METHOD AND DEVICE FOR GENERATING AND STORING HEAT

Description

[0001] The invention relates to a method and a device for generating heat and to a method and a device for storing heat.

[0002] Such methods and devices are known.

[0003] The use of storage tanks for sensible heat storage is worth mentioning. The use of water-filled containers as heat storage is particularly popular due to water's high heat capacity, as well as its low cost and low environmental impact. The disadvantage is that the temperature change of the water in the container is proportional to the amount of heat absorbed or released by the water. When storing larger amounts of heat, the temperature of the storage tank rises significantly compared to the ambient temperature inside or outside a building, resulting in high heat losses from the storage tank to its surroundings through conduction, radiation, and convection. Even with extensive thermal insulation measures, seasonal heat storage is virtually impossible. The only viable option is the use of vast bodies of water with the smallest possible surface-to-volume ratio.

[0004] Also worth mentioning is the use of storage devices for storing latent heat. The use of containers filled with phase change materials as heat storage devices is very interesting due to their high energy density. Particularly popular are solid / liquid systems, such as ice storage devices (frozen / thawed water), wax storage devices (solidified / melted wax), and paraffin storage devices (solidified / melted paraffin). In these systems, the gas phase is negligible during normal operation near the respective melting temperature of the system due to the typically low vapor pressure there. The melting temperatures or melting temperature ranges of such solid / liquid systems can be adjusted over a wide range by selecting the molecules (length of the carbon chains, degree of branching, presence of polar groups, etc.) or by mixing different types of molecules. For example, melting temperatures, i.e.Phase change storage systems can operate at temperatures of 0°C (ice storage), around 30 to 60°C (wax / paraffin storage), or around 60 to 90°C (molecules that are even longer than wax / paraffin, or molecules with polar groups). These phase change storage systems have a much higher energy storage density than sensible heat storage systems. Such phase change storage systems can be used advantageously in buildings, particularly in conjunction with solar thermal energy and with storage temperatures of, for example, 30°C and 80°C, to store heat for periods of several weeks. Seasonal heat storage is also only possible to a limited extent, and if so, only with a high level of effort and expense in terms of thermal insulation of the storage system.

[0005] DE 10 2016 217 090 A1 discloses a method for storing and recovering thermal energy in a system designed for this purpose with a reaction chamber. Heat storage occurs by means of an endothermic reaction in which heat is added to a starting substance, e.g., Ca(OH) 2 or Mg(OH) 2 , causing the starting substance to react to form a heat storage substance, e.g., CaO or MgO, while releasing water. Heat recovery occurs by means of an exothermic reaction in which water is added to the previously formed heat storage substance, causing the heat storage substance to react back to the starting substance, absorbing water and releasing heat.

[0006] DE 10 2015 212 406 A1 discloses a device for heat storage, in particular for motor vehicles with internal combustion engines. The reactor is a container containing a substance that can be in a first state (e.g., salt anhydrate) and a second state (e.g., salt hydrate). In its first state (salt anhydrate), a fluid (e.g., water) can be supplied to the substance, releasing heat and causing the substance to transition to its second state (salt hydrate). In its second state (salt hydrate), heat can be supplied to the substance, releasing the fluid (e.g., water) and causing the substance to return to its first state (salt anhydrate). This enables the storage of waste heat in an internal combustion engine, which can then be used to preheat the engine at a later time, thus avoiding the disadvantages of a cold start.

[0007] DE 11 2015 005 092 T5 discloses a chemical heat pump in which a hydrate, e.g., Ca(OH) 2 or Mg(OH) 2 , and its corresponding anhydrate, e.g., CaO or MgO, can be converted into one another by an endothermic or exothermic reaction and by the release or absorption of water vapor. This document discloses the features in the preamble of method patent claim 1 and device patent claim 3.

[0008] The invention is based on the object of enabling long-term, in particular and at least seasonal, storage of heat without measures for thermal insulation of the storage.

[0009] To achieve the object, the invention according to claim 1 provides a method for generating (discharging, releasing) or storing heat (W).

[0010] The invention thus provides, on the one hand, 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) (ammonia, water, alcohol, ketone), wherein the resulting reaction heat (W) is dissipated, wherein a1) on the one hand, a metered amount of the solid and / or the first liquid (1) is fed to a reaction chamber (R) and a2) on the other hand, a metered amount of the gas and / or the second liquid (2) is fed to the reaction chamber (R), wherein in the reaction chamber (R) a1) 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 released heat is removed from the reaction chamber (R), wherein the solid and / or the first liquid (1) is an anhydrate, wherein the heat is generated by reaction involving anhydrate on the one hand and water and / or water vapor on the other hand, wherein on the one hand, a metered amount of the anhydrate and on the other hand, a metered amount of water and / or water vapor is fed to the reaction chamber (R), and wherein an interior of a container (K, K*) is partially filled with the anhydrate and / or the hydrate and the container (K,K*) has a semipermeable wall region (WB1, WB2) which is impermeable to the anhydrate or hydrate contained therein and permeable to water or water vapor.

[0011] The invention thus provides, on the other hand, 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) (ammonia, water, alcohol, ketone), wherein the reaction heat (W) to be stored is supplied, wherein b1) on the one hand, a metered amount of the solid and / or the first liquid (1) is fed to a reaction chamber (R) and b2) on the other hand, a metered amount of heat (W) is fed to the reaction chamber (R), wherein in the reaction chamber (R) b1) the solid and / or the first liquid (1) and b2) the heat (W) are brought into contact with one another and the gas released and / or the second liquid (2) released is or are removed from the reaction chamber (R), wherein the solid and / or the first liquid (1) is a hydrate, wherein the heat is stored by reaction involving hydrate on the one hand and water and / or water vapor on the other hand, wherein a metered amount of the hydrate on the one hand and a metered amount of heat on the other hand are fed to the reaction chamber (R).and wherein an interior of a container (K, K*) is partially filled with the anhydrate and / or the hydrate and the container (K, K*) has a semipermeable wall region (WB1, WB2) which is impermeable to the anhydrate or hydrate contained therein and permeable to water or water vapor.

[0012] The use of such a container or cartridge is advantageous because the anhydrate or hydrate always remains in the container, eliminating the need to fill or empty the container's interior. Since the container is only partially filled with the anhydrate and / or hydrate, the anhydrate can convert into the more voluminous hydrate during heating without endangering the container.

[0013] Preferably, the semipermeable wall region (WB1, WB2, WB) is made of metal. Since the semipermeable wall regions of the container are made of metal, they can effectively transport both water or water vapor and heat.

[0014] Preferably, the interior of the container (K) is bounded by a first semipermeable metal wall region (WB1) and a second semipermeable metal wall region (WB2), between which the interior of the container (K) extends. As a result, all areas of the interior are close to a semipermeable wall region, providing short paths for the diffusion of water molecules during heating and charging operations.

[0015] Preferably, at least part of the semipermeable wall regions (WB1, WB2, WB) is formed from metal ceramic.

[0016] Preferably, at least a part of the semipermeable wall regions (WB1, WB2, WB) is formed from metal and has a plurality of through-bores (DB) which each extend from the outer wall surface (WBa) of the semipermeable wall region (WB) to the inner wall surface (WBi) of the semipermeable wall region (WB).

[0017] Preferably, the cross-section of the through-bores (DB) each has a constriction (V). Due to the constriction, the escape of anhydrate particles or hydrate particles from the reaction chamber is impeded, while during heating operation, water and water vapor can easily enter the reaction chamber R at the constrictions V, and during charging operation, water and water vapor can easily escape from the reaction chamber R at the constrictions V.

[0018] Preferably, the container (K, K*) has a constant cross-section transverse to the container axis (BA) along a container axis (BA), wherein it is advantageously provided that the container (K, K*) has impermeable partition walls (TW) arranged at a distance along its container axis (BA), which partition walls are impermeable to the anhydrate, the hydrate, water and water vapor and which divide the interior of the container (K) into partial chambers (TK) or partial volumes (TV) arranged along the container axis (BA).

[0019] Preferably, a container (K, K*) is also provided for use in the process according to the invention, wherein the interior of the container (K, K*) is partially filled with an anhydrate and / or a hydrate and the container (K) has a semipermeable wall region (WB1, WB2) which is impermeable to the anhydrate or hydrate contained therein and permeable to water or water vapor.

[0020] Preferably, the semipermeable wall region (WB1, WB2, WB) is formed from metal; and / or the interior of the container (K) is delimited by a first semipermeable wall region (WB1) made from metal and a second semipermeable wall region (WB2) made from metal, between which the interior of the container (K) extends; and / or at least a part of the semipermeable wall regions (WB1, WB2, WB) is formed from metal-ceramic.

[0021] Preferably, at least a part of the semipermeable wall regions (WB1, WB2, WB) is formed from metal and has a plurality of through-bores (DB) which each extend from the outer wall surface (WBa) of the semipermeable wall region (WB) to the inner wall surface (WBi) of the semipermeable wall region (WB), wherein it is advantageously provided that the cross section of the through-bores (DB) has a constriction (V).

[0022] Preferably, at least a portion of the semipermeable wall regions (WB1, WB2, WB) is formed from a three-dimensional metal chip matrix (MSM), in which metal chips (MS) are bonded together with an inorganic adhesive (WG) and which contains cavities between the metal chips (MS); and / or the interior of the container (K) contains a filling containing a first phase formed by salt hydrate, which is continuous and porous, and particles (MP) distributed within the first phase made of a material with high specific thermal conductivity as the second phase; and / or the interior of the container (K) contains a filling containing a first phase formed by salt hydrate, which is continuous and porous, and a lattice structure (MG) extending within the first phase made of a material with high specific thermal conductivity as the second phase;and / or the interior of the container (K) contains a filling in which metal chips (MS) are bonded together with an inorganic adhesive and form a three-dimensional metal chip matrix (MSM) and in which interstices of the metal chip matrix are at least partially filled with hydrate, ie the hydrated form of a salt hydrate;

[0023] Preferably, a container (K*) is also provided for use in the method according to the invention, 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.

