JP2009149838A - Formed product of chemical thermal storage medium, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a formed product of a chemical thermal storage medium capable of making reactivity compatible with heat transfer properties for thermal storage and heat release, and to provide a method for producing the formed product of the chemical thermal storage medium. <P>SOLUTION: A chemical thermal storage reaction part 10 is a porous structure obtained by forming powdery chemical thermal storage medium particles 12 into a prescribed shape, and has flow channels 15 in the interior thereof. The flow channels 15 are, e.g. discharge routes for a reaction product produced according to a thermal storage reaction of the powdery chemical thermal storage medium particles 12, and further feed routes for reactants required for a heat release reaction of the powdery chemical thermal storage medium particles 12. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a chemical heat storage material molded body obtained by molding 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. In addition, in the configurations of Patent Documents 2 and 3, due to the increase in heat conduction resistance due to the adoption of the capsule and the complexity of the heat transfer path, heat due to the exothermic reaction of the chemical heat storage material cannot be taken out efficiently, and further in the heat storage reaction There was a problem that heat 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 a some evaporating dish, there are few heat exchange areas and it causes a heat-transfer regulation.

  In view of the above facts, the present invention aims to obtain a chemical heat storage material molded body capable of achieving both heat storage and heat dissipation reactivity and heat transfer, and a method for producing the chemical heat storage material molded body. It is.

  The chemical heat storage material molded body according to the invention of claim 1 is formed by molding a chemical heat storage material in the form of powder, and a flow path for supplying reactants or discharging reaction products therein is formed. .

  The molded product of the chemical heat storage material according to claim 1 is formed as a whole by forming a gap (diffusion path) between the powders (chemical heat storage material) by forming the powdered chemical heat storage material. It is formed as a porous structure having a predetermined shape. And in this chemical heat storage material molded object, since the flow path for discharging the reaction product produced by heat storage or heat dissipation for introducing the reactant used for heat storage or heat dissipation is formed, these The flow path of the reactant or reaction product is structurally ensured.

  Thereby, in this chemical heat storage material molded body, introduction of the reactant through the channel, diffusion (permeation) of the reactant or reaction product through the pores of the porous structure, discharge of the reaction product through the channel Is achieved, and the reactivity for heat storage and heat dissipation is good. And since this flow path is formed in the inside of a chemical heat storage material molded object, the heat transfer property by a chemical heat storage material molded object is not inhibited.

  Thus, in the chemical heat storage material molded body according to claim 1, both the reactivity for heat storage and heat dissipation and the heat transfer can be achieved.

  The chemical heat storage material molded body according to the invention described in claim 2 is the chemical heat storage material molded body according to claim 1, wherein the representative dimension of the flow path is larger than the particle diameter of the chemical heat storage material.

  In the chemical heat storage material molded body according to claim 2, the reactant and reaction product are transported by a flow path having a sufficiently large cross section for the pores between the chemical heat storage materials for transporting the reactants and the like by diffusion. Therefore, good reactivity can be ensured.

  The chemical heat storage material molded body according to the invention described in claim 3 is the chemical heat storage material molded body according to claim 1 or 2, wherein a plurality of the flow paths are formed.

  In the chemical heat storage material molded body according to claim 3, by forming a plurality of flow paths, the diffusion path to each part of the molded body increases, and the degree of freedom in selecting the dimensional shape of the chemical heat storage material molded body increases.

  The chemical heat storage material molded body according to the invention described in claim 4 is the chemical heat storage material molded body according to any one of claims 1 to 3, wherein the thickness between the flow path and the surface of the molded body is 4 mm. It is as follows.

  In the chemical heat storage material molded body according to claim 4, since the thickness between the flow path and the surface of the molded body is 4 mm or less, for example, the reactant can be favorably diffused on the surface side of the molded body with respect to the flow path. it can.

  The chemical heat storage material molded body according to the invention described in claim 5 is the chemical heat storage material molded body according to any one of claims 1 to 4, wherein the thickness between the flow path and the molded body surface is 2 mm. It is as follows.

  In the chemical heat storage material molded body according to claim 5, the thickness between the flow path and the molded body surface is 2 mm or less. ) Can be diffused.

  The chemical heat storage material molded body according to the invention described in claim 6 is the chemical heat storage material molded body according to any one of claims 1 to 5, wherein a plurality of the flow paths are formed in parallel. The thickness of the molded body between the flow paths is 8 mm or less.

  In the chemical heat storage material molded body according to claim 6, since the interval between the parallel flow paths is 8 mm or less, in other words, because the diffusion distance from the flow path to the central portion in the thickness direction of the molded body is 4 mm or less, For example, the reactant can be favorably diffused in a portion between the flow paths in the molded body.

