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WO1991000324A1 - Compositions a base d'hexahydrate de chlorure de calcium utilisees pour l'accumulation de chaleur a basse temperature - Google Patents

Compositions a base d'hexahydrate de chlorure de calcium utilisees pour l'accumulation de chaleur a basse temperature Download PDF

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Publication number
WO1991000324A1
WO1991000324A1 PCT/AU1990/000264 AU9000264W WO9100324A1 WO 1991000324 A1 WO1991000324 A1 WO 1991000324A1 AU 9000264 W AU9000264 W AU 9000264W WO 9100324 A1 WO9100324 A1 WO 9100324A1
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WO
WIPO (PCT)
Prior art keywords
per cent
chloride hexahydrate
phase change
calcium chloride
weight
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.)
Ceased
Application number
PCT/AU1990/000264
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English (en)
Inventor
Stephen Kaneff
Aharon Brandstetter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Australian National University
Original Assignee
Australian National University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Australian National University filed Critical Australian National University
Priority claimed from AU59275/90A external-priority patent/AU640154B2/en
Priority to KR1019910701939A priority Critical patent/KR920702712A/ko
Publication of WO1991000324A1 publication Critical patent/WO1991000324A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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

  • This invention concerns heat storage systems. More particularly, it concerns phase change materials based upon calcium chloride hexahydrate for use in thermal storage systems (such as low energy greenhouses) .
  • phase change material first used in low energy heat storage systems was Glauber's salt, sodium sulphate decahydrate (Na 2 S0 4 .lOH-0) , which has a phase change temperature of about 32 C.
  • sodium sulphate decahydrate changes its composition when cycled through a number of phase changes, and it exhibits a strong "undercooling” (called “supercooling” by some workers in this field) before it solidifies spontaneously. Undercooling by as much as 11 C is reported by Stein in his specification.
  • phase change materials based on calcium chloride hexahydrate, CaCl ? .6H_0 are now preferred.
  • his own- invention aimed at avoiding the known problems of sodium sulphate decahydrate, involves the use of another phase change material - paraffin wax - in small structures with metal wool dividers.
  • phase change material sodium sulphate decahydrate, bisodium phosphate dodecahydrate and bisodium phosphate heptahydrate.
  • phase change materials in small parcels - or microencapsulation of such materials - was a solution adopted by other workers and referred to by B Carlsson, H Stymne and G Wettermark in their paper entitled "An incongruent heat-of-fusion system - Ca.Cl ⁇ . 6E ⁇ 0 - made congruent through modification of the chemical composition of the system", which was published in Solar Energy, volume 23, 1979, pages 343 to 350.
  • phase change materials in buildings have been suggested on a number of occasions. Some workers have recognised the problems inherent in the use of phase change materials and have suggested techniques or special arrangements to overcome the problems. Others have tended to ignore the problems. Examples of proposals involving the use of phase change materials in buildings include (i) the specification of Australian patent application No 47850/85 in the name of R K Prudhoe (a proposal for controlling the temperature fluctuations in buildings which contain electronic equipment and the like); (ii) the specification of Australian patent application No 49046/85 in the name of Kubota Ltd, which describes a greenhouse in which a phase change material is stored in a tank structure; and (iii) the paper by A Brandstetter, entitled “Phase change storage for greenhouses", published in Advances in Solar Energy Technology (Pergamon Press, 1988), pages 3353 to 3357, which describes a low energy greenhouse in which the heat storage medium is calcium chloride hexahydrate "appropriately formulated against supercooling and degradation".
  • phase change materials have been proposed for use in a variety of situations.
  • concept of the use of phase change materials as low temperature heat storage media, in greenhouses and other buildings, in heat pumps, in solar energy storage tanks and in industrial waste heat utilisation facilities is now well accepted. (This list is not exhaustive.)
  • the production of a satisfactory phase change material, which can be cycled numerous times through the melting and freezing point has posed many problems to researchers in this field.
  • the specification of Australian patent application No 55769/86 describes a number of phase change materials which have been investigated by N Yano, T Ueno and S Tsuboi.
