WO2021136959A1 - Procédé et dispositif permettant de produire et de stocker de la chaleur - Google Patents

Procédé et dispositif permettant de produire et de stocker de la chaleur Download PDF

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Publication number
WO2021136959A1
WO2021136959A1 PCT/IB2020/001020 IB2020001020W WO2021136959A1 WO 2021136959 A1 WO2021136959 A1 WO 2021136959A1 IB 2020001020 W IB2020001020 W IB 2020001020W WO 2021136959 A1 WO2021136959 A1 WO 2021136959A1
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WO
WIPO (PCT)
Prior art keywords
container
heat
liquid
cartridge
water
Prior art date
Application number
PCT/IB2020/001020
Other languages
German (de)
English (en)
Inventor
Kim VAN WAGTENDONK
Erhard Krumpholz
Jens Markus ADAMCZYK
Steffen PORSCHE
Thomas Schneider
Original Assignee
Trebuchet B.V.
Zehnder Group International Ag
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 Trebuchet B.V., Zehnder Group International Ag filed Critical Trebuchet B.V.
Priority to EP20848993.0A priority Critical patent/EP4084980A1/fr
Publication of WO2021136959A1 publication Critical patent/WO2021136959A1/fr

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Classifications

    • 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
    • F28D20/003—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using thermochemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60H—ARRANGEMENTS OF HEATING, COOLING, VENTILATING OR OTHER AIR-TREATING DEVICES SPECIALLY ADAPTED FOR PASSENGER OR GOODS SPACES OF VEHICLES
    • B60H1/00—Heating, cooling or ventilating [HVAC] devices
    • B60H1/00492—Heating, cooling or ventilating [HVAC] devices comprising regenerative heating or cooling means, e.g. heat accumulators
    • 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
    • C09K5/16—Materials undergoing chemical reactions when used
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24D—DOMESTIC- OR SPACE-HEATING SYSTEMS, e.g. CENTRAL HEATING SYSTEMS; DOMESTIC HOT-WATER SUPPLY SYSTEMS; ELEMENTS OR COMPONENTS THEREFOR
    • F24D11/00—Central heating systems using heat accumulated in storage masses
    • F24D11/002—Central heating systems using heat accumulated in storage masses water heating system
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24D—DOMESTIC- OR SPACE-HEATING SYSTEMS, e.g. CENTRAL HEATING SYSTEMS; DOMESTIC HOT-WATER SUPPLY SYSTEMS; ELEMENTS OR COMPONENTS THEREFOR
    • F24D2220/00—Components of central heating installations excluding heat sources
    • F24D2220/10—Heat storage materials, e.g. phase change materials or static water enclosed in a space
    • 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

Definitions

  • the invention relates to a method and a device for generating heat and to a method and a device for storing heat.
  • Solid / liquid systems are particularly popular, such as ice storage (frozen / thawed water), wax storage (solidified / melted wax), paraffin storage (solidified / melted paraffin), in which the gas phase in normal operation is close to the respective melting temperature of the system due to the there usually low vapor pressure is negligible.
  • the melting temperatures or melting temperature ranges of such solid / liquid systems can be adjusted over a wide range by the choice of molecules (length of the carbon chains, degree of branching, presence of polar groups, etc.) or by mixing different types of molecules.
  • phase change storage operating temperatures ie phase change storage operating temperatures of 0 ° C (ice storage), from about 30 to 60 ° C (wax / paraffin storage) or from about 60 to 90 ° C (compared to wax / paraffin even longer or with polar groups labeled molecules) are provided.
  • phase change storage systems have a much higher energy storage density than storage of sensible heat.
  • Such phase change storage systems can be used in buildings, especially in connection with solar thermal energy and with storage temperatures of e.g. 30 ° C and 80 ° C, for heat storage for a period of a few weeks. Seasonal storage of heat is only possible here to a limited extent and, if so, then only with a high level of effort in terms of thermal insulation measures for the storage tank.
  • the invention is therefore based on the object of enabling long-term, in particular and at least seasonal, storage of heat without measures for thermal insulation of the memory.
  • the invention provides, according to a first aspect, a method for generating (releasing, releasing) heat (W) by reaction between on the one hand a solid and / or a first liquid (1) and on the other hand a gas and / or a second Liquid (2), the resulting heat of reaction (W) being dissipated.
  • a metered amount of the solid and / or the first liquid (1) is fed to a reaction space (R); and a2) on the other hand, a metered amount of the gas and / or the second liquid (2) is supplied to the reaction space (R).
  • the solid and / or the first liquid (1); and a2) the gas and / or the second liquid (2) are brought into contact with one another, and the heat released is removed from the reaction space (R).
  • the solid and / or the first liquid on the one hand and the gas and / or the second liquid on the other hand have a sufficiently high affinity for one another that a large amount of heat is given off during the reaction.
  • the gas and / or the second liquid are e.g. ammonia, water, an alcohol, a ketone, etc.
  • the solid and / or the first liquid (1) used in the process contains an anhydrate, also referred to as an anhydrous salt or dehydrated hydrate, the heat being generated by reaction with the participation of anhydrate on the one hand and water and / or water vapor on the other hand is generated.
  • anhydrate also referred to as an anhydrous salt or dehydrated hydrate
  • the heat being generated by reaction with the participation of anhydrate on the one hand and water and / or water vapor on the other hand is generated.
  • a metered amount of the anhydrate and, on the other hand, a metered amount of water and / or steam are fed to the reaction space.
  • the heat output released during the process can be controlled.
  • the anhydrate or dehydrated hydrate can be fed to the reaction space in the form of a liquid, e.g. as a non-aqueous slurry or suspension.
  • a metered amount of the anhydrate is expediently fed to the reaction space in the form of solid particles.
  • a metered amount of the anhydrate is preferably fed to the reaction space in the form of a powder.
  • the particles of the powder preferably have an average particle size in the range from 100 pm to 800 pm.
  • the metered amount of the anhydrate can be fed to the reaction space in the form of pellets (pressed pieces).
  • the pellets preferably have an average size in the range from 3 mm to 15 mm.
  • the pellets preferably contain particles of the anhydrate which are held together by a matrix of binder, the binder being able to be water-soluble or water-insoluble.
  • the proportion of binder in% by weight of the pellets is preferably 1% to 10%, preferably 2% to 5%.
  • hydration also called hydration
  • hydration of part of the anhydrate to be bound or pelletized is inevitable. If this binder is used in 1% to 10% by weight of the anhydrate in the pellet, only a negligible part of the anhydrate in the pellet is hydrated due to the water content of the binder, so that its potential for later hydration and release of heat is only reduced minimally. It is advantageous that the heat released during the pellet production by hydration of a small portion of the pellet material evaporates a portion of the water in the binding agent of the pellets that participates in the partial hydration of the pellet material before it can react with the anhydrate. This ensures that the binder in the pellets dries and solidifies very quickly.
  • a binder which is soluble in water and in another solvent can also be used for the production of the pellets.
  • the other solvent is a substance which does not react with the anhydrate.
  • low molecular weight volatile organic substances can be used. This has the advantage that the other solvent, ie no water, can be used when producing the pellets, as a result of which the pellet material is not hydrated at all, so that its potential for subsequent hydration and release of heat is not reduced.
  • a pellet press is preferably used to produce the pellets from anhydrate.
  • a spraying method or a dripping method can also be used.
  • the suspension or slurry of anhydrate, the other solvent and the binder dissolved therein is conveyed through a nozzle. This can be done by gravity, inertial force, e.g. centrifugal force, or hydraulic pressure.
  • the jet emerging from the nozzle can be separated into pellets in the atmosphere of a pellet collecting chamber after the nozzle.
  • a pulsating pressure gradient is preferably generated in the fluid flow of the suspension or slurry in order to promote the separation of the fluid into pellets.
  • the use of a drop tower with a nozzle plate in the upper part of the drop tower is particularly preferred.
  • the suspension or slurry is fed into a first chamber above the nozzle plate, and the nozzle plate is vibrated, the vibration of the nozzle plate preferably occurring parallel to the direction of gravity, ie alternately up and down.
  • the drops of suspension or slurry emerging from the nozzles on the underside of the vibrating nozzle plate fall into the atmosphere of a second chamber below the nozzle plate. During the fall, the solvent of the binder evaporates, so that solidified pellets arrive at the bottom of the second chamber.
  • a metered amount of water is expediently supplied to the reaction space in the form of droplets or as an aerosol. This can be done by means of an air stream.
  • the mean diameter of a droplet is preferably in the range from 100 pm to 2 mm.
  • the metered amount of water can be fed to the reaction space in the form of a water jet, the cross-sectional area of which is preferably in the range from 0.2mm 2 to 500mm 2 and the speed of which is preferably in the range of 0.5m / s to 10m / s.
