WO2012130285A1 - Thermal energy storage medium with carbonate salts and use of the thermal energy storage medium - Google Patents

Thermal energy storage medium with carbonate salts and use of the thermal energy storage medium Download PDF

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Publication number
WO2012130285A1
WO2012130285A1 PCT/EP2011/054812 EP2011054812W WO2012130285A1 WO 2012130285 A1 WO2012130285 A1 WO 2012130285A1 EP 2011054812 W EP2011054812 W EP 2011054812W WO 2012130285 A1 WO2012130285 A1 WO 2012130285A1
Authority
WO
WIPO (PCT)
Prior art keywords
storage medium
thermal energy
energy storage
carbonate
percentage
Prior art date
Application number
PCT/EP2011/054812
Other languages
French (fr)
Inventor
Shai BINYAMINI
Zvi Kotler
Eli Lipman
Original Assignee
Siemens Aktiengesellschaft
Siemens Concentrated Solar Power Ltd.
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 Siemens Aktiengesellschaft, Siemens Concentrated Solar Power Ltd. filed Critical Siemens Aktiengesellschaft
Priority to PCT/EP2011/054812 priority Critical patent/WO2012130285A1/en
Publication of WO2012130285A1 publication Critical patent/WO2012130285A1/en

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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
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S60/00—Arrangements for storing heat collected by solar heat collectors
    • F24S60/10—Arrangements for storing heat collected by solar heat collectors using latent heat
    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers

Definitions

  • THERMAL ENERGY STORAGE MEDIUM WITH CARBONATE SALTS AND USE OF THE THERMAL ENERGY STORAGE MEDIUM
  • This invention relates to a thermal energy storage medium and a use of the thermal storage medium.
  • a TES medium The purpose of a TES medium is to store and to transport an excess of solar energy provided by the heat transfer fluid of a solar field. The stored excess of thermal energy can be delivered back to the heat transfer fluid according to needs of the solar power plant.
  • a thermal energy storage medium comprising at least one phase change material with a mixture of at least three different carbonate salts.
  • the carbonate salts have metal ions of metals which are selected from the group consisting of alkaline metals and alkaline earth metals. Other metal ions are possible, too.
  • thermal storage medium in a solar power plant for converting solar energy into electrical energy is provided.
  • the mixture is a phase change material.
  • thermal energy can be stored.
  • reversed phase change of the phase change material the stored thermal energy can be delivered again.
  • the mixture is a ternary or quaternary system of carbonate salts with metal ions of the first main group and of the second main group.
  • metal ions e.g. metal ions of the subgroup of the table of the elements
  • the individual carbonate salts can exist isolated.
  • the carbonate salts can additionally combine to new chemical compounds with two or more metal ions.
  • Such a compound is for instance sodium potassium carbonate (NaKCOs) .
  • the carbonate salts are lithium carbonate (Li 2 C0 3 ) , sodium carbonate ( a2C0 3 ) , potassium carbonate (K 2 CO3) and calcium carbonate ( CaCOs ) .
  • other carbonate salt such as magnesium carbonate (MgCOs) , barium carbonate (BaCOs) and strontium carbonate ( S rCOs ) can be used as part of the mixture.
  • MgCOs magnesium carbonate
  • BaCOs barium carbonate
  • S rCOs strontium carbonate
  • a percentage by weight of lithium carbonate in the mixture is selected from the range between 20 wt% and 35 wt% and more preferably selected from the range between 27 wt% and 33 wt%.
  • a percentage by weight of sodium carbonate in the mixture is preferably selected from the range between 25 wt% and 40 wt% and more preferably selected from the range between 30 wt% and 35 wt%.
  • potassium carbonate in the mixture is preferably selected from the range between 25 wt% and 40 wt% and more preferably selected from the range between 30 wt% and 35 wt%.
  • a percentage by weight of calcium carbonate in the mixture is preferably selected from the range between 1 wt% and 10 wt% and more preferably selected from the range between 2 wt% and 6 wt%.
  • the percentage by weight of lithium carbonate is about 30 wt%
  • the percentage by weight of sodium carbonate is about 33 wt%
  • the percentage by weight of potassium carbonate is about 33 wt%
  • the percentage by weight of calcium carbonate is about 4 wt%.
  • lithium carbonate ranges from 28.5 wt% to 32.5 wt%.
  • the percentage by weight of lithium carbonate is 29.70 wt%
  • the percentage by weight of sodium carbonate is 33.01 wt%
  • the percentage by weight of potassium carbonate is 32.9 wt%
  • the percentage by weight of calcium carbonate is 4.38 wt%.
  • the described heat storage medium has excellent physical characteristics. It has an appropriate melting and
  • the thermal energy storage medium comprises a phase change material with a mixture of four different carbonate salts.
  • the carbonate salts have metal ions of metals which are selected from the group consisting of alkaline metals and alkaline earth metals.
  • the mixture of the thermal energy storage medium is a