  The chemical heat storage material molded body according to the invention described in claim 7 is the chemical heat storage material molded body according to any one of claims 1 to 6, wherein a plurality of the flow paths are formed in parallel. The molded body thickness between the flow paths is 4 mm or less.

  In the chemical heat storage material molded body according to claim 7, since the interval between the parallel flow paths is 4 mm or less, in other words, the diffusion distance from the flow path to the central portion in the thickness direction of the molded body is 2 mm or less, For example, the reactant can be diffused more satisfactorily (sufficiently) to the portion between the flow paths in the molded body.

  The chemical heat storage material molded body according to claim 8 is the chemical heat storage material molded body according to any one of claims 1 to 7, wherein the chemical heat storage material is molded by being held dispersed in clay minerals. Has been.

  In the chemical heat storage material molded body according to claim 8, since the chemical heat storage material is dispersed and held in the skeleton of the porous clay mineral, the strength as the porous structure is high, and the porous structure The structure is easily maintained stably.

  The chemical heat storage material molded body according to the invention described in claim 9 is the chemical heat storage material molded body according to claim 8, wherein a clay mineral having a layer ribbon structure is used as the clay mineral.

  In the chemical heat storage material molded body according to claim 9, 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 by its fiber and plasticity. And can be structured.

  The chemical heat storage material molded body according to the invention described in claim 10 is the chemical heat storage material molded body according to claim 8, wherein the clay mineral includes a clay mineral having a layer ribbon structure and bentonite having a plate-like structure. Yes.

  In the chemical heat storage material molded body according to claim 10, since the clay mineral includes a fibrous form of a layer ribbon structure having a porous and large specific surface area, a fine chemical heat storage material is well organized by its fiber and plasticity. And can be structured. In addition, since bentonite having a plate-like structure is included as a clay mineral, shrinkage in the in-plane direction of the molded body accompanying firing is suppressed. That is, bentonite has the property of being oriented along the wall surface of the molded body (the property due to self-organization of the plate-like crystals) in accordance with the molding before firing. By being oriented along, shrinkage of the molded body is suppressed. Thereby, it is easy to ensure the dimensional accuracy of the chemical heat storage material molded body.

  The chemical heat storage material molded body according to claim 11 is the chemical heat storage material molded body according to claim 9 or claim 10, wherein sepiolite, palygorskite or kaolinite is used as the clay mineral having the layer ribbon structure. ing.

  In the chemical heat storage material molded body according to claim 11, since at least a part of the clay mineral is sepiolite, palygorskite (attapulgite) or kaolinite having a layer ribbon structure, the chemical heat storage material in powder form due to its fiber and plasticity. Can be well organized and structured.

  The chemical heat storage material molded body according to the invention described in claim 12 is the chemical heat storage material molded body according to claim 8, wherein bentonite is used as the clay mineral.

  Since the bentonite which is a clay mineral with strong adhesive force is used in the chemical heat storage material molded body according to claim 12, the chemical heat storage material in powder form can be well organized and structured by this adhesive force.

  The chemical heat storage material molded body according to claim 13 is the chemical heat storage material molded body according to any one of claims 8 to 12, wherein the clay mineral is larger than the particle diameter of the chemical heat storage material. Made of fine fibers.

  In the chemical heat storage material molded body according to claim 13, since the clay mineral forms a fiber having a fine fiber diameter, the organization and structure of the powder chemical heat storage material can be achieved using a small amount of clay mineral. Is possible. 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 chemical heat storage material molded body according to claim 14 is the chemical heat storage material molded body according to any one of claims 1 to 13, wherein the chemical heat storage material has fine cracks.

  In the chemical heat storage material molded body according to claim 14, since the specific surface area of the chemical heat storage material having fine cracks is large, the reaction rate improvement in the heat storage and heat dissipation reaction is shown. Thereby, the efficiency of heat storage and heat dissipation can be improved.

  The chemical heat storage material molded body according to the invention described in claim 15 is the chemical heat storage material molded body according to any one of claims 1 to 14, wherein the chemical heat storage material molded body absorbs heat in accordance with a dehydration reaction, Hydration reaction type chemical heat storage materials that dissipate heat during the sum reaction are used.

  In the chemical heat storage material molded body according to claim 15, the chemical heat storage material repeats volume expansion and contraction in accordance with a hydration reaction and a dehydration (reverse hydration) reaction. By forming the gap, the pulverization of the chemical heat storage material is effectively suppressed or prevented.

  The chemical heat storage material molded body according to the invention described in claim 16 is oxidized according to the dehydration reaction in the chemical heat storage material molded body according to any one of claims 1 to 15, and is hydroxylated along with the hydration reaction. Hydration reaction type chemical heat storage material is used.

