JP5223314B2 - Heat storage device - Google Patents

Description

The present invention relates to a heat storage equipment, which is configured to include a chemical heat storage material molded element of the chemical heat storage material.

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 (for example, see 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). ).

The present invention is, in view of the aforementioned, an object of obtaining a heat storage equipment which can be effectively heat storage or heat radiation in a chemical heat storage material.

Heat storage device according to the first aspect of the present invention, Ri formed by molding a powder of the chemical heat storage material, and the powder of the chemical heat storage material dispersion held chemical heat storage material is configured to include a clay mineral moldings A wall made of a metal material and in contact with the surface of the chemical heat storage material molded body, and a porous film of silica or alumina as an inorganic porous film having a higher density than the chemical heat storage material molded body, An adhesive heat transfer layer that fills a gap between the heat storage material molded body and the wall body .

  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 an adhesive heat transfer layer including an inorganic porous film having a higher density (dense) than the chemical heat storage material molded body, the chemical heat storage material molding High adhesion between body and wall. Further, due to the presence of the adhesive 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.

Heat storage device according to a second aspect of the invention, Ri formed by molding a powder of the chemical heat storage material, and the powder of the chemical heat storage material dispersion held chemical heat storage material is configured to include a clay mineral moldings The heat storage material housing portion housing the chemical heat storage material molded body and the inside of the heat storage material housing portion are partitioned by a wall body and for exchanging heat with the chemical heat storage material molded body through the wall body. A heat exchange structure composed of a metal material , including a heat exchange medium flow part for circulating the heat exchange medium, and a porous film of silica or alumina as an inorganic porous film having a higher density than the chemical heat storage material molded body. And an adhesive 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 bonding between the chemical heat storage material molded body, which is a porous structure, and the wall of the heat exchange structure is made of an inorganic porous film having a higher density (dense) than the chemical heat storage material molded body. Since it is buried in the heat transfer layer, the adhesion between the chemical heat storage material molded body and the wall body is high. Further, due to the presence of the adhesive 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.

In the heat storage device according to the first and second aspects, the adhesive heat transfer layer can ensure adhesion between the chemical heat storage material molded body and the metal wall body and the interfacial adhesion strength.

In the heat storage device according to claims 1 and 2 , since silica or alumina is employed as the inorganic porous film constituting the adhesive heat transfer layer, the adhesiveness with the metal interface is particularly high. In addition, since silica or alumina is employed as the inorganic porous film constituting the adhesion heat transfer layer, for example, these sols are bonded between the chemical heat storage material molded body and the wall body and heated. A heat transfer layer can be obtained.
Further, in the heat storage device according to claims 1 and 2, 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 porous structure The structure is easily maintained stably. Moreover, the adhesiveness to the wall body of a chemical heat storage material molded object also improves.

A heat storage device according to a third aspect of the present invention is the heat storage device according to the first or second aspect , wherein the adhesive heat transfer layer is a chemical heat storage material having a smaller interparticle distance than the chemical heat storage material of the powder. In addition.

In the heat storage device according to claim 3 , since the chemical heat storage material is included in the adhesive heat transfer layer, the density of the chemical heat storage material as the whole heat storage device is increased, and heat storage and heat dissipation performance are improved.

A 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 a clay mineral having a layer ribbon structure is used as the clay mineral.

In the heat storage device according to claim 4 , since the clay mineral is porous and has a fibrous form of a layer ribbon structure having a large specific surface area, the chemical structure of the powder chemical heat storage material is well organized and structured by its fiber and plasticity. It can be made.

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

In the heat storage device according to claim 5 , since at least a part of the clay mineral is sepiolite or palygorskite (attapulgite) having a layered ribbon structure, a fine chemical heat storage material is well organized by its fiber and plasticity. Can be structured.

A heat storage device according to a sixth aspect of the present invention is the heat storage device according to any one of the first to third aspects, wherein bentonite is used as the clay mineral.

In the heat storage device according to the sixth aspect , bentonite, which is a clay mineral having a strong adhesive force, is used, so that the chemical heat storage material can be well organized and structured by this adhesive force.

A heat storage device according to a seventh aspect of the present invention is the heat storage device according to any one of the first to sixth aspects, wherein the clay mineral has a fiber shape smaller than the particle diameter of the chemical heat storage material. ing.