  • the dosed amount of water is overstoichiometric with respect to the dosed amount of anhydrate, the water excess based on the stoichiometric molar amount of water preferably being in the range from 2% to 15% and particularly preferably in the range from 5% to 10% lies.
  • the reaction product in which the heat is generated is more or less moist or even pasty.
  • the viscosity of the water with the solid particles (paste) dispersed in it is greater than the viscosity of the water.
  • the dosed amount of water is substoichiometric with respect to the dosed amount of anhydrate, the water deficit based on the stoichiometric molar amount of water preferably being in the range from 2% to 15% and particularly preferably in the range from 5% to 10 % lies.
  • the reaction product in which the heat is generated is more or less dry and more or less free-flowing.
  • the flowability of the dry reaction product is usually very good.
  • the excess anhydrate in the dry reaction product acts as a drying agent and prevents unwanted wetting.
  • the process can be carried out continuously.
  • the metered amount of the solid and / or the first liquid (1) are continuously fed to the reaction chamber (R) and a2) the metered amount of the gas and / or the second liquid (2) is continuously fed to the reaction chamber (R) .
  • the process can be carried out at least partially discontinuously.
  • a1) a metered cumulative amount of the solid and / or the first liquid (1) are fed to the reaction space (R) in advance in a first step for a period of time and a2) then in a second step a metered amount of the gas and / or the second liquid (2) is continuously fed to the reaction space (R).
  • a2) a metered cumulative amount of the gas and / or the second liquid (2) are fed to the reaction space (R) beforehand in a first step and al) then in a second step a metered amount of the solid and / or the first liquid (1) is fed to the reaction space (R), the feeding at a1) preferably taking place continuously.
  • the reaction space is a container, in particular a cartridge, cartridge, plate, etc.
  • This cartridge can be used as a heating cartridge HK in a heating mode Can be used to give off heat.
  • the cartridge is preferably a thermally conductive cartridge in which a salt hydrate is preferably enclosed as anhydrate (in the dehydrated state).
  • the cartridge is preferably permeable to water or water vapor at least in a partial area.
  • the invention provides, according to a second aspect, a device for carrying out the method described above, the device having a reaction chamber forming the reaction space (R) with a means (WT) for dissipating reaction heat and a first supply means (SF; ZF) for the metered supply of a solid and / or a first liquid (1) into the reaction chamber (R) and a second supply means (DP, ZD) for the metered supply of a gas and / or a second liquid (2) into the reaction chamber (R ) having.
  • WT means
  • SF first supply means
  • ZF first supply means
  • DP, ZD second supply means
  • the means for removing the heat of reaction expediently contains a water / reaction medium heat exchanger (WT) or an air / reaction medium heat exchanger.
  • WT water / reaction medium heat exchanger
  • air / reaction medium heat exchanger an air / reaction medium heat exchanger
  • the first feed means preferably contains a screw conveyor (SF).
  • the screw conveyor is a twin screw conveyor with two intermeshing screw shafts which clean each other during operation and which preferably have an Erdmenger profile.
  • a multi-screw conveyor with several intermeshing screw shafts can also be used as the screw conveyor, of which two adjacent screw shafts clean each other during operation, the screw shafts preferably having an Erdmenger profile.
  • the first supply means can contain a toothed belt conveyor (ZF).
  • the toothed belt conveyor is preferably formed from a polymer material and particularly preferably formed from a fiber-reinforced polymer material.
  • the toothed belt conveyor preferably has depressions which are spaced apart from one another along its longitudinal extent or along its length and which extend over the entire transverse extent or over the entire width of the toothed belt conveyor.
  • the depressions preferably have a constant profile along the transverse extent or over the entire width of the toothed belt conveyor. It is particularly advantageous if the profile is a V-profile or a U-profile.
  • the second supply means preferably contains a metering pump (DP) and / or a nozzle, in particular an atomizing nozzle (ZD).
  • DP metering pump
  • ZD atomizing nozzle
  • the atomizing nozzle preferably has a nozzle block with a plurality of nozzle openings arranged next to one another.
  • the second supply means can contain a supply channel (pump / gravity) (ZK).
  • ZK a supply channel
  • the reaction space (R) has a container with a filling opening for feeding the solid and / or the first liquid (1) into the container, a closure for closing the filling opening and a semi-permeable wall area which is suitable for the solid and / or the first liquid (1) is impermeable and permeable to the gas and / or the second liquid (2).
  • the reaction space (R) can have a container with a filling opening for feeding the gas and / or the second liquid (2) into the container and for feeding the solid and / or the first liquid (1) into the container.
  • the semipermeable wall area preferably contains a wall with a plurality of holes.
  • the holes in the wall can be round holes or longitudinal holes or cross holes or star holes.
  • the smallest dimension of the holes i.e. the diameter of the round holes or the width of the longitudinal holes, is preferably in the range from 50pm to 10000mhh, preferably in the range from 50pm to 500pm and most preferably in the range from 50pm to 200miti.
  • the reaction space (R) preferably has a container with a filling opening for feeding the gas and / or the second liquid (2) into the container and for feeding the solid and / or the first liquid (1) into the container.
  • the container is a heating cartridge HK, which can be brought into thermal contact with a central heating system or several decentralized heating devices.
  • the heating cartridge can be inserted in a form-fitting manner and in thermal contact into a recess of a heating center or a decentralized heating device that is complementary to the cartridge and can be guided out of this.
  • the form fit and the thermal contact are preferably established by means of a screw connection or a bayonet connection.
  • the heating cartridge preferably contains a first wall area, which is the abovementioned semipermeable wall area with the plurality of holes, in particular with the round holes or longitudinal holes or cross holes or star holes.
  • This semipermeable first wall area can be formed from metal or from ceramic, for example from metal ceramic or from oxide ceramic, or from a combination of metal and ceramic in the manner of a ceramic filter.
  • the heating cartridge preferably contains a second wall area which is formed from a highly thermally conductive material, preferably from metal, e.g. copper, aluminum, steel, etc., or graphite.
  • the heating cartridge preferably contains a reaction chamber between the first wall area and the second wall area.
  • This reaction chamber is filled with the anhydrate.
  • the reaction chamber is preferably filled with anhydrate in the form of a solid.
  • the reaction chamber is preferably only partially filled with the anhydrate.
  • the first wall area prevents the solid particles of the anhydrate from escaping from the reaction chamber.
  • the first wall area enables water to enter the reaction chamber as a liquid or as a gas / vapor.
  • the reaction chamber of the heating cartridge is fed in metered amounts through the first wall area as liquid or as steam, which reacts exothermically with the anhydrate. The released heat of hydration is dissipated from the cartridge through the second wall area.
  • the first wall area and the second wall area of the heating cartridge each have flat areas which are arranged parallel to and spaced from one another, the space between the spaced apart flat areas containing anhydrate.
  • anhydrate plate cartridge we call this version of the heating cartridge "anhydrate plate cartridge”.
  • the first wall area and the second wall area of the heating cartridge each have areas in the form of a cylinder jacket, which are arranged concentrically spaced from one another, the space between the spaced apart concentric areas containing anhydrate.
  • anhydrate hollow cylinder cartridge we call this version of the heating cartridge "anhydrate hollow cylinder cartridge”.
  • a plurality of heating cartridges are preferably arranged connected in parallel in terms of fluid technology, the second wall area being contacted by a heat transfer fluid of a heating system.
  • the heating cartridges for heating one or more of them are immersed in a water tank.
  • liquid water can penetrate into the reaction chamber of the heating cartridge in a metered manner via the first, semipermeable wall area.
  • the heat of hydration released in a metered manner in the reaction chamber is passed through the second, highly heat-conducting wall area into the water of the water tank, whereby its temperature rises in a metered manner.
  • the invention provides, according to a third aspect, a method for storing heat (W) by reaction between on the one hand a solid and / or a first liquid (1) and on the other hand a gas and / or a second liquid (2), the heat of reaction (W) to be stored being supplied.
  • bl on the one hand a metered amount of the solid and / or the first liquid (1) is fed to a reaction space (R) and b2) on the other hand a metered amount of heat (W) is fed to the reaction space (R).
  • the solid and / or the first liquid (1) and b2) the heat (W) are brought into contact with one another in the reaction space (R) bl), and the gas released and / or the second liquid released (2) is discharged from the reaction space (R).
  • the solid and / or the first liquid on the one hand and the gas and / or the second liquid on the other hand have a sufficiently high affinity for one another that a large amount of heat is supplied during the reaction.
  • the gas and / or the second liquid are, for example, ammonia, water, an alcohol, a ketone, etc.
