EP0000099B1 - Thermal energy storage material - Google Patents
Thermal energy storage material Download PDFInfo
- Publication number
- EP0000099B1 EP0000099B1 EP78300030A EP78300030A EP0000099B1 EP 0000099 B1 EP0000099 B1 EP 0000099B1 EP 78300030 A EP78300030 A EP 78300030A EP 78300030 A EP78300030 A EP 78300030A EP 0000099 B1 EP0000099 B1 EP 0000099B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- thermal energy
- energy storage
- storage material
- material according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
Definitions
- the present invention is concerned with thermal energy storage materials and heat-exchange devices containing such materials.
- Thermal energy storage materials may store thermal energy as specific heat and/or as latent heat. It is often desirable to use materials which store thermal energy as latent heat, since this enables the volume occupied by the storage material to be minimised. This is advantageous, for example, in materials operating in the temperature range 10°C to 100°C for the storage of solar energy or of heat extracted during refrigeration.
- a number of hydrated inorganic salts are known which undergo transition to the anhydrous or a less hydrated form at a characteristic temperature on heating and revert to the more hydrated form on cooling.
- a potential drawback in the use of many of these hydrated salts is incongruency of the phase transition, that is, the transformation of the low-temperature solid phase to a two-phase condition where a solid and liquid coexist.
- the difference in densities of the two phases causes segregation thereof, which limits their ability to recombine and form the low-temperature single solid phase. Consequently the amount of heat recoverable on cooling is reduced.
- Thermal energy storage materials have been proposed in which the hydrated inorganic salt is thickened by an organic thickening agent, for example, cellulosic polymers, starch, aliginates or an inorganic thickening agent, such as a clay (as disclosed in U.S. Patent 3 986 969).
- organic thickening agents are natural polymers (or derivatives thereof) and are therefore unstable to hydrolysis and bacterial and enzyme action, which considerably shortens the life of the material.
- the above-mentioned inorganic thickening agents are more stable, but it appears that thermal energy storage materials containing such thickening agents can only be used in very shallow depths (for example, about one inch) and must therefore be disposed horizontally.
- thermo energy storage material in which a hydrated inorganic salt having a transition temperature to the anhydrous or a less hydrated form in the range 10° to 100°C is dispersed and suspended in a hydrogel formed from a water-soluble synthetic polymer having pendant carboxylic or sulphonic acid groups cross-linked with cations of a polyvalent metal.
- this material is that the hydrated inorganic salt is immobilised in close proximity in small volumes throughout the gel. This minimises any segregation which could arise, after fusion of the hydrate phase, by any solid sinking to the bottom of the mixture.
- the material according to the invention in flat horizontal trays; the material can be arranged in vertical columns of substantial height (for example 50 cm. to one metre).
- a further advantage of the material according to the invention is that the cross-linked hydrogel can be prepared in situ by reaction between the respective water-soluble polymer or an alkali metal or ammonium salt thereof and a water-soluble salt of the polyvalent metal.
- Suitable polyvalent metals include, for example, chromium, iron, tin, magnesium and aluminium. Aluminium and magnesium are preferred in view of the ready availability of water-soluble salts thereof. Suitable water-soluble salts of the above metals include, for example, chlorides, nitrates or sulphates, of which aluminium sulphate and magnesium sulphate are preferred.
- the polyvalent metal is preferably present in an amount sufficient to react with all the acid groups in the polymer to form ionic cross-links. The actual amount necessary to achieve complete reaction depends on factors such as the valency of the metal, the proportion of acid groups in the polymer and the amount of polymer in the material. Typical amounts of polyvalent metal are 0.5 to 5% (expressed as the weight of water-soluble salt, based on the weight of the storage material).
- the water-soluble polymer preferably has a backbone containing units of acrylic acid or methacrylic acid, for example, a homopolymer or copolymer or acrylic acid or methacrylic acid, partially hydrolysed polyacrylamide or polymethacrylamide, or an alkali metal or ammonium salt thereof.
- the polymer preferably contains 5 to 50% (for example 10 to 40%) carboxylic groups, the percentages being based on the number of repeating units in the polymer backbone.
- the molecular weight of the polymer may vary over a wide range. For some applications it may be advantageous to use polymers of relatively low molecular weight (for example, 100,000 to 500,000), while for other applications, higher molecular weights (for example 1 million to 8 million) may be preferred.
