JP5401782B2 - Thermal storage device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a heat storage device including a chemical heat storage material molded body obtained by forming a chemical heat storage material, and a method for manufacturing the same.

After heating the crystalline limestone having a particle size of 0.3 mm to 4 mm within a range of 850 ° C. to 1100 ° C. for a predetermined time, the limestone is heated within a range of 500 ° C. to 600 ° C. for a predetermined time, so that There is known a technique for obtaining quicklime in which a large number of pores toward the surface are formed (see, for example, Patent Document 1). Moreover, the technique which fills the reactor or reaction tower with the capsule which accommodated the powder chemical thermal storage material in the ratio of 10-60 volume% of internal space is known (for example, refer patent document 2, patent document 3). . Further, there is known a chemical heat storage type refrigeration apparatus having an evaporator having a plurality of evaporating dishes provided with overflow pipes, a refrigerant liquid pipe flower, a condenser, an adsorbent container, and a communication pipe communicating these. (For example, see Patent Document 4).
JP-A-1-225686 Japanese Patent Publication No. 6-80395 Japanese Patent Publication No. 6-80394 JP-A-7-332788

  However, as described in Patent Document 1, when quick lime having pores formed therein is used as a chemical heat storage material in a powder form, the hydration reaction and the dehydration reaction are repeated during operation. For this reason, the powder of the chemical heat storage material rubs against other powders by repeated volume expansion and contraction, and is pulverized, resulting in a problem that the reactivity as the heat storage system is lowered. Also. In the configurations of Patent Documents 2 and 3, due to the increase in heat conduction resistance due to the use of capsules and the complexity of the heat transfer path, the heat due to the exothermic reaction of the chemical heat storage material cannot be taken out efficiently, and the heat in the heat storage reaction is further reduced. There was a problem that could not be supplied efficiently. On the other hand, although the structure of patent document 4 can ensure the evaporation area of the refrigerant | coolant in an evaporator by using several evaporating dishes, there are few heat exchange areas with a heat exchange medium, and heat transfer is insufficient (Rule control). ).

  In view of the above facts, the present invention provides a heat storage device in which good heat transfer is performed between a chemical heat storage material molded body formed by molding a powder chemical heat storage material and a wall, and the manufacture of the heat storage device The purpose is to obtain a method.

The heat storage device according to claim 1 is a chemical heat storage material molded body formed by molding a powder chemical heat storage material, and a wall made of a metal material and in contact with the surface of the chemical heat storage material molded body Body , an alkaline earth metal compound that is higher in density than the chemical heat storage material molded body and the same type of chemical heat storage material as the chemical heat storage material molded body, and a clay mineral, and the chemical heat storage material molding A heat transfer layer that fills a gap between the body and the wall .

  In the heat storage device according to claim 1, in the chemical heat storage material molded body, a powdery chemical heat storage material is formed, and as a whole, a gap (diffusion path) is formed between the powders (chemical heat storage material). And a porous structure having a predetermined shape as a whole. Since the space between the chemical heat storage material molded body and the wall body is filled with a heat transfer layer made of a chemical heat storage material having a higher density (dense) than the chemical heat storage material molded body, the chemical heat storage material molded body Adhesion between the wall and the body is high. Further, due to the presence of the heat transfer layer, the adhesion strength between the chemical heat storage material molded body and the wall body is high, and the good adhesion is easily maintained. As a result, in this heat storage device, the thermal resistance between the chemical heat storage material molded body and the wall body is small, and heat transfer and heat transfer associated with the chemical heat storage material molded body are performed well.

  Thus, in the heat storage device according to the first aspect, good heat transfer is performed between the chemical heat storage material molded body formed by molding the powder chemical heat storage material and the wall body. Moreover, since the heat-transfer layer is comprised with the chemical heat storage material, the density of the chemical heat storage material as the whole heat storage apparatus is high, and heat storage and heat dissipation performance are favorable.

A heat storage device according to the invention described in claim 2 is a chemical heat storage material molded body formed by molding a powder chemical heat storage material, a heat storage material storage section storing the chemical heat storage material molded body, and the heat storage material storage section. between the containing and heat exchange medium circulating unit for circulating a heat exchange medium for the chemical thermal storage medium molded body and the heat exchange through the wall member together are partitioned by walls, are composed of metal material A heat exchange structure , an alkaline earth metal compound that is higher in density than the chemical heat storage material molded body and the same type of chemical heat storage material as the chemical heat storage material molded body, and a clay mineral , A heat transfer layer that fills a gap between the chemical heat storage material molded body and the wall body .

  In the heat storage device according to claim 2, a gap (diffusion path) is formed between the powder (chemical heat storage material) as a whole by forming the chemical heat storage material molded body into a powdery chemical heat storage material. And a porous structure having a predetermined shape as a whole. In this heat storage device, heat is stored in the chemical heat storage material molded body by heat exchange with the heat exchange medium via the wall body, or the heat of the chemical heat storage material molded body is taken out, so at least one of the heat storage reaction and the heat dissipation reaction is The heat exchange for heat storage or heat dissipation can be performed by heat exchange with a heat exchange medium outside the heat storage material accommodation unit. For this reason, the movement of the reactant or reaction product accompanying the reaction is not hindered by mixing with the heat exchange medium flowing through the heat storage material container, and the moving speed of the reactant or reaction product is ensured, and the heat storage Or the reactivity for heat dissipation is still better.

  In this heat storage device, the gap between the chemical heat storage material molded body, which is a porous structure, and the wall of the heat exchange structure, is made of a chemical heat storage material having a higher density (dense) than the chemical heat storage material molded body. Since it is buried in the heat layer, the adhesion between the chemical heat storage material molded body and the wall body is high. Further, due to the presence of the heat transfer layer, the interfacial adhesion strength between the chemical heat storage material molded body and the wall body is high, and the good adhesion is easily maintained. As a result, in this heat storage device, the thermal resistance between the chemical heat storage material molded body and the wall body is small, and heat transfer and heat transfer associated with the chemical heat storage material molded body are performed well. That is, the heat exchange performance between the heat exchange medium and the chemical heat storage material molded body through the wall is good.

  Thus, in the heat storage device according to claim 2, good heat transfer is performed between the chemical heat storage material molded body formed by molding the powder chemical heat storage material and the wall body. Moreover, since the heat-transfer layer is comprised with the chemical heat storage material, the density of the chemical heat storage material as the whole heat storage apparatus is high, and heat storage and heat dissipation performance are favorable.

Moreover, in the heat storage apparatus of Claim 1, 2 , the adhesiveness of a chemical heat storage material molded object and a metal wall body and interface adhesion strength are securable by a heat-transfer layer.

In the heat storage device according to claims 1 and 2 , since the chemical heat storage material molded body and the heat transfer layer are formed of the same kind of chemical heat storage material, sintering (densification) of the chemical heat storage material molded body is performed. It is suppressed and the heat storage and heat dissipation performance of the chemical heat storage material heat storage body are easily maintained. Moreover, the deterioration of the interface adhesiveness resulting from the difference in the linear expansion coefficient between the chemical heat storage material molded body and the heat transfer layer is prevented.

Further, in the heat storage device according to claims 1 and 2 , since an alkaline earth metal compound is employed as the chemical heat storage material constituting the heat transfer layer, for example, a chemical heat storage using an alkaline earth metal salt as a starting material. A high-density heat transfer layer can be configured relatively easily with respect to the material molded body.

Further, in the heat storage device according to claims 1 and 2 , since the clay mineral having a fiber structure is included in the heat transfer layer, the fibers of the clay mineral exert an anchor effect, and the adhesion between the chemical heat storage material molded body and the wall surface Increases strength.

Heat storage device according to the invention of claim 3 the mounting, in the heat storage device according to claim 1 or claim 2, wherein the heat transfer layer is oxidized due to the dehydration reaction, hydration reaction that is hydroxylated with the hydration reaction It contains a system chemical heat storage material and is fired at a temperature of 350 ° C to 500 ° C.

In the heat storage device according to claim 3 , the hydration reaction type chemical heat storage material is fired at a temperature of 350 ° C. to 500 ° C., thereby generating chemical heat storage material microcracks in the heat transfer layer, and the ratio of the heat transfer layer Increases surface area. Since this large specific surface area contributes to the improvement of the reaction speed in heat storage and heat dissipation reaction, in this heat storage device, the efficiency of heat storage and heat dissipation can be improved.

The heat storage device according to a fourth aspect of the present invention is the heat storage device according to any one of the first to third aspects, wherein the chemical heat storage material molded body is a clay for dispersing and holding the powder chemical heat storage material. It is composed of minerals.

In the heat storage device according to claim 4 , since the chemical heat storage material is dispersed and held in the skeleton of the porous clay mineral, the strength as the porous structure described above is high, and the structure as the porous structure is stable. Easy to maintain.

A heat storage device according to a fifth aspect of the present invention is the heat storage device according to the fourth aspect , wherein a clay mineral having a layer ribbon structure is used as the clay mineral.

6. The heat storage device according to claim 5 , wherein at least one of the clay mineral mixed in the chemical heat storage material molded body and the clay mineral mixed in the heat transfer layer is porous and has a layer ribbon structure fiber having a large specific surface area. Since it has a shape, the chemical heat storage material molded body and / or the chemical heat storage material of the heat transfer layer can be well organized and structured by its fiber and plasticity.

A heat storage device according to a sixth aspect of the present invention is the heat storage device according to the fifth aspect , wherein sepiolite or palygorskite is used as the clay mineral having the layer ribbon structure.

In the heat storage device according to claim 6 , since at least a part of the clay mineral is sepiolite or palygorskite (attapulgite) having a layer ribbon structure, the chemical heat storage material molded body and / or the heat transfer layer is formed depending on its fiber and plasticity. The chemical heat storage material can be well organized and structured.