  • the preferred composition disclosed in that specification is a calcium chloride hexahydrate with additives including up to 5 per cent barium sulphide, from 0.001 to 5 per cent barium chloride dihydrate and from 0.001 to 0.1 per cent strontium chloride hexahydrate, with a bromide (potassium bromide, sodium bromide or ammonium bromide) added as a solidification point modifier and relatively large quantities of ultrafine silica powder and glycerine added as thickening agents.
  • a bromide potassium bromide, sodium bromide or ammonium bromide
  • the additives are (a) strontium chloride hexahydrate, as a nucleator, in quantities upward from 0.1 per cent (by weight) of the calcium chloride hexahydrate, (b) fumed silica in quantities ranging from 0.02 per cent to 1.0 per cent (by weight) of the calcium chloride hexahydrate, and (c) extra water above the stoichiometric quantity included in the calcium chloride hexahydrate in the range of from 1.0 per cent to 5.0 per cent (by weight) of the calcium chloride hexahydrate. In addition, from 0.001 per cent to 1.0 per cent (by weight) of sodium chloride may also be added.
  • the strontium chloride hexahydrate is present in quantities ranging from 0.1 per cent to 4.0 per cent (by weight) of the calcium chloride hexahydrate. More preferably the upper concentration of the strontium chloride hexahydrate is about 2.0 per cent, and most preferably the strontium chloride hexahydrate comprises about 0.3 per cent (by weight) of the calcium chloride hexahydrate.
  • compositions which are stable phase change materials is the outcome of a long-term investigation of the performance parameters of calcium chloride hexahydrate phase change materials in melt/freeze cycling experiments.
  • Strontium chloride hexahydrate is known to be isomorphous with calcium chloride hexahydrate and to be capable of forming nearly ideal solid solutions with CaCl 2 .6H 2 0; and is also known to be a nucleator of the solidification of calcium chloride hexahydrate.
  • the investigation showed that the minimum amount of strontium chloride hexahydrate that is required to sustain long-term nucleation stability is 0.1 per cent. Any lower concentration of strontium chloride hexahydrate is close to the limit of dissolution of SrCl-. ⁇ H-O in calcium chloride hexahydrate.
  • extra water that is, water in excess of the quantity required stoichiometrically for the hexahydrate formulation
  • the use of "extra water” has been proposed in relation to sodium sulphate decahydrate and some other salt hydrates by S Furbo in the article entitled “Heat Storage Units Using Salt Hydrates", which was published in Sunworld, volume 6, No 5, pages 134 to 139, 1982.
  • water in excess of the quantity required stoichiometrically was not proposed in this paper.
  • the investigation by the present inventors showed that the extra water is required to ensure the long-term stability of the phase change material.
  • the minimum quantity of extra water is 1.0 per cent (by weight), which corresponds to a degree of hydration of 6.123, and the maximum quantity of extra water is about 5.0 per cent, which corresponds to a degree of hydration of 6.61, which was determined on the basis of storage efficiency considerations.
  • Variations to the basic formulation of the present invention are possible.
  • sodium chloride is preferably included in concentrations of from 0.001 per cent to 1.0 per cent (by weight).
  • sodium chloride has been an implicit additive in most of the prior art formulations of phase change materials based on calcium chloride hexahydrate, • for technical grade CaCl 2 .6H 2 0 has sodium chloride as one of its impurities.
  • Up to approximately 0.4 per cent (by weight) of sodium chloride can form a solid solution with calcium chloride hexahydrate in the temperature range in which phase change materials are normally used.
  • the preferred addition of sodium chloride is in the range of from 0.2 per cent to 1.0 per cent (by weight) or the calcium chloride hexahydrate.
  • the preferred formulation of the present invention comprises calcium chloride hexahydrate to which has been added (a) about 0.3 wt per cent strontium chloride hexahydrate;
  • Such a formulation has a solid/liquid transition temperature of 29.6 JL 0.2 C. This transition temperature can be reduced down to about 22 C by the addition of up to 10 wt per cent each of ammonium chloride and potassium chloride.
  • phase change materials have a light colour.
  • the formulations of the present invention which have been discussed above have a light colour in the solid state and are colourless in the liquid state. Thus those formulations, like the other phase change materials, are not good absorbers of radiant energy. Indeed, most phase change materials used in the past have been stored in opaque containers and the heat transfer to, and from, the phase change materials has occurred by conduction.
  • phase change materials generally (including the formulations of the present invention) can be achieved by colouring the materials so that they have a dark colour, preferably black, and by holding the materials in transparent containers, such as containers made from glass or perspex.