- the water-soluble polymer is preferably present in the thermal energy storage material in a relatively minor amount, such as from 0.5 to 10% (for example, about 5%), based on the weight of the material.
- Suitable hydrated inorganic salts for use in the material according to the present invention include, for example, calcium chloride hexahydrate (the fusion point of which is 29°C); sodium sulphate decahydrate (the fusion point of which is 32°C); disodium hydrogen phosphate dodecahydrate (the fusion point of which is 35.5°C); sodium thiosulphate pentahydrate (the fusion point of which is 50°C); sodium acetate trihydrate (the fusion point of which is 58°C); barium hydroxide octahydrate (the fusion point of which is 75°C) and zinc nitrate hexahydrate (the fusion point of which is 35°C).
- the hydrated salt preferably has a fusion point in the range 20° to 90°C and is preferably non-toxic, noncorrosive and readily available at low cost.
- Preferred hydrated salts meeting some or all of the above requirements are sodium sulphate decahydrate, disodium hydrogen phosphate dodecahydrate, sodium thiosulphate pentahydrate and sodium carbonate decahydrate.
- the material may be nucleated, for example, by a heat transfer method as disclosed in U.S. Patent 2 677 243, by careful control of the proportions of the ingredients of the composition, or by addition of an insoluble nucleating agent.
- a preferred nucleating agent for sodium sulphate decahydrate is borax, as proposed in U.S. Patent 2 677 664.
- this agent like the inorganic salt, is dispersed and suspended in the hydrogel and effectively immobilized therein. This wide dispersion of immobilized nucleating agent ensures efficient nucleation of the hydrate phase during cooling cycles, thereby inhibiting supercooling.
- the thermal energy storage material according to the invention preferably contains the hydrated salt in an amount of from 66% to 95% by weight and, optionally, a nucleating agent in an amount of from 1 to 10%, based on the weight of the hydrated salt.
- Substantially all the balance of the thermal energy storage material according to the invention is preferably water and, optionally, an organic liquid which is miscible with water.
- a particularly preferred such organic liquid is a lower aliphatic alcohol, such as ethanol (for example, when the hydrated salt is sodium sulphate decahydrate).
- the water is preferably present in an amount sufficient to hydrate all the anhydrous inorganic salt, and is preferably present in a small excess.
- the material may contain water in an amount of, for example, from 25 to 75% by weight.
- a water-miscible organic liquid is included, it is preferably present in a relatively minor amount, compared with water, for example, from 5 to 25%, based on the weight of water.
- the material according to the invention is preferably used in a method of heat exchange in which the material is first heated to a temperature above the transition temperature of the hydrated salt, and the heat is extracted from the material by passing a fluid at a temperature below the above mentioned transition temperature in heat-exchange relationship therewith.
- the alternate heating and cooling of the material can be repeated for many cycles.
- the present invention also comprises a heat-exchange device, which comprises a tank containing the thermal energy storage material according to the invention and means for supplying a cooling fluid in heat-exchange relationship with the thermal energy storage material.
- a sample of the solid was sealed in a square section tube measuring 5 cm. x 5 cm. x 50 cm. long, made of inert plastics. The ends of the tube were sealed by cast epoxy resin plugs.
- the tube was disposed vertically and alternately heated to about 60°C (the heating time being about one hour) and cooled to about 20°C by heat-exchangeing with water circulating outside the tube (the cooling time being three to four hours). Reproducible thermal arrests were obtained for more than 500 cycles of heating and cooling.