Abstract

A thermal energy storage medium is provided comprising at least one phase change material with a mixture of at least three different carbonate salts. In a preferred embodiment the carbonate salts have metal ions of metals which are selected from the group consisting of alkaline metals and alkaline earth metals. The heat storage medium has excellent physical characteristics. It has appropriate melting and solidification temperatures as well as an appropriate heat of fusion. It has a high density. As a result relatively low costs per thermal energy storage volume capacity are available. Additionally degradation problems and corrosion with container materials play nearly no role. The use of such the thermal storage medium relates to a solar power plant for converting solar energy into electrical energy.

Description

Description
THERMAL ENERGY STORAGE MEDIUM WITH CARBONATE SALTS AND USE OF THE THERMAL ENERGY STORAGE MEDIUM
BACKGROUND OF THE INVENTION
1. Field of the Invention This invention relates to a thermal energy storage medium and a use of the thermal storage medium.
2. Description of the Related Art From US 6 828 990 Bl a low-melting point heat transfer fluid (HTF) with a mixture with alkali nitrate salts is known. This mixture can be used as thermal energy storage (TES) medium in a solar power plant for converting solar energy into
electrical energy.
The purpose of a TES medium is to store and to transport an excess of solar energy provided by the heat transfer fluid of a solar field. The stored excess of thermal energy can be delivered back to the heat transfer fluid according to needs of the solar power plant.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a thermal energy storage medium which can be used in solar energy power plants .
This object is achieved by the invention specified in the claims . A thermal energy storage medium is provided comprising at least one phase change material with a mixture of at least three different carbonate salts. In a preferred embodiment the carbonate salts have metal ions of metals which are selected from the group consisting of alkaline metals and alkaline earth metals. Other metal ions are possible, too.
Additionally a use of the thermal storage medium in a solar power plant for converting solar energy into electrical energy is provided.
The mixture is a phase change material. By a phase change of the phase change material thermal energy can be stored. By a reversed phase change of the phase change material the stored thermal energy can be delivered again.
For instance, the mixture is a ternary or quaternary system of carbonate salts with metal ions of the first main group and of the second main group. Other metal ions, e.g. metal ions of the subgroup of the table of the elements, are possible, too. The individual carbonate salts can exist isolated. The carbonate salts can additionally combine to new chemical compounds with two or more metal ions. Such a compound is for instance sodium potassium carbonate (NaKCOs) .
In a preferred embodiment the carbonate salts are lithium carbonate (Li2C03 ) , sodium carbonate ( a2C03 ) , potassium carbonate (K2CO3) and calcium carbonate ( CaCOs ) . Additionally other carbonate salt such as magnesium carbonate (MgCOs) , barium carbonate (BaCOs) and strontium carbonate ( S rCOs ) can be used as part of the mixture. Preferably a percentage by weight of lithium carbonate in the mixture is selected from the range between 20 wt% and 35 wt% and more preferably selected from the range between 27 wt% and 33 wt%. A percentage by weight of sodium carbonate in the mixture is preferably selected from the range between 25 wt% and 40 wt% and more preferably selected from the range between 30 wt% and 35 wt%. A percentage by weight of
potassium carbonate in the mixture is preferably selected from the range between 25 wt% and 40 wt% and more preferably selected from the range between 30 wt% and 35 wt%. Finally a percentage by weight of calcium carbonate in the mixture is preferably selected from the range between 1 wt% and 10 wt% and more preferably selected from the range between 2 wt% and 6 wt%.
In a preferred embodiment the percentage by weight of lithium carbonate is about 30 wt%, the percentage by weight of sodium carbonate is about 33 wt%, the percentage by weight of potassium carbonate is about 33 wt% and the percentage by weight of calcium carbonate is about 4 wt%. Thereby a
deviation of up to 5% is possible. For instance, the
percentage by weight of lithium carbonate ranges from 28.5 wt% to 32.5 wt%. Preferably the percentage by weight of lithium carbonate is 29.70 wt%, the percentage by weight of sodium carbonate is 33.01 wt%, the percentage by weight of potassium carbonate is 32.9 wt% and the percentage by weight of calcium carbonate is 4.38 wt%.
The described heat storage medium has excellent physical characteristics. It has an appropriate melting and
solidification temperature as well as an appropriate heat of fusion. It has a high density. This leads to relatively low costs per thermal energy storage volume capacity.
Additionally degradation problems and corrosion with
container materials play nearly no role. DETAILED DESCRIPTION OF THE INVENTION
The thermal energy storage medium comprises a phase change material with a mixture of four different carbonate salts. The carbonate salts have metal ions of metals which are selected from the group consisting of alkaline metals and alkaline earth metals.
The mixture of the thermal energy storage medium is a
quarternery system with following composition:
29.70 wt% Li2C03;
33.01 wt% Na2C03;
32.90 wt% K2C03;
4.38 wt% CaC03.
The physical characteristics (liquidus temperature Tnq in °C, enthalpy of melting HM in kJ/kg at the liquidus temperature, enthalpy of melting Hv in MJ/m3 of liquid at the liquidus temperature, and solid phases formed for a total mass of 1 kg) of this mixture are calculated:
Table :
Tliq ( °C) H Hv
(kJ/kg) (MJ/m3)
393 306.2 645.2