The heat storage device according to an eighth aspect of the present invention is the heat storage device according to the fourth aspect , wherein bentonite is used as the clay mineral.

In the heat storage device according to claim 8 , bentonite which is a clay mineral having a strong adhesive force is used as at least one of the clay mineral mixed in the chemical heat storage material molded body and the clay mineral mixed in the heat transfer layer. By this adhesive force, the chemical heat storage material molded body and / or the chemical heat storage material of the heat transfer layer can be well organized and structured.

The heat storage device according to the invention of claim 9 is the heat storage device according to any one of claims 1 to 8 , wherein the clay mineral is a particle diameter of a chemical heat storage material constituting the chemical heat storage material molded body. It has a finer fiber shape.

In the heat storage device according to claim 9 , at least one of the clay mineral mixed in the chemical heat storage material molded body and the clay mineral mixed in the heat transfer layer has a fibrous shape having a fine fiber diameter. Using a small amount of clay mineral, the chemical heat storage material molded body and / or the chemical heat storage material of the heat transfer layer can be organized and structured. Thereby, the occupation amount of the chemical heat storage material per mass per mass in the chemical heat storage material molded body can be increased.

A heat storage device according to a tenth aspect of the present invention is the heat storage device according to any one of the first to ninth aspects, wherein the chemical heat storage material forming the chemical heat storage material molded body and the heat transfer layer are configured. At least one of the chemical heat storage materials has fine cracks.

In the heat storage device according to the tenth aspect, since the specific surface area of the chemical heat storage material having fine cracks is large, the chemical heat storage material molded body and / or the heat transfer layer exhibit improved reaction rates in heat storage and heat release reactions. Thereby, the efficiency of heat storage and heat dissipation can be improved.

In claims 1 and 2, when a hydration reaction type chemical heat storage material that absorbs heat during dehydration reaction and dissipates heat during hydration reaction is used as the chemical heat storage material constituting the chemical heat storage material molded body, The hydration reaction type chemical heat storage material repeats volume expansion and contraction with dehydration (reverse hydration) reaction, but the chemical heat storage material is finely divided by organizing the chemical heat storage material and forming gaps in the structure using clay mineral. Is effectively suppressed or prevented.

Moreover, as a chemical heat storage material constituting the chemical heat storage material molded body, a hydration reaction type chemical heat storage material that is oxidized with dehydration reaction and hydroxylated with hydration reaction is used. Hydration reaction type chemical heat storage material repeats volume expansion and contraction with the reaction, but the chemical heat storage material is finely pulverized effectively by organization and formation of gaps in the structure using clay minerals. Or prevented.

Further, when an inorganic compound is used as a chemical heat storage material, the heat storage, a material having high stability against heat radiation reaction (hydration, dehydration). For this reason, a stable heat storage effect can be obtained over a long period of time.

Moreover, the use of alkaline earth metal compound (hydroxide) as the chemical thermal storage medium, in other words, the use of material having a low environmental load, manufacture, use, facilitates ensuring safety, including recycling. Further, in the configuration using sepiolite as the clay mineral, the alkalinity of the hydroxide helps vitrification by reaction with the clay mineral (especially described above), which contributes to improving the strength of the porous structure.

The heat storage apparatus according to the invention of claim 7, wherein, in the heat storage device according to claim 6, wherein the chemical thermal storage medium molded body includes a chemical heat storage material is an alkaline earth metal compound of the powder, as the clay mineral What is kneaded with sepiolite and formed into a predetermined shape is fired at a temperature of 350 ° C. to 500 ° C.

The heat storage device according to claim 7 is configured as a porous structure by sintering a molded body in which a hydration reaction type chemical heat storage material and sepiolite are kneaded to sinter sepiolite. The hydration reaction type chemical heat storage material, which is an inorganic compound, is fired at a temperature of 350 ° C. to 500 ° C., thereby generating microcracks and increasing the specific surface area. Since this large specific surface area contributes to improving the reaction rate in heat storage and heat dissipation reactions, the chemical heat storage material molded body can improve the efficiency of heat storage and heat dissipation.

  Moreover, since the sintering temperature of sepiolite is 350 ° C. to 400 ° C., the sintering of sepiolite and the generation of microcracks in the chemical heat storage material proceed simultaneously. In other words, the sintering of sepiolite and the generation of microcracks in the chemical heat storage material do not adversely affect each other. The chemical heat storage material dispersed and held in sepiolite is suppressed from being pulverized by microcracks.

Method for producing a heat storage device according to the invention of claim 1 1, wherein the configuration at a molding step of obtaining a chemical thermal storage medium molded body from a powder of the chemical thermal storage medium, the chemical thermal storage medium molded body and the metal member which are in contact with each other A heat transfer layer raw material supply step for supplying a mixture of an alkaline earth metal salt solution as a raw material for the chemical heat storage material of the same type as the chemical heat storage material molded body and a clay mineral between the formed wall body, The chemical heat storage material forming body comprises a mixture of the chemical heat storage material raw material and the clay mineral supplied between the chemical heat storage material forming body and the wall body in the heat transfer layer raw material supply step. A heat transfer layer generating step of changing to a heat transfer layer made of a chemical heat storage material having a higher density than the material.

In the method of manufacturing the heat storage device of claim 1 1, wherein, in the forming step, to give the chemical thermal storage medium molded body by molding a powder of the chemical thermal storage medium, then, it proceeds to the heat transfer layer feed step. In the heat transfer layer raw material supply step, the chemical heat storage material is supplied between the chemical heat storage material molded body and the wall body that are in contact with each other (interface), and the process proceeds to the heat transfer layer generation step. In the heat transfer layer generating step, the chemical heat storage material raw material between the chemical heat storage material molded body and the wall is changed to a heat transfer layer made of the chemical heat storage material. Thereby, a heat transfer layer made of a chemical heat storage material having a higher density (dense) than the chemical heat storage material molded body is formed between the chemical heat storage material molded body and the wall body.

  In the heat storage device manufactured in this way, the chemical heat storage material molded body is formed with a powdery chemical heat storage material, and as a whole, a gap (diffusion path) is formed between the powders (chemical heat storage material). In addition, it is formed as a porous structure having a predetermined shape as a whole. Since the space between the chemical heat storage material molded body and the wall body is filled with a heat transfer layer made of a chemical heat storage material having a higher density (dense) than the chemical heat storage material molded body, the chemical heat storage material molded body Adhesion between the wall and the body is high. Further, due to the presence of the heat transfer layer, the adhesion strength between the chemical heat storage material molded body and the wall body is high, and the good adhesion is easily maintained. As a result, in this heat storage device, the thermal resistance between the chemical heat storage material molded body and the wall body is small, and heat transfer and heat transfer associated with the chemical heat storage material molded body are performed well.

Thus, in the manufacturing method of the heat storage apparatus according to claim 1 1, wherein the heat storage device good heat transfer between the formed by molding a powder of the chemical thermal storage medium chemical thermal storage medium molded body and the wall are carried out Can be manufactured. Moreover, since a heat-transfer layer is comprised with a chemical heat storage material, it is possible to make the density of the chemical heat storage material as the whole heat storage apparatus manufactured high, and to make heat storage and heat dissipation performance favorable.

The manufacturing method of the heat storage device according to the invention of claim 12 is a method of forming a chemical heat storage material molded body having an outer shape that can be inserted into a heat storage material accommodation portion of a heat exchange structure using a powdered chemical heat storage material. Inserting the chemical heat storage material molded body formed in the process and the forming step into a heat storage material accommodation section partitioned by a wall body from the heat exchange medium flow in the heat exchange structure formed of a metal material Raw material of the chemical heat storage material of the same type as the chemical heat storage material molded body between the chemical heat storage material molded body and the wall body inserted into the heat storage material housing portion of the heat exchange structure in the insertion step A heat transfer layer raw material supply step for supplying a mixture of an alkaline earth metal salt solution and a clay mineral, and supply between the chemical heat storage material molded body and the wall body in the heat transfer layer raw material supply step the mixture of the raw material and the clay mineral of the chemical heat storage material which is the Including a heat transfer layer forming step of changing the heat transfer layer made of a high density of the chemical heat storage material than the chemical heat storage material constituting the academic thermal storage medium molded body.

In the method for manufacturing a heat storage device according to claim 12 , in the forming step, the powder chemical heat storage material is formed into a chemical heat storage material molded body having a shape and a flow path into which the heat storage material housing portion of the heat exchange structure can be inserted. Then, the process proceeds to the insertion process. In the insertion step, the chemical heat storage material molded body is inserted into the heat storage material accommodation portion of the heat exchange structure, and then the process proceeds to the heat transfer layer material supply step. In the heat transfer layer raw material supply step, the chemical heat storage material is supplied between the contacted chemical heat storage material molded body and the wall (interface), and the process proceeds to the heat transfer layer generation step. In the heat transfer layer generating step, the chemical heat storage material raw material between the chemical heat storage material molded body and the wall is changed to a heat transfer layer made of the chemical heat storage material. Thus, a chemical heat storage material molded body that is a porous structure is provided in the heat storage material accommodating portion of the heat exchange structure, and a chemical heat storage material is provided between the chemical heat storage material molded body and the wall body. A heat transfer layer made of a chemical heat storage material having a higher density (dense) than the molded body is formed.