  • the solid and / or the first liquid (1) used in the process contains a hydrate, also referred to as a salt containing water of crystallization or hydrated anhydrate, the heat being generated by reaction with the participation of hydrate on the one hand and water and / or water vapor on the other hand is stored.
  • a metered amount of the hydrate and, on the other hand a metered amount of heat are supplied to the reaction space. By metered addition of the hydrate and the heat, the thermal output supplied in the process can be controlled.
  • a metered amount of the hydrate is expediently fed to the reaction space in the form of solid particles.
  • a metered amount of the hydrate is preferably fed to the reaction space in the form of a powder.
  • the metered amount of hydrate can be fed to the reaction space in the form of pellets (pressed pieces).
  • the metered amount of heat is expediently supplied to the reaction space in the form of hot air.
  • the metered amount of heat is preferably supplied to the reaction space by means of a fluidized bed.
  • the metered amount of heat is overstoichiometric with respect to the metered amount of hydrate.
  • the reaction product in which the heat is stored is more or less dry and more or less free-flowing.
  • the flowability of the dry reaction product is usually very good.
  • the excess of heat in the dry reaction product removes non-bound residual water and briefly increases the temperature of the reaction product until it cools.
  • the metered amount of heat is substoichiometric with respect to the metered amount of hydrate.
  • the reaction product in which the heat is stored is more or less moist or even pasty.
  • the process can be carried out continuously.
  • the metered amount of the solid and / or the first liquid (1) are continuously fed to the reaction space (R) and b2) the metered amount of heat (W) is continuously fed to the reaction space (R).
  • the process can be carried out at least partially discontinuously.
  • bl in a first step a metered, cumulative amount of the solid and / or the first liquid (1) is fed to the reaction space (R) for a period of time and b2) then in a second step a metered amount of heat ( W) fed continuously to the reaction space (R).
  • a metered, cumulative amount of heat (W) is supplied to the reaction space (R) in advance in a first step, bl) then a metered amount in a second step Amount of the solid and / or the first liquid (1) is supplied to the reaction space (R), the supply at bl) preferably taking place continuously.
  • the reaction space is a container, in particular a cartridge, cartridge, plate, etc.
  • This cartridge can be used as a charging cartridge LK in a charging mode for storing heat.
  • the cartridge is preferably a thermally conductive cartridge in which a salt hydrate is preferably enclosed as the hydrate (in the hydrated state).
  • the cartridge is preferably permeable to water or water vapor at least in a partial area.
  • the invention provides, according to a fourth aspect, a device for carrying out the method described above, the device having a reaction chamber forming the reaction space with a means (WT; WB) for supplying reaction heat and a first means (SF; ZF ) for the metered supply of a solid or a first liquid into the reaction chamber (R) and a second means (V; P) for the metered discharge of a gas or a second liquid (2) from the reaction chamber (R).
  • WT means
  • SF first means
  • V second means
  • the means for supplying heat of reaction expediently contains a heat exchanger (WT).
  • WT heat exchanger
  • the means for supplying heat of reaction preferably contains a fluidized bed (WB).
  • WB fluidized bed
  • the first means includes a screw conveyor (SF).
  • SF screw conveyor
  • the first means contains a toothed belt conveyor (ZF).
  • the means for supplying heat of reaction preferably contains a fan (V).
  • the means for supplying heat of reaction contains a pump (P).
  • the reaction space (R) has a container with a filling opening for feeding the solid and / or the first liquid (1) into the container, a closure for closing the filling opening and a semi-permeable wall area which is suitable for the solid and / or the first liquid (1) is impermeable and permeable to the gas and / or the second liquid (2).
  • the reaction space (R) can have a container with a filling opening and / or a heat introduction area for supplying the metered cumulative amount of heat (W) and the metered amount of solid and / or the first liquid (1) into the container, a Closure for closing the filling opening and a semipermeable wall area which is impermeable to the solid and / or the first liquid (1) and permeable to the gas and / or the second liquid (2).
  • the container is a charging cartridge LK, which can be brought into thermal contact with a heat source.
  • the charging cartridge can be inserted in a form-fitting manner and in thermal contact into a recess of a heat source that is complementary to the cartridge and guided out of it.
  • the form fit and the thermal contact are preferably established by means of a screw connection or a bayonet connection.
  • the loading cartridge preferably contains a first wall area, which is the above-mentioned semipermeable wall area with the plurality of holes, in particular with the round holes or longitudinal holes or cross holes or star holes.
  • This semipermeable first wall area can be formed from metal or from ceramic, for example from metal ceramic or from oxide ceramic, or from a combination of metal and ceramic in the manner of a ceramic filter.
  • the loading cartridge preferably contains a second wall area which is formed from a highly thermally conductive material, preferably from metal, e.g. copper, aluminum, steel, etc., or graphite.
  • the charging cartridge preferably contains a reaction chamber between the first wall area and the second wall area.
  • This reaction chamber is filled with the hydrate.
  • the reaction chamber is preferably filled with hydrate in the form of a solid.
  • the reaction chamber is preferably only partially filled with the hydrate, in particular with a degree of filling in% by volume of 90% to 100%, in particular from 95% to 100%.
  • the first wall area prevents the solid particles of the hydrate from escaping from the reaction chamber.
  • the first wall area enables water to exit the reaction chamber as a liquid or as a gas / vapor.
  • the first wall area and the second wall area of the loading cartridge each have flat areas which are arranged parallel to and spaced apart from one another, the space between the spaced apart flat areas containing hydrate.
  • this version of the loading cartridge «hydrate plate cartridge».
  • the first wall area and the second wall area of the loading cartridge each have areas in the form of a cylinder jacket which are arranged concentrically spaced from one another, the space between the spaced apart concentric areas containing hydrate.
  • this version of the charging cartridge «hydrate hollow cylinder cartridge».
  • a plurality of charging cartridges are preferably arranged connected in parallel in terms of fluid technology, the second wall region being thermally contacted directly by a heat source or indirectly contacted by the heat source via a heat transfer fluid.
  • one or more of them are positioned in a solar thermal system.
  • It is preferably positioned in a solar thermal system in which large-area solar radiation is concentrated in a small area in order to generate heat in this area at temperatures which are high enough to cause rapid and complete dehydration of the hydrate to anhydrate.
  • gaseous water or water vapor can be dosed out of the first, semi-permeable wall area Exit the reaction chamber of the loading cartridge.
  • the dehydration heat absorbed in the reaction chamber in a dosed or non-dosed manner is conducted via the second, highly heat-conducting wall area into the reaction chamber of the loading cartridge, whereby the temperature of the loading cartridge is dosed or non-dosed raised to a sufficiently high value to achieve complete dehydration of the hydrate .
  • the charging cartridges are preferably charged with thermal energy in a parabolic trough solar power plant.
  • the charging cartridges are brought into thermal contact with a heat transfer medium, e.g. oil, which flows in a channel, e.g. pipe, running in the focal line of the paraboir interior, in order to be heated to temperatures of several 100 ° C, in particular to temperatures above 300 ° C become.
  • a heat transfer medium e.g. oil
  • the concentrated solar energy captured in the parabolic trough solar power plant is used as required to generate superheated steam such as water steam to drive a steam engine such as a steam turbine to drive an electrical generator to generate electrical energy , and / or the captured concentrated solar energy is used to charge the charging cartridge.
  • superheated steam such as water steam
  • a steam engine such as a steam turbine
  • an electrical generator to generate electrical energy
  • the captured concentrated solar energy is used to charge the charging cartridge.
  • the charging cartridges for charging with thermal energy one or more of them are positioned in or on a power plant which generates a considerable proportion of waste heat during its operation.
  • the positioning in the power plant is preferably carried out in an area where the waste heat is conventionally dissipated in order to generate heat in this area at temperatures which are sufficiently high to cause rapid and complete dehydration of the hydrate to anhydrate.
  • gaseous water or water vapor can exit the reaction chamber of the charging cartridge in a metered manner via the first, semi-permeable wall area.
  • the dehydration heat absorbed in the reaction chamber in a dosed or non-dosed manner is conducted via the second, highly heat-conducting wall area into the reaction chamber of the loading cartridge, whereby the temperature of the loading cartridge is dosed or non-dosed raised to a sufficiently high value to achieve complete dehydration of the hydrate .
  • large thermal power plants such as nuclear power plants and combustion power plants, in which fossil chemical energy carriers or regeneratively produced chemical energy carriers are burned in order to generate electrical energy in a direct or indirect way, but always with a more or less large proportion of waste heat is generated.
  • stationary and mobile systems for power / heat coupling or cogeneration are also understood, such as internal combustion engines (Otto engine or diesel engine), jet engines or fuel cells in which fossil chemical energy carriers or regeneratively produced chemical energy carriers are burned to generate electrical energy or mechanical energy in a direct or indirect way, but always producing a more or less large proportion of waste heat.