In the heat storage device according to claim 7 , since the clay mineral has a fibrous shape having a fine fiber diameter, it is possible to achieve organization and structure of the powder chemical heat storage material using a small amount of clay mineral. . 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.

The heat storage device according to an eighth aspect of the present invention is the heat storage device according to any one of the first to seventh aspects, wherein the chemical heat storage material has fine cracks.

In the heat storage device according to the eighth aspect, since the specific surface area of the chemical heat storage material having fine cracks is large, the reaction rate is improved in the heat storage and heat dissipation reaction. Thereby, the efficiency of heat storage and heat dissipation can be improved.

A heat storage device according to a ninth aspect of the present invention is the heat storage device according to any one of the first to eighth aspects, wherein the chemical heat storage material absorbs heat with a dehydration reaction and dissipates heat with a hydration reaction. Hydration reaction type chemical heat storage material is used.

In the heat storage device according to claim 9 , the hydration reaction type chemical heat storage material repeats volume expansion and contraction with the hydration reaction and dehydration (reverse hydration) reaction, but the chemical heat storage material is organized in a structure using clay minerals. And the formation of gaps effectively suppresses or prevents the chemical heat storage material from being pulverized.

Heat storage device according to the invention of claim 1 0, wherein, in the heat storage device according to any one of claims 1 to 9, is oxidized with the dehydration reaction, hydration reaction that is hydroxylated with the hydration reaction System chemical heat storage material is used.

In heat storage device according to claim 1 0, wherein the hydration reaction, dewatering (Gyakumizuwa) reaction with hydration reaction chemical heat storage material volume expansion is repeated contractions, the chemical heat storage material in the structure using the clay mineral structure By crystallization or formation of gaps, the chemical heat storage material is effectively prevented or prevented from being pulverized.

Heat storage device according to the invention of claim 1 1, wherein, in the heat storage device according to claim 1 0, wherein the hydration reaction system the chemical heat storage material is an inorganic compound.

In heat storage device of claim 1 1, wherein, since 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.

Heat storage device according to the invention of claim 1 wherein, in the heat storage device according to claim 1 1, wherein the inorganic compound is an alkaline earth metal compound.

In heat storage device according to claim 1 wherein, in order to use the alkaline earth metal compound (hydroxide), in other words, for using a material with a low environmental load, manufacture, use, to ensure safety, including recycling It becomes easy. 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.

Heat storage device according to the invention of claim 1 3, wherein, in the heat storage device of any one of claims 1 0 to Claim 1 2, and the hydration reaction chemical thermal storage medium of the powder, as the clay mineral A product formed by kneading with sepiolite was molded into a predetermined shape and fired at a temperature of 350 ° C to 500 ° C.

Heat storage device according to claim 1 3, wherein, by the hydration reaction chemical thermal storage medium and sepiolite firing the shaped body being kneaded, sepiolite is sintered, and is configured as a porous structure. 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.

According to a first aspect of the present invention, there is provided a method for producing a heat storage device comprising: a step of obtaining a chemical heat storage material molded body from a powdered chemical heat storage material; and the chemical heat storage material molded body and the wall body that are in contact with each other; Baking is performed at an adhesive supply step for supplying an adhesive in which fine particles are dispersed, and at a temperature at which the adhesive supplied between the chemical heat storage material molded body and the wall body in the adhesive supply step is solidified. And a firing step.

In the manufacturing method of this heat storage device, the molding process, to give the chemical thermal storage medium molded body by molding a powder of the chemical thermal storage medium, then proceeds to the adhesive supplying step. In the adhesive supply process, the adhesive is supplied between the chemical heat storage material molded body and the wall body (interface) in contact with each other, and the process proceeds to the firing process (heating process). In the firing step, the adhesive between the chemical heat storage material molded body and the wall body is solidified. As a result, an adhesive heat transfer layer made of an inorganic porous film 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 an adhesive heat transfer layer made of an inorganic porous film having a higher density (dense) than the chemical heat storage material molded body, the chemical heat storage material molding High adhesion between body and wall. Further, due to the presence of the adhesive 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 thermal storage apparatus which concerns on a 1st aspect, the thermal storage apparatus with which favorable heat transfer is performed between the chemical thermal storage material molded object and the wall body which shape | mold the powdered chemical thermal storage material. Can be manufactured.