  In the chemical heat storage material molded body according to claim 16, the hydration reaction type chemical heat storage material repeats volume expansion and contraction with a hydration reaction and a dehydration (reverse hydration) reaction, but the chemical heat storage material in a structure using clay minerals As a result of the organization and the formation of gaps, the pulverization of the chemical heat storage material is effectively suppressed or prevented.

  The chemical heat storage material molded body according to claim 17 is the chemical heat storage material molded body according to claim 16, wherein the hydration reaction type chemical heat storage material is an inorganic compound.

  In the chemical heat storage material molded body according to claim 17, since an inorganic compound is used as the chemical heat storage material, the material stability against heat storage and heat radiation reaction (hydration, dehydration) is high. For this reason, a stable heat storage effect can be obtained over a long period of time.

  The chemical heat storage material molded body according to claim 18 is the chemical heat storage material molded body according to claim 17, wherein the inorganic compound is an alkaline earth metal compound.

  In the chemical heat storage material molded body according to claim 18, since an alkaline earth metal compound (hydroxide) is used, in other words, a material having a small environmental load is used, and therefore, safety including manufacturing, use, and recycling is ensured. Securement 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.

  The chemical heat storage material molded body according to claim 19 is the chemical heat storage material molded body according to any one of claims 16 to 18, wherein the powder hydration reaction system chemical heat storage material, What knead | mixed and shape | molded the sepiolite as a clay mineral in a predetermined shape and baked at the temperature of 400 to 500 degreeC.

  The chemical heat storage material molded body according to claim 19 is configured as a porous structure in which sepiolite is sintered by firing a molded body in which the hydration reaction type chemical heat storage material and sepiolite are kneaded. Yes. 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.

  The method for producing a chemical heat storage material molded body according to the invention of claim 20 includes a kneading step of obtaining a high-viscosity kneaded material using a powdered chemical heat storage material, and a flow path formed inside the kneaded material. And a firing step of firing the molded body of the kneaded product molded in the molding step.

  In the manufacturing method of the chemical heat storage material molded body according to claim 20, a kneaded material including at least the chemical heat storage material is generated in the kneading step, and then the process proceeds to the molding step. In the forming step, the kneaded material containing the chemical heat storage material is formed into a predetermined shape having a flow path, and then the process proceeds to the firing step. In the firing step, the kneaded product molded in the molding step is fired by heating. Thereby, while forming a pore between powder (chemical heat storage material), the chemical heat storage material molded object which has a predetermined shape (hollow shape) which has a channel as a whole is formed.

  In the thus produced chemical heat storage material molded body, a gap (flow path) capable of diffusing reactants and the like is formed between the powders (chemical heat storage material), and a reaction provided for heat storage or heat dissipation inside. A flow path for introducing an object or discharging a reaction product generated by heat storage or heat dissipation is formed. For this reason, the flow path of the reactant or reaction product is structurally secured separately from the diffusion path of the reactant and the like. Thereby, in this chemical heat storage material molded body, introduction of the reactant through the channel, diffusion (permeation) through the pores of the porous structure, release, discharge of the reaction product through the channel, were achieved, Reactivity for heat storage and heat dissipation is good. And since this flow path is formed in the inside of a chemical heat storage material molded object, the heat transfer property by a chemical heat storage material molded object is not inhibited.

  Thus, in the manufacturing method of the chemical heat storage material molded body according to claim 20, it is possible to obtain a chemical heat storage material molded body capable of achieving both heat storage and heat release reactivity and heat transfer.

  According to a twenty-first aspect of the present invention, there is provided a method for producing a chemical heat storage material molded body, wherein the molding step is performed by extruding the kneaded product.

  In the method for producing a chemical heat storage material molded body according to claim 21, a high-viscosity kneaded product can be molded by extrusion molding in the molding process through the kneading process. That is, the said chemical heat storage material molded object can be obtained with a simple manufacturing method.

  A method for producing a chemical heat storage material molded body according to an invention according to claim 22 is the method for producing a chemical heat storage material molded body according to claim 20 or claim 21, wherein the chemical heat storage material has a predetermined ratio in the kneading step. A kneaded material kneaded with clay mineral is obtained.

  In the manufacturing method of the chemical heat storage material molded body according to claim 22, in the kneading step, the clay mineral is kneaded at a predetermined ratio to the powder chemical heat storage material, so that the chemical heat storage material is contained in the skeleton of the porous clay mineral. It can be dispersedly held. For this reason, the chemical heat storage material molded body manufactured by the method for manufacturing the chemical heat storage material molded body has high strength as the porous body described above, and the structure as the porous body is easily maintained stably.