  • internal combustion engines Otto engine or diesel engine
  • jet engines or fuel cells in which fossil chemical energy carriers or regeneratively produced chemical energy carriers are burned to generate electrical energy or mechanical energy in a direct or indirect way, but always producing a more or less large proportion of waste heat.
  • a particularly preferred system is CaO / Ca (OH) 2
  • the preferred CaO / Ca (OH) 2 system can be operated in terms of energy technology solely with sustainably available energy sources.
  • the CaO In order to convert chemical energy stored in the anhydrate CaO into heat, the CaO is allowed to react with water using the methods and devices described above, thereby producing the hydrate Ca (OH) 2 .
  • the hydrate Ca (OH) 2 is supplied with heat at temperatures above 400 ° C, which expels gaseous water.
  • the repeated production of the anhydrate CaO from the hydrate Ca (OH) 2 can also be carried out by means of a solar power plant in which the solar energy is strongly concentrated in a small area in which temperatures above 400 ° C. can be reached.
  • a parabolic trough solar power plant is particularly suitable for this.
  • Another preferred system is K 2 C0 3 / K 2 C0 3 -H 2 0.
  • anhydrate-containing heating cartridge and the hydrate-containing charging cartridge can be designed differently.
  • anhydrate-containing heating cartridge and the hydrate-containing charging cartridge have the same shape. It is then not necessary to remove the hydrate from the used cartridge after a completed heating process and to refill the cartridge with anhydrate before the next heating process.
  • the invention provides, according to a fifth aspect, a container (K) for use in a method or in a device according to one of the preceding paragraphs, the interior of the container (K) partially containing an anhydrate and / or a hydrate is filled and the container (K) has a semipermeable wall area (WB1, WB2) which is impermeable to the anhydrate or hydrate contained in it and is permeable to water or water vapor.
  • WB1, WB2 semipermeable wall area
  • the use of such a container or such a cartridge or cartridge is advantageous since the anhydrate or the hydrate always remains in the container and it is not necessary to fill or empty the interior of the container. Since the container is only partially filled with the anhydrate and / or the hydrate, the anhydrate can be converted into the more voluminous hydrate during the heating operation without endangering the container.
  • the semipermeable wall area (WB1, WB2, WB) is preferably formed from metal. Since the semi-permeable wall areas of the container are made of metal, both water or water vapor and heat can be transported well on them.
  • the interior of the container (K) is preferably delimited by a first semipermeable wall area (WB1) made of metal and a second semipermeable wall area (WB2) made of metal, between which the interior of the container (K) extends.
  • WB1 first semipermeable wall area
  • WB2 second semipermeable wall area
  • At least some of the semipermeable wall areas are preferably formed from metal ceramic.
  • At least some of the semipermeable wall areas (WB1, WB2, WB) are preferably made of metal and have a large number of through-holes (DB), each of which extends from the outer wall surface (WBa) of the semipermeable wall area (WB) to the inner wall surface (WBi) of the semipermeable wall area (WB) extend.
  • DB through-holes
  • the cross-section of the through-bores (DB) preferably each has a constriction (V). Due to the constriction, the exit of anhydrate particles or hydrate particles from the reaction space is made more difficult, while during heating operation water and steam can easily get into the reaction space R at the constrictions V and water and water vapor easily escape at the constrictions V during charging the reaction space R can get out.
  • At least some of the semi-permeable wall areas are preferably formed from a three-dimensional metal chip matrix (MSM) in which metal chips (MS) are connected to one another with an inorganic adhesive (WG) and which are between the metal chips (MS) Has cavities.
  • MSM three-dimensional metal chip matrix
  • WG inorganic adhesive
  • This structure has a similar effect to the sintered structures of a metal ceramic mentioned above.
  • the three-dimensional metal chip matrix has a sieve function. It does not allow powdery or granular salt hydrate to pass through, while water or water vapor can pass through the semipermeable wall area formed in this way in one direction or the other during loading or unloading in accordance with a pressure gradient or concentration gradient.
  • the metal chip matrix ensures good thermal conductivity, so that heat can pass through the semipermeable wall area formed in this way in one direction or the other in accordance with a temperature gradient during charging or discharging.
  • the metal chips are preferably bonded to at least two further metal chips, whereby a three-dimensional structure with a high resulting thermal conductivity is formed.
  • the metal chips preferably have an average length in the range from 1 mm to 10 mm.
  • Aluminum chips are preferably used as metal chips.
  • the inorganic adhesive used is preferably water glass, ie sodium silicate and / or potassium silicate.
  • a flowable, moist mixture of aluminum chips and water glass is brought into the desired geometric shape (e.g. plate shape, corrugated plate shape) and compressed.
  • the geometric shape obtained in this way is dried at temperatures in the range from 200.degree. C. to 700.degree.
  • the water glass used as an adhesive can contain aluminum powder and / or graphite particles.
  • the graphite particles preferably contain expanded graphite or expandable graphite.
  • the interior of the container (K) preferably has a filling which contains a first phase formed by salt hydrate, which is continuous and porous, and particles (MP) distributed in the first phase made of a material with high specific thermal conductivity as the second phase.
  • the second phase formed by the distributed particles ensures good thermal conductivity, so that heat can flow well during charging or discharging according to a temperature gradient in one direction or the other within the filling of the container (K) thus formed.
  • Aluminum shavings, aluminum powder, graphite powder or expanded graphite, i.e. expandable graphite, are preferably used as the distributed particles.
  • the interior of the container (K) preferably has a filling which contains a first phase formed by salt hydrate, which is continuous and porous, and a lattice structure (MG) extending within the first phase and made of a material with high specific thermal conductivity as the second phase .
  • the second phase formed by the lattice structure ensures good thermal conductivity, so that heat can flow well during charging or discharging according to a temperature gradient in one direction or the other within the filling of the container (K) thus formed.
  • Aluminum or copper or iron or steel is preferably used for the lattice structure.
  • the elongate elements or rod-like elements of the lattice structure preferably have a diameter in the range from 0.5 mm to 3 mm.
  • a distance between adjacent grid elements in the grid structure is preferably between 5 mm and 50 mm.
  • the interior of the container (K) preferably has a filling in which metal chips (MS) are connected to one another with an inorganic adhesive and form a three-dimensional metal chip matrix (MSM) and in which gaps of the metal chip matrix with hydrate, ie the hydrated one Form of a salt hydrate, are at least partially filled. Since the salt hydrate in its hydrated state (hydrate state) takes up a larger volume than in its dehydrated state (anhydrate state), this ensures that the metal chip matrix does not explode when discharging, ie when changing from the more compact anhydrate to the more voluminous hydrate becomes. As a result, many charge / discharge cycles of the container (K) can be achieved without impairing the microscopic structure of its salt hydrate metal chip matrix and thus its functionality.
  • MSM three-dimensional metal chip matrix
  • the metal chips are preferably bonded to at least two further metal chips, whereby a three-dimensional structure with a high resulting thermal conductivity is formed.
  • the metal chips preferably have an average length in the range from 1 mm to 10 mm.
  • Aluminum chips are preferably used as metal chips.
  • the inorganic adhesive used is preferably water glass, ie sodium silicate and / or potassium silicate.
  • S1 a flowable, moist mixture of aluminum chips and water glass is formed and pressed into a desired porous structure, in particular a block-like or plate-like structure (e.g. rectangular block, cylinder block, prism block, etc.).
  • a second step (S2) the structure obtained in this way is dried at temperatures in the range from 200.degree. C. to 700.degree.
  • the water glass used as an adhesive can contain aluminum powder and / or graphite particles.
  • the graphite particles preferably contain expanded graphite or expandable graphite.
  • the porous structure obtained in the first step and in the second step is in a third step (S3) with an aqueous slurry of salt hydrate, eg Ca (OH) 2 slurry, which contains dissolved salt hydrate and undissolved suspended salt hydrate particles, soaked or impregnated.
  • This third step is preferably carried out using at least one of the following two variants:
  • the porous structure is immersed in the slurry in a tank;
  • Measures 1) and / or 2) cause the metal chip matrix to be wetted and thus at least partially fill its interstices with salt hydrate.
  • the porous structure so impregnated or impregnated in this way can be positioned in a pressure vessel filled with a fluid, after which the fluid in the pressure vessel is isotropically pressurized in order to transfer the salt hydrate slurry into the spaces between the metal chips.
  • This fourth step is preferably carried out using at least one of the following four variants:
  • the pressurized fluid is the salt hydrate slurry into which the porous structure is immersed, the tank or vessel preferably being the pressure vessel.
  • the pressurized fluid is a gas, especially air.