[0024] The use of such a container is advantageous because the anhydrate or hydrate always remains in the pores of the container, eliminating the need to fill or empty the interior of the container. Since the pores of the container are only partially filled with the anhydrate and / or hydrate, the anhydrate can convert into the more voluminous hydrate during heating without endangering the container.

[0025] Preferably, the metallic matrix contains metal particles (MP) that are bonded together by sintering to form a metal sintered block or a metal-ceramic block, forming a three-dimensional metal-ceramic matrix (MKM); and / or the metallic matrix contains metal chips (MS) that are bonded together with an inorganic adhesive, forming a three-dimensional metal chip matrix (MSM); and / or particles (MP, GP) made of a material with high specific thermal conductivity are contained in the salt hydrate; and / or a lattice structure (MG, WR) with high specific thermal conductivity is contained in the salt hydrate; and / or the salt hydrate has a porous structure; and / or the metallic matrix contains aluminum; wherein it is advantageously provided that the inorganic adhesive contains water glass, in particular sodium silicate and / or potassium silicate; and / or aluminum particles and / or graphite particles are distributed in the salt hydrate.

[0026] Preferably, the container (K, K*) has a constant cross-section transverse to the container axis (BA) along a container axis (BA), wherein it is advantageously provided that the container (K, K*) has impermeable partition walls (TW) arranged at a distance along its container axis (BA), which partition walls are impermeable to the anhydrate, the hydrate, water and water vapor and which divide the interior of the container (K) into partial chambers (TK) or partial volumes (TV) arranged along the container axis (BA).

[0027] Preferably, the cross-section of the container (K, K*) has the shape of a rectangle, a square, a circle or an annulus, a triangle or a hexagon; or the shape of a periodic pattern, in particular a wave with a sinusoidal profile or triangular profile.

[0028] Preferably, a container arrangement is also provided which comprises a plurality of containers (K) and / or containers (K*) of the type defined above arranged side by side and parallel to one another.

[0029] Preferably, a method is also provided for producing a container (K*) for use in the method according to the invention for generating or storing heat, the method for producing the container comprising the following steps: a) forming a three-dimensional metallic matrix having microscopic interstices; and b) filling the microscopic interstices with an aqueous slurry of a salt hydrate, wherein it is advantageously provided that step a) is carried out by sintering metallic particles; and / or by bonding metallic particles by means of an inorganic adhesive, wherein it is advantageously provided that step b) is carried out by pressing the aqueous slurry into the microscopic interstices.

[0030] Preferably, a method is also provided for producing a container (K*) for use in the method according to the invention for generating or storing heat, the method for producing the container comprising 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, wherein it is advantageously provided that in step b) sintering of the metallic particles; and / or the metallic particles are bonded together using an inorganic adhesive.

[0031] The solid and / or the first liquid, on the one hand, and the gas and / or the second liquid, on the other, have a sufficiently high affinity for each other that a large amount of heat is released during the reaction. Depending on the choice of solid and / or the first liquid, the gas and / or the second liquid can be, for example, ammonia, water, an alcohol, a ketone, etc.

[0032] Preferably, the solid and / or the first liquid (1) used in the process contains an anhydrate, also referred to as a salt free of crystallization water or dehydrated hydrate, wherein the heat is generated by a reaction involving the anhydrate on the one hand and water and / or steam on the other. A metered amount of the anhydrate and a metered amount of water and / or steam are fed into the reaction chamber. The metered addition of the anhydrate and the water and / or steam allows the heat released during the process to be controlled.

[0033] The anhydrate or dehydrated hydrate can be fed into the reaction chamber in the form of a liquid, e.g. as a non-aqueous slurry or suspension.

[0034] It is advisable to add a metered amount of the anhydrate to the reaction chamber in the form of solid particles.

[0035] Preferably, a metered amount of the anhydrate is fed into the reaction chamber in powder form. The powder particles preferably have an average grain size in the range of 100 µm to 800 µm.

[0036] Alternatively or additionally, the metered amount of anhydrate can be fed into the reaction chamber in the form of pellets. The pellets preferably have an average size in the range of 3 mm to 15 mm.

[0037] The pellets preferably contain particles of the anhydrate held together by a matrix of binder, which may be water-soluble or water-insoluble. The binder content in weight percent of the pellets is preferably 1% to 10%, preferably 2% to 5%.

[0038] When using a water-soluble binder in the production of pellets from anhydrate or dehydrated hydrate, a portion of the anhydrate to be bound or pelletized inevitably undergoes hydration, also known as hydration. If this binder is used at a concentration of 1 to 10 wt.% of the anhydrate in the pellet, the water content of the binder hydrates only a negligible portion of the anhydrate in the pellet, so that its potential for subsequent hydration and heat release is only minimally reduced. The advantage here is that the heat released during pellet production by hydrating a small portion of the pellet material causes a portion of the water in the binder of the pellets that participates in the partial hydration of the pellet material to evaporate before it can react with the anhydrate.This ensures very rapid drying and solidification of the binder in the pellets.

[0039] A binder that is soluble in water and another solvent can also be used to produce the pellets. Preferably, the other solvent is a substance that does not react with the anhydrate. For example, low-molecular-weight volatile organic substances can be used. This has the advantage that the other solvent, i.e., not water, can be used during pellet production, preventing the pellet material from being hydrated at all, thus preserving its potential for subsequent hydration and heat release.

[0040] Even when using a water-insoluble binder, the pellet material is not hydrated during pellet production, thus preserving its potential for subsequent hydration and heat release. To prevent encapsulation of the pellets with a water-insoluble binder, i.e., sealing off the pellet material from water, a binder content of 1% to 2% by weight of the pellets is preferred.

[0041] Regardless of the type of binder, a pellet press is preferably used to produce the pellets from anhydrate.

[0042] When producing pellets with a binder that is soluble in water and another solvent, and which is dissolved in the other solvent, a spraying or dropletizing process 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 achieved by gravity, inertial force (e.g., centrifugal force), or hydraulic pressure. Depending on the viscosity of the suspension or slurry, the jet emerging from the nozzle can be separated into pellets in the atmosphere of a pellet collecting chamber downstream of the nozzle.

[0043] Preferably, a pulsating pressure gradient is created in the fluid flow of the suspension or slurry to promote the separation of the fluid into pellets. The use of a drip tower with a nozzle plate in the upper part of the drip tower is particularly preferred. The suspension or slurry is fed into a first chamber above the nozzle plate, and the nozzle plate is vibrated, with the vibration of the nozzle plate preferably occurring parallel to the direction of gravity, i.e. alternating 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 in the binder evaporates, so that solidified pellets arrive at the bottom of the second chamber.

[0044] Conveniently, a metered amount of water is introduced into the reaction chamber in the form of droplets or as an aerosol. This can be done via an air stream. The average diameter of a droplet is preferably in the range of 100 µm to 2 mm.

[0045] Alternatively or additionally, the metered amount of water can be supplied to the reaction chamber in the form of a water jet, the cross-sectional area of which is preferably in the range of 0.2mm 2< to 500mm 2< and the speed of which is preferably in the range of 0.5m / s to 10m / s.

[0046] According to a preferred variant (wet process), the metered amount of water is superstoichiometric with respect to the metered amount of anhydrate, with the excess water relative to the stoichiometric molar amount of water preferably being in the range of 2% to 15%, and particularly preferably in the range of 5% to 10%. Depending on the extent of the excess water, the reaction product in which the heat is generated is more or less moist, even pasty. The viscosity of the water with the solid particles dispersed therein (paste) is greater than the viscosity of the water itself.

[0047] According to another preferred variant (dry process), the metered amount of water is substoichiometric with respect to the metered amount of anhydrate, with the water deficiency relative to the stoichiometric molar amount of water preferably being in the range of 2% to 15%, and particularly preferably in the range of 5% to 10%. Depending on the extent of the water deficiency, the reaction product in which the heat is generated is more or less dry and more or less free-flowing. The free-flowing nature of the dry reaction product is usually very good. The excess of anhydrate in the dry reaction product acts as a desiccant and prevents unwanted moistening.

[0048] The process can be carried out continuously.

[0049] Preferably, a1) the metered amount of the solid and / or the first liquid (1) is continuously fed to the reaction space (R) and a2) the metered amount of the gas and / or the second liquid (2) is continuously fed to the reaction space (R).

[0050] Alternatively, the process can be carried out at least partially discontinuously.

[0051] In a first variant, a1) in a first step, a metered cumulative amount of the solid and / or the first liquid (1) is fed to the reaction space (R) over a period of time and a2) thereafter, in a second step, a metered amount of the gas and / or the second liquid (2) is continuously fed to the reaction space (R).

[0052] In a second variant, a2) in a first step, a metered cumulative amount of the gas and / or the second liquid (2) is fed to the reaction space (R) and a1) then in a second step, a metered amount of the solid and / or the first liquid (1) is fed to the reaction space (R), wherein the feeding in a1) preferably takes place continuously.

[0053] In a particularly preferred embodiment, the reaction chamber is a container, in particular a cartridge, cartridge, plate, etc. This cartridge can be used as a heating cartridge HK in a heating mode for dissipating heat. The cartridge is preferably a heat-conducting cartridge, in which a salt hydrate is preferably enclosed as an anhydrate (in a dehydrated state). The cartridge is preferably permeable to water or water vapor, at least in a partial region.

[0054] A device for carrying out the method described above can be provided, the device comprising a reaction chamber forming the reaction space (R) with a means (WT) for dissipating reaction heat and a first feed means (SF; ZF) for metered feeding of a solid and / or a first liquid (1) into the reaction chamber (R) and a second feed means (DP, ZD) for metered feeding of a gas and / or a second liquid (2) into the reaction chamber (R).

