMANN M, et al. Thermochemical investigation of the water uptake behavior of MgSO₄ hydrates in host materials with different pore size[J]. Thermochimica Acta, 2015, 611: 562-571.
46	CASEY S, ELVINS J, RIFFAT S, et al. Salt impregnated desiccant matrices for ‘open’ thermochemical energy storage—Selection, synthesis and characterisation of candidate materials[J]. Energy and Buildings, 2014, 84: 412-425.
47	DONKERS P A J, PEL L, ADAN O C G. Experimental studies for the cyclability of salt hydrates for thermochemical heat storage[J]. Journal of Energy Storage, 2016, 5: 25-32.
48	CORTÉS F B, CHEJNE F, CARRASCO-MARÍN F, et al. Water sorption on silica and zeolite-supported hygroscopic salts for cooling system applications[J]. Energy Conversion and Management, 2012, 53(1): 219-223.
49	CHENG W P, GAO W, CUI X, et al. Phenol adsorption equilibrium and kinetics on zeolite X/activated carbon composite[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016, 62: 192-198.
50	HAUER A. Adsorption systems for TES-design and demonstration projects[M]. Springer Netherlands: Thermal Energy Storage for Sustainable Energy Consumption, 2007.
51	谢云云. 基于水合盐复合材料的热化学储热性能实验和数值研究[D]. 北京: 华北电力大学, 2018.
	XIE Y Y. Experiment and numerical study on the thermochemical heat storage based on hydrate composite materials[D]. Beijing: North China Electric Power University,2018.
52	WHITING G, GRONDIN D, BENNICI S, et al. Heats of water sorption studies on zeolite-MgSO₄ composites as potential thermochemical heat storage materials[J]. Solar Energy Materials and Solar Cells, 2013, 112: 112-119.
53	PALOMBA V, FRAZZICA A. Recent advancements in sorption technology for solar thermal energy storage applications[J]. Solar Energy, 2019, 192: 69-105.
54	WANG Q, XIE Y, DING B, et al. Structure and hydration state characterizations of MgSO₄-zeolite 13X composite materials for long-term thermochemical heat storage[J]. Solar Energy Materials and Solar Cells, 2019, 200: 110047.
55	LINNOW K, NIERMANN M, BONATZ D, et al. Experimental studies of the mechanism and kinetics of hydration reactions[J]. Energy Procedia, 2014, 48: 394-404.
56	RISTIĆ A, HENNINGER S K. Sorption composite materials for solar thermal energy storage[J]. Energy Procedia, 2014, 48: 977-981.
57	COURBON E, D’ANS P, PERMYAKOVA A, et al. Further improvement of the synthesis of silica gel and CaCl₂ composites: enhancement of energy storage density and stability over cycles for solar heat storagecoupled with space heating applications[J]. Solar Energy, 2017, 157: 532-541.
58	ZHU D, WU H, WANG S. Experimental study on composite silica gel supported CaCl₂ sorbent for low grade heat storage[J]. International Journal of Thermal Sciences, 2005, 45(8): 804-813.
59	MROWIEC-BIAŁOŃET J, JARZȨBSKI A B, LACHOWSKI A I, et al. Effective inorganic hybrid adsorbents of water vapor by the sol-gel method[J]. Chem. Mater., 1997, 9(11): 2486-2490.
60	JABBARI-HICHRI A, BENNICI S, AUROUX A. CaCl₂-containing composites as thermochemical heat storage materials[J]. Solar Energy Materials & Solar Cells, 2017, 172: 177-185.
61	LIU H, NAGANO K, TOGAWA J. A composite material made of mesoporous siliceous shale impregnated with lithium chloride for an open sorption thermal energy storage system[J]. Solar Energy, 2015, 111: 186-200.
62	BRANCATO V, CALABRESE L, PALOMBA V, et al. MgSO₄·7H₂O filled macro cellular foams: an innovative composite sorbent for thermo-chemical energy storage applications for solar buildings[J]. Solar Energy, 2018, 173: 1278-1286.
63	CALABRESE L, BRANCATO V, PALOMBA V, et al. Assessment of the hydration/dehydration behaviour of MgSO₄·7H₂O filled cellular foams for sorption storage applications through morphological and thermo-gravimetric analyses[J]. Sustainable Materials and Technologies, 2018, 17: 00073.
64	CALABRESE L, BRANCATO V, PALOMBA V, et al. Magnesium sulphate-silicone foam composites for thermochemical energy storage: assessment of dehydration behaviour and mechanical stability[J]. Solar Energy Materials and Solar Cells, 2019, 200: 109992.
65	LELE A F, N'TSOUKPOE K E, OSTERLAND T, et al. Thermal conductivity measurement of thermochemical storage materials[J]. Applied Thermal Engineering, 2015, 89: 916-926.
66	KLEINER F, POSERN K, OSBURG A. Thermal conductivity of selected salt hydrates for thermochemical solar heat storage applications measured by the light flash method[J]. Applied Thermal Engineering, 2017, 113: 1189-1193.
67	SHERE L, TRIVEDI S, ROBERTS S, et al. Synthesis and characterization of thermochemical storage material combining porous zeolite and inorganic salts[J]. Heat Transfer Engineering, 2019, 40(13/14): 1176-1181.
68	XU S J, TEH L, WANG R Z, et al. A zeolite 13X/magnesium sulfate-water sorption thermal energy storage device for domestic heating[J]. Energy Conversion and Management, 2018, 171:98-109.
69	XU C, YU Z, XIE Y, et al. Study of the hydration behavior of zeolite-MgSO₄ composites for long-term heat storage[J]. Applied Thermal Engineering, 2018, 129: 250-259.
70	XU S Z, WANG R Z, WANG L W, et al. Performance characterizations and thermodynamic analysis of magnesium sulfate-impregnated zeolite 13X and activated alumina composite sorbents for thermal energy storage[J]. Energy, 2019, 167: 889-901.
71	MAHON D, HENSHALL P, CLAUDIO G, et al. Feasibility study of MgSO₄+zeolite based composite thermochemical energy stores charged by vacuum flat plate solar thermal collectors for seasonal thermal energy storage[J]. Renewable Energy, 2020, 145: 1799-1807.

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