  In the heat storage device manufactured in this way, heat is stored in the chemical heat storage material molded body by heat exchange with the heat exchange medium, or the heat of the chemical heat storage material molded body is taken out, so at least one of the heat storage reaction and the heat dissipation reaction is heat storage. Alternatively, heat exchange for heat dissipation can be performed by heat exchange with a heat exchange medium outside the heat storage material accommodation unit. For this reason, the movement of the reactant or reaction product accompanying the reaction is not hindered by mixing with the heat exchange medium flowing through the heat storage material container, and the moving speed of the reactant or reaction product is ensured, and the heat storage Or the reactivity for heat dissipation is still better.

  In this heat storage device, the gap between the chemical heat storage material molded body, which is a porous structure, and the wall of the heat exchange structure, is made of a chemical heat storage material having a higher density (dense) than the chemical heat storage material molded body. Since it is buried in the heat layer, the adhesion between the chemical heat storage material molded body and the wall body is high. Further, due to the presence of the heat transfer layer, the interfacial adhesion strength between the chemical heat storage material molded body and the wall body is high, and the good adhesion is easily maintained. As a result, in this heat storage device, the thermal resistance between the chemical heat storage material molded body and the wall body is small, and heat transfer and heat transfer associated with the chemical heat storage material molded body are performed well. That is, the heat exchange performance between the heat exchange medium and the chemical heat storage material molded body through the wall is good.

Thus, in the method for manufacturing a heat storage device according to claim 12, a heat storage device is obtained in which good heat transfer is performed between the chemical heat storage material molded body formed by molding a powder chemical heat storage material and the wall body. be able to.

Method for producing a heat storage device according to the invention of claim 13, wherein the kneading method of manufacturing a heat storage device according to claim 1 1 or claim 12, wherein, in the forming step, the clay mineral in a predetermined ratio to the chemical thermal storage medium The said chemical heat storage material molded object is shape | molded using the kneaded material.

In the method for manufacturing a heat storage device according to claim 13 , the chemical heat storage material can be dispersed and held in the skeleton of the porous clay mineral by mixing the chemical heat storage material with the clay mineral. As a result, a chemical heat storage material molded body having a high strength as the above-described porous structure and a stable structure as the porous structure, that is, a heat storage device can be obtained.

Moreover, in the manufacturing method of the heat storage apparatus of Claim 11, 12 , the mixture of the raw material of a chemical heat storage material and a clay mineral is supplied between a chemical heat storage material molded object and a wall body at a heat-transfer layer raw material supply process. Thus, a heat transfer wall containing the clay mineral fiber is formed. For this reason, the adhesion strength between the chemical heat storage material molded body and the wall surface is increased by the anchor effect of the fibers of the clay mineral.

Moreover, in the manufacturing method of the heat storage apparatus of Claim 11, 12, since the solution of the alkaline earth metal salt is supplied between the chemical heat storage material molded body and the wall body as the raw material of the chemical heat storage material, the chemical heat storage material It is possible to obtain a high-density heat transfer layer that satisfactorily fills the space between the molded body and the wall body.

Method for producing a heat storage device according to the invention of claim 1 4, wherein, in the manufacturing method of the heat storage apparatus according to any one of claims 1 1 to claim 1 3, as the clay mineral, clay having a layered ribbon structure Use minerals.

14. The method of manufacturing a heat storage device according to claim 14, wherein at least one of the clay mineral mixed in the chemical heat storage material molded body and the clay mineral mixed in the heat transfer layer is porous and has a large specific surface area. Therefore, the chemical heat storage material formed body and / or the chemical heat storage material of the heat transfer layer can be well organized and structured using the fiber and plasticity.

Method for producing a heat storage device according to the invention of claim 1 5, wherein, in the method for manufacturing a heat storage device according to claim 1 4, wherein, as a clay mineral having a layer ribbon structure, using sepiolite or palygorskite.

The method for producing a heat storage device according to claim 15, wherein sepiolite or palygorskite (attapulgite) having a layered ribbon structure is used as at least a part of the clay mineral. And / or the chemical heat storage material of the heat transfer layer can be well organized and structured.

Method for producing a heat storage device according to the invention of claim 1 6, wherein, in the manufacturing method of claim 1 1 to claim 1 3 heat storage device according to any one of, as the clay mineral, using bentonite.

In the method of manufacturing the heat storage device according to claim 1 6, wherein, as at least one of clay mineral clay minerals to be mixed with the clay mineral and the heat transfer layer is mixed in the chemical thermal storage medium molded body, is strong adhesion clay mineral Since bentonite is used, the chemical heat storage material molded body and / or the chemical heat storage material of the heat transfer layer can be well organized and structured by this adhesive force.

Method for producing a heat storage device according to the invention of claim 1 7, wherein, in the manufacturing method of the heat storage apparatus according to any one of claims 1 1 to claim 1 6, wherein in the molding process, particles of the chemical thermal storage medium The clay mineral having a fiber shape thinner than the diameter is used.

In the method of manufacturing the heat storage device according to claim 1 7, wherein, the clay minerals of at least one clay mineral clay minerals to be mixed with the clay mineral and the heat transfer layer is mixed in the chemical thermal storage medium molded body, a fine fiber diameter In order to form a fibrous form, a small amount of clay mineral is mixed in the mixing step, whereby the chemical heat storage material formed body and / or the chemical heat storage material of the heat transfer layer can be organized and structured. Thereby, it becomes possible to obtain a chemical heat storage material molded body having a large occupation amount of the chemical heat storage material per mass and per volume.

Method for producing a heat storage device according to the invention of claim 1 8 wherein, in the manufacturing method of the heat storage apparatus according to any one of claims 1 1 to claim 1 7, as a chemical heat storage material of the alkaline earth metals, A hydration reaction-type chemical heat storage material that absorbs heat with a dehydration reaction and dissipates heat with a hydration reaction is used. In the molding step, the hydrated chemical heat storage material is kneaded with the clay mineral.

In the claims 1 8 production method of the heat storage apparatus described in the molding process, since the chemical thermal storage medium in a hydrated state a kneading and clay mineral, react with water of concern when using a chemical heat storage material is dehydrated is It does not occur. For this reason, water can be used as a binder during kneading in the molding step.

Method for producing a heat storage device according to the invention of claim 1 9, wherein, in the manufacturing method of the heat storage apparatus according to any one of claims 1 1 to claim 1 8, as a chemical heat storage material of the alkaline earth metals, is oxidized with the dehydration reaction, hydration is hydroxylated with the hydration reaction reaction chemical thermal storage medium is used and in the forming step, the clay mineral the chemical thermal storage medium in the state of hydroxide And knead.

In the method of manufacturing the heat storage device according to claim 1 9, wherein, in the molding process, for mixing with the clay mineral to a chemical heat storage material of the hydroxide state, with water of concern when using a chemical heat storage material is dehydrated There is no reaction. For this reason, water can be used as a binder during kneading in the kneading step.

Incidentally, in claim 11, when an inorganic compound is used as a chemical heat storage material, the chemical heat storage material moldings produced, the heat storage, a material having high stability against heat radiation reaction (hydration, dehydration). For this reason, a stable heat storage effect can be obtained over a long period of time.

Moreover, since an alkaline earth metal compound (hydroxide) is used as the chemical heat storage material, it is easy to ensure safety during production. In addition, it is easy to ensure safety, including when the product (chemical heat storage material molded body) is used and recycled. Further, in the configuration using sepiolite as the clay mineral, the alkalinity of the hydroxide helps vitrification by reaction with the clay mineral (especially described above), which contributes to improving the strength of the porous structure.

The method for manufacturing a heat storage device according to claim 20 is the method for manufacturing a heat storage device according to any one of claims 11 to 19 , wherein the heat transfer layer generation is performed in the heat transfer layer material supply step. In the process, a raw material solution of the chemical heat storage material is obtained between the chemical heat storage material molded body and the wall body in order to obtain a hydration reaction type chemical heat storage material that is oxidized with a dehydration reaction and hydroxylated with a hydration reaction. In the heat transfer layer generating step, the raw material of the chemical heat storage material supplied between the chemical heat storage material molded body and the wall body is baked to change into an oxide of a hydration reaction type chemical heat storage material. Including the step of

In the heat storage device manufacturing method according to claim 20, the raw material solution supplied between the chemical heat storage material molded body and the wall body in the heat transfer layer raw material supply step is baked in the heat transfer layer generation step. The heat transfer layer is composed of a hydration reaction type chemical heat storage material in an oxide state. Thereby, the heat-transfer layer which consists of a high-density chemical heat storage material can be easily formed with respect to a chemical heat storage material molded object.

A method for manufacturing a heat storage device according to claim 21 is the method for manufacturing a heat storage device according to claim 20 , wherein, in the heat transfer layer generation step, firing is performed at a temperature at which fine cracks are formed in the chemical heat storage material. To do.

In the method for manufacturing a heat storage device according to claim 21 , since a fine crack is formed at least in the chemical heat storage material constituting the heat transfer layer through the heat transfer layer generation step, the specific surface area of the chemical heat storage material is increased. Can contribute to the improvement of heat storage and heat dissipation reaction rate. In particular, if firing is performed at a temperature at which fine cracks are formed in the chemical heat storage material constituting the chemical heat storage material molded body, the specific surface area of the chemical heat storage material can be increased as the entire heat storage device. This contributes to the improvement of the heat dissipation reaction rate.

The method for manufacturing a heat storage device according to the invention of claim 22 is performed before the heat transfer layer material supply step in the method of manufacturing a heat storage device according to any one of claims 11 to 21 , It further includes a preliminary firing step of firing the chemical heat storage material molded body at a temperature at which the chemical heat storage material is not converted to an oxide.

  In the preliminary firing step, the chemical heat storage material of the chemical heat storage material molded body is maintained in a hydroxide state, so that the raw material solution supplied between the chemical heat storage material molded body and the wall body in the heat transfer layer raw material supply step Can be made into an aqueous solution.