- Example 1 was repeated, except that the aluminium sulphate was replaced by the same amount of MgS0 4 .7H 2 0.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Sorption Type Refrigeration Machines (AREA)
- Thermotherapy And Cooling Therapy Devices (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB24279/77A GB1584559A (en) | 1977-06-10 | 1977-06-10 | Thermal energy storage materials |
GB2427977 | 1977-06-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000099A1 EP0000099A1 (en) | 1978-12-20 |
EP0000099B1 true EP0000099B1 (en) | 1980-07-23 |
Family
ID=10209224
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78300030A Expired EP0000099B1 (en) | 1977-06-10 | 1978-06-09 | Thermal energy storage material |
Country Status (23)
Country | Link |
---|---|
US (1) | US4209413A (no) |
EP (1) | EP0000099B1 (no) |
JP (1) | JPS5416387A (no) |
AR (1) | AR217299A1 (no) |
AT (1) | AT379407B (no) |
AU (1) | AU513058B2 (no) |
BR (1) | BR7803722A (no) |
CA (1) | CA1103454A (no) |
DE (1) | DE2860041D1 (no) |
DK (1) | DK259778A (no) |
ES (1) | ES470660A1 (no) |
FI (1) | FI64808C (no) |
GB (1) | GB1584559A (no) |
GR (1) | GR64536B (no) |
IE (1) | IE47083B1 (no) |
IL (1) | IL54932A (no) |
IN (1) | IN148032B (no) |
IT (1) | IT1112264B (no) |
MX (1) | MX147710A (no) |
NO (1) | NO147797C (no) |
NZ (1) | NZ187511A (no) |
PT (1) | PT68155A (no) |
ZA (1) | ZA783256B (no) |
Families Citing this family (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4187189A (en) * | 1978-05-02 | 1980-02-05 | American Technological University | Phase change thermal storage materials with crust forming stabilizers |
IE49097B1 (en) * | 1978-11-10 | 1985-07-24 | Ic Gas Int Ltd | Thermal energy storage material |
US4332690A (en) * | 1979-04-23 | 1982-06-01 | Mitsubishi Denki Kabushiki Kaisha | Heat storage system comprising a phase change medium and a nucleating agent |
DE2952166A1 (de) * | 1979-12-22 | 1981-07-23 | Haase-Bau GmbH, 2350 Neumünster | Thermisches energiespeicher-system zum speichern von phasenumwandlungsenthalpie |
US4309980A (en) * | 1980-03-07 | 1982-01-12 | Thermal Energy Storage, Inc. | Closed vaporization heat transfer system |
US4349446A (en) * | 1981-03-05 | 1982-09-14 | University Of Delaware | Glauber's salt heat storage compositions, crystal habit modifiers |
JPS57207673A (en) * | 1981-06-15 | 1982-12-20 | Sekisui Chem Co Ltd | Heat-accumulating composition |
EP0087859B1 (en) * | 1982-02-23 | 1986-04-30 | Ciba Specialty Chemicals Water Treatments Limited | Thermal energy storage compositions |
US4508632A (en) * | 1982-06-15 | 1985-04-02 | Matsushita Electric Industrial Co., Ltd. | Heat storage materials |
US4585572A (en) * | 1983-10-11 | 1986-04-29 | The Dow Chemical Company | Reversible phase change composition for storing thermal energy |
FR2566789B1 (fr) * | 1984-06-29 | 1986-12-26 | Centre Nat Rech Scient | Procede de preparation de materiaux composites pour le stockage et le transport de l'energie |
US4687573A (en) * | 1984-08-13 | 1987-08-18 | Pall Corporation | Sorbing apparatus |
US4851291A (en) * | 1986-06-19 | 1989-07-25 | The United States Of America As Represented By The Secretary Of Agriculture | Temperature adaptable textile fibers and method of preparing same |
US4702853A (en) * | 1986-10-06 | 1987-10-27 | The United States Of America As Represented By The Department Of Energy | Phase change thermal energy storage material |
EP0273779A1 (en) * | 1987-01-02 | 1988-07-06 | Sumitomo Chemical Company, Limited | Process for producting heat storage materials |
US4830641A (en) * | 1987-04-13 | 1989-05-16 | Pall Corporation | Sorbing apparatus |
