Research progress of phase change cold storage slurry materials

doi:10.16085/j.issn.1000-6613.2018-0557

Abstract

Abstract: Phase change cold storage slurry material has good fluidity and large cold storage density. It can be used as cold storage material and secondary refrigerant to transport cooling capacity as well, so it has a broad application prospect.Phase change cold storage slurry material includes ice slurry, clathrate hydrate slurry, microcapsule emulsion, phase change emulsion and microemulsion. In addition, the clathrate hydrate comprises CO₂ hydrate, organic refrigerant hydrate and quaternary salt hydrate. This article reviews the basic physical properties, preparation methods, flow and heat transfer characteristics of the above phase change cold storage slurry materials, analyzes the advantages and disadvantages of several phase change storage materials and lists several typical applications of slurry materials in cold storage air conditioning systems. At the same time, the research trend of phase change cold storage slurry materials is pointed out. The good thermal properties of natural refrigerants such as urea water, ethanol water and ethylene glycol water provide the possibility for the preparation of phase change cold storage materials.

Key words: cold storage, slurry, phase change materials, preparation methods, flow and heat transfer characteristics

摘要： 相变蓄冷浆体材料具有良好的流动性和高蓄冷密度，既可用作蓄冷材料，也可作为载冷剂来输送冷量，应用前景广阔。相变蓄冷浆体材料包含冰浆、笼型水合物浆体、微胶囊乳液、相变乳状液和微乳液等，其中笼型水合物又包含CO₂水合物、有机制冷剂水合物和季盐类水合物。本文综述了上述相变蓄冷浆体材料的基础物性、制备方法和流动传热特性，并介绍了水合物浆体生成的强化以及浆体流动特性的改善研究，分析比较了几种相变蓄冷材料的优缺点，列举了浆体材料在蓄冷空调系统中的典型应用，并指出了蓄冷技术未来的发展趋势，如尿素–水，乙醇–水和乙二醇–水等自然工质良好的热学性能均为其制备相变蓄冷材料提供了可能。

关键词: 蓄冷, 浆体, 相变材料, 制备方法, 流动传热特性

CLC Number:

TK02

LI Zhaoning, ZHAO Yanjie, FAN Yaru. Research progress of phase change cold storage slurry materials[J]. Chemical Industry and Engineering Progress, 2018, 37(S1): 108-116.

李兆宁, 赵彦杰, 范亚茹. 相变蓄冷浆体材料研究进展[J]. 化工进展, 2018, 37(S1): 108-116.