  As described above, the heat storage device according to the present invention has an excellent effect that the chemical heat storage material can efficiently store or dissipate heat.

  A heat exchange type heat storage and heat dissipation device 10 as a heat storage device according to an embodiment of the present invention and a manufacturing method thereof will be described with reference to FIGS.

  FIG. 2 is a schematic perspective view showing a schematic configuration of the heat exchange type heat storage and heat dissipation device 10. As shown in this figure, the heat exchange heat storage and heat dissipation device 10 includes a heat exchanger body 20 as a heat exchange structure, and a chemical heat storage material composite formed body 11 provided in the heat exchanger body 20. ing. The heat exchanger body 20 includes a shell (outer wall) 22 and a partition wall 24 as a wall body that divides the inside of the shell 22 into a plurality of spaces. Thereby, the inside of the heat exchanger main body 20 is heat exchange which performs heat exchange between the heat storage material accommodating part 25 in which the chemical heat storage material composite molded body 11 is stored and the chemical heat storage material composite molded body 11. Fluid flow paths 26 through which a fluid as a medium flows are alternately arranged.

  In this embodiment, the heat storage material accommodating part 25 and the fluid flow path 26 are each a prismatic space having a flat rectangular opening end in which the partition wall 24 has a long side. In this embodiment, the heat exchanger main body 20 is configured such that the heat storage material accommodating portion 25 and the fluid channel 26 are adjacent to each other in the flat direction of the cross section, and the fluid channel 26 is disposed at both ends in the adjacent direction. Yes. In this embodiment, the heat exchanger body 20 is made of a metal material such as stainless steel or aluminum (including an aluminum alloy).

  As shown in FIG. 2, the chemical heat storage material composite formed body 11 is formed in a flat prismatic shape (exactly, a honeycomb shape as will be described later) corresponding to the heat storage material accommodating portion 25, and its outer peripheral surface is The heat storage material storage unit 25 is accommodated in the heat storage material storage unit 25 so as to be in contact with or in close proximity to the inner peripheral surface (hereinafter simply referred to as contact). That is, both end surfaces in the flat direction of the chemical heat storage material composite molded body 11 are in contact with the partition walls 24.

  FIG. 3 shows a schematic cross-sectional view of the chemical heat storage material composite molded body 11. As shown in this figure, the chemical heat storage material composite formed body 11 is a structure in which a large number of powder chemical heat storage materials 12 are organized and structured. A pore 14 is formed. Therefore, the chemical heat storage material composite formed body 11 according to this embodiment is configured as a porous structure (porous body) and the powder chemical heat storage material 12 is exposed on the inner surfaces of the pores 14. It is grasped as a thing.

  In this chemical heat storage material composite molded body 11, sepiolite 16, which is a clay mineral, is interposed between a large number of powder chemical heat storage materials 12 so as to be entangled with a large number of powder chemical heat storage materials 12. In other words, the chemical heat storage material composite molded body 11 is grasped as a structure in which a large number of powder chemical heat storage materials 12 are dispersedly held in the skeleton of the sepiolite 16 that is porous. Thereby, in the chemical heat storage material composite molded body 11, the structure as a porous structure in which pores 14 are formed between a large number of powder chemical heat storage materials 12 is held (reinforced) by the sepiolite 16. ing.

In this embodiment, the powder chemical heat storage material 12 is made of calcium hydroxide (Ca (OH) ₂ ), stores heat (absorbs heat) along with dehydration, and accompanies hydration (restoration to calcium hydroxide). Heat dissipation (heat generation). That is, a large number of powder chemical heat storage materials 12 are configured to reversibly repeat heat storage and heat release by the reactions shown below. Ca (OH) ₂ Ｃａ CaO + H ₂ O

When the heat storage amount and the heat generation amount Q are shown together in this equation,
Ca (OH) ₂ + Q → CaO + H ₂ O
CaO + H ₂ O → Ca (OH) ₂ + Q
It becomes.

Sepiolite 16 is grasped as a clay mineral having a layered ribbon structure, more specifically, one of clay minerals in which a plurality of single chains resembling pyroxene are combined to form a tetrahedral ribbon. Sepiolite 16 is a hydrous magnesium silicate that can be represented by the chemical formula Mg ₈ S1i ₁₂ O ₃₀ (OH) ₄ (OH ₂ ) ₄ · 8H ₂ O, for example, and is itself porous and has a specific surface area. Made of large fibers. In this embodiment, variants of those represented by the above chemical formula are also included in the sepiolite 16.

  As shown in FIG. 2, the heat exchange type heat storage and heat dissipation device 10 discharges water vapor as a reaction product during heat storage, and supplies a flow path (path) for supplying water vapor as a reaction during heat dissipation. ) 15. The flow path 15 is formed so as to penetrate through the inside of the heat exchange type heat storage and heat dissipation device 10 in a predetermined direction, and has a sufficiently large representative dimension with respect to the pores 14. In this embodiment, the opening edge of the flow path 15 has a substantially rectangular shape, and the representative dimension which is the length of one side (shortest side) is the average diameter of the pores 14, the powder chemical heat storage material 12. It is sufficiently large with respect to the average particle diameter. In this embodiment, for example, the representative dimension of the flow path 15 is approximately 1 mm, the average particle diameter of the powder chemical heat storage material 12, and the average diameter of the pores 14 are each several tens of μm.

  In addition, the chemical heat storage material composite formed body 11 has a plurality of flow paths 15. In this embodiment, the chemical heat storage material composite molded body 11 is formed in a honeycomb shape (lattice shape) having a large number of flow paths 15 as shown in FIG. And in the chemical heat storage material composite molded object 11, the thickness of the partition wall part which partitions off between the adjacent flow paths 15 is 8 mm or less. In this embodiment, the thickness of the partition wall is about 1.5 mm which is 4 mm or less. Furthermore, in the heat exchange type heat storage and heat dissipation device 10, the thickness of the peripheral wall part located between the flow path 15 and the outer peripheral surface (contact surface with the partition wall 24) is 4 mm or less. In this embodiment, the thickness of the peripheral wall portion is approximately 1.5 mm which is 2 mm or less.

  In the chemical heat storage material composite molded body 11 described above, when the powder chemical heat storage material 12 is supplied with calcium hydroxide in the state of calcium hydroxide, the powder chemical heat storage material 12 is oxidized using the heat as reaction heat. It has become. That is, in the heat exchange type heat storage and heat dissipation device 10, the powder chemical heat storage material 12 is converted into calcium oxide by dehydration while discharging water vapor from the flow path 15 through the pores 14 or directly, and the heat corresponding to the reaction heat. It is set as the structure which stores heat. On the other hand, the heat exchange type heat storage / heat dissipating device 10, when water vapor is supplied to the powder chemical heat storage material 12 in the calcium oxide state directly or through the pores 14 (by diffusion), from the powder chemistry, The heat storage material 12 dissipates heat while being hydroxylated by a hydration reaction.

  In the heat exchange type heat storage and heat dissipation device 10, the heat supply during the heat storage to the chemical heat storage material composite molded body 11 in the heat storage material accommodation unit 25 is performed through the partition wall 24 with the fluid (gas) flowing through the fluid flow path 26. It is set as the structure performed by the heat exchange via. Further, in the heat exchange type heat storage and heat dissipation device 10, the heat radiated by the chemical heat storage material composite molded body 11 is received by the fluid (gas) flowing through the fluid flow path 26 by heat exchange via the partition wall 24. It has become.

  On the other hand, in the heat exchange type heat storage / heat dissipating device 10, the chemical heat storage material composite molded body 11 stores heat in the heat storage material accommodating portion 25 (flow path connected to) the flow path 15 of the chemical heat storage material composite molded body 11. It is a configuration used as a reaction channel for supplying water vapor as a reactant when the water vapor as a reaction product generated by the reaction is discharged and a heat release reaction is caused in the chemical heat storage material composite molded body 11. .

  Here, as shown in FIG. 1, the heat exchange type heat storage and heat dissipation device 10 includes a heat transfer layer 40 formed between the chemical heat storage material composite molded body 11 and the partition wall 24 arranged in contact with each other. . In FIG. 1, the sepiolite 16 is not shown. The heat transfer layer 40 is formed by organizing and structuring sufficiently fine (submicron order) particles 42 with respect to the powder chemical heat storage material 12 at a high density, and a part thereof is formed by chemical heat storage material composite molding. It is inserted into the pore 14 located (opened) on the surface side of the body 11. With the heat transfer layer 40, the chemical heat storage material composite molded body 11 and the partition wall 24 are in close contact with each other in the heat exchange type heat storage and heat dissipation device 10. In other words, the heat transfer layer 40 can be understood as forming a heat transfer path between the chemical heat storage material composite formed body 11 and the partition wall 24.

  Moreover, in this embodiment, the particle | grains 42 which comprise the heat-transfer layer 40 are comprised with the compound of the alkaline-earth metal which is a hydration type chemical heat storage material. Specifically, the particles 42 are calcium hydroxide (calcium oxide) which is a chemical heat storage material of the same type as the powder chemical heat storage material 12. Therefore, in the heat exchange type heat storage and heat dissipation device 10, the powder chemical heat storage material 12 and the particles 42 partially entering the pores 14 between the powder chemical heat storage material 12 have the same linear expansion coefficient. .

  Hereinafter, a method for manufacturing the heat exchange type heat storage and heat dissipation device 10 will be described.