  • phase change material formulation of the present invention is the addition of a chemically inert colouring agent.
  • a colouring agent preferably a black, or at least a dark, colouring agent
  • a convenient technique for tinting the phase change material is to mix black drawing ink into the formulation, using ultrasonic activation to ensure a substantially uniform distribution of colour within the material.
  • phase change materials 60 grams of a calcium chloride hexahydrate formulation containing additives against incongruent melting and supercooling, in accordance with the present invention as described above, was placed in an 80 ml glass jar. 0.12 gram (0.2 wt per cent) of ROTRING " (trade mark) black drawing ink was added to the sample of the formulation. The formulation and the glass jar were held in warm water for 5 minutes in a 3-litres tank of an ultrasonic cleaner (model FX 10 having an output of 100 watts at 40 kHz). The resultant ultrasonic activation distributed the ink uniformly throughout the phase change material.
  • an ultrasonic cleaner model FX 10 having an output of 100 watts at 40 kHz
  • phase change material containing the black drawing ink was then subjected to freezing (at about 10°C), then melting (at about 45°C).
  • the formulation was then held in its molten state for several days. At the end of this period, no segregation of the ink from the other components was observed.
  • tinted and untinted phase change materials were placed in identical transparent containers and the containers were exposed to full solar radiation.
  • the tinted (black) formulation consistently melted in less than one third the time taken for the untinted samples to melt. Measurements of the temperatures of the formulations during heating showed that the dark pphhaassee cchhaannggee mmaatteerriiaall wwaass uupp to 8 C hotter than the untinted control formulation.
  • the tinted formulation In over 20 melt/freeze cycles, the tinted formulation has shown no indication of deterioration in its performance as a heat storage medium.
  • tinted phase change material is particularly suitable for use within greenhouses, where it will be able to be exposed to radiant energy when stored in a transparent container.
  • phase change material In another experiment, some 300 kg of calcium chloride phase change material, held in 6 litre plastic containers, was used as the basis of an off peak heating system for a laboratory. In this experiment, the phase change material was heated with off-peak electricity and, with the aid of a water circulation heat transport system, delivered its stored heat when required. At the time of writing this specification, the material is still in satisfactory working order in the fourth winter season of the use of the heating system.
  • Phase change materials having untinted formulations in accordance with the present invention have also been tested in a low energy greenhouse mounted on a roof of a building of The Australian National University, in Canberra, Australia.
  • one of the formulations of the present invention was the calcium chloride hexahydrate "appropriately formulated against supercooling and degradation" used to obtain the experimental data reported in the aforementioned paper by A Brandstetter, entitled “Phase change storage for greenhouses”.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'utilisation de matériaux à changement de phase à base d'hexahydrate de chlorure de calcium dans des systèmes d'accumulation de chaleur à basse température est connue. Les additifs ajoutés à l'hexahydrate de chlorure de calcium nuisent à sa performance. Pour éviter les problèmes rencontrés lors de l'utilisation des matériaux à changement de phase de la technique actuelle, la présente invention propose d'ajouter de l'hexahydrate de chlorure de strontium (en quantités supérieures ou égales à 0,1 %), de la silice fumée dans des proportions comprises entre 0,02 et 1,0 %, ainsi qu'une quantité supplémentaire d'eau supérieure à la quantité st÷chiométrique contenue dans l'hexahydrate de chlorure de calcium selon des proportions comprises entre 1,0 et 5,0 %. Les autres additifs qui peuvent être inclus sont le chlorure de sodium (selon des proportions comprises entre 0,001 et 1,0 %), le chlorure d'ammonium (dans des proportions allant jusqu'à 10 %), ainsi que le chlorure de potassium (dans des proportions allant jusqu'à 10 %). Tous ces pourcentages sont exprimés en poids par rapport à l'hexahydrate de chlorure de calcium. Pour obtenir une meilleure efficacité de fonctionnement, un matériau colorant chimiquement inerte, tel que de l'encre de chine noire, peut également être ajouté aux matériaux à changement de phase renfermés dans des récipients transparents.
PCT/AU1990/000264 1989-06-23 1990-06-22 Compositions a base d'hexahydrate de chlorure de calcium utilisees pour l'accumulation de chaleur a basse temperature Ceased WO1991000324A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019910701939A KR920702712A (ko) 1989-06-23 1990-06-24 저온 열저장에 이용되는 칼슘 클로라이드 헥사히드레이트 제제