  According to a twenty-third aspect of the present invention, there is provided a method for producing a chemical heat storage material molded body, wherein the clay mineral having a layered ribbon structure is used as the clay mineral.

  In the method for producing a chemical heat storage material molded body according to claim 23, since the clay mineral forms a fibrous form having a large porous surface area and a large specific surface area, a good chemical heat storage material is obtained by utilizing the fiber and plasticity. Can be organized and structured.

  The method for producing a chemical heat storage material molded body according to the invention described in claim 24 is the chemical heat storage material molded body according to claim 22, wherein the clay mineral includes a clay mineral having a layered ribbon structure and a bentonite having a plate-like structure. It is used.

  In the manufacturing method of the chemical heat storage material molded body according to claim 24, since a part of the clay mineral is porous and has a fibrous form with a large specific surface area, the chemical heat storage of the powder is made using the fiber and plasticity. The material can be well organized and structured. Moreover, since the clay mineral contains bentonite having a plate-like structure, shrinkage in the in-plane direction of the molded body accompanying firing of the chemical heat storage material molded body is suppressed. That is, bentonite has the property of being oriented along the wall surface of the molded body along with the molding before firing, so that the bentonite having a plate-like structure is oriented along the wall surface of the molded body due to this property. Shrinkage of the molded body is suppressed. Thereby, it is easy to ensure the dimensional accuracy of the chemical heat storage material molded body.

  The method for manufacturing a chemical heat storage material molded body according to the invention described in claim 25 is the chemical heat storage material molded body manufacturing method according to claim 23 or claim 24, wherein the clay mineral having the layer ribbon structure is sepiolite, palygorskite. Alternatively, kaolinite is used.

  In the method for producing a chemical heat storage material molded body according to claim 25, because sepiolite, palygorskite (attapulgite) or kaolinite having a layered ribbon structure is used as at least a part of the clay mineral, the fiber, plasticity is used, The powder chemical heat storage material can be well organized and structured.

  A chemical heat storage material molded body according to a twenty-sixth aspect of the present invention uses the bentonite as the clay mineral in the chemical heat storage material molded body of the twenty-second aspect.

  In the manufacturing method of the chemical heat storage material molded body according to claim 26, since bentonite which is a clay mineral having strong adhesive force is used, the chemical heat storage material of powder can be well organized and structured by this adhesive force. it can.

  A method for producing a chemical heat storage material molded body according to an invention described in claim 27 is the method for producing a chemical heat storage material molded body according to any one of claims 22 to 26, wherein the chemical heat storage material in the kneading step. The clay mineral having a fiber shape smaller than the particle diameter of the material is used.

  In the manufacturing method of the chemical heat storage material molded body according to claim 27, since the clay mineral forms a fiber having a fine fiber diameter, a small amount of the clay mineral is kneaded in the kneading step to form a powder chemical heat storage material structure. And can be 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.

  The method for producing a chemical heat storage material molded body according to the invention described in claim 28 is the chemical heat storage material molded body production method according to any one of claims 22 to 27, wherein the chemical heat storage material is a dehydration reaction. In this kneading step, the hydrated chemical heat storage material is kneaded with the clay mineral.

  In the method for producing a chemical heat storage material molded body according to claim 28, in the kneading step, the hydrated chemical heat storage material is kneaded with the clay mineral. There is no reaction. For this reason, in the kneading step, water can be used as a binder during the kneading.

  A method for producing a chemical heat storage material molded body according to an invention described in claim 29 is the method for producing a chemical heat storage material molded body according to any one of claims 22 to 28, wherein a dehydration reaction is performed as the chemical heat storage material. A hydration reaction type chemical heat storage material that is oxidized along with hydration reaction is used, and in the kneading step, the chemical heat storage material in a hydroxide state is kneaded with the clay mineral. .

  In the method for producing a chemical heat storage material molded body according to claim 29, water that is a concern when a dehydrated chemical heat storage material is used to knead the chemical heat storage material in a hydroxide state with clay mineral in the kneading step. Reaction with does not occur. For this reason, in the kneading step, water can be used as a binder during the kneading.

  A chemical heat storage material molded body according to a thirty-third aspect of the present invention is the chemical heat storage material molded body manufacturing method according to the twenty-ninth aspect, wherein the hydration reaction type chemical heat storage material is an inorganic compound.

  In the method for manufacturing a chemical heat storage material molded body according to claim 30, since an inorganic compound is used as the chemical heat storage material, the manufactured chemical heat storage material molded body has material stability against heat storage and heat release reaction (hydration, dehydration). high. For this reason, a stable heat storage effect can be obtained over a long period of time.