  • the porous structure is brought into contact with the salt hydrate slurry at least in parts of its outer surface, and the porous structure is set in a rotary motion together with the salt hydrate slurry. Centrifugal forces (inertial forces) press the salt hydrate slurry into the spaces between the metal chip matrix of the porous structure.
  • the porous structure is preferably centrifuged in a centrifuge filled with the salt hydrate slurry, the centrifugal force field forcing the salt hydrate slurry into the porous structure.
  • the porous structure is a hollow body, preferably a hollow sphere or a hollow cylinder sealed at its ends, and the porous structure is immersed in the salt hydrate slurry which is put under pressure. Due to the pressure gradient between the outside of the porous structure and the inside or the macroscopic cavity of the porous structure, the salt hydrate slurry is pressed from the outside inwards through the porous structure and thus its microscopic cavities or interstices or pores are practically completely pressed with it filled with the salt hydrate in a hydrated state.
  • the container (K) preferably has a constant cross section along a container axis (BA) transversely to the container axis (BA). This turns the container into a “cartridge” which can be pushed into a complementary shaped cavity and pulled out of it (e.g. for heating or loading the cartridge).
  • the container (K) preferably has impermeable partitions arranged at a distance along its container axis (BA), which are impermeable to the anhydrate, hydrate, water and water vapor and which divide the interior of the container (K) into sub-chambers arranged along the container axis (BA) .
  • BA container axis
  • the cross section of the container (K) can have the shape of a rectangle, a square, a circle or a circular ring, a triangle or a hexagon. Containers with these shapes can be arranged side by side in a compact manner.
  • the cross section of the container (K) can also have the shape of a periodic pattern, in particular a wave with a sinusoidal profile or a triangular profile. Containers with these shapes can also be arranged next to one another in a compact manner.
  • the invention provides, according to a sixth aspect, a container (K *) for use in a method for generating or storing heat, in particular for use in a method or in a device according to one of the preceding paragraphs, wherein the container (K *) is a porous structure which has a metallic matrix and a salt hydrate which at least partially fills the pores or microscopic interstices of the metallic matrix in the hydrated state of the salt hydrate and is permeable to water or water vapor.
  • the use of such a container is advantageous because the anhydrate or the hydrate always remains in the pores of the container and the interior of the container does not need to be filled or emptied. Since the pores of the container are only partially filled with the anhydrate and / or the hydrate, the anhydrate can be converted into the more voluminous hydrate during the heating operation without endangering the container.
  • the metallic matrix preferably contains metal particles (MP) which are connected to one another by sintering to form a metal-sintered block or a metal-ceramic block and form a three-dimensional metal-ceramic matrix (MKM).
  • the metallic matrix preferably contains metal chips (MS) which are connected to one another with an inorganic adhesive and form a three-dimensional metal chip matrix (MSM).
  • the salt hydrate preferably contains particles (MP, GP) made of a material with a high specific thermal conductivity.
  • the salt hydrate preferably contains a lattice structure (MG, WR) with a high specific thermal conductivity.
  • All of the mentioned metallic structures contribute to good thermal conductivity of the porous structure, whereby the penetration of heat into the container during loading and the escape of heat from the container during unloading is facilitated and takes place quickly.
  • the salt hydrate has a porous structure.
  • the aforementioned porous structure of the salt hydrate contributes to the good transportability of water molecules of the porous structure, whereby the penetration of water molecules into the container during unloading and the escape of water molecules from the container during loading is facilitated and takes place quickly.
  • the metallic matrix preferably contains aluminum.
  • the inorganic adhesive preferably contains water glass, in particular sodium silicate and / or potassium silicate.
  • the combination of aluminum, preferably in the form of chips as a waste product from the machining of aluminum parts, with water glass as the inorganic binder is particularly advantageous because the aluminum chips are oxidized on their surface and have an oxide layer on their surface, which with the silicate of the Binder enters into an intimate and particularly stable connection.
  • Aluminum particles and / or graphite particles are preferably distributed in the salt hydrate. These improve the thermal conductivity of the salt hydrate.
  • the container (K *) preferably has a constant cross section along a container axis (BA) transversely to the container axis (BA). This turns the container into a “cartridge” which can be pushed into a complementary shaped cavity and pulled out of it (e.g. for heating or loading the cartridge).
  • the container (K *) preferably has impermeable partitions arranged at a distance along its container axis (BA), which are impermeable to the anhydrate, the hydrate, water and water vapor and which the volume of the container (K *) is arranged along the container axis (BA) Subdivide partial volumes. This prevents uncontrolled diffusion of water or water vapor in the interior of the container along the container axis, and water or water vapor can be supplied to the container in sections in the heating mode or withdrawn in the loading mode. This in particular facilitates a metered heating operation, ie a metered unloading of the container by gradually lowering the container into a water bath, for example along its container axis BA.
  • the cross section of the container (K *) can have the shape of a rectangle, a square, a circle or a circular ring, a triangle or a hexagon. Containers with these shapes can be arranged side by side in a compact manner.
  • the cross section of the container (K *) can also have the shape of a periodic pattern, in particular a wave with a sinusoidal profile or a triangular profile. Containers with these shapes can also be arranged next to one another in a compact manner.
  • the invention provides, according to a seventh aspect, a container arrangement which has a plurality of containers (K and / or K *) according to one of the preceding paragraphs arranged next to one another and parallel to one another.
  • the invention provides, according to an eighth aspect, a method for producing a container (K *) for use in a method for generating or storing heat, in particular for producing a container (K *) according to one of the preceding paragraphs, wherein the method comprises the following steps: a) forming a three-dimensional metallic matrix which has microscopic interstices; and b) filling the microscopic spaces with an aqueous slurry of a salt hydrate.
  • Step a) is preferably carried out by sintering metallic particles.
  • Step a) is preferably carried out by gluing metallic particles by means of an inorganic adhesive.
  • Step b) is preferably carried out by pressing the aqueous slurry into the microscopic interspaces.
  • the invention provides, according to a ninth aspect, a method for producing a container (K *) for use in a method for generating or storing heat, in particular for producing a container (K *) according to one of the preceding paragraphs, wherein the method comprises the following steps: a) providing an aqueous slurry of a salt hydrate in which metallic particles are suspended; and b) forming a three-dimensional metallic matrix by compressing the slurry.
  • the metallic particles are preferably sintered in step b).
  • the metallic particles are preferably glued in step b) by means of an inorganic adhesive.
  • 1 shows a schematic representation of the method according to the invention for generating heat according to an exemplary embodiment
  • 2 shows a schematic representation of the method according to the invention for storing heat according to an exemplary embodiment
  • FIG. 3 shows a schematic representation of the device according to the invention for generating heat according to an exemplary embodiment
  • FIG. 4 shows a schematic representation of the device according to the invention for storing heat according to an exemplary embodiment
  • FIG. 5 shows a schematic representation of an exemplary application of a method according to the invention and a device according to the invention
  • FIG. 6a shows a top view of a first embodiment of a cartridge according to the invention in the loading mode
  • 6b shows a sectional view along the section plane A-A of the first embodiment of the cartridge in the loading mode
  • 6c shows a sectional view along the section plane B-B of the first embodiment of the cartridge in the loading mode
  • FIG. 7a shows a plan view of the first embodiment of the cartridge according to the invention in heating mode
  • 7c shows a sectional view along the section plane B-B of the first embodiment of the cartridge in the heating mode
  • FIG. 8a shows a plan view of a plate-like cartridge in the loading mode
  • FIG. 9a shows a perspective view of a first variant of a block-like cartridge, shown transparently;
  • 9b shows a perspective view of a second variant of a block-like cartridge, shown transparently;
  • FIG. 10 shows a stack of block-like cartridges from FIG. 9a, which are fluidly connected in series;
  • FIG. 11 shows a stack of block-like cartridges from FIG. 9a, provided with engagement formations, which are fluidly connected in series;
  • FIG. 12 shows a perspective view of a further variant of a plate-like cartridge with engagement formations
  • FIG. 13 shows a side view of a vehicle provided with an internal combustion engine, on which two stacks of plate-like cartridges are arranged for their loading process;
  • FIG. 14 shows a sectional view of a further variant of a plate-like cartridge
  • 15 is a sectional view of a cylindrical cartridge; 16 shows a sectional view of a further variant of a plate-like cartridge;
  • FIG. 17 shows a sectional view of a further variant of a plate-like cartridge
  • Fig. 18 is a sectional view of a rod-shaped cartridge
  • FIG. 19 shows a sectional view of a further variant of a rod-shaped cartridge
  • FIG. 20 shows a sectional view of an embodiment of a semipermeable wall region of a cartridge along a sectional plane perpendicular to the plane of the wall region or perpendicular to the tangential plane of the wall region;
  • FIG. 21 shows a sectional view of a further embodiment of a semipermeable wall area of a cartridge K along a sectional plane perpendicular to the plane of the wall area WB or perpendicular to the tangential plane of the wall area;
  • FIG. 22 is a sectional view of a first embodiment of a cartridge filling
  • FIG. 23 is a sectional view of a second embodiment of a cartridge filling
  • FIG. 24 is a sectional view of a third embodiment of a cartridge filling
  • 25 is a sectional view of a fourth embodiment of a cartridge filling
  • 26 is a sectional view of a further embodiment of a cartridge.