The manufacturing method of the heat storage apparatus which concerns on a 2nd aspect WHEREIN: The shaping | molding process which shape | molds the chemical heat storage material molded object which has the external shape which can be inserted in the heat storage material accommodating part of a heat exchange structure using a powder chemical heat storage material, An insertion step of inserting the chemical heat storage material molded body molded in the molding step into a heat storage material accommodation section partitioned by a wall body from the heat exchange medium flow in the heat exchange structure, and the heat in the insertion step. In the adhesive supply step of supplying an adhesive in which inorganic fine particles are dispersed between the chemical heat storage material molded body inserted into the heat storage material accommodating portion of the exchange structure and the wall body, and in the adhesive supply step A firing step of firing at a temperature at which the adhesive supplied between the chemical heat storage material molded body and the wall body is solidified.

In the manufacturing method of this heat storage device, the molding process, the particles of chemical thermal storage medium is formed into the chemical thermal storage medium molded body having a shape and flow path may be inserted in the heat storage material accommodation unit of the heat exchanger structure, then, Move to the insertion process. In the insertion step, the chemical heat storage material molded body is inserted into the heat storage material housing portion of the heat exchange structure, and then the process proceeds to the adhesive supply step. In the adhesive supply process, the adhesive is supplied between the contacted chemical heat storage material molded body and the wall (interface), and the process proceeds to the firing process (heating process). In the firing step, the adhesive between the chemical heat storage material molded body and the wall body is solidified. 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. An adhesive heat transfer layer made of an inorganic porous film 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 bonding 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 transfer layer, the adhesion between the chemical heat storage material molded body and the wall body is high. Further, due to the presence of the adhesive 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 manufacturing method according to the second aspect, it is possible to obtain 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 body. it can.

The manufacturing method of the heat storage device according to the third aspect is the manufacturing method of the heat storage device according to the first aspect or the second aspect , wherein the adhesive includes a sol in which the inorganic fine particles are dispersed.

In the manufacturing method of this heat storage device, the adhesive supplying step, so to supply the inorganic fine particles are dispersed in a dispersion medium sol between the chemical thermal storage medium molded body and the wall, the chemical thermal storage medium molded body and the wall It is possible to supply inorganic fine particles at a high density and substantially uniformly between the body and the body. Thereby, it is possible to obtain an adhesive heat transfer layer having a high density and a substantially uniform overall.

A method for manufacturing a heat storage device according to a fourth aspect is the method for manufacturing a heat storage device according to the third aspect , wherein the adhesive contains alumina sol or silica sol in which alumina or silica is dispersed as the inorganic fine particles.

In the manufacturing method of this thermal storage device, since the alumina or silica is used as inorganic particles, in particular good adhesion between the metal surface (metal wall).

The method for manufacturing a heat storage device according to a fifth aspect is the method for manufacturing a heat storage device according to any one of the first to fourth aspects , wherein the adhesive is changed to a chemical heat storage material by being baked in the baking step. A metal salt.

In the manufacturing method of this heat storage device, the metal salt is for Fukumaru the adhesive supplied between the chemical thermal storage medium molded body and the wall in the adhesive supplying step, formed through the firing process bonding heat transfer The layer includes a chemical heat storage material finer than the chemical heat storage material constituting the chemical heat storage material molded body. That is, since a part of the adhesion heat transfer layer is composed of the chemical heat storage material, the density of the chemical heat storage material as the whole heat storage device is increased, and the heat storage and heat dissipation performance is improved.

The manufacturing method of the heat storage device according to the invention of the sixth aspect is the manufacturing method of the heat storage device according to any one of the first to fifth aspects, in the molding step, at a predetermined ratio to the chemical heat storage material. The said chemical heat storage material molded object is shape | molded using the kneaded material which knead | mixed the clay mineral.

In the manufacturing method of this heat storage device, a chemical heat storage material by kneading and clay minerals, can be dispersed hold the chemical heat storage material in the skeleton of the clay mineral porous. 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.

A manufacturing method of a heat storage device according to a seventh aspect uses a clay mineral having a layered ribbon structure as the clay mineral in the manufacturing method of the heat storage device of the sixth aspect .

In the manufacturing method of this thermal storage device, since the clay mineral forms a large filamentous morphology specific surface area porous, its fiber, by utilizing the plasticity, well organized particles of chemical thermal storage medium, structured can do.