  A chemical heat storage material molded body according to a thirty-first aspect of the invention is the chemical heat storage material molded body manufacturing method according to the thirty-third aspect, wherein the inorganic compound is an alkaline earth metal compound.

  In the method for producing a chemical heat storage material molded body according to claim 31, since an alkaline earth metal compound (hydroxide) is used, 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 chemical heat storage material molded body according to the invention described in claim 32 is the method for manufacturing a chemical heat storage material molded body according to any one of claims 29 to 31, wherein the hydration is performed in the firing step. The kneaded product is fired at a temperature at which the system chemical heat storage material is dehydrated.

  In the method for producing a chemical heat storage material molded body according to claim 32, since the hydrated chemical heat storage material is dehydrated after firing in the firing step, the specific surface area of the chemical heat storage material can be easily adjusted.

  A chemical heat storage material molded body according to a thirty-third aspect of the present invention is the chemical heat storage material molded body manufacturing method according to the thirty-second aspect, wherein fine cracks are formed in the chemical heat storage material in the firing step. Bake at temperature.

  The method for producing a chemical heat storage material molded body according to claim 33, wherein the clay mineral is structured together with the chemical heat storage material by the firing in the firing step (a sintered state is ensured), and the dehydrated state of the chemistry. Fine cracks are formed in the heat storage material. 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 chemical heat storage material molded body according to the present invention has an excellent effect that a gap is formed between the powdered chemical heat storage materials.

  The chemical heat storage reaction part 10 as a chemical heat storage material molded body according to the first embodiment of the present invention and a manufacturing method thereof will be described with reference to FIGS.

  FIG. 2 shows a schematic cross-sectional view of the chemical heat storage reaction unit 10. As shown in this figure, the chemical heat storage reaction section 10 is a structure in which a large number of powder chemical heat storage materials 12 are organized and structured. Is formed. Therefore, the chemical heat storage reaction unit 10 according to this embodiment is understood as a porous structure (porous body) and is configured such that the powder chemical heat storage material 12 is exposed on the inner surface of the pores 14. It is what is done.

  In this chemical heat storage reaction section 10, 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 reaction unit 10 is grasped as a structure in which a large number of powder chemical heat storage materials 12 are dispersed and held in the skeleton of the sepiolite 16 that is porous. Thereby, in the chemical heat storage reaction part 10, a 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.

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, many powder chemical heat storage materials 12 are set as the structure which can reversibly repeat heat storage and heat dissipation by reaction 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 layer 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 Si 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.

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

  Further, the chemical heat storage reaction section 10 has a plurality of flow paths 15. In this embodiment, the chemical heat storage reaction section 10 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 reaction part 10, thickness tb of the partition wall part 10A which partitions off between the adjacent flow paths 15 is 8 mm or less. In this embodiment, the thickness tb of the partition wall portion 10A in the chemical heat storage reaction portion 10 is approximately 1.5 mm which is 4 mm or less. Furthermore, in the chemical heat storage reaction part 10, the thickness tc of the peripheral wall part 10C which comprises the part between the outer edge 10B and the flow path 15 is 4 mm or less. In this embodiment, the thickness tc of the peripheral wall portion 10C in the chemical heat storage reaction portion 10 is approximately 1.5 mm which is 2 mm or less.

  In the chemical heat storage reaction unit 10 described above, when the powder chemical heat storage material 12 is supplied with calcium hydroxide in the state, the powder chemical heat storage material 12 is oxidized using the heat as reaction heat. Yes. That is, in the chemical heat storage reaction unit 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 stores heat corresponding to the reaction heat. It is supposed to be configured. On the other hand, when the chemical heat storage reaction unit 10 is supplied with water vapor directly or through the pores 14 (by diffusion) from the flow channel 15 to the powder chemical heat storage material 12 in a calcium oxide state, the chemical chemical heat storage material 10 No. 12 releases heat while being hydroxylated by a hydration reaction.

  The chemical heat storage reaction unit 10 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. Thus, it is used for applications such as a hot probe for warming up the catalytic converter early (in a short time).

  Next, the manufacturing method of the chemical heat storage reaction part 10 is demonstrated.

  FIG. 3 schematically shows a method for manufacturing the chemical heat storage reaction unit 10. In manufacturing the chemical heat storage reaction unit 10, first, as shown in FIG. 3A, a powder chemical heat storage material 12 and a sepiolite 16 as raw materials 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. 3B, the powder chemical heat storage material 12 and sepiolite 16 in a dry powder state are respectively mixed in the mixing container 18 and uniformly mixed. Next, the process proceeds to the kneading step. In the kneading step, as shown in FIG. 3C, the mixture of the powder chemical heat storage material 12 and the sepiolite 16 is put into a kneading machine 19, 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 material M thickened in the kneading step as described above is transferred to the extrusion mold 20 and extruded. Thereby, the kneaded material M is formed in a predetermined shape according to the shape of the extrusion die 20. In this embodiment, the honeycomb formed body Fh having a large number of flow paths 15 is formed.