RU2042695C1 (ru) * | 1990-06-15 | 1995-08-27 | Институт катализа СО РАН | Теплоаккумулирующий материал и способ его получения |
US5585174A (en) * | 1990-06-15 | 1996-12-17 | Institut Kataliza Sibirskogo Otdelenia Rossiiskoi Akademii Nauk | Heat-accumulating material and use thereof |
WO1993004137A1 (fr) * | 1990-06-15 | 1993-03-04 | Institut Kataliza Sibirskogo Otdelenia Akademii Nauk Sssr | Materiau accumulant la chaleur et son utilisation |
USRE35586E (en) * | 1990-06-15 | 1997-08-19 | Prism Enterprises, Inc. | Reusable warmers of the type employing a super-cooled solution and an activator |
US5058563A (en) * | 1990-06-15 | 1991-10-22 | Prism Technologies, Inc. | Reusable warmers of the type employing a super-cooled solution and an activator |
JP3103927B2 (ja) * | 1991-01-31 | 2000-10-30 | 住化プラステック株式会社 | 蓄熱材組成物及びその製造方法 |
US5285798A (en) * | 1991-06-28 | 1994-02-15 | R. J. Reynolds Tobacco Company | Tobacco smoking article with electrochemical heat source |
CA2069687A1 (en) * | 1991-06-28 | 1992-12-29 | Chandra Kumar Banerjee | Tobacco smoking article with electrochemical heat source |
US5882542A (en) * | 1993-02-12 | 1999-03-16 | Sumitomo Chemical Company, Limited | Sodium sulfate base heat-storage composition and process for producing the same |
NL1002506C2 (nl) * | 1996-03-01 | 1997-09-03 | Jan Van Turnhout | Warmte- of koude-element. |
JPH1180722A (ja) * | 1997-09-05 | 1999-03-26 | Sumika Purasutetsuku Kk | リン酸ナトリウム系蓄熱材 |
IL130883A0 (en) * | 1999-07-11 | 2001-01-28 | Maoz Betzer Tsilevich | An endothermic heat shield composition and a method for the preparation thereof |
NL1025910C2 (nl) | 2004-04-08 | 2005-10-11 | Kobato Polytechnologie B V | Polymeersamenstelling met warmteaccumulerende fasevergangsmaterialen, een werkwijze voor het bereiden daarvan, producten en voorbrengselen die deze samenstelling bevatten en toepassing daarvan. |
WO2010066775A1 (en) | 2008-12-09 | 2010-06-17 | Carlsberg Breweries A/S | A self cooling container and a cooling device |
EP2196752A1 (en) | 2008-12-09 | 2010-06-16 | Carlsberg Breweries A/S | A self cooling container |
WO2011157735A2 (en) | 2010-06-15 | 2011-12-22 | Carlsberg Breweries A/S | A self cooling container and a cooling device |
EP2397796A1 (en) | 2010-06-15 | 2011-12-21 | Carlsberg Breweries A/S | A self cooling container and a cooling device |
JP2013079300A (ja) * | 2011-10-03 | 2013-05-02 | User Kk | 気泡を含有した含水ゲル組成物 |
EP2695560A1 (en) | 2012-08-10 | 2014-02-12 | Carlsberg Breweries A/S | A cooling device including coated reactants |
WO2014166867A1 (en) | 2013-04-08 | 2014-10-16 | Carlsberg Breweries A/S | A system for externally cooling a beverage holder and a method of externally cooling a beverage holder |
GB201314880D0 (en) * | 2013-08-20 | 2013-10-02 | C G I Internat Ltd | Fire resistant glazing unit |
DE102017117599A1 (de) * | 2017-08-03 | 2019-02-07 | i-select SA | Latentwärmespeichermedium |
CN113136167B (zh) * | 2020-01-20 | 2022-09-30 | 中国科学院青海盐湖研究所 | 具有流动性的水溶胶-水合盐-多孔材料复合体系及其制备方法和应用 |
CN113136168B (zh) * | 2020-01-20 | 2022-10-04 | 中国科学院青海盐湖研究所 | 基于三重锁定的水合盐-多孔载体复合材料及其制备方法和应用 |
CN113174806B (zh) * | 2020-05-22 | 2023-03-14 | 中国科学院青海盐湖研究所 | 一种道路融雪装置及其使用方法 |
CN113175774B (zh) * | 2020-06-05 | 2023-03-24 | 中国科学院青海盐湖研究所 | 一种冷藏箱、冷藏车及其冷藏方法 |
CN116656071A (zh) * | 2023-04-25 | 2023-08-29 | 东南大学 | 一种导热相变水凝胶及其制备方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2677664A (en) * | 1951-02-19 | 1954-05-04 | Telkes Maria | Composition of matter for the storage of heat |
US2827438A (en) * | 1954-01-04 | 1958-03-18 | Allied Chem & Dye Corp | Heat storage media |