[0055] Advantageously, the means for removing reaction heat contains a water / reaction medium heat exchanger (WT) or an air / reaction medium heat exchanger.

[0056] Preferably, the first feed means comprises a screw conveyor (SF).

[0057] It is particularly advantageous if the screw conveyor is a twin-screw conveyor with two meshing screw shafts that clean each other during operation and preferably have an Erdmenger profile.

[0058] A multi-screw conveyor with several intermeshing screw shafts can also be used as a screw conveyor, with two adjacent screw shafts cleaning each other during operation, whereby the screw shafts preferably have an Erdmenger profile.

[0059] Alternatively or additionally, the first feed means may comprise a toothed belt conveyor (ZF).

[0060] Preferably, the toothed belt conveyor is formed from a polymer material and particularly preferably from a fiber-reinforced polymer material.

[0061] Preferably, the toothed belt conveyor has recesses spaced apart from one another along its longitudinal extent or along its length, which extend over the entire transverse extent or over the entire width of the toothed belt conveyor.

[0062] Preferably, the recesses have a constant profile along the transverse dimension or across the entire width of the timing belt conveyor. It is particularly advantageous if the profile is a V-profile or a U-profile.

[0063] Preferably, the second supply means contains a metering pump (DP) and / or a nozzle, in particular an atomizing nozzle (ZD).

[0064] Preferably, the atomizing nozzle has a nozzle block with several nozzle openings arranged next to one another.

[0065] Alternatively or additionally, the second supply means may contain a supply channel (pump / gravity) (ZK).

[0066] It is particularly advantageous if, in the device, the reaction space (R) comprises a container with a filling opening for supplying the solid and / or the first liquid (1) into the container, a closure for closing the filling opening and a semi-permeable wall region which is impermeable to the solid and / or the first liquid (1) and permeable to the gas and / or the second liquid (2).

[0067] Alternatively, in the device, the reaction space (R) may comprise a container with a filling opening for supplying the gas and / or the second liquid (2) into the container and for supplying the solid and / or the first liquid (1) into the container.

[0068] Preferably, the semipermeable wall region includes a wall having a plurality of holes.

[0069] The holes in the wall can be round holes or longitudinal holes or cross holes or star holes.

[0070] Preferably, the smallest dimension of the holes, ie the diameter of the round holes or the width of the longitudinal holes, is in the range of 50µm to 1000µm, preferably in the range of 50µm to 500µm and most preferably in the range of 50µm to 200µm.

[0071] Preferably, in the device, the reaction space (R) has a container with a filling opening for supplying the gas and / or the second liquid (2) into the container and for supplying the solid and / or the first liquid (1) into the container.

[0072] In a particularly preferred embodiment, the container is a heating cartridge HK, which can be brought into thermal contact with a central heating unit or several decentralized heating devices. In particular, the heating cartridge can be inserted into and removed from a recess of a central heating unit or a decentralized heating device that is complementary to the cartridge, with a positive fit and thermal contact. The positive fit and thermal contact are preferably established by means of a screw connection or a bayonet connection.

[0073] Preferably, the heating cartridge contains a first wall region, which is the aforementioned semipermeable wall region with the plurality of holes, in particular with the round holes, longitudinal holes, cross holes, or star holes. This semipermeable first wall region can be formed from metal or ceramic, e.g., metal-ceramic or oxide ceramic, or from a combination of metal and ceramic in the manner of a ceramic filter.

[0074] Preferably, the heating cartridge contains a second wall region which is formed from a highly thermally conductive material, preferably from metal, e.g. copper, aluminum, steel, etc., or graphite.

[0075] The heating cartridge preferably contains a reaction chamber between the first wall region and the second wall region. This reaction chamber is filled with the anhydrate. The reaction chamber is preferably filled with anhydrate in solid form. The reaction chamber is preferably only partially filled with the anhydrate. On the one hand, the first wall region prevents the solid particles of the anhydrate from escaping from the reaction chamber. On the other hand, the first wall region allows water to enter the reaction chamber as a liquid or as a gas / vapor.

[0076] During heating operation, water, either liquid or vapor, is metered into the reaction chamber of the heating cartridge through the first wall region, which reacts exothermically with the anhydrate. The released hydration heat is dissipated from the cartridge through the second wall region.

[0077] According to a first preferred embodiment of the heating cartridge, the first wall region and the second wall region of the heating cartridge each have flat regions arranged parallel to one another and spaced apart, with the space between the spaced-apart flat regions containing anhydrate. We refer to this embodiment of the heating cartridge as an "anhydrate plate cartridge."

[0078] According to a second preferred embodiment of the heating cartridge, the first wall region and the second wall region of the heating cartridge each have cylindrical shell-shaped regions arranged concentrically spaced from one another, with the space between the spaced-apart concentric regions containing anhydrate. We refer to this embodiment of the heating cartridge as the "anhydrate hollow cylinder cartridge."

[0079] Preferably, several heating cartridges are arranged in parallel fluidically connected manner, wherein the second wall region is contacted by a heat transfer fluid of a heating system.

[0080] According to a preferred use of the heating cartridges for heating, one or more of them are immersed in a water tank. This allows liquid water to penetrate the reaction chamber of the heating cartridge in a controlled manner via the first, semi-permeable wall area. The hydration heat released in a controlled manner in the reaction chamber is conducted into the water in the water tank via the second, highly heat-conducting wall area, causing its temperature to rise in a controlled manner.

[0081] To dose the heat output of the heat introduced into the water tank by a heating cartridge with a specified cartridge geometry, the following parameters can be used individually or in combination: Immersion depth of the cartridge(s) partially immersed in the water in the water tank. Lowering speed of the cartridge(s) partially immersed in the water in the water tank. Pressure inside the water tank or water pressure.

[0082] The solid and / or the first liquid, on the one hand, and the gas and / or the second liquid, on the other, have a sufficiently high affinity for each other that a large amount of heat is added during the reaction. Depending on the choice of solid and / or the first liquid, the gas and / or the second liquid can be, for example, ammonia, water, an alcohol, a ketone, etc.

[0083] Preferably, 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 anhydride, wherein the heat is stored by a reaction involving the hydrate on the one hand and water and / or steam on the other. A metered amount of hydrate and a metered amount of heat are supplied to the reaction chamber. The metered supply of hydrate and heat allows the heat output supplied during the process to be controlled.

[0084] It is advisable to add a metered amount of the hydrate to the reaction chamber in the form of solid particles.

[0085] Preferably, a metered amount of the hydrate is fed into the reaction chamber in the form of a powder.

[0086] Alternatively or additionally, the dosed amount of hydrate can be fed into the reaction chamber in the form of pellets.

[0087] Conveniently, the metered amount of heat is supplied to the reaction chamber in the form of hot air.

[0088] Preferably, the metered amount of heat is supplied to the reaction chamber by means of a fluidized bed.

[0089] According to a preferred variant (dry process), the amount of heat added is superstoichiometric with respect to the amount of hydrate added. Depending on the extent of the excess heat, the reaction product, in which the heat is stored, is more or less dry and more or less free-flowing. The free-flowing properties of the dry reaction product are usually very good. The excess heat in the dry reaction product removes unbound residual water and briefly increases the temperature of the reaction product until it cools down.

[0090] According to another preferred variant (wet process), the amount of heat added is substoichiometric with respect to the amount of hydrate added. Depending on the extent of the heat deficiency, the reaction product, in which the heat is stored, is more or less moist, even pasty.

[0091] The process can be carried out continuously.

[0092] Preferably, b1) the metered amount of the solid and / or the first liquid (1) is continuously supplied to the reaction space (R) and b2) the metered amount of heat (W) is continuously supplied to the reaction space (R).

[0093] Alternatively, the process can be carried out at least partially discontinuously.

[0094] In a first variant, b1) in a first step, a metered cumulative amount of the solid and / or the first liquid (1) is supplied to the reaction space (R) over a period of time and b2) thereafter, in a second step, a metered amount of heat (W) is continuously supplied to the reaction space (R).

[0095] In a second variant, b2) in a first step, a metered cumulative amount of heat (W) is supplied to the reaction space (R) b1) then, in a second step, a metered amount of the solid and / or the first liquid (1) is supplied to the reaction space (R), wherein the supply in b1) preferably takes place continuously.

[0096] In a particularly preferred embodiment, the reaction chamber 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 heat-conducting cartridge, in which a salt hydrate is preferably enclosed as a hydrate (in a hydrated state). The cartridge is preferably permeable to water or water vapor, at least in a partial region.

[0097] A device can be provided for carrying out the method described above, the device comprising a reaction chamber forming the reaction space with a means (WT; WB) for supplying reaction heat and a first means (SF; ZF) for metered feeding of a solid or a first liquid into the reaction chamber (R) and a second means (V; P) for metered removal of a gas or a second liquid (2) from the reaction chamber (R).

[0098] Advantageously, the means for supplying reaction heat contains a heat exchanger (WT).

[0099] Preferably, the means for supplying reaction heat contains a fluidized bed (WB).

[0100] Preferably, the first means comprises a screw conveyor (SF).

[0101] Alternatively or additionally, the first means contains a toothed belt conveyor (ZF).

[0102] Preferably, the means for supplying reaction heat comprises a fan (V).

[0103] Alternatively or additionally, the means for supplying reaction heat contains a pump (P).

[0104] It is particularly advantageous if, in the device, the reaction space (R) comprises a container with a filling opening for supplying the solid and / or the first liquid (1) into the container, a closure for closing the filling opening and a semi-permeable wall region which is impermeable to the solid and / or the first liquid (1) and permeable to the gas and / or the second liquid (2).

