WO2003012002A2 - Moyens pour l'accumulation de chaleur - Google Patents

Moyens pour l'accumulation de chaleur Download PDF

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Publication number
WO2003012002A2
WO2003012002A2 PCT/EP2002/007217 EP0207217W WO03012002A2 WO 2003012002 A2 WO2003012002 A2 WO 2003012002A2 EP 0207217 W EP0207217 W EP 0207217W WO 03012002 A2 WO03012002 A2 WO 03012002A2
Authority
WO
WIPO (PCT)
Prior art keywords
agent
storing heat
heat
mixture
hydrates
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/EP2002/007217
Other languages
German (de)
English (en)
Other versions
WO2003012002A3 (fr
Inventor
Ralf Glausch
Mark Neuschütz
Wolfgang Voigt
Carsten Rudolph
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.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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 Merck Patent GmbH filed Critical Merck Patent GmbH
Priority to EP02791439A priority Critical patent/EP1563033A2/fr
Publication of WO2003012002A2 publication Critical patent/WO2003012002A2/fr
Anticipated expiration legal-status Critical
Publication of WO2003012002A3 publication Critical patent/WO2003012002A3/fr
Ceased legal-status Critical Current

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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D20/02—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E70/00—Other energy conversion or management systems reducing GHG emissions
    • Y02E70/30—Systems combining energy storage with energy generation of non-fossil origin

Definitions

  • the present invention relates to phase change materials (PCM) for storing thermal energy in the form of phase change heat based on sodium acetate trihydrate and their use.
  • PCM phase change materials
  • Heat exchangers are usually used for this. They contain heat transfer media that transport heat from one place or medium to another. To dissipate heat peaks e.g. the heat is released into the air via a heat exchanger. This heat is then no longer available to compensate for heat deficits. The use of heat stores solves this problem.
  • Known storage media are e.g. Water or stones / concrete to store sensible (“sensitive”) heat or phase change materials (PCM) such as salts, salt hydrates or their mixtures to store heat in the form of heat of fusion (“latent" heat).
  • sensitive sensible
  • PCM phase change materials
  • a higher temperature is required for charging a heat store than can be obtained when unloading, since a temperature difference is required for the transport / flow of heat.
  • the quality of the heat depends on the temperature at which it is available again: the higher the temperature, the more versatile the heat can be used. For this reason, it is desirable that the temperature level drop as little as possible during storage.
  • Latent heat storage In the case of sensitive heat storage (e.g. by heating water), the entry of heat is associated with a constant heating of the storage material (and vice versa when discharging), while latent heat is stored and discharged at the melting temperature of the PCM. Latent heat storage therefore has the advantage over sensitive heat storage that the Temperature loss is limited to the loss in the heat transport from and to the storage.
  • Inorganic salts and in particular their hydrates are known to be substances with the highest specific heat of fusion and thus favored as latent heat storage (PCM).
  • PCM latent heat storage
  • their technical use depends on a number of other properties, such as supercooling and stratification, which greatly limits the use of the few PCMs known to date.
  • numerous efforts have been made in the past to find effective crystallization initiators.
  • Na 4 P 2 0 7 • 10H 2 O or Na 2 HP0 4 are added to the PCM sodium acetate trihydrate as nucleating agents.
  • JP 04053913 a mixture of Na 2 C0 and NaH 2 P0 is added to the sodium acetate trihydrate as a nucleating agent. Contradicting statements are made about the reliability of the described and partially patented nucleating agents.
  • JP 61007376 describes a method for activating Na 2 HP0 or Na 4 P 2 0 7 as a nucleating agent. Studies cannot prove reliable nucleation of these substances. For industrial use it also appears disadvantageous that the mixture of the hydrate melts PCM and nucleating agent has to be cooled to less than 5 ° C. in order to activate the nucleating agent. For a possible use in hot water storage tanks, the maximum loading temperature of the PCM of 70 ° C should also prove to be critical, since higher temperatures are preferred here.
  • the task was to avoid the hypothermia of sodium acetate trihydrate.
  • a maximum loading temperature of the PCM of 80 ° C should be guaranteed.
  • cooling steps below room temperature should be avoided.
  • a first object of the present invention is an agent for storing heat, containing sodium acetate trihydrate and a mixture of at least two compounds of the formula (I)
  • a Li, Na, K, Rb, Cs x 1 or 2, y 1 or 2 and x + y 3 and / or their hydrates.
  • a second subject is the process for the preparation of an agent, characterized in that a) the compounds of the formula (I) are dissolved in water or in a mixture with a suitable organic solvent, b) the solution is evaporated and the crystals obtained are rehydrated, c) the crystals are mixed with sodium acetate trihydrate, optionally in gelled or thickened form, and melted and, after cooling below the melting point, crystallized by initiating nucleation.
  • Another object of the invention is the use of the above-mentioned agent, optionally with auxiliary substances, as a storage medium in latent heat stores, in hot water stores, in devices for cooling electronic components and for thermostatting buildings.
  • Thermostat in the sense of the present invention means both the thermal insulation and thus keeping a temperature constant, as well as the interception of short-term temperature fluctuations or peaks.
  • Applications can include heat storage and targeted release, as well as heat absorption and cooling.
  • the agents according to the invention show a significantly more reliable nucleation for supercooled sodium acetate trihydrate melts than the alkali metal phosphate, hydrates and alkali metal phosphate, hydrates described in the literature.
  • alkali hydrogen phosphates and / or their hydrates are used as nucleating agents. Mixtures of lithium, sodium, potassium, rubidium and cesium hydrogen phosphates and their hydrates are preferably used. Binary, ternary and quaternary mixtures are preferred used. The systems disodium hydrogenphosphate are particularly preferred.
  • composition of the mixtures is in the range from 10 to 90 mol%, preferably from 30 to 70 mol%, of the corresponding one
  • the salts are dissolved in water or in a mixture with organic solvents. Preference is given to water and mixtures thereof with acetone or
  • the solution is in at temperatures between room temperature and 70 ° C.
  • the PCM can optionally be gelled or thickened.
  • Auxiliaries known to those skilled in the art can be added to the PCM for gelation or thickening, such as e.g. Derivatives of cellulose or gelatin.
  • the PCM is melted with a proportion of 0.5 to 30% by mass of nucleating agent.
  • the melting temperature of sodium acetate trihydrate is 58-60 ° C, in mixtures with nucleating agents and additives it is in the range of 45-
  • the system can be loaded acoustically or mechanically for initiation. It is advantageous to add your own germs.
  • mixtures of PCM and nucleating agents according to the invention can be microencapsulated or macroencapsulated, if appropriate with the addition of further auxiliaries.
  • At least one auxiliary is a binder, preferably a polymer Binder.
  • the heat storage material is preferably present in a fine distribution in the binder.
  • the preferably polymeric binders that can be contained can be any polymers that are suitable as binders for the intended use.
  • the polymeric binder is preferably selected from crosslinkable polymers or polymer precursors, which in turn are preferably selected from the group consisting of polyurethanes, nitrile rubber, chloroprene, polyvinyl chloride, silicones, ethylene-vinyl acetate copolymers and polyacrylates. How the heat storage materials are appropriately incorporated into these polymeric binders is well known to those skilled in the art. He has no difficulty in finding the necessary additives, such as emulsifiers, for example, which stabilize such a mixture.
  • composition of the mixtures takes place in a range between 10 and 90 mol% of the corresponding hydrogen phosphate.
  • an aqueous solution consisting of the two salts in the above ratio is prepared.
  • the solution is evaporated to dryness at a maximum of 50 ° C. and the crystals are rehydrated in air for 24 h.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Medicinal Preparation (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