  FIG. 4 schematically shows a method for manufacturing the heat exchange type heat storage and heat dissipation device 10. In manufacturing the heat exchange type heat storage and heat dissipation device 10, first, the chemical heat storage material composite formed body 11 is formed (manufactured) in the formed body forming step shown in FIGS. 4 (A) to 4 (D). Specifically, first, as shown in FIG. 4A, a powder chemical heat storage material 12 and a sepiolite 16 which are raw materials of the chemical heat storage material composite formed body 11 are prepared.

  As the powder chemical heat storage material 12, for example, a material having an average particle diameter D = 10 μm (laser diffraction measurement method, by SALD-2000A manufactured by Shimadzu Corporation) is used, and sepiolite 16 is used when suspended in water. A fiber having a fiber diameter smaller than the average particle diameter D of the powder chemical heat storage material 12 is used. Specifically, it is desirable to use the sepiolite 16 having a wire diameter (fiber diameter) of 1 μm or less and a length (fiber length) of 200 μm or less. In this embodiment, Turkish sepiolite having a wire diameter of about 0.01 μm and a length of about several tens of μm is used. Instead of Turkish sepiolite, for example, Spanish sepiolite having a wire diameter of approximately 0.1 μm and a length of approximately 100 μm can be used. Moreover, in this embodiment, the mixing ratio of the sepiolite 16 with respect to the powder chemical heat storage material 12 is about 5-10 mass%, for example.

  Next, the process proceeds to the mixing step. In the mixing step, as shown in FIG. 4B, the powder chemical heat storage material 12 and sepiolite 16 in the dry powder state are respectively mixed in the mixing container 28 and uniformly mixed. Next, the process proceeds to the kneading step. In the kneading step, as shown in FIG. 4C, the mixture of the powder chemical heat storage material 12 and sepiolite 16 is put into a kneading machine 29, and kneading (kneading) thickening while gradually adding water as a binder. Make it. Thereby, the kneaded material M of the powder chemical heat storage material 12 and the sepiolite 16 is produced | generated. This kneaded material M shows a clay state as a whole. In this embodiment, an organic binder (for example, CMC (carboxyl methylcellulose)) is mixed and kneaded as a lubricant and a binder. This organic binder disappears in a baking step at 400 ° C. or higher, which will be described later, and does not remain in the molded product. This organic binder exhibits a glue function and is effective in improving accuracy and density at the time of forming a structure.

  Next, the process proceeds to the molding step shown in FIG. In the molding step, the kneaded product M of the powder chemical heat storage material 12 and sepiolite 16 thickened in the kneading step as described above is transferred to the extrusion die 30 and extruded. Thereby, the kneaded material M is formed in a predetermined shape corresponding to the shape of the extrusion die 30, that is, in a flat honeycomb shape corresponding to the heat storage material accommodation portion 25 of the heat exchanger body 20. Thereby, the chemical heat storage material composite molded body 11 is molded.

  Next, as shown in FIG. 4E, the process proceeds to the insertion step. In the insertion step, the chemical heat storage material composite molded body 11 is press-inserted into the heat storage material accommodation portion 25 of the heat exchanger body 20. Under the present circumstances, the flexible chemical heat storage material composite molded object 11 before baking is inserted in this fluid flow path 26, adjusting to the inner surface of the heat storage material accommodating part 25 of the heat exchanger main body 20. FIG.

  Next, as shown in FIG. 4 (F), the process proceeds to a preliminary firing step. In the preliminary firing step, the heat exchanger body 20 into which the chemical heat storage material composite molded body 11 is inserted is placed in a firing furnace 32, and the chemical heat storage material composite molded body 11 is fired at a predetermined temperature for a predetermined time. Thereby, the chemical heat storage material composite molded body 11 is solidified in the heat storage material accommodating portion 25 of the heat exchanger main body 20, and the chemical heat storage material composite molded body 11 is integrated with the heat exchanger main body 20. The firing temperature in this preliminary firing step is in the range of 300 ° C. or lower. This pre-baking temperature is set to a range not lower than the lower limit temperature at which the sepiolite 16 is sintered and lower than the lower limit temperature at which dehydration (oxidation) of the powder chemical heat storage material 12 occurs.

  Next, as shown in FIG. 4G, an aqueous solution 44 of calcium nitrate, which is an alkaline earth metal salt, and sepiolite 16 are prepared as raw materials for the heat transfer layer 40. Next, the process proceeds to the heat transfer layer raw material mixing step. In the heat transfer layer raw material mixing step, as shown in FIG. 4 (H), the aqueous solution 44 and sepiolite 16 are placed in a mixing vessel 34, and the aqueous solution 44 and sepiolite 16 are mixed to form a mixed slurry S.

  Next, as shown in FIG. 4I, the process proceeds to a heat transfer layer raw material supply step. In the heat transfer layer raw material supply step, between the chemical heat storage material composite molded body 11 in the heat storage material container 25 of the heat exchanger main body 20 and the inner surface of the heat storage material container 25, that is, the partition wall 24 and the shell 22, Supply mixed slurry S. At this time, for example, as shown in FIG. 5, by forming chamfers 11 </ b> A at corners of the chemical heat storage material composite molded body 11, the highly viscous mixed slurry S is converted into the chemical heat storage material composite molded body 11. It can be easily supplied between the chamfer 11 </ b> A and the inner surface of the heat storage material accommodation unit 25. The mixed slurry S thus supplied is molded into the chemical heat storage material composite by the capillary force generated by the gap (pore 14) located between the chemical heat storage material composite formed body 11, the partition wall 24, and the shell 22. It is supplied substantially uniformly between the body 11, the partition wall 24, and the shell 22.

  Next, as shown in FIG. 4J, the process proceeds to the firing step. In the firing step, the heat exchanger body 20 to which the mixed slurry S is supplied between the chemical heat storage material composite molded body 11 in which the heat storage material accommodating portion 25 is inserted is placed in the firing furnace 32, and a predetermined temperature is set. The chemical heat storage material composite molded body 11 and the mixed slurry S are fired for the time. This firing temperature is set to 400 ° C. to 500 ° C., which is a temperature of 280 ° C. to 300 ° C. or higher, at which calcium nitrate in the mixed slurry S is oxidized and converted to calcium oxide.

  Thereby, in the manufacturing method of the heat exchange type heat storage and heat dissipation device 10, the calcium nitrate in the mixed slurry S is changed to calcium oxide, and heat is transferred between the chemical heat storage material composite molded body 11, the partition wall 24, and the shell 22. Layer 40 is formed. With the above, the manufacture of the heat exchange type heat storage and heat dissipation device 10 is completed.

  Further, this firing temperature is the dehydration temperature of the powder chemical heat storage material 12 constituting the chemical heat storage material composite molded body 11, that is, calcium hydroxide (the dehydration temperature varies depending on the atmospheric water vapor pressure, but is approximately 400 ° C to 450 ° C). Since it is above, the powder chemical heat storage material 12 comprises the chemical heat storage material composite molded object 11 in the state of calcium oxide immediately after manufacture. That is, the chemical heat storage material composite molded body 11 is in a heat storage state in which heat can be dissipated by supplying moisture (water vapor) at the time of manufacture. Moreover, the baking temperature in the range of 400 ° C. to 500 ° C. in the baking step is a temperature at which microcracks are formed in the powder chemical heat storage material 12 (calcium oxide), and thus the chemical heat storage material composite molded body 11 is formed. Each of the many powder chemical heat storage materials 12 is composed of microcracks as shown in FIG. Thereby, the specific surface area of the powder chemical heat storage material 12 is increased by passing through a baking process.

  In the heat exchange type heat storage / heat dissipating device 10 manufactured as described above, since the flow path 15 is formed inside the chemical heat storage material composite formed body 11, each powder of the chemical heat storage material composite formed body 11 during heat storage. A discharge path of water vapor generated by the body chemical heat storage material 12 and a water supply path required to be supplied to each powder chemical heat storage material 12 of the chemical heat storage material composite molded body 11 during heat dissipation are ensured. That is, in the heat exchange type heat storage and heat dissipation device 10, the pores 14 are formed inside the chemical heat storage material composite molded body 11, which is a porous structure in which pores 14 are formed between a large number of powder chemical heat storage materials 12. Since the larger flow path 15 is formed, it is possible to quickly discharge and supply water vapor through the flow path 15 while forming a porous structure having a high filling degree of the powder chemical heat storage material 12 as a whole. ing.

  For this reason, the heat exchange type heat storage and heat dissipation device 10 is required for ensuring (improving) the heat storage capacity per unit volume and mass due to the high filling degree (high density) of the powder chemical heat storage material 12, and for heat dissipation and heat storage reaction. It is possible to achieve compatibility with ensuring the moving speed of the discharged steam and the supplied steam. And in the heat exchange type heat storage and heat dissipation device 10, the heat storage material accommodating portion 25 constituting the flow path of water vapor discharged from the chemical heat storage material composite formed body 11 or supplied to the chemical heat storage material composite formed body 11 In order to exchange heat with the chemical heat storage material composite molded body 11 because the heat storage material composite molded body 11 is partitioned from the fluid flow path 26 through which the fluid that receives heat from the heat dissipation or chemical heat storage material composite molded body 11 flows. This fluid does not affect the moving speed of the discharged steam and the supplied steam.

  Thereby, in the heat exchange type heat storage and heat dissipation device 10, heat can be efficiently stored while discharging water vapor from the heat storage material storage unit 25 by receiving heat from the fluid flowing through the fluid flow path 26, and the heat storage material storage unit It is possible to efficiently dissipate heat by the water vapor supplied from 25 and exchange heat with the fluid flowing through the fluid flow path 26.