Claims

Claims
1. Thermal energy storage medium comprising at least one phase change material with a mixture of at least three different carbonate salts.
2. Thermal energy storage medium according to claim 1, wherein the carbonate salts have metal ions of metals which are selected from the group consisting of alkaline metals and alkaline earth metals.
3. Thermal energy storage medium according to claim 2, wherein the carbonate salts are lithium carbonate, sodium carbonate, potassium carbonate and calcium carbonate.
4. Thermal energy storage medium according to claim 3, wherein a percentage by weight of lithium carbonate in the mixture is selected from the range between 20 wt% and 35 wt% and preferably selected from the range between 27 wt% and 33 wt%.
5. Thermal energy storage medium according to claim 3 or claim 3, wherein a percentage by weight of sodium carbonate in the mixture is selected from the range between 25 wt% and 40 wt% and preferably selected from the range between 30 wt% and 35 wt%.
6. Thermal energy storage medium according to one of the claims 3 to 5, wherein a percentage by weight of potassium carbonate in the mixture is selected from the range between 25 wt% and 40 wt% and preferably selected from the range between 30 wt% and 35 wt%.
7. Thermal energy storage medium according to one of the claims 3 to 6, wherein a percentage by weight of calcium carbonate in the mixture is selected from the range between 1 wt% and 10 wt% and preferably selected from the range between 2 wt% and 6 wt%.
8. Thermal energy storage medium according to claim 7, wherein the percentage by weight of lithium carbonate is about 30 wt%, the percentage by weight of sodium carbonate is about 33 wt%, the percentage by weight of potassium carbonate is about 33 wt% and the percentage by weight of calcium carbonate is about 4 wt%.
9. Thermal energy storage medium according to claim 8, wherein the percentage by weight of lithium carbonate is
29.70 wt%, the percentage by weight of sodium carbonate is 33.01 wt%, the percentage by weight of potassium carbonate is 32.9 wt% and the percentage by weight of calcium carbonate is 4.38 wt%.
10. Use of the thermal storage medium according to one of the previous claims in a solar power plant for converting solar energy into electrical energy.
PCT/EP2011/054812 2011-03-29 2011-03-29 Thermal energy storage medium with carbonate salts and use of the thermal energy storage medium WO2012130285A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2011/054812 WO2012130285A1 (en) 2011-03-29 2011-03-29 Thermal energy storage medium with carbonate salts and use of the thermal energy storage medium

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PCT/EP2011/054812 WO2012130285A1 (en) 2011-03-29 2011-03-29 Thermal energy storage medium with carbonate salts and use of the thermal energy storage medium