A method for manufacturing a heat storage device according to an eighth aspect uses sepiolite or palygorskite as the clay mineral having the layer ribbon structure in the method for manufacturing a heat storage device according to the seventh aspect .

In the manufacturing method of this thermal storage device, since the use of sepiolite or palygorskite having a layered ribbon structure as at least a portion of the clay mineral (attapulgite), its fiber, by utilizing the plasticity, good particles of chemical thermal storage medium Can be organized and structured.

A method for manufacturing a heat storage device according to a ninth aspect uses bentonite as the clay mineral in the method for manufacturing a heat storage device according to the sixth aspect .

In the manufacturing method of this thermal storage device, since the use of bentonite is strong adhesion clay mineral, this adhesion, better organize the particles of chemical thermal storage medium can be structured.

The method for manufacturing a heat storage device according to a tenth aspect is the method for manufacturing a heat storage device according to any one of the sixth to ninth aspects , wherein in the molding step, a fiber shape that is thinner than the particle diameter of the chemical heat storage material. The above clay mineral is used.

In the manufacturing method of this thermal storage device, since the clay mineral forms a fibrous having fine fiber diameters, serves organization of particles of chemical thermal storage medium, structured by kneading the molding process a small amount of the clay mineral be able to. 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.

The method for manufacturing a heat storage device according to an eleventh aspect is the method for manufacturing a heat storage device according to any one of the sixth to tenth aspects , wherein the chemical heat storage material absorbs heat in accordance with a dehydration reaction and undergoes a hydration reaction A hydration reaction type chemical heat storage material that dissipates heat is used, and the chemical heat storage material in a hydrated state is kneaded with the clay mineral in the molding step.

In the manufacturing method of this heat storage device, in the molding process, since the chemical thermal storage medium in a hydrated state a kneading and clay minerals, that reaction with the water is a concern when using a chemical heat storage material of the dehydration condition occurs Absent. For this reason, water can be used as a binder during kneading in the molding step.

The method for manufacturing a heat storage device according to a twelfth aspect is the method for manufacturing a heat storage device according to any one of the sixth to eleventh aspects , wherein the chemical heat storage material is oxidized along with a dehydration reaction and is subjected to a hydration reaction. A hydration reaction type chemical heat storage material that is hydroxylated is used, and in the molding step, the chemical heat storage material in a hydroxide state is kneaded with the clay mineral.

In the manufacturing method of this heat storage device, in the molding process, for mixing with the clay mineral to a chemical heat storage material of the hydroxide state, reaction occurs between the water to be feared in the case of using a chemical heat storage material is dehydrated There is nothing. For this reason, water can be used as a binder during kneading in the molding step.

A method for manufacturing a heat storage device according to a thirteenth aspect is the method for manufacturing a heat storage device according to the twelfth aspect , wherein the hydration reaction type chemical heat storage material is an inorganic compound.

In the manufacturing method of this thermal storage device, since 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.

The manufacturing method of the heat storage device according to the fourteenth aspect is the manufacturing method of the heat storage device according to the thirteenth aspect , wherein the inorganic compound is an alkaline earth metal compound.

In the manufacturing method of this thermal storage device, since the use of alkaline earth metal compound (hydroxide), it is easy to ensure the safety during manufacturing. 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 a fifteenth aspect is the method for manufacturing a heat storage device according to any one of the twelfth to fifteenth aspects , wherein the hydrated chemical heat storage material is dehydrated in the firing step. The kneaded product is baked at a temperature.

In the manufacturing method of this thermal storage device, since hydration based chemical heat storage material is dewatered after firing of the firing process, it is easy to adjust the specific surface area of the chemical thermal storage medium.

The method for manufacturing a heat storage device according to a sixteenth aspect is the method for manufacturing a heat storage device according to the fifteenth aspect , wherein, in the baking step, baking is performed at a temperature at which fine cracks are formed in the chemical heat storage material.

In the manufacturing method of this heat storage device, as the clay mineral is structured with a chemical heat storage material by sintering at sintering step (sintering condition is ensured), minute cracks in the chemical thermal storage medium is dehydrated Is formed. Thereby, the specific surface area of the chemical heat storage material in the chemical heat storage material molded body formed as a porous structure can be increased, which contributes to improvement of heat storage and heat dissipation reaction rate. In addition, it is preferable that the firing temperature of the clay mineral is close to the dehydration temperature of the hydration reaction type chemical heat storage material. As such a combination, for example, an alkaline earth metal compound (dehydration temperature of 400 ° C. to 450 ° C.) and sepiolite ( And a combination with a firing temperature of 350 ° C. or higher.