US3720198A (en) * | 1969-06-04 | 1973-03-13 | Laing Nikolaus | Heat storage elements, a method for producing them and devices comprising heat storage elements |
DE2010110A1 (de) * | 1970-03-04 | 1971-09-16 | Farbenfabriken Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Mikrokapseln mit Hilfe von synthetischen Koazervaten |
US3986969A (en) * | 1975-02-06 | 1976-10-19 | The University Of Delaware | Thixotropic mixture and method of making same |
JPS5190989A (en) * | 1975-02-07 | 1976-08-10 | Honetsutaino seizohoho | |
DE2517920C2 (de) * | 1975-04-23 | 1985-10-24 | Philips Patentverwaltung Gmbh, 2000 Hamburg | Latentwärmespeichermittel und dessen Verwendung |
US4003426A (en) * | 1975-05-08 | 1977-01-18 | The Dow Chemical Company | Heat or thermal energy storage structure |
US4111189A (en) * | 1977-01-03 | 1978-09-05 | Cities Service Company | Combined solar radiation collector and thermal energy storage device |
FR2376893A1 (fr) * | 1977-01-10 | 1978-08-04 | Comp Generale Electricite | Materiau de stockage de chaleur |
-
1977
- 1977-06-10 GB GB24279/77A patent/GB1584559A/en not_active Expired
-
1978
- 1978-06-06 IN IN417/DEL/78A patent/IN148032B/en unknown
- 1978-06-06 IE IE1152/78A patent/IE47083B1/en unknown
- 1978-06-06 NO NO781971A patent/NO147797C/no unknown
- 1978-06-07 AU AU36895/78A patent/AU513058B2/en not_active Expired
- 1978-06-07 US US05/913,351 patent/US4209413A/en not_active Expired - Lifetime
- 1978-06-07 ZA ZA00783256A patent/ZA783256B/xx unknown
- 1978-06-08 AR AR272497A patent/AR217299A1/es active
- 1978-06-08 FI FI781830A patent/FI64808C/fi not_active IP Right Cessation
- 1978-06-08 PT PT68155A patent/PT68155A/pt unknown
- 1978-06-09 GR GR56482A patent/GR64536B/el unknown
- 1978-06-09 EP EP78300030A patent/EP0000099B1/en not_active Expired
- 1978-06-09 DK DK259778A patent/DK259778A/da not_active Application Discontinuation
- 1978-06-09 AT AT0423478A patent/AT379407B/de not_active IP Right Cessation
- 1978-06-09 ES ES470660A patent/ES470660A1/es not_active Expired
- 1978-06-09 NZ NZ187511A patent/NZ187511A/xx unknown
- 1978-06-09 MX MX173765A patent/MX147710A/es unknown
- 1978-06-09 DE DE7878300030T patent/DE2860041D1/de not_active Expired
- 1978-06-09 BR BR787803722A patent/BR7803722A/pt unknown
- 1978-06-09 IT IT24388/78A patent/IT1112264B/it active
- 1978-06-10 JP JP7028078A patent/JPS5416387A/ja active Granted
- 1978-06-12 CA CA305,211A patent/CA1103454A/en not_active Expired
- 1978-06-16 IL IL54932A patent/IL54932A/xx unknown
Also Published As
Publication number | Publication date |
---|---|
NZ187511A (en) | 1980-08-26 |
ZA783256B (en) | 1979-06-27 |
EP0000099A1 (en) | 1978-12-20 |
JPS5730873B2 (no) | 1982-07-01 |
AT379407B (de) | 1986-01-10 |
IT7824388A0 (it) | 1978-06-09 |
NO147797B (no) | 1983-03-07 |
PT68155A (en) | 1978-07-01 |
ES470660A1 (es) | 1979-02-16 |
AU513058B2 (en) | 1980-11-13 |
AR217299A1 (es) | 1980-03-14 |
AU3689578A (en) | 1979-12-13 |
MX147710A (es) | 1983-01-06 |
IE47083B1 (en) | 1983-12-14 |
DK259778A (da) | 1978-12-11 |
FI64808B (fi) | 1983-09-30 |
DE2860041D1 (en) | 1980-11-13 |
IE781152L (en) | 1978-12-10 |
CA1103454A (en) | 1981-06-23 |
IL54932A (en) | 1981-01-30 |
BR7803722A (pt) | 1979-01-16 |
IN148032B (no) | 1980-09-27 |
JPS5416387A (en) | 1979-02-06 |
ATA423478A (de) | 1985-05-15 |
IT1112264B (it) | 1986-01-13 |
FI64808C (fi) | 1984-01-10 |
NO781971L (no) | 1978-12-12 |
NO147797C (no) | 1983-06-15 |
US4209413A (en) | 1980-06-24 |
GB1584559A (en) | 1981-02-11 |
FI781830A (fi) | 1978-12-11 |
GR64536B (en) | 1980-04-10 |
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