  • a method for generating (releasing, releasing) heat W is shown schematically.
  • the release of heat W takes place during a reaction between on the one hand a solid and / or a first liquid 1 and on the other hand a gas and / or a second liquid 2.
  • the heat of reaction W produced in the process is dissipated.
  • a metered amount of the solid and / or the first liquid 1 is fed to the reaction space R.
  • a metered amount of the gas and / or the second liquid 2 is fed to the reaction space R.
  • the solid and / or the first liquid 1 and the gas and / or the second liquid 2 are brought into contact with one another.
  • the heat W released is removed from the reaction space R.
  • a method for storing heat W is shown schematically in FIG.
  • a reaction between, on the one hand, a solid and / or a first liquid 1 and, on the other hand, a gas and / or a second liquid 2, the heat of reaction W to be stored is supplied.
  • a metered amount of the solid and / or the first liquid 1 is fed to a reaction space R.
  • a metered amount of heat W is supplied to the reaction space R.
  • the solid and / or the first liquid 1 and the heat W are brought into contact with one another, ie the solid and / or the first liquid 1 is exposed to the heat W.
  • the released gas and / or the released second liquid 2 is discharged from the reaction space R.
  • Fig. 3 a device or system for performing the method for generating heat is shown schematically.
  • the device contains a reaction chamber which forms the reaction space R and has a means for dissipating the heat of reaction in the form of a heat exchanger WT.
  • the device also contains a first supply means in the form of a screw conveyor SF and / or a toothed belt conveyor ZF for the metered supply of a solid and / or a first liquid 1 into the reaction chamber R.
  • a first supply means in the form of a screw conveyor SF and / or a toothed belt conveyor ZF for the metered supply of a solid and / or a first liquid 1 into the reaction chamber R.
  • the device also contains a second feed means in the form of a metering pump DP and / or an atomizing nozzle ZD for metered feeding of a gas and / or a second liquid 2 into the reaction chamber R.
  • a second feed means in the form of a metering pump DP and / or an atomizing nozzle ZD for metered feeding of a gas and / or a second liquid 2 into the reaction chamber R.
  • a device or system for performing the method for storing heat is shown schematically.
  • the device contains a reaction chamber which forms the reaction space and has a means for supplying heat of reaction in the form of a heat exchanger WT and / or a fluidized bed WB.
  • the device also contains a first means in the form of a screw conveyor SF and / or a toothed belt conveyor ZF for the metered supply of a solid or a first liquid 1 into the reaction chamber R.
  • the device also contains a second means in the form of a blower or ventilator V and / or a pump P for discharging a gas or a second liquid 2 from the reaction chamber R.
  • FIG. 5 shows a schematic representation of an exemplary application of the method according to the invention and the devices according to the invention.
  • a house in which a cartridge K is used as a fleece cartridge HK.
  • the cartridge filled with an anhydrate e.g. CaO
  • anhydrate e.g. CaO
  • the corresponding flydrate e.g. Ca (OH) 2
  • This Flydratations Sue W can be used for meat, for example domestic water heating and room air heating.
  • a vehicle equipped with an internal combustion engine in which a cartridge K is used as a charging cartridge LK.
  • the cartridge filled with a flydrat e.g. Ca (OH) 2
  • heat W waste heat from the combustion engine
  • the flydrat contained in the cartridge is dehydrated, whereby the corresponding anhydrate (e.g. CaO) is produced again and flydratation heat W in the Cartridge K is stored. This heat of flow W can then be used again for meat meat.
  • a cartridge exchange station In the middle of the picture of FIG. 5, a cartridge exchange station is shown. There, the loaded cartridges (anhydrate cartridges) that can be used as fleece cartridges HK are exchanged for loading cartridges LK (hydrate cartridges).
  • FIG. 6a shows a top view of a first embodiment of a cartridge K according to the invention in the loading mode.
  • the cartridge K can be seen with a reaction space R which is filled with a hydrate in powder form and is traversed by a coil S, which, for example, consists of a metal is formed.
  • a hot fluid is allowed to flow through the pipe coil S, the heat W of which flows through the wall of the pipe coil S into the hydrate.
  • the hot fluid can be a hot gas, for example hot air or hot exhaust gas from an internal combustion engine, or a hot liquid, for example hot oil from a parabolic trough power plant.
  • the heat flowing into the hydrate dehydrates the hydrate, with water (H 2 O) emerging from the cartridge K and the corresponding anhydrate being formed in the reaction space.
  • the coil S can also contain small openings (indicated by dashed lines) through which the hot gas penetrates the hydrate powder and gradually dehydrates it and converts it to the corresponding anhydrate.
  • a hot gas e.g. hot exhaust gas
  • FIG. 6b shows a sectional view along the sectional plane A-A of the first embodiment of the cartridge K in the loading mode.
  • the reaction space R can be seen with the coiled pipe S running through it.
  • the reaction space R is filled with a hydrate / anhydrate powder (indicated by dotted lines), the hydrate almost completely filling the reaction space R in the discharged state, while the anhydrate fills the reaction space in the charged state R to a greater extent or at least almost completely.
  • 6c shows a sectional view along the sectional plane B-B of the first embodiment of the cartridge in the loading mode.
  • FIG 7a shows a top view of the first embodiment of the cartridge K according to the invention in the heating mode.
  • the cartridge K can be seen with a reaction space R which is filled with an anhydrate in powder form and is traversed by a pipe coil S, which is formed e.g. from a metal.
  • the coil S contains small openings (indicated by dashed lines).
  • Water is allowed to flow through the coil S as a liquid and / or as water vapor.
  • the liquid water and / or the steam penetrate through the small openings of the coil S into the anhydrate powder, as a result of which it is gradually hydrated and thus converted to the corresponding hydrate.
  • the heat of hydration W released in the process can be given off via at least one highly thermally conductive wall of the cartridge K to a heat transfer fluid for the purpose of heating.
  • the water flowing through the pipe coil S can also be used as a heat transfer fluid.
  • FIG. 7b shows a sectional view along the sectional plane A-A of the first embodiment of the cartridge K in the heating mode.
  • the reaction space R can be seen with the coiled pipe S running through it.
  • the reaction space R is filled with a hydrate / anhydrate powder (indicated by dotted lines), the hydrate almost completely filling the reaction space R in the discharged state, while the anhydrate fills the reaction space in the charged state R to a greater extent or at least almost completely fills out.
  • FIG. 7c shows a sectional view along the sectional plane BB of the first embodiment of the cartridge K in heating mode.
  • Fig. 8a a plan view of a plate-like cartridge K is shown in the loading mode.
  • heat W penetrating into the cartridge K by means of a hot gas can be seen, which dehydrates the hydrate contained in the cartridge K and converts it into the corresponding anhydrate.
  • the upper part of the cartridge K indicated by arrows, can be seen emerging as water vapor.
  • Fig. 8b a sectional view along the section plane A-A of the plate-like cartridge K is shown.
  • the reaction space R and the filling with hydrate / anhydrate powder can be seen again (indicated by dotted lines).
  • Fig. 9a a perspective view of a first variant of a block-like cartridge K shown transparently is shown.
  • a coil S extending inside the cartridge K, which is in fluid connection with two diametrically opposed openings 01 and 02 on a first large area of the cartridge K and each with two diametrically opposed openings 03 and 04 on a second large area of the cartridge K is in fluid communication.
  • the coil S has along the entire fluid path defined by it a multiplicity of small openings or a semipermeable wall area through which water or water vapor can pass and through which neither hydrate nor anhydrate can pass.
  • a hot fluid as a heat source preferably hot air or hot exhaust gas from a combustion process
  • a hot air or hot exhaust gas from a combustion process is passed from the third opening 03 to the fourth opening 04 through the pipe coil S.
  • heat gets into the hydrate inside the cartridge K, as a result of which the hydrate is gradually converted into anhydrate and heat that comes from the heat source is gradually stored in the cartridge K.
  • the water vapor formed in the cartridge K passes through the large number of small openings or via the semi-permeable wall area into the pipe coil S and is carried away from the cartridge K in the air flow or exhaust gas flow.