  Next, as shown in FIG. 3E, the process proceeds to the firing step. In the firing step, the honeycomb formed body Fh is placed in the firing furnace 22, and the honeycomb formed body Fh is fired at a predetermined temperature for a predetermined time. Thereby, the above-described honeycomb-shaped chemical heat storage reaction section 10 is formed. That is, the production of the chemical heat storage reaction unit 10 is completed. The firing temperature in this firing step is in the range of 350 ° C to 500 ° C.

  Since this firing temperature is equal to or higher than the dehydration temperature of the powder chemical heat storage material 12, that is, calcium hydroxide (the dehydration temperature varies depending on the atmospheric water vapor pressure, approximately 400 ° C. to 450 ° C.), Immediately after production, the chemical heat storage reaction section 10 is configured in the form of calcium oxide. That is, the chemical heat storage reaction unit 10 is in a heat storage state in which heat can be released by supplying moisture (water vapor) at the time of manufacture.

  Moreover, the firing temperature in the range of 400 ° C. to 500 ° C. in the firing step is a temperature at which microcracks are formed in the powder chemical heat storage material 12, and thereby a large number of powder chemistry constituting the chemical heat storage reaction unit 10. Each of the heat storage materials 12 has 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.

  Here, in the chemical heat storage reaction part 10, since the flow path 15 is formed inside, the discharge path | route of the water vapor | steam produced | generated at the time of heat storage, and the supply path | route of the water vapor | steam required at the time of heat radiation are ensured. That is, in the chemical heat storage reaction part 10, a flow path 15 larger than the pores 14 is formed inside the porous structure in which the pores 14 are formed between a large number of powder chemical heat storage materials 12. It is possible to quickly discharge and supply water vapor through the flow path 15 while forming a porous structure having a high degree of filling of the powder chemical heat storage material 12 as a whole.

  For this reason, in the chemical heat storage reaction part 10, the discharge | emission water vapor | steam requested | required for unit volume and heat storage capacity per mass by the high filling degree (high density) of the powder chemical heat storage material 12, and heat dissipation and heat storage reaction are requested | required. In addition, the coexistence with securing the moving speed of the supplied water vapor can be achieved. 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 effective heat storage amount with respect to the heat storage capacity based on the filling degree is reduced. On the other hand, in a configuration in which pores of a size that can ensure sufficient movement of water vapor for the reaction are provided approximately evenly among a large number of powder chemical heat storage materials, the degree of filling, that is, the heat storage capacity decreases, and the heat storage as a whole The amount becomes smaller. On the other hand, in the chemical heat storage reaction part 10, since the flow path 15 is formed inside the porous structure as described above, the trade-off between the filling degree of the powder chemical heat storage material 12 and the water vapor moving speed is eliminated. Thus, the utilization factor of the powder chemical heat storage material 12 having a high filling degree is increased.

  Furthermore, in the chemical heat storage reaction section 10, since the thickness tb of the partition wall portion 10A in the chemical heat storage reaction section 10 is 8 mm or less, the discharge and supply of water vapor by diffusion through the pores 14 is a reaction regulation (hereinafter referred to as diffusion). It is not called a rule. That is, in the chemical heat storage reaction section 10, the distance from the flow path wall surface of the flow path 15 to the middle portion in the thickness direction of the partition wall section 10A is 4 mm or less, and the diffusion distance of water vapor is short. , A decrease in the heat dissipation reaction rate is suppressed. In particular, in the chemical heat storage reaction section 10, the thickness tb of the partition wall 10A is 4 mm or less, that is, the distance from the flow path wall surface of the flow path 15 to the middle portion in the thickness direction of the partition wall 10A is 2 mm or less. The diffusion distance is shorter, and the decrease in heat storage and heat dissipation reaction rate due to the diffusion rule can be almost ignored.

  Similarly, in the chemical heat storage reaction part 10, since the thickness tc of the peripheral wall part 10C is 4 mm or less, the diffusion distance of water vapor is short, and the decrease in heat storage and heat dissipation reaction rate due to diffusion regulation is suppressed. In particular, in the chemical heat storage reaction part 10, since the thickness tc of the peripheral wall part 10C is 2 mm or less, the diffusion distance of water vapor is shorter, and the decrease in the heat storage and heat dissipation reaction rate due to the diffusion law can be almost ignored. it can.