[0105] Alternatively, in the device, the reaction space (R) can comprise a container with a filling opening and / or a heat introduction region 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 semi-permeable wall region which is impermeable to the solid and / or the first liquid (1) and permeable to the gas and / or the second liquid (2).

[0106] In a particularly preferred embodiment, the container is a charging cartridge LK, which can be brought into thermal contact with a heat source. In particular, the charging cartridge can be inserted into and removed from a recess of a heat source that is complementary to the cartridge, with a positive fit and thermal contact. The positive fit and thermal contact are preferably established by means of a screw connection or a bayonet connection.

[0107] Preferably, the charging cartridge contains a first wall region, which is the aforementioned semipermeable wall region with the plurality of holes, in particular with the round holes, longitudinal holes, cross holes, or star holes. This semipermeable first wall region can be formed from metal or ceramic, e.g., metal-ceramic or oxide ceramic, or from a combination of metal and ceramic in the manner of a ceramic filter.

[0108] Preferably, the charging cartridge contains a second wall region which is formed from a highly heat-conducting material, preferably from metal, e.g. copper, aluminum, steel, etc., or graphite.

[0109] The charging cartridge preferably contains a reaction chamber between the first wall region and the second wall region. This reaction chamber is filled with the hydrate. The reaction chamber is preferably filled with hydrate in solid form. The reaction chamber is preferably only partially filled with the hydrate, in particular with a filling level in vol.% of 90% to 100%, in particular of 95% to 100%. On the one hand, the first wall region prevents the solid particles of the hydrate from escaping from the reaction chamber. On the other hand, the first wall region allows water to escape from the reaction chamber as a liquid or as a gas / vapor.

[0110] During charging, heat is metered into the reaction chamber of the charging cartridge through the second wall region and, to a lesser extent, through the first wall region, causing an endothermic reaction with the hydrate. The released water of hydration or water of crystallization is discharged from the cartridge through the first wall region, depending on the reaction conditions, in the form of liquid water and / or water vapor.

[0111] According to a first preferred embodiment of the charging cartridge, the first wall region and the second wall region of the charging cartridge each have flat regions arranged parallel to one another and spaced apart, with the space between the spaced-apart flat regions containing hydrate. We refer to this embodiment of the charging cartridge as a "hydrate plate cartridge."

[0112] According to a second preferred embodiment of the charging cartridge, the first wall region and the second wall region of the charging cartridge each have cylindrical shell-shaped regions arranged concentrically spaced from one another, with the space between the spaced-apart concentric regions containing hydrate. We refer to this embodiment of the charging cartridge as a "hollow hydrate cylinder cartridge."

[0113] Preferably, several charging cartridges are arranged in parallel fluidically connected manner, wherein the second wall region is thermally contacted directly by a heat source or indirectly by the heat source via a heat transfer fluid.

[0114] According to a first preferred use of the charging cartridges for charging with thermal energy, one or more of them are positioned in a solar thermal system. Preferably, the positioning takes place in a solar thermal system in which solar radiation captured over a large area is concentrated into a small area to generate heat in this area at temperatures sufficiently high to cause rapid and complete dehydration of the hydrate to anhydrate. This allows gaseous water or water vapor to escape from the reaction chamber of the charging cartridge in a metered manner via the first, semi-permeable wall region.The dehydration heat absorbed in the reaction chamber, either dosed or not, is conducted via the second, highly heat-conducting wall area into the reaction chamber of the loading cartridge, whereby its temperature is raised, either dosed or not, to a sufficiently high value to achieve complete dehydration of the hydrate.

[0115] Preferably, the charging cartridges are 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., a pipe, running in the focal line of the parabolic troughs, where they are heated to temperatures of several hundred degrees Celsius, particularly above 300 degrees Celsius.

[0116] According to a particularly preferred method for charging the charging cartridge with thermal energy, the captured concentrated solar energy is used in the parabolic trough solar power plant, as needed, to generate hot steam, such as water vapor, to drive a steam engine, such as a steam turbine, to drive an electric generator to generate electrical energy, and / or the captured concentrated solar energy is used to charge the charging cartridge. This allows the excess captured solar energy to be stored in the form of an anhydrate in an anhydrate heating cartridge during periods of peak performance of a parabolic trough solar power plant, such as during strong solar radiation in summer.

[0117] According to a second preferred use of the charging cartridges for charging with thermal energy, one or more of them are positioned in or at a power plant that generates a significant amount of waste heat during its operation. Preferably, the positioning in the power plant is in an area where waste heat is conventionally dissipated, in order to generate heat in this area at temperatures sufficiently high to cause rapid and complete dehydration of the hydrate to anhydrate. This allows gaseous water or water vapor to escape from the reaction chamber of the charging cartridge in a metered manner via the first, semipermeable wall region.The dehydration heat absorbed in the reaction chamber, either dosed or not, is conducted via the second, highly heat-conducting wall area into the reaction chamber of the loading cartridge, whereby its temperature is raised, either dosed or not, to a sufficiently high value to achieve complete dehydration of the hydrate.

[0118] Power plants in this sense are understood to be large thermal power plants, such as nuclear power plants and combustion power plants, in which fossil chemical energy sources or renewably produced chemical energy sources are burned in order to generate electrical energy directly or indirectly, although a greater or lesser proportion of waste heat is always generated.

[0119] Power plants in this sense also include stationary and mobile plants for combined heat and power or cogeneration, such as internal combustion engines (gasoline engines or diesel engines), jet engines or fuel cells, in which fossil chemical energy sources or renewably produced chemical energy sources are burned in order to generate electrical energy or mechanical energy directly or indirectly, although a greater or lesser proportion of waste heat is always generated.

[0120] It should be noted at this point that the methods and devices described here are particularly well suited for use with hydrate / anhydrate systems. A particularly preferred system is CaO / Ca(OH) 2 . It is particularly noteworthy that the preferred CaO / Ca(OH) 2 system can be operated solely using sustainably available energy sources.

[0121] This applies, first of all, to the one-time production of CaO from CaCO3, in which gaseous CO2 is expelled from CaCO3 at temperatures above 900°C, producing solid CaO (burnt lime). This can be done in a conventional calcination kiln (lime kiln) using sustainably produced chemical energy sources. However, it can also be achieved using a solar power plant, in which solar energy is highly concentrated into a small area using a large number of mirrors, where temperatures above 1000°C can be reached.

[0122] To convert chemical energy stored in the anhydrate CaO into heat, the CaO is reacted with water using the methods and apparatus described above to form the hydrate Ca(OH) 2.

[0123] To store heat again, heat is applied to the Ca(OH)2 hydrate at temperatures above 400°C, which expels gaseous water. The repeated production of CaO anhydrate from Ca(OH)2 hydrate can also be achieved using a solar power plant, in which the solar energy is highly concentrated in a small area where temperatures above 400°C can be reached. A parabolic trough solar power plant is particularly suitable for this purpose.

[0124] And when the anhydrate CaO is no longer needed, it can be easily disposed of by exposing it to the Earth's atmosphere, which contains H 2 O and CO 2, with which the CaO gradually reacts again to form CaCO 3, thus closing the carbonate cycle.

[0125] Another preferred system is K 2 CO 3 / K 2 CO 3 -H 2 O.

[0126] It should also be noted that the anhydrate-containing heating cartridge and the hydrate-containing charging cartridge can be designed differently. In this case, the anhydrate-containing heating cartridge is optimized for the process and device for generating (discharging, releasing) heat, and the hydrate-containing charging cartridge is optimized for the process and device for storing heat.

[0127] It is particularly advantageous if the anhydrate-containing heating cartridge and the hydrate-containing charging cartridge have the same shape. This eliminates the need to remove the hydrate from the used cartridge after a completed heating process and refill the cartridge with anhydrate before the next heating process.

[0128] Preferably, at least a portion of the semipermeable wall regions (WB1, WB2, WB) is formed from a three-dimensional metal chip matrix (MSM), in which metal chips (MS) are bonded together with an inorganic adhesive (WG) and which has cavities between the metal chips (MS). This structure functions similarly to the above-mentioned sintered structures of a metal ceramic. The three-dimensional metal chip matrix has a sieving function. It prevents powdered or granular salt hydrate from passing through, while water or water vapor can pass through the thus-formed semipermeable wall region in one direction or the other according to a pressure gradient or concentration gradient during charging or discharging.At the same time, the metal chip matrix ensures good thermal conductivity, so that heat can pass through the semi-permeable wall area thus formed during charging or discharging in one direction or the other according to a temperature gradient.

[0129] Preferably, at least 90% of the metal chips in the metal chip matrix are bonded to at least two other metal chips, forming a three-dimensional structure with high resulting thermal conductivity. The metal chips preferably have an average length in the range of 1 mm to 10 mm.

[0130] Aluminum shavings are preferably used as metal shavings. Water glass, i.e., sodium silicate and / or potassium silicate, is preferably used as the inorganic adhesive. In a first step, a flowable, moist mixture of aluminum shavings and water glass is formed into the desired geometric shape (e.g., plate shape, corrugated plate shape) and compressed. In a second step, the resulting geometric shape is dried at temperatures in the range of 200°C to 700°C. The water glass used as the adhesive can contain aluminum powder and / or graphite particles. The graphite particles preferably contain expanded graphite or expandable graphite.

[0131] Preferably, the interior of the container (K) has a filling containing a continuous and porous first phase formed by salt hydrate, and particles (MP) of a material with high specific thermal conductivity distributed within the first phase as a second phase. The second phase formed by the distributed particles ensures good thermal conductivity, so that heat can flow easily in one direction or the other within the thus formed filling of the container (K) according to a temperature gradient during charging or discharging.

[0132] Preferably, aluminum chips, aluminum powder, graphite powder or expanded graphite, i.e. expandable graphite, are used as distributed particles.