  • FIG. 9b shows a perspective view of a second variant of a block-like cartridge K, which is shown transparently.
  • a coil S extending inside the cartridge K, which has a first opening 01 on a first large surface of the cartridge K, a second opening 02 on a second large surface of the cartridge K and a third opening 03 on an end surface or small surface the cartridge K is in fluid communication.
  • the coil S has a large number of small openings or a semipermeable wall area along the entire fluid path defined by it, through which water or steam can pass and through which neither hydrate nor anhydrate can pass.
  • a hot fluid as a heat source preferably hot air or hot exhaust gas from a combustion process
  • a hot air or hot exhaust gas from a combustion process is passed from the second opening 02 to the third opening 03 through the pipe coil S.
  • heat gets into the hydrate inside the cartridge K, as a result of which the hydrate is gradually converted into anhydrate and heat that comes from the heat source is gradually stored in the cartridge K.
  • the water vapor formed in the cartridge K passes through the large number of small openings or via the semi-permeable wall area into the pipe coil S and is carried away from the cartridge K in the air flow or exhaust gas flow.
  • FIG. 10 shows a stack of block-like cartridges K from FIG. 9a, which are fluidly connected in series.
  • Each of the cartridges K in the stack contains a coil S (not shown) (see Figure 9a).
  • all of the pipe coils S of the respective cartridges K are connected in series to form a very long series pipe coil.
  • a hot gas e.g. a hot exhaust gas, or a hot liquid, e.g. a hot oil
  • the water vapor emerging from the hydrate can, as described above, emerge from the cartridge via a semipermeable wall area (not shown) of the respective cartridge K.
  • the coil S can also contain small openings (see FIGS. 6a, 7a, 9a, 9b, each indicated by dashed lines) through which the heat of the hot Gas and / or the hot gas itself can penetrate into the hydrate powder and gradually dehydrate it and convert it to the corresponding anhydrate.
  • a hot gas eg hot exhaust gas
  • the cartridge stack can be arranged in any spatial orientation when installed. In particular, it can be arranged vertically or horizontally depending on the installation situation.
  • FIG. 11 shows a stack of block-like cartridges K from FIG. 9a, which are provided with engagement formations F1 and which are connected in series in terms of fluid.
  • the cartridges K can be stacked on top of one another like Lego bricks.
  • FIG. 12 shows a perspective view of a further variant of a plate-like cartridge K with engagement formations F2 and engagement formations F2 'complementary thereto.
  • the cartridges can be positively connected to one another by means of the engagement formations F2 and F2 '.
  • FIG. 13 shows a side view of a vehicle provided with an internal combustion engine, on which two stacks of plate-like cartridges K are arranged for their loading process.
  • the two stacks correspond to the stacks shown in FIG. 14 shows a sectional view of a further variant of a plate-like cartridge K.
  • the cutting plane is orthogonal to a longitudinal axis of the plate-like cartridge K.
  • the cartridge K contains a flat first wall area WB1 (shown as cross-hatching), which is formed as a semipermeable wall area with a large number of holes, in particular with round holes or longitudinal holes or cross holes or star holes.
  • the first wall area WB1 can be formed from metal or from ceramic, for example from metal ceramic or from oxide ceramic, or from a combination of metal and ceramic in the manner of a ceramic filter.
  • the cartridge contains a flat second wall area WB2, which is formed from a highly thermally conductive material, preferably from metal, e.g. copper, aluminum, steel, etc., or graphite.
  • the cartridge K contains a reaction chamber R between the flat first wall area WB1 and the flat second wall area WB2.
  • This reaction chamber R is filled with hydrate and / or with anhydrate, depending on the state of charge of the cartridge K.
  • the left oval area shows schematically the heating operation of this cartridge K, namely “water in, heat out”.
  • the right oval-shaped area shows schematically the loading operation of this cartridge K, namely “heat in, water out”.
  • Fig. 15 a sectional view of a cylindrical cartridge K is shown.
  • the cutting plane is orthogonal to a longitudinal axis of the cylindrical cartridge K.
  • the cartridge K contains a first wall area WB1 in the form of an inner cylinder jacket (shown as cross hatching), which is formed as a semipermeable wall area with a large number of holes, in particular with round holes or longitudinal holes or cross holes or star holes.
  • the first wall area WB1 can be made of metal or Ceramic, for example from metal ceramic or oxide ceramic, or from a combination of metal and ceramic in the manner of a ceramic filter.
  • the cartridge contains a second wall area WB2 in the form of an outer cylinder jacket, which is formed from a highly thermally conductive material, preferably from metal, e.g. copper, aluminum, steel, etc., or graphite.
  • a highly thermally conductive material preferably from metal, e.g. copper, aluminum, steel, etc., or graphite.
  • the cartridge K contains a reaction chamber R between the first wall area WB1 and the second wall area WB2.
  • This reaction chamber R is filled with hydrate and / or with anhydrate, depending on the state of charge of the cartridge K.
  • the upper oval-shaped area shows schematically the heating operation of this cartridge K, namely “water in, heat out”.
  • the lower oval-shaped area shows schematically the loading operation of this cartridge K, namely “heat in, water out”.
  • FIG. 16 shows a sectional view of a further variant of a plate-like cartridge K.
  • the cutting plane is orthogonal to a longitudinal axis BA of the plate-like cartridge K.
  • the cartridge K contains a flat first wall area WB1 made of metal (shown as cross-hatching), which is formed as a semipermeable wall area with a large number of holes, in particular with round holes or longitudinal holes or cross holes or star holes.
  • the first wall area WB1 can be formed from metal-ceramic in the manner of a ceramic filter.
  • the cartridge K contains a flat second wall area WB2 made of metal (shown as cross-hatching), which is formed as a semipermeable wall area with a large number of holes, in particular with round holes or longitudinal holes or cross holes or star holes.
  • the second Wall area WB2 can be formed from metal-ceramic in the manner of a ceramic filter.
  • the metal used is e.g. copper, aluminum, steel, etc.
  • the cartridge K contains a reaction chamber R between the flat first wall area WB1 and the flat second wall area WB2.
  • This reaction chamber R is filled with hydrate and / or with anhydrate, depending on the state of charge of the cartridge K.
  • the left oval area shows schematically the heating operation of this cartridge K, namely “water in, heat out”.
  • the right oval-shaped area shows schematically the loading operation of this cartridge K, namely “heat in, water out”.
  • both water or water vapor and heat can be transported well into and out of the cartridge K on each of them.
  • FIG. 17 shows a sectional view of a further variant of a plate-like cartridge.
  • the cutting plane is orthogonal to a longitudinal axis BA of the plate-like cartridge K.
  • the cartridge K of FIG. 17 differs from the cartridge K of FIG. 16 only in the shape of its cross-section or profile cross-section transverse to the longitudinal axis BA. Instead of the rectangular profile of FIG. 16, the cartridge of FIG. 17 has a sine wave profile. It could also have a triangular wave profile (not shown).
  • the left oval area shows schematically the heating operation of this cartridge K, namely “water in, heat out”.
  • the right oval-shaped area shows schematically the loading operation of this cartridge K, namely “heat in, water out”.
  • both water or water vapor and heat can be transported well into and out of the cartridge K on each of them.
  • Fig. 18 a sectional view of a rod-shaped cartridge K is shown.
  • the cutting plane is orthogonal to a longitudinal axis BA of the plate-like cartridge K.
  • the cartridge K of FIG. 18 differs from the cartridge K of FIG. 16 only in the shape of its cross-section or profile cross-section transverse to the longitudinal axis BA. Instead of the rectangular profile of FIG. 16, the cartridge of FIG. 18 has a square profile. It could also have a triangular profile (not shown).
  • the upper oval-shaped area shows schematically the heating operation of this cartridge K, namely “water in, heat out”.
  • the lower oval-shaped area shows schematically the loading operation of this cartridge K, namely “heat in, water out”.
  • FIG. 19 shows a sectional view of a further variant of a rod-shaped cartridge.
  • the cutting plane is orthogonal to a longitudinal axis BA of the plate-like cartridge K.
  • the cartridge K of FIG. 19 differs from the cartridge K of FIG. 18 only in the shape of its cross-section or profile cross-section transverse to the longitudinal axis BA. Instead of the square profile of FIG. 18, the cartridge of FIG. 19 has a circular profile. You could also have a circular ring profile (not shown). The upper oval-shaped area shows schematically the heating operation of this cartridge K, namely “water in, heat out”.
  • the lower oval-shaped area shows schematically the loading operation of this cartridge K, namely “heat in, water out”.
  • FIG. 20 shows a sectional view of a further embodiment of a semipermeable wall area of a cartridge K along a sectional plane perpendicular to the plane of the wall area WB or perpendicular to the tangential plane of the wall area.