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPJ4878 1989-06-23
AUPJ487889 1989-06-23
AU59275/90A AU640154B2 (en) 1989-06-23 1990-06-22 Calcium chloride hexahydrate formulations for low temperature heat storage applications

Publications (1)

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WO1991000324A1 true WO1991000324A1 (fr) 1991-01-10

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EP (1) EP0478637A4 (fr)
WO (1) WO1991000324A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5882361A (en) * 1997-02-05 1999-03-16 Ct Umwelttechnik Ag Method for producing calcium chloride scales
US7641812B2 (en) 2007-06-13 2010-01-05 Alderman Robert J Thermal insulation with thin phase change layer
US7704584B2 (en) * 2007-06-13 2010-04-27 Alderman Robert J Thermal insulation with thin phase change layer
CN102268245A (zh) * 2011-08-15 2011-12-07 天津科技大学 一种室温无机相变材料的制备方法
CN102268244A (zh) * 2011-08-01 2011-12-07 天津科技大学 一种低温无机共晶盐相变材料的制备方法
CN102827575A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为32℃的无机相变材料(pcm-32)
CN102827576A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为33℃的无机相变材料(pcm-33)
CN102827574A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为31℃的无机相变材料(pcm-31)
CN102827582A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为39℃的无机相变材料(pcm-39)
CN102827578A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为35℃的无机相变材料(pcm-35)
CN103484074A (zh) * 2012-06-15 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为15℃的无机相变材料
CN103484070A (zh) * 2012-06-15 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为19℃的无机相变材料
CN103484065A (zh) * 2012-06-14 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为5℃的无机相变材料
CN105062429A (zh) * 2015-07-31 2015-11-18 江苏启能新能源材料有限公司 一种粉体相变储能材料及其制备方法
US12195665B2 (en) 2019-06-03 2025-01-14 Yazaki Corporation Heat storage material composition, and heat storage system for heating and cooling building

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011357A1 (fr) * 1978-09-29 1980-05-28 National Research Development Corporation Utilisation d'un mélange d'hydrates pour emmagasiner la chaleur à une température constante et accumulateur de chaleur contenant ce mélange
US4392971A (en) * 1981-05-08 1983-07-12 Mitsubishi Denki Kabushiki Kaisha Heat storage material
US4397752A (en) * 1980-08-21 1983-08-09 Mitsubishi Denki Kabushiki Kaisha Heat storage material
US4613444A (en) * 1981-04-15 1986-09-23 The Dow Chemical Company Reversible phase change compositions of calcium chloride hexahydrate with potassium chloride
US4715978A (en) * 1986-04-08 1987-12-29 Kubota Tekko Kabushiki Kaisha Heat storage composition, latent heat storage capsules containing said heat-storage composition and temperature control apparatus using said capsules