[0133] Preferably, the interior of the container (K) has a filling comprising a continuous and porous first phase formed by salt hydrate, 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 easily in one direction or the other within the thus formed filling of the container (K) according to a temperature gradient during charging or discharging.

[0134] Preferably, aluminum, copper, iron, or steel is used for the grid structure. The elongated elements or rod-like elements of the grid structure preferably have a diameter in the range of 0.5 mm to 3 mm. The spacing between adjacent grid elements in the grid structure is preferably between 5 mm and 50 mm.

[0135] The interior of the container (K) preferably has a filling in which metal chips (MS) are bonded together with an inorganic adhesive to form a three-dimensional metal chip matrix (MSM), and in which interstices of the metal chip matrix are at least partially filled with hydrate, i.e. the hydrated form of a salt hydrate. Since the salt hydrate takes up a larger volume in its hydrated state (hydrate state) than in its dehydrated state (anhydrate state), this ensures that the metal chip matrix is not burst during discharging, i.e. during the transition from the more compact anhydrate to the more voluminous hydrate. This allows the container (K) to achieve many charge / discharge cycles without impairing the microscopic structure of its salt hydrate-metal chip matrix and thus its functionality.

[0136] Preferably, at least 90% of the metal chips in the metal chip matrix are bonded to at least two other metal chips, forming a three-dimensional structure with high resulting thermal conductivity. The metal chips preferably have an average length in the range of 1 mm to 10 mm.

[0137] Preferably, aluminum chips are used as metal chips. Preferably, water glass, i.e. sodium silicate and / or potassium silicate, is used as the inorganic adhesive. In a first step (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., cuboid block, cylinder block, prism block, etc.). In a second step (S2), the structure thus obtained is dried at temperatures in the range from 200°C to 700°C. The water glass used as the adhesive can contain aluminum powder and / or graphite particles. The graphite particles preferably contain expanded graphite or expandable graphite.

[0138] In order to at least partially fill the interstices of the metal chip matrix with hydrate, i.e., the hydrated form of a salt hydrate, the porous structure obtained in the first and second steps is soaked or impregnated in a third step (S3) with an aqueous slurry of salt hydrate, e.g., Ca(OH) 2 slurry, which contains dissolved salt hydrate and undissolved suspended salt hydrate particles. This third step preferably takes place using at least one of the following two variants: 3-1) The porous structure is immersed in the slurry in a tank or vessel; 3-2) The porous structure is sprayed with the slurry; Measures 1) and / or 2) result in wetting of the metal chip matrix and thus at least partial filling of its interstices with salt hydrate.

[0139] In an optional fourth step (S4), the soaked or impregnated porous structure can be placed in a fluid-filled pressure vessel, after which the fluid in the pressure vessel is isotropically pressurized to force the salt hydrate slurry into the interstices of the metal chip matrix of the porous structure. This fourth step is preferably carried out using at least one of the following four variants: 4-1) The pressurized fluid is the salt hydrate slurry in which the porous structure is immersed, with the tank or vessel preferably being the pressure vessel. 4-2) The pressurized fluid is a gas, in particular air.

[0140] Since the pressure in the fluid is isotropic everywhere and in particular also acts on the porous structure from the outside, there is no risk of bursting or breaking of the impregnated porous structure during the pressing of the salt hydrate slurry into the cavities or pores of the porous structure. 4-3) The porous structure is brought into contact with the salt hydrate slurry, at least in partial areas of its outer surface, and the porous structure is set in rotation together with the salt hydrate slurry. Centrifugal forces (inertial forces) force the salt hydrate slurry into the interstices of the metal chip matrix of the porous structure. Preferably, the porous structure is centrifuged in a centrifuge filled with the salt hydrate slurry, with the centrifugal force field forcing the salt hydrate slurry into the porous structure. 4-4) 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 pressurized. Due to the pressure gradient between the outside of the porous structure and the inside orThe salt hydrate slurry is forced through the macroscopic cavity of the porous structure from the outside to the inside, thus filling its microscopic cavities, gaps, or pores almost completely with the salt hydrate in a hydrated state.

[0141] Since the pressure in the salt hydrate slurry is isotropic everywhere on the outside and the hollow body represents a vault, there is no danger of bursting or breaking of the impregnated porous structure during the pressing of the salt hydrate slurry into the microscopic cavities or pores of the porous structure.

[0142] Preferably, the container (K) has a constant cross-section along a container axis (BA) transverse to the container axis (BA). This transforms the container into a "cartridge" that can be pushed into and pulled out of a complementarily shaped cavity (e.g., for heating or charging the cartridge).

[0143] Preferably, the container (K) has impermeable partition walls arranged at a distance along its container axis (BA), which are impermeable to the anhydrate, the hydrate, water and water vapor and which divide the interior of the container (K) into sub-chambers arranged along the container axis (BA). This prevents uncontrolled diffusion of water or water vapor inside the container along the container axis, and water or water vapor can be added to the container in sections during heating operation or removed from it during loading operation. This particularly facilitates metered heating operation, i.e. metered unloading of the container, for example by gradually lowering the container into a water bath along its container axis BA.

[0144] The cross-section of the container (K) can be in the shape of a rectangle, a square, a circle or annulus, a triangle, or a hexagon. Containers with these shapes can be arranged compactly next to one another.

[0145] The cross-section of the container (K) can also have the shape of a periodic pattern, in particular a wave with a sinusoidal or triangular profile. Containers with these shapes can also be arranged compactly next to one another.

[0146] The use of such a container is advantageous because the anhydrate or hydrate always remains in the pores of the container, eliminating the need to fill or empty the interior of the container. Since the pores of the container are only partially filled with the anhydrate and / or hydrate, the anhydrate can convert into the more voluminous hydrate during heating without endangering the container.

[0147] Preferably, the metallic matrix contains metal particles (MP) which are bonded together by sintering to form a metal sintered block or a metal-ceramic block and form a three-dimensional metal-ceramic matrix (MKM).

[0148] Preferably, the metallic matrix contains metal chips (MS) which are bonded together with an inorganic adhesive and form a three-dimensional metal chip matrix (MSM).

[0149] Preferably, the salt hydrate contains particles (MP, GP) made of a material with high specific thermal conductivity.

[0150] Preferably, the salt hydrate contains a lattice structure (MG, WR) with high specific thermal conductivity.

[0151] All of the metallic structures mentioned contribute to a good thermal conductivity of the porous structure, which facilitates and quickly facilitates the penetration of heat into the container during loading and the escape of heat from the container during unloading.

[0152] Preferably, the salt hydrate has a porous structure.

[0153] The mentioned porous structure of the salt hydrate contributes to a good transport capacity of water molecules of the porous structure, which facilitates and quickly facilitates the penetration of water molecules into the container during unloading and the escape of water molecules from the container during loading.

[0154] Preferably, the metallic matrix contains aluminum.

[0155] The inorganic adhesive preferably contains water glass, in particular sodium silicate and / or potassium silicate.

[0156] The combination of aluminum, preferably in the form of chips as a waste product of the machining of aluminum parts, with water glass as an inorganic binder is particularly advantageous because the aluminum chips are oxidized on their surface and have an oxide layer on their surface, which forms an intimate and particularly stable bond with the silicate of the binder.

[0157] Preferably, aluminum particles and / or graphite particles are distributed throughout the salt hydrate. These improve the thermal conductivity of the salt hydrate.

[0158] Preferably, the container (K*) has a constant cross-section along a container axis (BA) transverse to the container axis (BA). This transforms the container into a "cartridge" that can be pushed into and pulled out of a complementarily shaped cavity (e.g., for heating or charging the cartridge).

[0159] Preferably, the container (K*) has impermeable partition walls arranged at a distance along its container axis (BA), which are impermeable to the anhydrate, the hydrate, water and water vapor and which divide the volume of the container (K*) into partial volumes arranged along the container axis (BA). This prevents uncontrolled diffusion of water or water vapor inside the container along the container axis, and water or water vapor can be added to the container in sections during heating operation or removed from it during loading operation. This particularly facilitates metered heating operation, i.e. metered unloading of the container, for example by gradually lowering the container into a water bath along its container axis BA.

[0160] The cross-section of the container (K*) can be in the shape of a rectangle, a square, a circle or annulus, a triangle, or a hexagon. Containers with these shapes can be arranged compactly next to each other.

[0161] The cross-section of the container (K*) can also have the shape of a periodic pattern, particularly a wave with a sinusoidal or triangular profile. Containers with these shapes can also be arranged compactly next to each other.

[0162] Further advantages, features, and possible applications of the invention will become apparent from the following non-limiting description of exemplary embodiments of the invention with reference to the drawings. They show: Fig. 1 a schematic representation of a known method for generating heat; Fig. 2 a schematic representation of a known method for storing heat; Fig. 3 a schematic representation of a known device for generating heat; Fig. 4 a schematic representation of a known device for storing heat; Fig. 5 a schematic representation of an exemplary application of a method according to the invention and a device according to the invention; Fig. 6a a plan view of a first embodiment of a cartridge according to the invention in loading mode; Fig. 6b a sectional view along the section plane AA of the first embodiment of the cartridge in loading mode; Fig. 6c a sectional view along the section plane BB of the first embodiment of the cartridge in loading mode; Fig. 7a a plan view of the first embodiment of the cartridge according to the invention in heating mode; Fig. 7b a sectional view along the section plane AA of the first embodiment of the cartridge in heating mode; Fig. 7c a sectional view along the section plane BB of the first embodiment of the cartridge in heating mode; Fig. 8a a top view of a plate-like cartridge in loading mode; Fig. 8b a sectional view along the section plane AA of the plate-like cartridge; Fig. 9a a perspective view of a transparent first variant of a block-like cartridge; Fig. 9b a perspective view of a transparent second variant of a block-like cartridge; Fig. 10 a stack of block-like cartridges of the Fig. 9a which are fluidically connected in series; Fig. 11 a stack of block-like cartridges with engagement formations of the Fig. 9a which are fluidically connected in series; Fig. 12 a perspective view of another variant of a plate-like cartridge with engagement formations; Fig. 13 a side view of a vehicle equipped with an internal combustion engine, on which two stacks of plate-like cartridges are arranged for their loading process; Fig. 14 a sectional view of another variant of a plate-like cartridge; Fig. 15 a sectional view of a cylindrical cartridge; Fig. 16 a sectional view of another variant of a plate-like cartridge; Fig. 17 a sectional view of another variant of a plate-like cartridge; Fig. 18 a sectional view of a rod-shaped cartridge; Fig. 19 a sectional view of another variant of a rod-shaped cartridge; Fig. 20 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 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; Fig. 22 a sectional view of a first embodiment of a cartridge filling; Fig. 23 a sectional view of a second embodiment of a cartridge filling; Fig. 24 a sectional view of a third embodiment of a cartridge filling; Fig. 25 a sectional view of a fourth embodiment of a cartridge filling; Fig. 26 a sectional view of another design of a cartridge.