  As described above, in the chemical heat storage reaction section 10, almost all the powder chemical heat storage material 12 can be used for heat storage and heat dissipation (utilization rate is about 100%), and as described above, heat storage per unit volume and unit mass. In a configuration with a large capacity, heat storage and heat dissipation by the powder chemical heat storage material 12 can be performed efficiently. That is, the effective heat storage capacity is increased in the chemical heat storage reaction unit 10.

  Furthermore, since the chemical heat storage reaction section 10 is provided with a plurality of flow paths 15, the dimensional shape of the chemical heat storage reaction section 10 can be arbitrarily set while ensuring the thickness tb of the partition wall section 10A and the thickness tc of the peripheral wall section 10C. Dimensional shape can be used. That is, the chemical heat storage reaction unit 10 has a high degree of freedom in setting (selecting) its dimensional shape.

  Further, in the method for producing the chemical heat storage reaction section 10, since the sepiolite 16 having a large porous surface area is kneaded into the powder chemical heat storage material 12 at a predetermined ratio in the kneading step, the thixotropy of the sepiolite 16 is performed. Thus, the sepiolite 16 is stirred together with the powder chemical heat storage material 12 and water to exhibit a thickening effect. Thereby, the honeycomb formed body Fh can be formed with higher accuracy and high density (high filling degree of the powder chemical heat storage material 12) using the kneaded material M based on the powder chemical heat storage material 12.

  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 the chemical heat storage reaction section 10 as one structure and maintained as the chemical heat storage reaction section 10.

  Further, the chemical heat storage reaction section 10 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 between them. It is prevented or remarkably suppressed that the volume expansion and shrinkage accompanying the hydration and dehydration reactions of the chemical heat storage material 12 interfere with other powder chemical heat storage materials 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 reaction unit 10, 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 reaction unit 10 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 absorbs water. Thus, the chemical heat storage reaction part 10 is prevented or suppressed from being liquefied and sintered by deliquescence.

  Here, in the manufacturing method of the chemical heat storage reaction section 10, since sepiolite 16 having a fiber diameter finer than the average particle diameter D of the powder chemical heat storage material 12 in a state suspended in water is used, a small amount is used. The chemical heat storage reaction part 10 which reinforce | strengthened the porous structure in which the pore 14 was formed between the powder chemical heat storage materials 12 with the said sepiolite 16 can be obtained. Therefore, the chemical heat storage reaction unit 10 can increase the amount of the powder chemical heat storage material 12 per unit mass and unit volume. That is, the chemical heat storage reaction part 10 with a large heat storage capacity can be obtained. In addition, in the chemical heat storage reaction unit 10, the powder chemical heat storage material 12 itself forms the main structure of the chemical heat storage reaction unit 10, so that the heat transfer path is simple and the heat storage efficiency and the utilization efficiency of the stored heat are high.

  Furthermore, since the chemical heat storage reaction unit 10 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 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, a material with a small environmental load is used, so that the chemical heat storage reaction section 10 is manufactured, used, and recycled. It is easy to ensure safety including

  Furthermore, in the manufacturing method of the chemical heat storage reaction section 10, since powder of calcium hydroxide as a hydroxide is used, the powder chemical heat storage material 12 and the sepiolite 16 are kneaded and thickened in the kneading step. Water can be used as the binder. Thereby, the chemical heat storage reaction part 10 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 chemical heat storage reaction part 10, since calcium hydroxide is used as a starting material as described above, a thickening effect is obtained by kneading with sepiolite 16 using water as a binder, 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 article 10, since alkaline calcium hydroxide is kneaded into sepiolite, sepiolite reacts slightly with alkali and changes to glassy. For this reason, the strength of the chemical heat storage material composite formed body 10 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.

  On the other hand, in the manufacturing method of the chemical heat storage reaction unit 10, 400 ° C. to 500 ° C. is employed as the firing temperature, so that the powder chemical heat storage material 12 and the sepiolite 16 are structured (immobilized), and the powder chemistry The dehydration reaction of the heat storage material 12 can be advanced. And since the micro crack is formed in the powder chemical heat storage material 12 by the calcination temperature of 400 degreeC-500 degreeC, in the manufacturing method of the chemical heat storage reaction part 10, organization and structure of the powder chemical heat storage material 12 and The specific surface area can be increased at the same time.

  In addition, as a baking temperature which produces the micro crack in the powder chemical thermal storage material 12 used as calcium oxide, about 450 degreeC is the most preferable. When the firing temperature is 400 ° C. or less, the generation of microcracks is small, and when the firing temperature is 500 ° C. or more, the probability of cracking of the powder chemical heat storage material 12 increases and the specific surface area of the powder chemical heat storage material 12 decreases due to sintering. It has been confirmed. 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).