L'invention concerne des moyens pour l'accumulation de chaleur, qui contiennent du trihydrate d'acétate de sodium en tant que matériau à changement de phase (PCM) et des mélanges de phosphates d'hydrogène alcalins de formule AxHyPO4, dans laquelle A représente Li, Na, K, Rb, Cs, x vaut 1 ou 2, y vaut 1 ou 2 et x+y=3, ou leurs hydrates en tant qu'agents de germination.
PCT/EP2002/007217 2001-07-27 2002-07-01 Moyens pour l'accumulation de chaleur Ceased WO2003012002A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02791439A EP1563033A2 (fr) 2001-07-27 2002-07-01 Moyens pour l'accumulation de chaleur

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10136487A DE10136487A1 (de) 2001-07-27 2001-07-27 Mittel zur Speicherung von Wärme
DE10136487.3 2001-07-27

Publications (2)

Publication Number Publication Date
WO2003012002A2 true WO2003012002A2 (fr) 2003-02-13
WO2003012002A3 WO2003012002A3 (fr) 2005-05-06

Family

ID=7693217

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/007217 Ceased WO2003012002A2 (fr) 2001-07-27 2002-07-01 Moyens pour l'accumulation de chaleur

Country Status (4)

Country Link
EP (1) EP1563033A2 (fr)
DE (1) DE10136487A1 (fr)
TW (1) TW548328B (fr)
WO (1) WO2003012002A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005041861B3 (de) * 2005-09-02 2007-04-19 Siemens Ag Anordnung zum Temperieren einer Elektronikeinheit

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL191418C (nl) * 1981-03-09 1995-07-17 Mitsubishi Electric Corp Materiaal voor het opslaan van warmte; werkwijze voor het bereiden van dit materiaal.
JPS5922986A (ja) * 1982-07-30 1984-02-06 Pentel Kk 蓄熱材
JPS59138290A (ja) * 1983-01-28 1984-08-08 Nok Corp 蓄熱材
JPS617376A (ja) * 1984-06-20 1986-01-14 Matsushita Electric Ind Co Ltd 結晶核形成材の活性化方法
JPS6153386A (ja) * 1984-08-21 1986-03-17 Hitachi Chem Co Ltd 蓄熱材

Also Published As

Publication number Publication date
TW548328B (en) 2003-08-21
EP1563033A2 (fr) 2005-08-17
DE10136487A1 (de) 2003-02-13
WO2003012002A3 (fr) 2005-05-06

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