  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 3 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 an adhesive 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. Have. In addition, in FIG. 1, illustration of the sepiolite 16 which comprises the chemical heat storage material composite molded object 11 is abbreviate | omitted. The adhesive heat transfer layer 40 is a dense structure formed by organizing and structuring fine particles (or a porous film) 42 having a sufficiently small interparticle distance (submicron order) 42 with respect to the powder chemical heat storage material 12 at a high density. A porous structure is formed, and a part of the porous structure is inserted into the pores 14 located (opened) on the surface side of the chemical heat storage material composite molded body 11. With the adhesive 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 adhesive 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.

  In this embodiment, the fine particles 42 constituting the adhesive heat transfer layer 40 include inorganic metal fine particles and fine particles of an alkaline earth metal compound that is a hydrated chemical heat storage material. Specifically, the fine particles 42 include alumina fine particles and 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 adhesive heat transfer layer 40 can be grasped as a mixture of the inorganic adhesive and the chemical heat storage material.

  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. In this embodiment, the kneading ratio of the sepiolite 16 to the powder chemical heat storage material 12 is, for example, about 5 to 10% by mass.

  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. 4F, the process proceeds to the first firing step. In the first firing step, the heat exchanger main body 20 in which the chemical heat storage material composite molded body 11 is inserted is placed in the 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 the first firing step is set to 300 ° C. or lower. This firing 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, in the method of manufacturing the heat exchange type heat storage and heat dissipation device 10, as shown in FIG. 4G, alumina (Al ₂ O ₃ ) is used as an adhesive (starting material) for forming the adhesive heat transfer layer 40. An alumina sol 45 dispersed in a colloidal state in a dispersion medium is prepared. In this embodiment, as the adhesive, an alumina sol 45 mixed with an aqueous solution 44 of calcium nitrate which is a salt of an alkaline earth metal is used. For this reason, in the manufacturing method of the heat exchange type heat storage / heat dissipating device 10, the process proceeds to the adhesive mixing step shown in FIG. 4H, and the aqueous solution 44 and the alumina sol 45 are mixed to obtain the adhesive 46. In this mixed state, the adhesive 46 has a sol shape.

  Next, as shown in FIG. 4I, the process proceeds to an adhesive supply process. In the adhesive supply step, an adhesive is provided between the chemical heat storage material composite molded body 11 in the heat storage material housing portion 25 of the heat exchanger body 20 and the inner surface of the heat storage material housing portion 25, that is, the partition wall 24 and the shell 22. 46 is supplied. At this time, for example, as shown in FIG. 5, by forming chamfers 11 </ b> A at the corners of the chemical heat storage material composite molded body 11, the high-viscosity adhesive 46 is removed from 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 adhesive 46 supplied in this way is molded into the chemical heat storage material composite by the capillary force due to 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 second firing step. In the second firing step, the heat exchanger main body 20 to which the adhesive 46 is supplied between the heat storage material accommodating portion 25 and the chemical heat storage material composite molded body 11 is placed in the firing furnace 32, and at a predetermined temperature. The chemical heat storage material composite molded body 11 and the adhesive 46 are fired for a predetermined time. The firing temperature is approximately 450 ° C., which is 280 ° C. to 300 ° C. or higher at which calcium nitrate in the adhesive 46 is oxidized and converted to calcium oxide, and 400 ° C. or higher at which the alumina sol 45 is fired. .

  Thereby, in the manufacturing method of the heat exchange type heat storage and heat dissipation device 10, while the alumina of the alumina sol 45 is crystallized, the calcium nitrate in the adhesive 46 is changed to calcium oxide, and the chemical heat storage material composite molded body 11 and An adhesive heat transfer layer 40 in which fine particles 42 of alumina and a powder chemical heat storage material (calcium oxide) are structured with high density is formed between the partition wall 24 and the shell 22. In addition, since the firing temperature in the second firing step is a temperature at which microcracks are formed in the powder chemical heat storage material (calcium oxide) as described above, the fine particles 42 of the chemical heat storage material have microcracks (not shown). Thus, the specific surface area of the fine particles 42 of the chemical heat storage material is expanded. With the above, the manufacture of the heat exchange type heat storage and heat dissipation device 10 is completed.