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016188347A (en) * 2015-03-30 2016-11-04 綜研テクニックス株式会社 Molten salt type heat transfer medium
WO2016199454A1 (en) * 2015-06-10 2016-12-15 綜研テクニックス株式会社 Molten-salt type heat medium, method for using molten-salt type heat medium, and solar heat utilization system
WO2017217390A1 (en) * 2016-06-16 2017-12-21 綜研テクニックス株式会社 Molten salt-type heat medium, method for using molten salt-type heat medium and solar heat utilization system
CN108003843A (en) * 2017-12-12 2018-05-08 天津琪臻节能科技有限公司 A kind of high-temperature phase-change thermal energy storage material and preparation method thereof
US10266420B2 (en) 2015-04-23 2019-04-23 University Of Florida Research Foundation, Inc Method for the generation of power
CN113831899A (en) * 2021-10-19 2021-12-24 北京工业大学 High decomposition temperature mixed molten salt heat transfer and storage medium
US11740031B1 (en) 2022-03-04 2023-08-29 Battelle Savannah River Alliance, Llc High temperature thermochemical energy storage materials

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4512388A (en) * 1981-06-19 1985-04-23 Institute Of Gas Technology High-temperature direct-contact thermal energy storage using phase-change media
US6828990B2 (en) 2000-12-28 2004-12-07 Xerox Corporation System for processing tabbed pages in the document
DE102007023766A1 (en) * 2007-05-22 2008-11-27 Rational Ag Partially filling an arrangement having storage elements of heat accumulator with salt melt, comprises heating storage medium at its melting point and then sucking over pressure difference between interior of accumulator and arrangement
CN101508888A (en) * 2009-02-24 2009-08-19 中山大学 Lithium-containing molten salt creosote thermal transmission heat storage medium, preparation and uses thereof
US20110067398A1 (en) * 2009-09-18 2011-03-24 Massachusetts Institute Of Technology Concentrated solar power system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4512388A (en) * 1981-06-19 1985-04-23 Institute Of Gas Technology High-temperature direct-contact thermal energy storage using phase-change media
US6828990B2 (en) 2000-12-28 2004-12-07 Xerox Corporation System for processing tabbed pages in the document
DE102007023766A1 (en) * 2007-05-22 2008-11-27 Rational Ag Partially filling an arrangement having storage elements of heat accumulator with salt melt, comprises heating storage medium at its melting point and then sucking over pressure difference between interior of accumulator and arrangement
CN101508888A (en) * 2009-02-24 2009-08-19 中山大学 Lithium-containing molten salt creosote thermal transmission heat storage medium, preparation and uses thereof
US20110067398A1 (en) * 2009-09-18 2011-03-24 Massachusetts Institute Of Technology Concentrated solar power system

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200959, Derwent World Patents Index; AN 2009-N04866, XP002667198 *
NAN REN ET AL: "Experimental study on optimized composition of mixed carbonate for phase change thermal storage in solar thermal power plant", JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY, KLUWER ACADEMIC PUBLISHERS, DORDRECHT, NL, vol. 104, no. 3, 15 February 2011 (2011-02-15), pages 1201 - 1208, XP019902898, ISSN: 1572-8943, DOI: 10.1007/S10973-011-1364-5 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016188347A (en) * 2015-03-30 2016-11-04 綜研テクニックス株式会社 Molten salt type heat transfer medium
US10266420B2 (en) 2015-04-23 2019-04-23 University Of Florida Research Foundation, Inc Method for the generation of power
US11117810B2 (en) 2015-04-23 2021-09-14 University Of Florida Research Foundation, Inc. Method for the generation of power
WO2016199454A1 (en) * 2015-06-10 2016-12-15 綜研テクニックス株式会社 Molten-salt type heat medium, method for using molten-salt type heat medium, and solar heat utilization system
WO2017217390A1 (en) * 2016-06-16 2017-12-21 綜研テクニックス株式会社 Molten salt-type heat medium, method for using molten salt-type heat medium and solar heat utilization system
CN108003843A (en) * 2017-12-12 2018-05-08 天津琪臻节能科技有限公司 A kind of high-temperature phase-change thermal energy storage material and preparation method thereof
CN113831899A (en) * 2021-10-19 2021-12-24 北京工业大学 High decomposition temperature mixed molten salt heat transfer and storage medium
CN113831899B (en) * 2021-10-19 2022-05-24 北京工业大学 High decomposition temperature mixed molten salt heat transfer and storage medium
US11740031B1 (en) 2022-03-04 2023-08-29 Battelle Savannah River Alliance, Llc High temperature thermochemical energy storage materials

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