References

[1] 樊栓狮, 谢应明, 郭开华, 等. 空调蓄冷及气体水合物蓄冷技术[J]. 化学工报, 2003, 54(1):131-134.
[2] 钱文强. 水合物浆体的流动相变换热与结晶过程可视化的研究[D]. 上海:上海交通大学, 2013.
[3] 马志伟. 水合物浆体流动相变和蓄冷特性研究[D]. 上海:上海交通大学, 2012.
[4] 朱昌盛, 刘妮, 齐亚茹. 笼型水合物浆体生成和流动特性的研究进展[J]. 制冷技术, 2015, 35(6):52-62.
[5] 郭开华, 舒碧芬. 空调蓄冷及气体水合物蓄冷[J]. 制冷, 1995, 53(3):15-21.
[6] 陈伟军, 刘妮, 肖晨, 等. CO₂水合物浆在蓄冷空调中的应用前景[J]. 制冷学报, 2012, 3:1-5.
[7] 王树立, 代文杰, 刘墨夫, 等. 鼠李糖脂促进CO₂水合物生成实验[J]. 常州大学学报(自然科学版), 2017(4):66-72.
[8] ANTHONY D, LAURENCE F, SANDRINE M, et al. Modeling of the available latent heat of a CO₂ hydrate slurry in an experimental loop applied to secondary refrigeration[J]. Chemical Engineering Process, 2006, 45(3):184-192.
[9] OSMANN Sari, JIN Hu, FREDERIC Brun, et al. In-situ study of the thermal properties of hydrate slurry by high pressure DSC[C]//International Congress of Refrigeration, Beijing, 2007.
[10] GOLOMBOK M, INEKE E, LUZARDO J C R, et al. Resolving CO₂ and methane hydrate formation kinetics[J]. Environmental Chemistry Letters, 2009, 7(4):325-330.
[11] 刘妮, 轩小波, 李菊, 等. 温度扰动促进CO₂水合物生成特性的实验研究[J]. 中国电机工程学报, 2010, 30(17):41-44.
[12] DELAHAYE A, FOURNAISON L, MARINHAS S, et al. Rheological study of CO₂ hydrate slurry in a dynamic loop applied to secondary refrigeration[J]. Chemical Engineering Science, 2008, 63(13):3551-3559.
[13] WEST O R, TSOURIS C, LEE S, et al. Negatively buoyant CO₂ hydrate composite forocean carbon sequestIation[J]. AIChE Journal, 2003, 49(1):283-285.
[14] MYRE Denis. Synthesis of carbon dioxide hydrates in a slury bubble column[D]. Ottawa:University of Ottawa, 2011.
[15] LIN W, DELAHAYE A, FOUMAISON L Phase equilibrium and dissociation enthalpy for semi-clathmte of CO₂+TBAB[J]. Fluid Phase Equilibria, 2008, 264:220-227.
[16] DELAHAYE A, FOURNAISON L, MARINHAS S. Effect of THF on equilibrium pressure and dissociation enthalpy of CO₂ hydrates applied to secondary refrigeration[J]. Ind. Eng. Chem. Res., 2006, 45(1):391-397.
[17] MARTINEZL M C, DALMAZZONE D, FURST W, et al. Thermodynamic properties of THF+CO₂ hydrates in relation with refrigeration applications[J]. AlChE J., 2008, 54(4):1088-1095.
[18] 李玉星, 朱超, 王武昌. 表面活性剂促进CO₂水合物生成的实验及动力学模型[J]. 石油化工, 2012, 41(6):699-703.
[19] 宋琦, 王树立, 武雪兰, 等. 水合物技术应用与展望[J]. 油气储运, 2009, 28(9):5-9.
[20] TOMLINSON J J, CLATHRATE S, CONJUGATING B. New materials for thermal storage[J]. ASHRAE Trans., 1985, 91(1):1931-1937.
[21] CARBAJO J J. A direct-contact-charged direct-contact-discharged cool storage system using gas hydrate[J]. ASHRAE Trans., 1985, 91(2):258-266.
[22] AKIYA T, TOMIO S, OSWA M, et al. Phase equilibria of some alternative refrigerants hydrates and their mixtures using for cool storage material[C]//IECEC Proc. of the 32th, Intersociety Energy Conversion Engineering Conference, 1997:1652-1655.
[23] HASHIMOTO S, MIYAUCHI H, INOUE Y, et al. Three-phase equilibrium relations and hydrate dissociation enthalpies for hydrofluorocarbon hydrate systems:HFC-134a, -125, and -143a hydrates[J]. J. Chen. Eng. Data. 2010, 55:4951-4955.
[24] MORI Y, MORI T. Formation of gas hydrate with CFC alternative R134a[J]. AlChE Journal, 1989, 35(7):1227-1228.
[25] 陈晶贵, 樊栓狮, 梁德青, 等. HCFC-141b水合物空调系统实验研究[J]. 化工学报, 2003, 54(1):125-130.
[26] KOBAYASHI M, NISHIUMI H. Vapor-liquid equilibria for the pure, binary and ternary systems containing HFC32, HFC125 and HFC134a[J]. Fluid Phase Equilib, 1998, 144(1/2):191-202.