[0163] In Fig. 1 A known method for generating (discharging, releasing) heat W is shown schematically. The release of heat W occurs 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 resulting reaction heat W is dissipated.

[0164] A metered amount of the solid and / or the first liquid 1 is fed to the reaction chamber R. A metered amount of the gas and / or the second liquid 2 is also fed to the reaction chamber R.

[0165] In the reaction chamber R, the solid and / or the first liquid 1 and the gas and / or the second liquid 2 are brought into contact with each other. The released heat W is removed from the reaction chamber R.

[0166] In Fig. 2 A known method for storing heat W is shown schematically. In 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 reaction heat W to be stored is supplied.

[0167] A metered amount of the solid and / or the first liquid 1 is fed to a reaction chamber R. In addition, a metered amount of heat W is fed to the reaction chamber R.

[0168] In the reaction space R, the solid and / or the first liquid 1 and the heat W are brought into contact with each other, 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.

[0169] In Fig. 3 a known device or system for carrying out the method for generating heat is shown schematically.

[0170] The device contains a reaction chamber forming the reaction space R with a means for dissipating reaction heat in the form of a heat exchanger WT.

[0171] The device also contains a first feed means in the form of a screw conveyor SF and / or a toothed belt conveyor ZF for the metered feeding of a solid and / or a first liquid 1 into the reaction chamber R.

[0172] The device also contains a second supply means in the form of a metering pump DP and / or an atomizing nozzle ZD for metered supply of a gas and / or a second liquid 2 into the reaction chamber R.

[0173] In Fig. 4 A known device or system for carrying out the method for storing heat is shown schematically.

[0174] The device contains a reaction chamber forming the reaction space with a means for supplying reaction heat in the form of a heat exchanger WT and / or a fluidized bed WB.

[0175] 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 feeding of a solid or a first liquid 1 into the reaction chamber R.

[0176] The device also contains a second means in the form of a blower or fan V and / or a pump P for removing a gas or a second liquid 2 from the reaction chamber R.

[0177] In Fig. 5 a schematic representation of an exemplary application of the methods and devices according to the invention is shown.

[0178] The left half of the image shows a house in which a cartridge K is used as a heating cartridge HK. Water is added to the cartridge filled with an anhydrate (e.g., CaO), which hydrates the anhydrate contained in the cartridge, producing the corresponding hydrate (e.g., Ca(OH) 2 ), and releasing hydration heat W from the cartridge K. This hydration heat W can be used for heating, e.g., domestic hot water and room air heating.

[0179] The right half of the image shows a vehicle equipped with an internal combustion engine, in which a cartridge K is used as a charging cartridge LK. Heat W (waste heat from the internal combustion engine) is supplied to the cartridge filled with a hydrate (e.g., Ca(OH) 2 ), which dehydrates the hydrate contained in the cartridge, producing the corresponding anhydrate (e.g., CaO), and storing hydration heat W in the cartridge K. This hydration heat W can then be reused for heating.

[0180] In the middle of the picture of Fig. 5 A cartridge exchange station is shown. There, the charged cartridges (anhydrate cartridges) that can be used as heating cartridges (HK) are exchanged for charging cartridges (LK) that are to be charged.

[0181] In Fig. 6a is a plan view of a first embodiment of a cartridge K according to the invention in charging mode. The cartridge K can be seen with a reaction chamber R, which is filled with a hydrate in powder form and is traversed by a pipe coil S, which is made, for example, of a metal. 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, e.g. hot air or hot exhaust gas from an internal combustion engine, or a hot liquid, e.g. hot oil from a parabolic trough power plant. The heat flowing into the hydrate dehydrates the hydrate, whereby water (H 2 O) escapes from the cartridge K and the corresponding anhydrate is formed in the reaction chamber. The water escapes via a semi-permeable wall region (not shown) of the cartridge K. In the case of charging mode using a hot gas (e.g.hot exhaust gas), the coil S can also contain small openings (indicated by dashed lines) through which the hot gas penetrates into the hydrate powder and gradually dehydrates it and converts it into the corresponding anhydrate.

[0182] In Fig. 6b A sectional view along the section plane AA of the first embodiment of the cartridge K in charging mode is shown. The reaction chamber R with the tubing coil S running therein can be seen. The reaction chamber R is filled with a hydrate / anhydrate powder (indicated by dotted lines), whereby in the discharged state the hydrate almost completely fills the reaction chamber R, while in the charged state the anhydrate fills the reaction chamber R to a greater extent or at least almost completely.

[0183] In Fig. 6c A sectional view along section plane BB of the first cartridge design during loading is shown. The reaction chamber R, part of the coil S, and the filling with hydrate / anhydrate powder (indicated by dotted lines) can be seen again.

[0184] In Fig. 7a is a plan view of the first embodiment of the cartridge K according to the invention in heating mode. The cartridge K can be seen with a reaction chamber R which is filled with an anhydrate in powder form and is traversed by a tube coil S which is made, for example, of a metal. The tube coil S contains small openings (indicated by dashed lines). Water is allowed to flow through the tube coil S as a liquid and / or as water vapor. The liquid water and / or the water vapor penetrates the anhydrate powder through the small openings in the tube coil S, whereby the powder is gradually hydrated and thus converted into the corresponding hydrate. The hydration heat W released in this process can be transferred to a heat transfer fluid for heating purposes via at least one highly heat-conducting wall of the cartridge K.In the case of heating operation using water in the pipe coil S, the water flowing through the pipe coil S can also be used as a heat transfer fluid. Thus, via the pipe coil S with its small openings, both a metered supply of water into the anhydrate powder and a removal of the hydration heat W in the water take place.

[0185] In Fig. 7b A sectional view along the section plane AA of the first embodiment of the cartridge K in heating mode is shown. The reaction chamber R with the pipe coil S running through it can be seen. The reaction chamber R is filled with a hydrate / anhydrate powder (indicated by dotted lines), whereby in the discharged state the hydrate almost completely fills the reaction chamber R, while in the charged state the anhydrate fills the reaction chamber R to a greater extent or at least almost completely.

[0186] In Fig. 7c A sectional view along section plane BB of the first version of the cartridge K in heating mode is shown. The reaction chamber R, part of the coil S, and the filling with hydrate / anhydrate powder (indicated by dotted lines) can be seen again.

[0187] In Fig. 8a A top view of a plate-like cartridge K during charging is shown. In the lower part of the cartridge K, heat W can be seen penetrating the cartridge K by a hot gas, which dehydrates the hydrate contained in the cartridge K and converts it into the corresponding anhydrate. In the upper part of the cartridge K, water can be seen escaping as steam, indicated by arrows.

[0188] In Fig. 8b A sectional view along the section plane AA of the plate-like cartridge K is shown. The reaction chamber R and the filling with hydrate / anhydrate powder (indicated by dotted lines) can be seen again.

[0189] In Fig. 9a is a perspective view of a transparent first variant of a block-like cartridge K. One can see a pipe coil S extending inside the cartridge K, which is in fluid communication with two diametrically opposed openings O1 and O2 on a first large surface of the cartridge K and is in fluid communication with two diametrically opposed openings O3 and O4 on a second large surface of the cartridge K. The pipe coil S has a plurality of small openings or a semi-permeable wall region along the entire fluid path defined by it, through which water or water vapor can pass and through which neither hydrate nor anhydrate can pass.

[0190] When unloading the cartridge K or during its use as a heating cartridge HK, water and / or water vapor is passed from the first opening O1 to the second opening O2 through the pipe coil S. In the process, water and / or water vapor passes through the multitude of small openings or through the semi-permeable wall area into the anhydrate inside the cartridge K, whereby the anhydrate is gradually converted into hydrate and heat is gradually generated in the cartridge K, which can be transferred to a heating system.

[0191] When charging the cartridge K or during its use as a charging cartridge LK, a hot fluid as a heat source, preferably hot air or hot exhaust gas from a combustion process, is passed from the third opening O3 to the fourth opening O4 through the coil S. Heat is thereby transferred into the hydrate inside the cartridge K, gradually converting the hydrate into anhydrate and gradually storing heat from the heat source in the cartridge K. The water vapor thus formed in the cartridge K passes through the multitude of small openings or the semi-permeable wall area into the coil S and is discharged from the cartridge K in the air stream or exhaust gas stream.

[0192] In Fig. 9b is a perspective view of a transparently illustrated second variant of a block-like cartridge K. One can see a pipe coil S extending inside the cartridge K, which is in fluid connection with a first opening O1 on a first large surface of the cartridge K, a second opening O2 on a second large surface of the cartridge K and with a third opening O3 on an end face or small surface of the cartridge K. Similar to the first variant in Fig. 9a the coil S has a multitude of small openings or a semi-permeable wall area along the entire fluid path defined by it, through which water or water vapor can pass and through which neither hydrate nor anhydrate can pass.