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011357A1 (fr) * 1978-09-29 1980-05-28 National Research Development Corporation Utilisation d'un mélange d'hydrates pour emmagasiner la chaleur à une température constante et accumulateur de chaleur contenant ce mélange
US4397752A (en) * 1980-08-21 1983-08-09 Mitsubishi Denki Kabushiki Kaisha Heat storage material
US4613444A (en) * 1981-04-15 1986-09-23 The Dow Chemical Company Reversible phase change compositions of calcium chloride hexahydrate with potassium chloride
US4392971A (en) * 1981-05-08 1983-07-12 Mitsubishi Denki Kabushiki Kaisha Heat storage material
US4715978A (en) * 1986-04-08 1987-12-29 Kubota Tekko Kabushiki Kaisha Heat storage composition, latent heat storage capsules containing said heat-storage composition and temperature control apparatus using said capsules

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Volume 100, No. 16, issued 1984, April 16 (Columbus, Ohio, USA) S. SARIG & F. KAHANA "Heat-storage material". See page 176, column 1, the Abstract No. 124178s, Israeli Patent IL 59,103 (30 September 1983). *
CHEMICAL ABSTRACTS, Volume 102, No. 10, issued 1985, March 11 (Columbus, Ohio, USA) H. FEILCHENFELD & S. SARIG, "Calcium chloride hexahydrate: a phase-changing material for energy storage" see page 166, column 2, the Abstract No. 81685b and Industrial & Engineering Chemistry Product Research and Development, Volume 24, No. 1, March 1985, pages 130-133. See page 131, second and fourth paragraphs, and page 133, sixth paragraph. *
See also references of EP0478637A4 *
Solar Energy, Volume 32, No. 6, 1984, pages 779-784, (Pergamon Press) H. FEILCHENFELD et al, "A Calorimetric Investigation of the Stability of stagnant calcium chloride hexahydrate melt". See page 779, second paragraph and page 781, Table 2 (molar ratio of 6.2). *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5882361A (en) * 1997-02-05 1999-03-16 Ct Umwelttechnik Ag Method for producing calcium chloride scales
US7641812B2 (en) 2007-06-13 2010-01-05 Alderman Robert J Thermal insulation with thin phase change layer
US7704584B2 (en) * 2007-06-13 2010-04-27 Alderman Robert J Thermal insulation with thin phase change layer
CN102827578A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为35℃的无机相变材料(pcm-35)
CN102827575A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为32℃的无机相变材料(pcm-32)
CN102827576A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为33℃的无机相变材料(pcm-33)
CN102827574A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为31℃的无机相变材料(pcm-31)
CN102827582A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为39℃的无机相变材料(pcm-39)
CN102268244A (zh) * 2011-08-01 2011-12-07 天津科技大学 一种低温无机共晶盐相变材料的制备方法
CN102268245A (zh) * 2011-08-15 2011-12-07 天津科技大学 一种室温无机相变材料的制备方法
CN103484065A (zh) * 2012-06-14 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为5℃的无机相变材料
CN103484074A (zh) * 2012-06-15 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为15℃的无机相变材料
CN103484070A (zh) * 2012-06-15 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为19℃的无机相变材料
CN105062429A (zh) * 2015-07-31 2015-11-18 江苏启能新能源材料有限公司 一种粉体相变储能材料及其制备方法
US12195665B2 (en) 2019-06-03 2025-01-14 Yazaki Corporation Heat storage material composition, and heat storage system for heating and cooling building

Also Published As

Publication number Publication date
EP0478637A4 (en) 1992-08-12
EP0478637A1 (fr) 1992-04-08

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