[27] PARK J Y, LIM J S, LEE B G, et al. Phase equilibria of CFC alternative refrigerant mixture:HFC-227ea +HFC-32+HFC-134a+HFC-152a[J]. Int. J. Thermophys, 2001, 22(3):901-917.
[28] 刘勇, 郭开华, 梁德青, 等. 混合制冷剂水合物晶体生成和分解过程研究[J]. 哈尔滨工业大学学报, 2004, 36(2):242-245.
[29] 毕月虹, 郭廷伟, 朱庭英, 等. 添加剂对气体水合物蓄冷过程影响的实验研究[J]. 应用基础与工程科学学报, 2003, 11(1):39-45.
[30] 葛华才, 王世平, 吕树申, 等. 一元醇类添加物对R12水合物形成的影响[J]. 华南理工大学学报, 2001, 29(3):1-4.
[31] 李刚, 谢应明, 刘道平. SDS影响蓄冷用异丁烷水合物生成特性的实验研究[J]. 化工学报, 2008, 59(1):60-63.
[32] 陈美园, 沈辉, 舒碧芬. 表面剂对HCFC-141b的静态水合物反应的作用[J]. 制冷学报, 2009, 30(1):14-18.
[33] 李金平, 郭开华, 梁德青, 等. HCFC-141b气体水合物快速生成实验研究[J]. 工程热物理学报, 2005(6):233-236.
[34] 刘勇, 郭开华, 梁德青, 等. 在磁场作用下HCFC-141b制冷剂水合物的生成过程[J]. 中国科学, 2003, 33(1):89-95.
[35] 叶楠. 季盐类水合物相平衡条件及生长动力学研究[D]. 上海:上海交通大学, 2014.
[36] OYAMA H, SHIMADA W, EBINUMA T, et al. Phase diagram, latent heat, and specific heat of TBAB semiclathrate hydrate crystals[J]. Fluid Phase Equilibria, 2005, 234:131-135.
[37] DARBOURET M, COURNIL M, HERRI J M. Rheological study of TBAB hydrate slurries as secondary two-phase refrigerants[J]. International Journal of Refrigeration, 2005, 28:663-671.
[38] OGOSHI H, TAKAO S. Air-conditioning system using clathrate hydrate slurry[J]. JFE Technical Report, 2004, 3:1-5.
[39] NAKAYAMA H. Hydrates of organic compounds. Ⅵ. Heats of fusion and of solution of quaternary ammonium halide clathrate hydrates[J]. Bulletin of the Chemical Society of Japan, 1987, 55:389-393.
[40] DYADIN Y A, UDACHIN K A. Clathrate formation in water-peralkylonium salts systems[J]. Journal of Inclusion Phenomena, 1984, 2:61-72.
[41] RODIONOVA T V, MANAKOV A Y, STENIN Y G, et al. The heats of fusion of tetrabutylammonium fluoride ionic clathrate hydrates[J]. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2008, 61:107-111.
[42] LORSCH H G, KAUFFMAN K W, DENTON J C. Thermal energy storage for solar heating and off-peak air conditioning[J]. Energy Connersion, 1975, 15:1-8.
[43] FUKUSHIMA S,TAKAO S,OGOSHI H, et al. Development of high density cold latent heat with clathrate hydrate[J]. NKK Technical Report, 1999, 166:65-70.
[44] KUMANO H, HIRATA T, KUDOH T. Experimental study on the flow and heat transfer characteristic of a tetra-n-butylammonium bromide hydrate slurry[J]. International Journal of Refrigeration, 2011, 34(8):1953- 1962.
[45] 肖睿, 宋文吉, 黄冲, 等. TBAB包络化合物浆的管内流动再层流化现象[J]. 工程热物理学报, 2009, 30(6):971-973.
[46] 张鹏, 叶健, 钱文强. 水合物浆体在水平细管中的流动相变换热[J]. 化工学报, 2014, 65(1):101-105.
[47] 张曼, 方贵银, 吴双茂, 等. 四丁基溴化铵相变蓄冷材料热物性实验研究[J]. 制冷学报, 2008, 29(5):8-11.
[48] MA Z W, ZHANG P. Pressure drop and heat transfer characteristics of clathrate hydrate slurry in a plate heat exchanger[J]. International Journal of Refrigeration, 2011, 34:796-806.
[49] TAKAO S, OGOSHI H, MATSUMOTO S, et al., New air-conditioning systems using hydrate slurry[J]. NKK Technical Report, 2001, 174:6-11.
[50] 巫术胜, 肖睿, 黄冲, 等. 四丁基溴化铵水合物在空调蓄冷中的应用研究[J]. 制冷学报, 2006, 27(6):48-51.
[51] 李刚, 刘道平, 谢应明, 等. 蓄冷用二元气体水合物工质匹配的研究[J]. 低温与超导, 2008, 4:53-56.
[52] 师欢, 王毅, 冯辉霞, 等. 微胶囊相变材料研究进展[J]. 应用化工, 2013, 42(1):122-127.
[53] 尚红波. 微胶囊相变材料的制备[D]. 南京:南京工业大学, 2006.
[54] CHOI J K, LEE J G, KIM J H, et al. Preparation of microcapsules containing phase change materials as heat transfer media by in-situ polymerization[J]. Journal of Industrial and Engineering Chemistry, 2007, 7(6):358-362.