  Here, in the heat exchange type heat storage / heat dissipating device 10, the heat transfer layer 40 is formed between the outer surface of the chemical heat storage material composite molded body 11 and the partition wall 24 that separates the heat storage material accommodating portion 25 and the fluid flow path 26. Therefore, the interfacial adhesion between the chemical heat storage material composite molded body 11 (porous structure) and the partition wall 24 (metal surface) is good. Thereby, in the heat exchange type heat storage and heat dissipation device 10, since the substantial contact area through the heat transfer layer 40 between the chemical heat storage material composite formed body 11 and the partition wall 24 becomes large, the chemical heat storage material composite formed body 11 and the partition wall 24 have high adhesion strength. That is, the above-mentioned good interface adhesion is easily maintained.

  Accordingly, in the heat exchange type heat storage and heat dissipation device 10, the heat exchange performance through the partition wall 24 between the fluid flowing through the fluid flow path 26 and the chemical heat storage material composite molded body 11 is good. That is, in the heat exchange type heat storage and heat dissipation device 10, high heat transport can be realized between the fluid flowing through the fluid flow path 26 and the chemical heat storage material composite molded body 11.

  For example, in a chemical heat storage reaction part simply filled with a powder chemical heat storage material, the filling degree of the powder chemical heat storage material can be increased, but sufficient discharge and supply of water vapor is not performed. The amount of heat storage with respect to the heat storage capacity based on the degree of filling is reduced. Further, in such a configuration, since the flow paths of the water vapor and the heat exchange medium fluid are common, it is difficult to achieve both heat storage and heat release reactivity and heat exchange performance. That is, for example, when the heat exchange medium fluid is radiated, the partial pressure of the supplied water vapor decreases to reduce the reactivity, or when a circulating fluid is used as the heat exchange medium fluid, a part of the circulating fluid stores heat. There is concern that the heat storage performance may be reduced by being discharged out of the system together with the generated steam.

  On the other hand, in the heat exchange type heat storage and heat dissipation device 10, the chemical heat storage material composite molded body 11 is provided with 15 as described above, and the heat storage material storage portion 25 is partitioned from the fluid flow path 26 to store heat and release heat. Reactivity is ensured, and the heat storage material container 25 is partitioned with respect to the fluid flow path 26 and the chemical heat storage material composite molded body 11 is brought into close contact with the partition wall 24 so that the fluid flowing through the fluid flow path 26 and the chemical heat storage The heat exchange performance with the material composite molded body 11 is ensured. That is, in the heat exchange type heat storage and heat dissipation device 10, the shortage of the amount of movement of water vapor (diffusion rule) is solved and the heat transfer from the chemical heat storage material composite compact 11 to the heat exchange medium fluid (heat transfer rule) is reduced. Since coexistence can be achieved, the heat storage performance can be improved and the recovery (utilization) rate of the stored heat can be improved.

  Further, in the heat exchange type heat storage and heat dissipation device 10, the chemical heat storage material composite molded body 11 has a plurality of flow paths 15, and the thickness of the partition wall between the flow paths 15 in the chemical heat storage material composite molded body 11. Is 8 mm or less (4 mm or less from the closer flow path 15), and the thickness of the peripheral wall portion between the flow path 15 and the outer peripheral surface is 4 mm or less. Or a diffusion path for discharging water vapor from the powder chemical heat storage material 12 to the flow path 15 is short.

  For this reason, in the comparatively large (thickness) chemical heat storage material composite molded body 11 constituting the heat exchange type heat storage and heat dissipation device 10, the required heat storage and heat release reaction for each part (powder chemical heat storage material 12). The required amount of water vapor movement is ensured. In particular, in this embodiment, the thickness of the partition wall portion between the flow channels 15 is 4 mm or less, and the thickness of the peripheral wall portion between the flow channel 15 and the outer peripheral surface is 2 mm or less. It is secured even better. Moreover, in the chemical heat storage material composite molded body 11 having a plurality of flow paths 15, the partition wall portion between the flow paths 15 also functions as a heat transfer path in the chemical heat storage material composite molded body 11. In a relatively thick structure, the heat dissipated inside is efficiently transmitted to the partition wall 24.

  Furthermore, in the heat exchange type heat storage and heat dissipation device 10, since the heat transfer layer 40 is a heat storage material, the density of the heat storage material per unit volume and mass as a whole increases, and heat storage and heat dissipation performance are improved. Moreover, in the heat exchange type heat storage and heat dissipation device 10, the powder chemical heat storage material 12 of the chemical heat storage material composite molded body 11 and the particles 42 of the heat transfer layer 40 are the same type of chemical heat storage material. The difference in expansion coefficient accompanying the temperature rise with the chemical heat storage material composite molded body 11 can be minimized, and for example, the above-mentioned interface adhesion is maintained even in applications where the temperature change range is large. In addition, the chemical heat storage material composite formed body 11 and the heat transfer layer 40 made of the same type of chemical heat storage material have no fear of sintering, for example, when different types of alkaline earth metals are used. It is possible to secure a pore 14 having a large size.

  Here, in the manufacturing method of the heat exchange type heat storage and heat dissipation device 10, the aqueous solution 44 of calcium nitrate, which is an alkaline earth metal salt, is used as the starting material of the heat transfer layer 40. It is possible to form the heat transfer layer 40 in which small particles 42 are organized with high density. This contributes to improvement and maintenance of the interfacial adhesion between the chemical heat storage material composite molded body 11 and the partition wall 24 as described above.

  Furthermore, in the manufacturing method of the heat exchange type heat storage and heat dissipation device 10, the heat transfer layer 40 is formed by the mixed slurry S in which the sepiolite 16 is mixed with the calcium nitrate aqueous solution 44, so that the heat transfer layer 40 is a dense film due to the fiber structure of the sepiolite 16. The film strength of the thermal layer 40 and the interfacial adhesion of the vapor are improved. That is, in the heat exchange type heat storage and heat dissipation device 10 in which the sepiolite 16 is included in the heat transfer layer 40, the strength of the heat transfer layer 40 is high, and the partition wall 24 and the chemical heat storage material composite molded body 11 by the heat transfer layer 40 are High adhesion strength.

  Furthermore, in the kneading step of the molded body molding step for molding the chemical heat storage material composite molded body 11, the powder chemical heat storage material 12 is kneaded at a predetermined ratio with the sepiolite 16 which is porous and has a large specific surface area. The sepiolite 16 is stirred with the powder chemical heat storage material 12 and water by thixotropy of the sepiolite 16 to exhibit a thickening effect. Thereby, the chemical heat storage material composite formed body 11 based on the powder chemical heat storage material 12 can be molded with higher accuracy and higher density.

  Then, organization of the powder chemical heat storage material 12 using the fiber of the sepiolite 16 (porous after crystallization) and structuring of the many powder chemical heat storage materials 12 using the plasticity of the sepiolite 16 are achieved. That is, by mixing the sepiolite 16 with the powder chemical heat storage material 12 at a predetermined ratio, pores 14 for releasing or introducing water vapor accompanying heat storage and heat dissipation are formed between the many powder chemical heat storage materials 12. On the other hand, it was realized that a large number of powder chemical heat storage materials 12 were made into a chemical heat storage material composite formed body 11 as one structure, and the chemical heat storage material composite formed body 11 was maintained. Similarly, in the heat transfer layer raw material mixing step for forming the heat transfer layer 40, the sepiolite 16 is mixed with the calcium nitrate aqueous solution 44, so that pores are formed between the particles 42 in the heat transfer layer 40, A diffusion path is secured.

  Further, the chemical heat storage material composite molded body 11 manufactured as described above is organized and structured so that a large number of powder chemical heat storage materials 12 are formed with pores 14 therebetween. Further, the hydration of the powder chemical heat storage material 12 and the volume expansion and contraction accompanying the dehydration reaction are prevented or significantly suppressed from interfering with the other powder chemical heat storage material 12. For this reason, pulverization resulting from the volume expansion and contraction of the powder chemical heat storage material 12 is prevented. In other words, the release and introduction of water vapor into the powder chemical heat storage material 12 is not delayed, and the reaction of heat storage and heat dissipation. Deterioration is prevented or markedly suppressed. Similarly, since pores are formed between the particles 42 in the heat transfer layer 40, the pulverization of the particles 42 is prevented, and the above-described interfacial adhesion between the chemical heat storage material composite molded body 11 and the partition wall 24 is maintained. The

  Furthermore, in the chemical heat storage material composite molded body 11, surplus water vapor is adsorbed to the sepiolite 16 (micropores) by the adsorptivity of the sepiolite 16 having a large specific surface area and being porous. Thereby, for example, when the heat storage system to which the chemical heat storage material composite molded body 11 is applied is in a low temperature state (when the powder chemical heat storage material 12 is calcium oxide), the powder chemical heat storage material 12 Is prevented or suppressed by absorbing water and liquefying the chemical heat storage material composite molded body 11. Similarly, since pores are formed between the particles 42 in the heat transfer layer 40, liquefaction in the heat transfer layer 40 is prevented or suppressed.

  Moreover, here, in the manufacturing method of the heat exchange type heat storage and heat dissipation device 10, the average of the powder chemical heat storage material 12 in a state of being suspended in water in the molded body forming step for forming the chemical heat storage material composite formed body 11. Since the sepiolite 16 having a finer fiber diameter than the particle diameter D is used, a chemical heat storage material in which a porous structure in which pores 14 are formed between the powder chemical heat storage material 12 with a small amount of sepiolite 16 is used. A composite molded body 11 can be obtained. Therefore, the chemical heat storage material composite molded body 11 can increase the amount of the powder chemical heat storage material 12 occupying per unit mass and unit volume. That is, the chemical heat storage material composite molded body 11 having a large heat storage capacity can be obtained. Moreover, in the chemical heat storage material composite molded body 11, since the powder chemical heat storage material 12 itself forms the main structure of the chemical heat storage material composite molded body 11, the heat transfer path is simple, the heat storage efficiency, and the heat stored. Use efficiency is high.