  • This design differs from the semipermeable metal-ceramic design mentioned above.
  • Several through-bores DB can be seen, each extending from the outer wall surface WBa of the semipermeable wall area WB to the inner wall surface WBi of the semipermeable wall area WB.
  • the cross-section of the through-holes DB has in each case in the area of the inner
  • the wall area WB consists of metal, both water or water vapor as well as heat can be transported well on it. Due to the constriction V, the exit of anhydrate particles or hydrate particles from the reaction space is made more difficult, while during heating operation water and steam can easily get into the reaction space R at the constrictions V and water and water vapor easily at the constrictions V during charging can get out of the reaction space R.
  • FIG. 21 schematically shows a sectional view of a further embodiment of a semipermeable wall region of a cartridge K along a sectional plane perpendicular to the plane of the wall region WB or perpendicular to the tangential plane of the wall region.
  • This design also differs from the semipermeable metal-ceramic design mentioned above.
  • metal chips MS which are connected to one another with an inorganic adhesive (not shown) and form a three-dimensional metal chip matrix.
  • a sectional view of a first embodiment of a cartridge filling is shown schematically.
  • b) evenly or at least almost evenly distributed particles MP, GP made of a material with a high specific thermal conductivity can be seen as the second phase (shown as hatched spots) in the first phase.
  • the particles can, for example, be metal particles MP or graphite particles GP.
  • FIG. 23 A sectional view of a second embodiment of a cartridge filling is shown schematically in FIG. 23.
  • a first phase formed by salt hydrate SH which can be more or less continuous or more or less porous (shown by cross-hatching).
  • c) a lattice structure MG extending within the first phase and made of a material with a high specific thermal conductivity can be seen as the second phase (shown as hatched dark bands).
  • FIG. 24 A sectional view of a third embodiment of a cartridge filling is shown schematically in FIG. 24.
  • GP made of a material with high specific thermal conductivity can be seen as the second phase (shown as hatched spots) and on the other hand c) a lattice structure MG extending within the first phase a material with high specific thermal conductivity as the third phase (shown as hatched dark bands).
  • Fig. 25 a sectional view of a fourth embodiment of a cartridge filling is shown schematically.
  • metal chips MS shown as dark hatched spots
  • MSM three-dimensional metal chip matrix
  • hydrate ie the hydrated form of a salt hydrate SH (shown by cross-hatching), at least partially filled interspaces ZR of the metal chip matrix MSM.
  • FIG. 26 a sectional view of a container in the form of a cartridge K or a cartridge K * is shown schematically.
  • the sectional plane is parallel to a longitudinal axis BA of the cartridge K or K *. It can be seen along its container axis BA spaced impermeable partitions TW which are impermeable to the anhydrate, the hydrate, water and water vapor and which the volume of the container K or K *, ie subdivide the reaction space R into sub-chambers TK or sub-volumes TV arranged along the container axis BA.
  • the cartridge K or K * contains a flat first wall area WB1 made of metal (shown as cross-hatching), which is formed as a semipermeable wall area with a large number of holes.
  • the first wall area WB1 can be formed from metal-ceramic in the manner of a ceramic filter.
  • the cartridge K or K * contains a flat second wall area WB2 made of metal (shown as cross-hatching), which is formed as a semipermeable wall area with a large number of holes.
  • the second wall area WB2 can be formed from metal-ceramic in the manner of a ceramic filter.
  • the metal used is e.g. copper, aluminum, steel, etc.
  • the double arrow DP shows the two directions parallel to the container axis BA along which the cartridge K or K * can be immersed in a water bath and emerged from the water bath.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention se rapporte à un procédé et à un dispositif permettant de produire de la chaleur (W) par une réaction entre, d'une part, un matériau solide et/ou un premier liquide (1) et, d'autre part, un gaz et/ou un second liquide (2), la chaleur de réaction (W) ainsi produite étant évacuée. L'invention se rapporte également à un procédé et à un dispositif permettant de stocker de la chaleur (W) par une réaction entre, d'une part, un matériau solide et/ou un premier liquide (1) et, d'autre part, un gaz et/ou un second liquide (2), la chaleur de réaction (W) à stocker étant fournie. L'invention est particulièrement appropriée pour être utilisée avec des hydrates de sel en tant que système anhydre/hydrate, tel que, par exemple, un système CaO/Ca(OH)2, l'hydrate de sel étant enfermé dans un récipient thermoconducteur pendant l'opération, dont au moins des parties sont perméables à l'eau ou à la vapeur d'eau.
PCT/IB2020/001020 2019-12-30 2020-12-30 Procédé et dispositif permettant de produire et de stocker de la chaleur WO2021136959A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20848993.0A EP4084980A1 (fr) 2019-12-30 2020-12-30 Procédé et dispositif permettant de produire et de stocker de la chaleur

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CH42019 2019-12-30
CHPRO-004-CH 2019-12-30

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4161211A (en) * 1975-06-30 1979-07-17 International Harvester Company Methods of and apparatus for energy storage and utilization
FR2455713A1 (fr) * 1979-04-30 1980-11-28 Wallsten Hans Dispositif contenant un corps sorbeur et procede de fabrication correspondant
US4303121A (en) * 1978-04-24 1981-12-01 Institute Of Gas Technology Energy storage by salt hydration
EP0216237A2 (fr) * 1985-09-09 1987-04-01 Gerhard Dipl.-Phys. Januschkowetz Accumulateur à sorption à marche discontinue avec un absorbeur contenant un solide
WO1999053257A1 (fr) * 1998-04-15 1999-10-21 Progetto Fa.Ro. S.R.L. Systeme permettant une accumulation thermochimique de chaleur
WO2011054676A2 (fr) * 2009-11-09 2011-05-12 Deutsches Zentrum für Luft- und Raumfahrt e.V. Accumulateur de chaleur thermochimique et procédé d'absorption, de conversion, d'accumulation et de restitution de chaleur de réaction
DE102012204722A1 (de) * 2011-03-31 2012-10-04 Denso Corporation Chemischer Wärmespeicher
WO2014063814A1 (fr) * 2012-10-24 2014-05-01 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. . Procédé d'accumulation thermochimique de chaleur et utilisation pour ce procédé d'une composition contenant un sel d'une base organique et d'un acide organique
DE102015212406A1 (de) * 2015-07-02 2017-01-05 Bayerische Motoren Werke Aktiengesellschaft Vorrichtung zur Wärmespeicherung
DE112015005092T5 (de) * 2014-11-10 2017-07-20 Ngk Insulators, Ltd. Chemische Wärmepumpe
DE102016217090A1 (de) * 2016-09-08 2018-03-08 Siemens Aktiengesellschaft Verfahren und System zum Speichern und Rückgewinnen von Wärmeenergie in einer Energieerzeugungsanlage

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4161211A (en) * 1975-06-30 1979-07-17 International Harvester Company Methods of and apparatus for energy storage and utilization
US4303121A (en) * 1978-04-24 1981-12-01 Institute Of Gas Technology Energy storage by salt hydration
FR2455713A1 (fr) * 1979-04-30 1980-11-28 Wallsten Hans Dispositif contenant un corps sorbeur et procede de fabrication correspondant
EP0216237A2 (fr) * 1985-09-09 1987-04-01 Gerhard Dipl.-Phys. Januschkowetz Accumulateur à sorption à marche discontinue avec un absorbeur contenant un solide
WO1999053257A1 (fr) * 1998-04-15 1999-10-21 Progetto Fa.Ro. S.R.L. Systeme permettant une accumulation thermochimique de chaleur
WO2011054676A2 (fr) * 2009-11-09 2011-05-12 Deutsches Zentrum für Luft- und Raumfahrt e.V. Accumulateur de chaleur thermochimique et procédé d'absorption, de conversion, d'accumulation et de restitution de chaleur de réaction
DE102012204722A1 (de) * 2011-03-31 2012-10-04 Denso Corporation Chemischer Wärmespeicher
WO2014063814A1 (fr) * 2012-10-24 2014-05-01 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. . Procédé d'accumulation thermochimique de chaleur et utilisation pour ce procédé d'une composition contenant un sel d'une base organique et d'un acide organique
DE112015005092T5 (de) * 2014-11-10 2017-07-20 Ngk Insulators, Ltd. Chemische Wärmepumpe
DE102015212406A1 (de) * 2015-07-02 2017-01-05 Bayerische Motoren Werke Aktiengesellschaft Vorrichtung zur Wärmespeicherung
DE102016217090A1 (de) * 2016-09-08 2018-03-08 Siemens Aktiengesellschaft Verfahren und System zum Speichern und Rückgewinnen von Wärmeenergie in einer Energieerzeugungsanlage

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