[55] YU F, CHEN Z H, ZENG X R. Preparation and characterization of thermal energy storage microencapsulated dodecanol by phase change[J]. Polymer Materials Science and Engineering, 2009, 25(6):135-138.
[56] CHEN L, XU L L, SHANG H B, et al. Microencapsulation of butyl stearate as a phase change material by interfacial polycondensation in a polyurea system[J]. Energy Conversion and Management, 2009, 50:723-729.
[57] 尚建丽, 王争军, 李乔明, 等. 界面聚合法制备微胶囊相变材料的试验研究[J]. 材料导报, 2010, 24(3):92-94.
[58] MA S, SONG G L, LI W, et al. UV irradiation-initiated MMA polymerization to prepare microcapsules containing phase change paraffin[J]. Solar Energy Materials & Solar Cells, 2010, 94:1643-1647.
[59] BORREGUERO A M, VALVERDE J L, RODFLGUEZ J F, et al. Synthesis and characterization of microcapsules containing Rubitherm RT27 obtained by spray drying[J]. Chemical Engineering Journal, 2011, 166:384-390.
[60] CHARUNYAKORN P, SENGUPTA S, ROY S K. Forced convection heat transfer in microencapsulated phase change material slurries:flow in circular ducts[J]. International Journal of Heat and Mass Transfer, 1991, 34(3):819-833.
[61] GOEL M, ROY S K, SENGUPTA S. Laminar forced convection heat transfer in microcapsulated phase change material suspensions[J]. International Journal of Heat and Mass Transfer, 1994, 37(4):593-604.
[62] INABA H, KIM M J, HORIBE A. Melting heat transfer characteristics of microencapsulated phase changematerial slurrieswith pluralmicrocapsules having different diameters[J]. ASME Journal of Heat Transfer, 2004, 126(4):558-565.
[63] ALVARADO J L, MARSH C, SOHN C, et al. Thermal performance of microencapsulated phase change material slurry in turbulent flow under constant heat flux[J]. International Journal of Heat and Mass Transfer, 2007, 50(9/10):1938-1952.
[64] INABA H, MORITA S. Flow and cold heat-storage characteristics of phase-change emulsion in a coiled double-tube heat exchanger[J]. Heat Transfer- Transactions of the ASME, 1995, 177:440-446.
[65] 徐慧, 杨睿, 张寅平, 等. 相变乳状液热物性及关键影响因素研究[J]. 科学通报, 2005, 50(1):92-96.
[66] 赵镇南, 时雨荃, 张毅, 等, 相变乳状液在蛇形管中的流动和传热特性[J]. 工程热物理学报, 2002, 23(6):730-734.
[67] ROYON L, GUIFFANT G. Heat transfer in paraffin oil/water emulsion involving supercooling phenomenon[J]. Energy Conversion and Management, 2001, 42(18):2155-2161.
[68] 张凯, 范敬辉, 马艳, 等. 一种室温相变乳状液的制备及表征[J]. 功能材料, 2007, 38:1588-1591.
[69] 邹得球, 肖睿, 冯自平. 石蜡乳状液潜热输送材料的研究进展[J]. 化工新型材料, 2012, 40:39-40.
[70] 胡小芳, 胡大为. 常温相变含水石蜡微乳液的制备[J]. 应用化工, 2007, 36(5):436-439.
[71] 黎宇坤, 马素德, 唐国翌. 对一种新型相变微乳液的物理性质及稳定性的研究[J]. 功能材料, 2010, 41(10):1813-1815.
[72] 孙志仁, 任德呈. 石蜡微乳液的研制[J]. 华东理工大学学报, 1999, 25(3):309-311.
[73] MORI T, MORI YH. Characterization of gas hydrate formation in direct-contact cool storage process[J]. Int. J. Refrig., 1989, 12(5):259-265.
[74] JERBI S, DELAHAYE A, FOURNAISON L. Design of a new circulation loop and heat transfer of CO₂ hydrate slurry[C]//Proceedings of 9th ⅡR Conference on PCMs and Slurries for Refrigeration and Air Conditioning. Sofia, Bulgaria, 2010.
[75] WATABABE S, OHKUBO H, INOUE M. Latent heat storage material using multi-component mixture[C]//Proceeding of the Asian Thermophysical Properties Conference. Fukuoka, Japan, 2007.