  In addition, since microcracks can be generated in the powder chemical heat storage material 12 constituting the chemical heat storage material composite molded body 11 in the second baking step, for example, the baking temperature in the first baking step is relatively about 300 ° C. Can be low temperature. In this case, in the chemical heat storage material composite molded body 11 after the first firing step, the powder chemical heat storage material 12 is maintained in a state of calcium hydroxide.

  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 transmit the heat to the fluid flowing through the fluid flow path 26.

  Here, in the heat exchange type heat storage and heat dissipation device 10, the fine particles 42 are densely 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 storage unit 25 and the fluid flow path 26. Since the structured adhesion heat transfer layer 40 is formed, 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, the contact area between the chemical heat storage material composite formed body 11 and the partition wall 24 via the adhesive heat transfer layer 40 is increased. Therefore, the chemical heat storage material composite formed body 11 and Adhesive strength with the partition wall 24 is high.

  In particular, the metal oxide layer (alumina) using sol as a starting material is excellent in adhesiveness with the metal interface of the partition wall 24 and can ensure high adhesion with the metal interface. Moreover, since such a metal oxide layer exhibits an anchor effect by impregnation into the chemical heat storage material composite molded body 11 (pore 14), a synergistic effect of the anchor effect and high adhesion to the metal interface is obtained. The chemical heat storage material composite molded body 11 and the partition wall 24 can be firmly attached. In particular, the metal oxide layer is excellent in bondability with the partition wall 24 in which an oxide of the same metal is formed on the surface layer. For this reason, in this embodiment in which the adhesive 46 includes alumina, for example, the partition wall 24 is preferably made of aluminum-containing stainless steel or the like. In addition, the effect which the chemical heat storage material composite molded object 11 itself reinforces by the said anchor effect is also acquired, and the fall of the interfacial adhesion product resulting from a deformation | transformation of the chemical heat storage material composite molded object 11 is suppressed.

  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 adhesive heat transfer layer 40 includes fine particles 42 of the chemical heat storage material, for example, the unit volume as a whole is compared with the case where the adhesive heat transfer layer 40 is composed of only alumina fine particles. The density of the heat storage material per mass is increased, and the heat storage and heat dissipation performance is improved. In addition, in the heat exchange type heat storage and heat dissipation device 10, since the powder chemical heat storage material 12 of the chemical heat storage material composite molded body 11 and the fine particles 42 of the adhesive heat transfer layer 40 are the same type of chemical heat storage material, the adhesive heat transfer layer 40 and the chemical heat storage material composite molded body 11 can be reduced in the difference in expansion coefficient due to the temperature rise, 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 adhesive heat transfer layer 40 made of the same type of chemical heat storage material have no fear of sintering, for example, which is a concern when using different types of alkaline earth metals, The pore 14 having an appropriate size can be ensured.

  Here, in the manufacturing method of the heat exchange type heat storage and heat dissipation device 10, the starting of the adhesive 46 adhesion heat transfer layer 40 including the alumina sol 45 in which alumina is colloidally dispersed in a dispersion medium as inorganic fine particles for forming a porous film. Since it is used as a raw material, the alumina fine particles 42 can be distributed at a high density and substantially uniformly between the chemical heat storage material composite molded body 11 and the partition wall 24. Thereby, the high-density and homogeneous adhesive heat transfer layer 40 excellent in interfacial adhesion and heat transfer can be configured.

  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 which is a salt of an alkaline earth metal is included as a part of the adhesive 46, the adhesive heat transfer layer 40 including the chemical heat storage material is formed. As described above, this contributes to obtaining the heat exchange type heat storage and heat dissipation device 10 having a high chemical heat storage material density. Moreover, since the aqueous solution of calcium nitrate is used as the starting material, the fine particles 42 of the chemical heat storage material can be distributed between the chemical heat storage material composite molded body 11 and the partition wall 24 at a high density and substantially uniformly. Also, for example, when obtaining a powder chemical heat storage material (calcium oxide) using calcium carbonate as a starting material, high-temperature firing at about 950 ° C. to 1000 ° C. is required in the decarbonation step, but an aqueous solution of calcium nitrate is used as a starting material. The firing temperature as a raw material can be kept low at 300 ° C. or lower.