[0193] When unloading the cartridge K or during its use as a heating cartridge HK, water and / or water vapor is passed from the first opening O1 to the third opening O3 through the pipe coil S. In the process, water and / or water vapor passes through the multitude of small openings or through the semi-permeable wall area into the anhydrate inside the cartridge K, whereby the anhydrate is gradually converted into hydrate and heat is gradually generated in the cartridge K, which can be transferred to a heating system.

[0194] When loading the cartridge K or during its use as a loading cartridge LK, a hot fluid as a heat source, preferably hot air or hot exhaust gas from a combustion process, is passed from the second opening O2 to the third opening O3 through the coil S. Heat is thereby transferred into the hydrate inside the cartridge K, whereby the hydrate is gradually converted into anhydrate and heat from the heat source is gradually stored in the cartridge K. The water vapor thus formed in the cartridge K passes through the multitude of small openings or the semi-permeable wall area into the coil S and is discharged from the cartridge K in the air stream or exhaust gas stream.

[0195] In Fig. 10 is a stack of block-like cartridges K of the Fig. 9a shown, which are fluidically connected in series. Each of the cartridges K in the stack contains a (not shown) coil S (see Fig. 9a ). In the stack, all the tube coils S of the respective cartridges K are connected in series to form a very long series tube coil. A hot gas, e.g., a hot exhaust gas, or a hot liquid, e.g., a hot oil, can be passed through this series tube coil, thereby dehydrating a hydrate contained in the respective cartridges K and gradually charging the cartridges. The water vapor escaping from the hydrate can, as described above, escape from the cartridge via a semi-permeable wall area (not shown) of the respective cartridge K. In the case of charging operation using a hot gas (e.g., hot exhaust gas), the tube coil S can also contain small openings (see Fig. 6a , Fig. 7a , Fig. 9a, Fig. 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 into the corresponding anhydrate.

[0196] When stacking the cartridges K, the two diametrically opposite openings O1 and O2 of the first large area (see Fig. 9a ) of a first cartridge K with the two diametrically opposite openings O3 and O4 of the second large surface (see Fig. 9a ) of a second cartridge K is brought into the registration position, whereby a fluid-tight connection is formed between the two adjacent cartridges K in the stack between the respective two openings in the registration position, thus forming the entire series tube coil of the cartridge stack. It is understood that 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.

[0197] In Fig. 11 is a stack of block-like cartridges K provided with engagement formations F1 of the Fig. 9a shown, which are fluidically connected in series. The cartridges K can be stacked on top of each other like Lego bricks.

[0198] In Fig. 12 A perspective view of another variant of a plate-like cartridge K with engagement formations F2 and complementary engagement formations F2' is shown. The cartridges can be positively connected to one another by means of the engagement formations F2 and F2'.

[0199] In Fig. 13 is a side view of a vehicle equipped 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 Fig. 10 stacks shown.

[0200] In Fig. 14 A sectional view of another variant of a plate-like cartridge K is shown. The sectional plane is orthogonal to a longitudinal axis of the plate-like cartridge K.

[0201] The cartridge K contains a flat first wall region WB1 (shown as cross-hatching), which is formed as a semipermeable wall region with a plurality of holes, in particular with round holes, longitudinal holes, cross holes, or star holes. The first wall region WB1 can be formed from metal or ceramic, e.g., from metal-ceramic or oxide ceramic, or from a combination of metal and ceramic in the manner of a ceramic filter.

[0202] The cartridge contains a flat second wall region WB2, which is made of a highly thermally conductive material, preferably metal, e.g. copper, aluminum, steel, etc., or graphite.

[0203] The cartridge K contains a reaction chamber R between the flat first wall region WB1 and the flat second wall region WB2. This reaction chamber R is filled with hydrate and / or anhydrate, depending on the charge level of the cartridge K.

[0204] The left oval-shaped area schematically shows the heating operation of this cartridge K, namely “water in, heat out”.

[0205] The right oval-shaped area schematically shows the charging operation of this cartridge K, namely “heat in, water out”.

[0206] In Fig. 15 A sectional view of a cylindrical cartridge K is shown. The sectional plane is orthogonal to a longitudinal axis of the cylindrical cartridge K.

[0207] The cartridge K contains a first wall region WB1 in the form of an inner cylindrical shell (shown as cross-hatching), which is formed as a semipermeable wall region with a plurality of holes, in particular with round holes, longitudinal holes, cross holes, or star holes. The first wall region WB1 can be formed from metal or ceramic, e.g., from metal-ceramic or oxide ceramic, or from a combination of metal and ceramic in the manner of a ceramic filter.

[0208] The cartridge contains a second wall region WB2 in the form of an outer cylinder shell, which is made of a highly thermally conductive material, preferably of metal, e.g. copper, aluminum, steel, etc., or graphite.

[0209] The cartridge K contains a reaction chamber R between the first wall region WB1 and the second wall region WB2. This reaction chamber R is filled with hydrate and / or anhydrate, depending on the charge level of the cartridge K.

[0210] The upper oval-shaped area schematically shows the heating operation of this cartridge K, namely “water in, heat out”.

[0211] The lower oval-shaped area schematically shows the charging operation of this cartridge K, namely “heat in, water out”.

[0212] In Fig. 16 A sectional view of another variant of a plate-like cartridge K is shown. The sectional plane is orthogonal to a longitudinal axis BA of the plate-like cartridge K.

[0213] The cartridge K contains a flat first wall region WB1 made of metal (shown as cross-hatching), which is formed as a semipermeable wall region with a plurality of holes, in particular with round holes, longitudinal holes, cross holes, or star holes. The first wall region WB1 can be formed of metal-ceramic in the manner of a ceramic filter.

[0214] The cartridge K contains a flat second wall region WB2 made of metal (shown as cross-hatching), which is formed as a semipermeable wall region with a plurality of holes, in particular with round holes, longitudinal holes, cross holes, or star holes. The second wall region WB2 can be formed of metal-ceramic in the manner of a ceramic filter.

[0215] Metals used include copper, aluminum, steel, etc.

[0216] The cartridge K contains a reaction chamber R between the flat first wall region WB1 and the flat second wall region WB2. This reaction chamber R is filled with hydrate and / or anhydrate, depending on the charge level of the cartridge K.

[0217] The left oval-shaped area schematically shows the heating operation of this cartridge K, namely “water in, heat out”.

[0218] The right oval-shaped area schematically shows the charging operation of this cartridge K, namely “heat in, water out”.

[0219] Since the two semi-permeable wall areas WB1 and WB2 are made of metal, both water or water vapor and heat can be easily transported into and out of the cartridge K at each of them.

[0220] In Fig. 17 A sectional view of another variant of a plate-like cartridge is shown. The sectional plane is orthogonal to a longitudinal axis BA of the plate-like cartridge K.

[0221] The cartridge K of the Fig. 17 differs from the cartridge K of the Fig. 16 only in the shape of their cross-section or profile cross-section transverse to the longitudinal axis BA. Instead of the rectangular profile of the

[0222] Fig. 16 has the cartridge of the Fig. 17 a sine wave profile. It could also have a triangular wave profile (not shown).

[0223] The left oval-shaped area schematically shows the heating operation of this cartridge K, namely “water in, heat out”.

[0224] The right oval-shaped area schematically shows the charging operation of this cartridge K, namely “heat in, water out”.

[0225] Since the two semi-permeable wall areas WB1 and WB2 are made of metal, both water or water vapor and heat can be easily transported into and out of the cartridge K at each of them.

[0226] In Fig. 18 A sectional view of a rod-shaped cartridge K is shown. The sectional plane is orthogonal to a longitudinal axis BA of the plate-like cartridge K.

[0227] The cartridge K of the Fig. 18 differs from the cartridge K of the Fig. 16 only in the shape of their cross-section or profile cross-section transverse to the longitudinal axis BA. Instead of the rectangular profile of the

[0228] Fig. 16 has the cartridge of the Fig. 18 a square profile. It could also have a triangular profile (not shown).

[0229] The upper oval-shaped area schematically shows the heating operation of this cartridge K, namely “water in, heat out”.

[0230] The lower oval-shaped area schematically shows the charging operation of this cartridge K, namely “heat in, water out”.

[0231] Since all wall areas WB are semi-permeable and made of metal, water or water vapor as well as heat can be easily transported into and out of the cartridge K at each of them.

[0232] In Fig. 19 A sectional view of another variant of a rod-shaped cartridge is shown. The sectional plane is orthogonal to a longitudinal axis BA of the plate-like cartridge K.

[0233] The cartridge K of the Fig. 19 differs from the cartridge K of the Fig. 18 only in the shape of their cross-section or profile cross-section transverse to the longitudinal axis BA. Instead of the square profile of the

[0234] Fig. 18 has the cartridge of the Fig. 19 a circular profile. It could also have a circular ring profile (not shown).

[0235] The upper oval-shaped area schematically shows the heating operation of this cartridge K, namely “water in, heat out”.

[0236] The lower oval-shaped area schematically shows the charging operation of this cartridge K, namely “heat in, water out”.

[0237] Since all wall areas WB are semi-permeable and made of metal, water or water vapor as well as heat can be easily transported into and out of the cartridge K at each of them.

[0238] In Fig. 20 is a sectional view of another 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 embodiment differs from the semipermeable metal-ceramic embodiment mentioned above. Several through-holes DB can be seen, each extending from the outer wall surface WBa of the semipermeable wall region WB to the inner wall surface WBi of the semipermeable wall region WB. The cross-section of the through-holes DB has a constriction V in the area of the inner wall surface WBi. Since the wall region WB is made of metal, both water or water vapor and heat can be transported well through it.Due to the constriction V, the escape of anhydrate particles or hydrate particles from the reaction space is made more difficult, while during heating operation water and water vapor can easily enter the reaction space R at the constrictions V and during charging operation water and water vapor can easily escape from the reaction space R at the constrictions V.