  Moreover, in the method for manufacturing the heat exchange type heat storage and heat dissipation device 10, the fiber diameter of the sepiolite 16 constituting the heat transfer layer 40 is finer than the average particle diameter D of the powder chemical heat storage material 12 in a state suspended in water. Since a fiber-like material is used, this sepiolite 16 extends into the chemical heat storage material composite molded body 11 and exhibits an anchor effect, and the chemical heat storage material composite molded body 11 and the heat transfer layer 40, that is, the partition wall 24. Contributes to improved interfacial adhesion. Further, the structure of the sepiolite 16 can improve both the film strength of the heat transfer layer 40.

  Furthermore, since the chemical heat storage material composite molded body 11 uses calcium hydroxide, which is an inorganic compound, as the powder chemical heat storage material 12, the material stability against heat storage and heat dissipation reactions (hydration and dehydration) is high. In particular, since calcium hydroxide is highly reversible with respect to magnesium hydroxide and the like (having almost 100% hydration and dehydration rate), a stable heat storage effect can be obtained over a long period of time. Further, since calcium hydroxide has low sensitivity to impurities with respect to magnesium hydroxide and the like, this point also contributes to long-term stable operation. In particular, since calcium hydroxide which is an alkaline earth metal compound is used as the powder chemical heat storage material 12, in other words, since a material with a small environmental load is used, the production of the chemical heat storage material composite molded body 11, Ensures safety including use and recycling.

  Furthermore, in the manufacturing method of the heat exchange type heat storage and heat dissipation device 10, since the chemical heat storage material composite molded body 11 is manufactured using calcium hydroxide powder which is a hydroxide, the powder chemical heat storage is performed in the kneading step. Water can be used as a binder for kneading and thickening the material 12 and sepiolite 16. Thereby, the chemical heat storage material composite molded body 11 can be obtained by a simple and inexpensive method. For example, when calcium oxide is used as a starting material, water (a liquid containing water) cannot be used as a binder because the calcium oxide reacts with water. For example, when obtaining the powder chemical heat storage material 12 (calcium hydroxide) using calcium carbonate as a starting material, high-temperature firing at about 950 ° C. to 1000 ° C. is required in the decarbonation step.

  On the other hand, in the manufacturing method of the heat exchange type heat storage and heat dissipation device 10, since the heat exchange type heat storage and heat dissipation device 10 is manufactured using calcium hydroxide as a starting material as described above, it is increased by kneading with sepiolite 16 using water as a binder. A sticky effect is obtained and moldability is improved. In addition, since the firing temperature can be lowered, the degree of freedom of materials used and processes (including materials for manufacturing equipment) is increased. Furthermore, in the chemical heat storage material composite molded body 11, since alkaline calcium hydroxide is kneaded into sepiolite, sepiolite slightly reacts with alkali and changes to glassy. For this reason, the strength of the chemical heat storage material composite formed body 11 which is a sintered structure formed by sintering the kneaded material M of the vitrified sepiolite 16 and the powder chemical heat storage material 12 is improved.

  Furthermore, in the manufacturing method of the heat exchange type heat storage and heat dissipation device 10, since the aqueous solution 44 of calcium nitrate is used as a starting material for the heat transfer layer 40, the heat transfer layer 40 is formed by firing at a relatively low temperature (280 ° C to 300 ° C). Change to calcium oxide). That is, in the manufacturing method of the heat exchange type heat storage and heat dissipation device 10, for example, the heat transfer layer is not subjected to firing at a high temperature of about 950 ° C. to 1000 ° C. as in the configuration in which the heat transfer layer 40 is obtained using calcium carbonate as a starting material. 40 can be obtained.

  On the other hand, in the manufacturing method of the heat exchange type heat storage / heat dissipating device 10, since the firing temperature is 400 ° C. to 500 ° C., the powder chemical heat storage material 12 and the sepiolite 16 are structured (fixed) The dehydration reaction of the body chemical heat storage material 12, the dehydration of the aqueous solution 44, and the oxidation can be advanced. And since the microcrack is formed in the particle | grains 42 and the microcrack which is not illustrated in the particle | grains 42 with the calcination temperature of 400 to 500 degreeC, the manufacturing method of the chemical heat storage material composite molded object 11 Then, the organization and structuring of the powder chemical heat storage material 12 and the increase of the specific surface area can be achieved at the same time.

  In addition, about 450 degreeC is the most preferable as a calcination temperature which produces the micro chemical crack in the powder chemical thermal storage material 12 and particle | grains 42 which became calcium oxide. When the firing temperature is 400 ° C. or lower, the generation of microcracks and the like is small, and when the firing temperature is 500 ° C. or higher, the probability of cracking of the powder chemical heat storage material 12 and particles 42 is increased and the powder chemical heat storage material 12 and particles are sintered. It has been confirmed that the specific surface area of 42 is reduced. Although this temperature range is slightly lower than that of calcium oxide, for example, magnesium oxide (dehydrated magnesium hydroxide) can also be used as a firing temperature for generating microcracks. In addition, although the dehydration temperature of magnesium hydroxide changes with atmospheric water vapor pressures, it is a little lower than the dehydration temperature of calcium hydroxide (about 350 to 400 degreeC).

  In the above-described embodiment, an example in which sepiolite as a clay mineral having a layer ribbon structure is used as the clay mineral is shown. However, the present invention is not limited thereto, and for example, a clay mineral having a layer ribbon structure is used. Palygorskite (attapulgite) may be used, and bentonite that does not belong to the clay mineral having a layer ribbon structure may be used. Note that when bentonite is supplemented, bentonite is a clay mineral that has a stronger adhesive strength than a clay mineral having a layered ribbon structure, and can obtain a strong porous structure, for example, bonding to a metal wall. Contributes to improving strength. The chemical heat storage material composite molded body 11 using bentonite also forms a porous structure in which pores 14 are formed between a large number of powder chemical heat storage materials 12. On the other hand, clay minerals having a layered ribbon structure have the advantage of less sintering (densification) compared to bentonite. In particular, sepiolite is sintered at a temperature close to the dehydration temperature (the temperature at which microcracks are generated) of the powder chemical heat storage material 12 as described above, and the specific surface area is less reduced by sintering at that temperature (due to microcracks). The increase in specific surface area is advantageous). What is necessary is just to determine the clay mineral used for manufacture of the chemical heat storage material composite molded object 11 according to a use etc. in consideration of these merit.

In the above-described embodiment, an example in which calcium hydroxide (Ca (OH) ₂ ), which is a hydrated chemical heat storage material, is used as the powder chemical heat storage material 12, but the present invention is not limited thereto. For example, magnesium hydroxide (Mg (OH) ₂ ), which is an inorganic compound of an alkaline earth metal, may be used as the powder chemical heat storage material 12. Similarly, Ba (OH) ₂ and Ba (OH) ₂ .H ₂ O, which are inorganic compounds of alkaline earth metals, may be used as the powder chemical heat storage material 12 and are inorganic compounds other than alkaline earth metals. LiOH.H ₂ O, Al ₂ O ₃ .3H ₂ O, or the like may be used as the powder chemical heat storage material 12. Furthermore, instead of the hydrated powder chemical heat storage material 12 that generates and stores heat by hydration and dehydration reactions, a powder chemical heat storage material 12 using other reactions may be used.

  Furthermore, in the above-described embodiment, an example in which the chemical heat storage material composite molded body 11 has a plurality of flow paths 15 has been shown, but the present invention is not limited to this, and the dimensions and shape of the heat exchange heat storage and heat dissipation device 10 Depending on the required heat transfer (heat storage) performance, the heat exchange type heat storage and heat dissipation device 10 may be configured using the chemical heat storage material composite molded body 11 having a single flow path 15.

  Furthermore, the flow path formed in the chemical heat storage material composite molded body 11 is not limited to the flow path 15 penetrating the chemical heat storage material composite molded body 11 in the flow direction of water vapor. It is also possible to set at least a part as the interparticle distance of the powder chemical heat storage material 12 having a larger flow path cross section than the pores 14. For example, the powder chemical heat storage material 12 is organized and structured to form granular primary particles, and a number of primary particles are secondarily organized and structured, so that the pores 14 in the primary particles Alternatively, a secondary molded body having a large flow path (gap) may be formed, and the heat exchange type heat storage and heat dissipation device 10 may be configured using the secondary molded body.

  In the above-described embodiment, the chemical heat storage material composite molded body 11 performs heat exchange with the fluid flowing through the fluid flow path 26 both when the chemical heat storage material composite molded body 11 stores heat and when heat is released. The present invention is not limited to this, and for example, a heat storage reaction can be caused in the chemical heat storage material composite molded body 11 by the high-temperature gas flowing through the heat storage material accommodation unit 25 (flow path 15). This configuration can be applied to a configuration that uses heat from a heat source that is released into the atmosphere, such as exhaust gas.

  Furthermore, in the above-described embodiment (FIG. 2), the counterflow or parallel flow type heat exchanger body 20 in which the opening directions of the heat storage material accommodation portion 25 and the fluid flow path 26 in the heat exchanger body 20 are the same is illustrated. However, for example, as shown in FIG. 6, the heat exchange type heat storage and heat dissipation device 10 may be configured using a cross flow type heat exchanger body 20.