  Furthermore, in the method of manufacturing the heat exchange type heat storage and heat dissipation device 10, in the kneading step of the molded body molding step for molding the chemical heat storage material composite molded body 11, a predetermined sepiolite 16 having a large porous surface area is used. In order to knead the powder chemical heat storage material 12 at a ratio, the sepiolite 16 is stirred together 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.

  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.

  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.

  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.

  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.

  The firing temperature at which microcracks 12A are generated in the powder chemical heat storage material 12 and the fine particles 42 that are calcium oxide is most preferably about 450 ° C. When the firing temperature is 400 ° C. or less, the generation of microcracks 12A and the like is small, and when the firing temperature is 500 ° C. or more, the probability of cracking of the powder chemical heat storage material 12 and the fine particles 42 is increased and the powder chemical heat storage material 12 It has been confirmed that the specific surface area of the fine particles 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, although the example in which the adhesive 46 includes the alumina sol 45 and the aqueous solution 44 of calcium nitrate has been shown in the above embodiment, the present invention is not limited to this. For example, the adhesive 46 is configured only by the alumina sol 45. Anyway. Further, silica sol may be used instead of the alumina sol 45, or a dispersion of inorganic fine particles such as alumina or silica may be used.

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 | mold thermal storage heat dissipation 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. 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: (A) is a figure which shows a raw material, (B) is a figure which shows the kneading | mixing 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 1st 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 raw material mixing process. The figure shown, (I) is a figure which shows an adhesive agent 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 portion 40 Heat transfer layer 42 Fine particles (inorganic fine particles, high-density chemical heat storage material)
44 Aqueous solution of calcium nitrate (raw material of chemical heat storage material constituting the adhesive heat transfer layer)
45 Alumina sol (with fine particles dispersed)
46 Adhesive

Claims (13)

Ri formed by molding a chemical heat storage material powder, and a chemical heat storage material molded body chemical heat storage material of the powder is structured to include a clay mineral dispersed held,
A wall body made of a metal material and in contact with the surface of the chemical heat storage material molded body,
An adhesive heat transfer layer that includes a porous film of silica or alumina as an inorganic porous film having a higher density than the chemical heat storage material molded body, and fills a gap between the chemical heat storage material molded body and the wall;
A heat storage device. Ri formed by molding a chemical heat storage material powder, and a chemical heat storage material molded body chemical heat storage material of the powder is structured to include a clay mineral dispersed held,
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 adhesive heat transfer layer that includes a porous film of silica or alumina as an inorganic porous film having a higher density than the chemical heat storage material molded body, and fills a gap between the chemical heat storage material molded body and the wall;
A heat storage device. The heat storage device according to claim 1, wherein the adhesive heat transfer layer further includes a chemical heat storage material having a distance between particles smaller than that of the powder chemical heat storage material . The heat storage device according to any one of claims 1 to 3, wherein a clay mineral having a layer ribbon structure is used as the clay mineral . The heat storage device according to claim 4 , wherein sepiolite or palygorskite is used as the clay mineral having the layer ribbon structure. The heat storage device according to any one of claims 1 to 3 , wherein bentonite is used as the clay mineral . The heat storage device according to any one of claims 1 to 6, wherein the clay mineral has a fiber shape smaller than a particle diameter of the chemical heat storage material . The heat storage device according to any one of claims 1 to 7 , wherein the chemical heat storage material has fine cracks . The heat storage device according to any one of claims 1 to 8, wherein a hydration reaction type chemical heat storage material that absorbs heat with a dehydration reaction and dissipates heat with a hydration reaction is used as the chemical heat storage material . 10. The heat storage device according to claim 1 , wherein the chemical heat storage material is a hydration reaction type chemical heat storage material that is oxidized with a dehydration reaction and hydroxylated with a hydration reaction. . The heat storage device according to claim 10 , wherein the hydration reaction type chemical heat storage material is an inorganic compound . The heat storage device according to claim 11 , wherein the inorganic compound is an alkaline earth metal compound . The chemical heat storage material molded body is a product obtained by kneading the powder hydration reaction type chemical heat storage material and sepiolite as the clay mineral into a predetermined shape, and firing it at a temperature of 350 ° C. to 500 ° C. and comprising claim 1 0 - heat storage device according to any one of claims 12.