[0239] In Fig. 21 A sectional view of another embodiment of a semipermeable wall region of a cartridge K is shown schematically along a sectional plane perpendicular to the plane of the wall region WB or perpendicular to the tangential plane of the wall region. This embodiment also differs from the semipermeable metal-ceramic embodiment mentioned above. It shows metal chips MS bonded together with an inorganic adhesive (not shown) to form a three-dimensional metal chip matrix.

[0240] In Fig. 22 A sectional view of a first embodiment of a cartridge filling is shown schematically. One can see a) a first phase formed by salt hydrate SH, which can be more or less continuous or more or less porous (represented by cross-hatching). Also visible b) in the first phase are uniformly or at least almost uniformly distributed particles MP, GP made of a material with high specific thermal conductivity as the second phase (represented as hatched spots). The particles can be, for example, metal particles MP or graphite particles GP.

[0241] In Fig. 23 A sectional view of a second embodiment of a cartridge filling is shown schematically. One can see a) a first phase formed by salt hydrate SH, which can be more or less continuous or more or less porous (represented by cross-hatching). Also visible c) is a lattice structure MG extending within the first phase, made of a material with high specific thermal conductivity, as the second phase (represented as hatched dark bands).

[0242] In Fig. 24 A sectional view of a third embodiment of a cartridge filling is shown schematically. One can see a) a first phase formed by salt hydrate SH, which can be more or less continuous or more or less porous (represented by cross-hatching). In addition, one can see, on the one hand, b) particles MP, GP made of a material with high specific thermal conductivity, which are uniformly or at least almost uniformly distributed in the first phase, as the second phase (represented as hatched spots), and on the other hand c) a lattice structure MG made of a material with high specific thermal conductivity, which extends within the first phase, as the third phase (represented as hatched dark bands).

[0243] In Fig. 25 A sectional view of a fourth embodiment of a cartridge filling is shown schematically. One can see, on the one hand, d) metal chips MS (shown as dark hatched spots) that are bonded together with an inorganic adhesive (not shown) and form a three-dimensional metal chip matrix MSM, and, on the other hand, a) interstices ZR of the metal chip matrix MSM that are at least partially filled with hydrate, i.e., the hydrated form of a salt hydrate SH (shown by cross-hatching).

[0244] In Fig. 26a 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*. Impermeable partition walls TW can be seen along the container axis BA, which are impermeable to the anhydrate, the hydrate, water and water vapor and which divide the volume of the container K or K*, i.e. 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 region WB1 made of metal (shown as cross-hatching), which is formed as a semi-permeable wall region with a plurality of holes. The first wall region WB1 can be formed from metal ceramic in the manner of a ceramic filter. The cartridge K orK* contains a flat second wall region WB2 made of metal (shown as cross-hatching), which is formed as a semipermeable wall region with a plurality of holes. The second wall region WB2 can be made of metal-ceramic in the manner of a ceramic filter. Examples of metals used include copper, aluminum, steel, etc. The double arrow DP indicates the two directions parallel to the container axis BA along which the cartridge K or K* can be immersed in and emerged from a water bath.

Claims

1. Method for generating (releasing, emitting) or 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) (ammonia, water, alcohol, ketone), wherein the reaction heat (W) generated during the generation of heat or to be stored during the storage of heat is dissipated during the generation of heat or supplied during the storage of heat, wherein a1) on the one hand, a metered quantity of the solid and / or the first liquid (1) is supplied to a reaction chamber (R) and a2) on the other hand, a metered quantity of the gas and / or the second liquid (2) or a metered quantity of heat (W) is supplied to the reaction chamber (R), wherein in the reaction chamber (R) a1) the solid and / or the first liquid (1) and a2) during the generation of heat the gas and / or the second liquid (2) or during the storage of heat the heat (W) are brought into contact with one another and during the generation of heat the heat released is removed from the reaction chamber (R) or during the storage of heat the gas and / or the second liquid (2) released is removed from the reaction chamber (R), wherein the solid and / or the first liquid (1) is an anhydrate during the generation of heat or a hydrate during the storage of heat, wherein the heat is generated or stored by reaction involving anhydrate during the generation of heat or hydrate during the storage of heat on the one hand and water and / or water vapor on the other hand, wherein a metered quantity of the anhydrate during the generation of heat or of the hydrate during the storage of heat is fed to the reaction chamber (R) on the one hand and a metered quantity of water and / or water vapor during the generation of heat or a metered quantity of heat during the storage of heat is fed to the reaction chamber (R) on the other hand, characterized in that an inner space of a container (K, K*) is partially filled with the anhydrate and / or the hydrate, and the container (K, K*) has a semipermeable wall region (WB1, WB2) which is impermeable to the anhydrate or hydrate contained therein and permeable to water or water vapor.

2. Method according to claim 1, characterized in that the container (K, K*) has a constant cross-section transverse to the container axis (BA) along a container axis (BA), it being advantageous for the container (K, K*) to has impermeable partition walls (TW) arranged at intervals along its container axis (BA), which are impermeable to the anhydrate, the hydrate, water and water vapour and which divide the interior of the container (K) into part chambers (TK) or part volumes (TV) arranged along the container axis (BA).

3. Container (K, K*) for use in a method according to claim 1, characterized in that the interior of the container (K, K*) is partially filled with an anhydrate and / or a hydrate and the container (K) has a semipermeable wall region (WB1, WB2) which is impermeable to the anhydrate or hydrate contained therein and permeable to water or water vapor.

4. Container (K) according to claim 3, characterized in that the semipermeable wall region (WB1, WB2, WB) is made of metal; and / or the interior of the container (K) is bounded by a first semipermeable wall region (WB1) made of metal and a second semipermeable wall region (WB2) made of metal, between which the interior of the container (K) extends; and / or at least part of the semipermeable wall areas (WB1, WB2, WB) is formed from metal ceramic.

5. Container (K) according to claim 3 or 4, characterized in that at least part of the semipermeable wall areas (WB1, WB2, WB) is formed from metal and has a plurality of through-bores (DB), which each extend from the outer wall surface (WBa) of the semipermeable wall region (WB) to the inner wall surface (WBi) of the semipermeable wall region (WB), wherein it is advantageously provided that the cross section of the through-bores (DB) has a constriction (V).

6. Container (K) according to any of claims 3 to 5, characterized in that at least part of the semipermeable wall areas (WB1, WB2, WB) is formed from a three-dimensional metal chip matrix (MSM) in which metal chips (MS) are bonded together with an inorganic adhesive (WG) and which has cavities between the metal chips (MS); and / or the interior of the container (K) 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 and made of a material with high specific thermal conductivity as a second phase; and / or the interior of the container (K) 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 a second phase; and / or the interior of the container (K) has a filling in which metal chips (MS) are bonded together with an inorganic adhesive and form a three-dimensional metal chip matrix (MSM), and in which interstices of the metal chip matrix are at least partially filled with hydrate, i.e., the hydrated form of a salt hydrate.

7. Container (K*) for use in a method for generating or storing heat, in particular for use in a method according to one of claims 1 or 2, characterized in that 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.

8. Container (K*) according to claim 7, characterized in that the metallic matrix comprises metal particles (MP) which are bonded together by sintering to form a metal sinter block or a metal-ceramic block and form a three-dimensional metal-ceramic matrix (MKM); and / or the metallic matrix comprises metal chips (MS) which are bonded together by an inorganic adhesive and form a three-dimensional metal chip matrix (MSM); and / or particles (MP, GP) of a material with high specific thermal conductivity are distributed in the salt hydrate; and / or a lattice structure (MG, WR) with high specific thermal conductivity is contained in the salt hydrate; and / or the salt hydrate has a porous structure; and / or the metallic matrix contains aluminum; wherein it is advantageously provided that the inorganic adhesive contains water glass, in particular sodium silicate and / or potassium silicate; and / or aluminum particles and / or graphite particles are distributed in the salt hydrate.

9. Container (K, K*) according to one of claims 3 to 6 or according to one of claims 7 or 8, characterized in that the container (K, K*) has a constant cross-section transverse to the container axis (BA) along a container axis (BA), it being advantageous that the container (K, K*) has impermeable partition walls (TW) spaced apart along its container axis (BA), which are impermeable to the anhydrate, the hydrate, water, and water vapor and which divide the interior of the container (K) into part chambers (TK) or part volumes (TV) arranged along the container axis (BA).

10. Container (K, K*) according to claim 9, characterized in that the cross-section of the container (K, K*) has the shape of a rectangle, a square, a circle or a circular ring, a triangle or a hexagon; or the shape of a periodic pattern, in particular a wave with a sinusoidal profile or a triangular profile.

11. Container arrangement, characterized in that it comprises several containers (K) and / or containers (K*) arranged next to each other and parallel to each other according to one of claims 3 to 10.

12. Method for manufacturing a container (K*) for use in a method for generating or storing heat, in particular for manufacturing a container (K*) according to one of claims 7 to 9, comprising the following steps: a) forming a three-dimensional metallic matrix having microscopic interstices; and b) filling the microscopic interstices with an aqueous slurry of a salt hydrate, wherein it is advantageous that step a) is carried out by sintering metallic particles; and / or by bonding metallic particles by means of an inorganic adhesive, wherein it is advantageously provided that step b) is carried out by pressing the aqueous slurry into the microscopic interstices.

13. 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 claims 7 to 9, comprising 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, wherein it is advantageously provided that in step b) sintering of the metallic particles; and / or bonding of the metallic particles by means of an inorganic adhesive takes place in step b).