  Furthermore, in the above-described embodiment, an example in which the present invention is applied to the heat exchange type heat storage and heat dissipation device 10 is shown, but the present invention is not limited to this, and the chemical heat storage material composite molded body 11 of various shapes and The present invention can be applied to all uses for bringing a wall body made of metal or the like into close contact. Therefore, for example, the present invention is applied to a hot probe or the like in which a chemical heat storage material composite formed body 11 having a cylindrical shape or a block shape (the presence or absence of the flow path 15 may be determined according to the size and shape) is covered with a metal plate. May be. The hot probe is built in, for example, a catalytic converter provided in an exhaust pipe of an internal combustion engine, stores the exhaust heat of the exhaust gas during operation of the internal combustion engine, and is supplied with water vapor when the internal combustion engine is started at a low temperature, so that the catalytic converter Can be grasped as a heat storage device used to warm up early (in a short time).

  Furthermore, in the said embodiment, although the heat transfer layer 40 showed the example comprised including the sepiolite 16 as a clay mineral, this invention is not limited to this, For example, the heat transfer layer 40 is heat storage material particle | grains. Only 42 may be comprised.

It is sectional drawing which expands and shows typically the boundary part of the chemical heat storage material composite molded object and partition 24 which comprise the heat exchange type heat storage and heat radiation apparatus which concerns on embodiment of this invention. It is a perspective view showing a schematic structure of a heat exchange type heat storage and heat dissipation apparatus according to an embodiment of the present invention. It is sectional drawing which shows typically the internal structure of the heat exchange type | mold thermal storage heat dissipation apparatus which concerns on embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the manufacturing method of the chemical heat storage material composite molded object which concerns on embodiment of this invention, Comprising: (A) is a figure which shows a raw material, (B) is a figure which shows the mixed state of each raw material and a binder. (C) is a figure which shows a kneading | mixing process, (D) is a figure which shows a shaping | molding process, (E) is a figure which shows an insertion process, (F) is a figure which shows a pre-baking process. It is a figure which shows typically the manufacturing method of the chemical heat storage material composite molded object which concerns on embodiment of this invention, Comprising: (G) is a figure which shows the weight loss of a heat-transfer layer, (H) is a heat-transfer layer raw material mixing process (I) is a figure which shows a heat-transfer layer raw material supply process, (J) is a figure which shows a baking process. It is a schematic diagram which illustrates the supply structure of the heat-transfer raw material in the heat exchange type heat storage and heat dissipation apparatus which concerns on embodiment of this invention. It is a perspective view which shows schematic structure of the heat exchange type | formula thermal storage heat dissipation apparatus which concerns on the modification of embodiment of this invention.

Explanation of symbols

10 Heat exchange type heat storage and heat dissipation device (heat storage device)
11 Chemical heat storage material composite molded body (Chemical heat storage material molded body)
12 Powder chemical heat storage material (chemical heat storage material)
12A micro crack (micro crack)
15 Channel 16 Sepiolite (clay mineral)
20 Heat exchange structure (heat exchanger body)
24 Bulkhead (wall)
26 Fluid flow path (heat exchange medium flow path)
25 Heat storage material accommodating part 40 Heat transfer layer 42 Particles (high-density chemical heat storage material)
44 Aqueous solution of calcium nitrate (raw material of chemical heat storage material constituting heat transfer layer)
M Kneaded material S Mixed slurry

Claims (22)

Chemical heat storage material molded body formed by molding powder chemical heat storage material,
A wall body made of a metal material and in contact with the surface of the chemical heat storage material molded body,
An alkaline earth metal compound that is higher in density than the chemical heat storage material molded body and is the same type of chemical heat storage material as the chemical heat storage material molded body, and a clay mineral, is configured, and the chemical heat storage material molded body and the A heat transfer layer that fills the gap with the wall ,
A heat storage device. Chemical heat storage material molded body formed by molding powder chemical heat storage material,
Heat for exchanging heat with the chemical heat storage material molded body is partitioned between the heat storage material storage section storing the chemical heat storage material molded body and the heat storage material storage section with a wall body. A heat exchange structure composed of a metal material , including a heat exchange medium distribution part for distributing the exchange medium;
An alkaline earth metal compound that is higher in density than the chemical heat storage material molded body and is the same type of chemical heat storage material as the chemical heat storage material molded body, and a clay mineral, is configured, and the chemical heat storage material molded body and the A heat transfer layer that fills the gap with the wall ,
A heat storage device. The heat transfer layer includes a hydration reaction-type chemical heat storage material that is oxidized with a dehydration reaction and hydroxylated with a hydration reaction, and is fired at a temperature of 350 ° C to 500 ° C. Or the thermal storage apparatus of Claim 2. The heat storage device according to any one of claims 1 to 3, wherein the chemical heat storage material molded body includes a clay mineral that disperses and holds the powder chemical heat storage material . The heat storage device according to claim 4 , wherein a clay mineral having a layer ribbon structure is used as the clay mineral . The heat storage device according to claim 5 , wherein sepiolite or palygorskite is used as the clay mineral having the layer ribbon structure . The chemical heat storage material molded body is obtained by kneading a chemical heat storage material which is an alkaline earth metal compound of the powder and sepiolite as the clay mineral into a predetermined shape, and having a shape of 350 ° C to 500 ° C. The heat storage device according to claim 6, which is fired at a temperature . The heat storage device according to claim 4 , wherein bentonite is used as the clay mineral . The heat storage device according to any one of claims 1 to 8 , wherein the clay mineral has a fiber shape that is thinner than a particle diameter of a chemical heat storage material forming the chemical heat storage material molded body . The heat storage device according to any one of claims 1 to 9 , wherein at least one of the chemical heat storage material forming the chemical heat storage material molded body and the chemical heat storage material forming the heat transfer layer has fine cracks . A molding process for obtaining a chemical heat storage material molded body from powder chemical heat storage material;
A solution of an alkaline earth metal salt as a raw material for the chemical heat storage material of the same type as the chemical heat storage material formed body, between the chemical heat storage material formed body and the wall made of a metal material in contact with each other; A heat transfer layer raw material supply process for supplying a mixture with clay minerals,
The chemical heat storage material constituting the chemical heat storage material molded body is a mixture of the chemical heat storage material raw material and the clay mineral supplied between the chemical heat storage material molded body and the wall body in the heat transfer layer material supply step. A heat transfer layer generation process for changing to a heat transfer layer made of a higher-density chemical heat storage material,
A method for manufacturing a heat storage device. A molding step of molding a chemical heat storage material molded body having an outer shape that can be inserted into the heat storage material housing portion of the heat exchange structure, using a powder chemical heat storage material,
Inserting the chemical heat storage material molded body formed in the forming step into a heat storage material accommodation section partitioned by a wall body from the heat exchange medium flow in the heat exchange structure formed of a metal material, and
Alkali as a raw material for the chemical heat storage material of the same kind as the chemical heat storage material molded body between the chemical heat storage material molded body and the wall body inserted in the heat storage material accommodating portion of the heat exchange structure in the insertion step A heat transfer layer raw material supplying step for supplying a mixture of a salt solution of an earth metal and a clay mineral;
The chemical heat storage material constituting the chemical heat storage material molded body is a mixture of the chemical heat storage material raw material and the clay mineral supplied between the chemical heat storage material molded body and the wall body in the heat transfer layer material supply step. A heat transfer layer generation process for changing to a heat transfer layer made of a higher-density chemical heat storage material,
A method for manufacturing a heat storage device. Wherein in the forming step, by using a kneaded material obtained by kneading the clay mineral in a predetermined ratio to the chemical thermal storage medium, manufacturing method of claim 11 or claim 1 2 Symbol placement of the heat storage device forming said chemical thermal storage medium molded body . Examples clay mineral, a manufacturing method of a thermal storage apparatus of any one of claims 1 1 to claim 13 using a clay mineral having a layered ribbon structure. The method for manufacturing a heat storage device according to claim 14 , wherein sepiolite or palygorskite is used as the clay mineral having the layer ribbon structure . The method for manufacturing a heat storage device according to any one of claims 11 to 13 , wherein bentonite is used as the clay mineral . The method for manufacturing a heat storage device according to any one of claims 11 to 16, wherein in the molding step, the clay mineral having a fiber shape smaller than a particle diameter of the chemical heat storage material is used . As the alkaline earth metal chemical heat storage material, a hydration reaction type chemical heat storage material that absorbs heat with a dehydration reaction and dissipates heat with a hydration reaction is used,
Wherein in the forming step, the manufacturing method of the heat storage device according to any one of claims 1 1 to claim 17, kneaded with the clay mineral the chemical thermal storage medium in a hydrated state. As the alkaline earth metal chemical heat storage material, a hydration reaction type chemical heat storage material that is oxidized with a dehydration reaction and hydroxylated with a hydration reaction is used,
The method for manufacturing a heat storage device according to any one of claims 11 to 18, wherein in the molding step, the chemical heat storage material is kneaded with the clay mineral in a hydroxide state . In the heat transfer layer raw material supply step, the raw material of the chemical heat storage material for obtaining a hydration reaction type chemical heat storage material that is oxidized in the heat transfer layer generation step and is hydroxylated in accordance with the hydration reaction. A solution is supplied between the chemical heat storage material molded body and the wall body,
The heat transfer layer generating step includes a step of firing the raw material of the chemical heat storage material supplied between the chemical heat storage material molded body and the wall body to change it to an oxide of a hydration reaction type chemical heat storage material. The manufacturing method of the thermal storage apparatus in any one of Claims 11-19 . 21. The method for manufacturing a heat storage device according to claim 20 , wherein in the heat transfer layer generation step, the chemical heat storage material is fired at a temperature at which fine cracks are formed . Performed before the heat transfer layer feed step, any one of claims 1 1 to claim 21, further comprising a preliminary firing step of the chemical heat storage material firing the chemical thermal storage medium molded body at a temperature which is not an oxide A method for manufacturing the heat storage device according to claim 1.