  Next, another embodiment of the present invention will be described.

  FIG. 4 is a schematic front view showing a chemical heat storage reaction part 30 as a chemical heat storage material molded body according to the second embodiment of the present invention. As shown in this figure, the chemical heat storage reaction part 30 is formed in a flat shape when viewed from the front, and has a single flow path 32 at the center in the flat direction. This is different from the chemical heat storage reaction section 10 formed in a honeycomb shape having the flow path 15.

  That is, it can be understood that the chemical heat storage reaction part 30 is entirely constituted by the peripheral wall part that is a porous structure surrounding the flow path 32. The flow path 32 is made flat in the same direction as the chemical heat storage reaction part 30, and the thickness tc is substantially constant in each part in the circumferential direction. In the chemical heat storage reaction part 30, the thickness from the flow path wall surface of the flow path 15 to the outer edge 30A of the chemical heat storage reaction part 30 is 4 mm or less.

  In this embodiment, the thickness of the chemical heat storage reaction unit 30 in the flat direction is ta, the length of the short side that is the channel width in the flat direction of the flow channel 15 is L, and the direction orthogonal to the flat direction of the chemical heat storage reaction unit 30 Assuming that the width along W is W, tc≈2 to 3 mm, L≈1 to 2 mm, ta≈5 to 8 mm, and W≈20 mm.

  The chemical heat storage reaction unit 30 is configured by, for example, a single or a plurality of the above-described hot probes, and is distributed in the catalytic converter. Other configurations and manufacturing methods of the chemical heat storage reaction unit 30 are the same as the corresponding configurations and manufacturing methods of the chemical heat storage reaction unit 10 except for the shape of the extrusion mold 20.

  Therefore, the chemical heat storage reaction unit 30 according to the second embodiment and the method for manufacturing the chemical heat storage reaction unit 30 also include the chemical heat storage reaction unit 10 and the method for manufacturing the chemical heat storage reaction unit 10 according to the first embodiment. Similar effects can be obtained by similar actions.

  Next, the chemical heat storage reaction unit 40 and the manufacturing method thereof according to the third embodiment of the present invention will be described with reference to FIG. Although the chemical heat storage reaction part 40 is different in composition and manufacturing method from the chemical heat storage reaction part 10, the shape as the chemical heat storage material molded body is the same as that of the chemical heat storage reaction parts 10, 30. The illustration of the structure as a body (the figures corresponding to FIGS. 1 and 4 to 6) is omitted.

  As shown in FIG. 7, the chemical heat storage reaction part 40 is the first embodiment in that bentonite 42, which is a clay mineral having a plate-like structure, is mixed with sepiolite 16, which is a clay mineral having a layered ribbon structure. It differs from the chemical heat storage reaction parts 10 and 30 which concern on. This will be specifically described below.

  As shown in FIG. 7A, when manufacturing the chemical heat storage reaction section 40, first, bentonite 42 and sepiolite 16 which are a part of raw materials are prepared. The bentonite 42 is a plate-like structure having anisotropy. Then, bentonite 42 and sepiolite 16 are mixed in a preliminary mixing step (not shown). In this embodiment, bentonite 42 and sepiolite 16 are mixed at a ratio of 50% by mass. Next, as shown in FIG. 7B, a mixture of the powder chemical heat storage material 12, sepiolite 16 and bentonite 42 as raw materials is prepared, and the process proceeds to the mixing step.

  In the mixing step, as shown in FIG. C (B), the powder chemical heat storage material 12 in a dry powder state and the mixture of sepiolite 16 and bentonite 42 are placed in the mixing vessel 18 and mixed uniformly. Thereafter, similarly to the manufacturing process of the chemical heat storage reaction section 10, the chemical heat storage reaction section 40 is manufactured through a kneading process, a molding process, and a baking process (all refer to FIG. 3).

  Here, in the manufacturing method of the chemical heat storage reaction part 40, since bentonite 42 is mixed with the powder chemical heat storage material 12 in addition to the sepiolite 16 as a clay mineral, the bentonite 42 becomes a wall surface (compartment) of the chemical heat storage reaction part 40 in the molding process. Oriented along the wall portion 10A, the peripheral wall portion 10C, the partition wall portion 30B and the like. That is, due to the nature of bentonite 42 having an anisotropic plate-like structure, the longitudinal direction of bentonite 42 substantially matches the extending direction of the wall surface. That is, self-organization of the plate crystal occurs.

  Thereby, the chemical heat storage reaction part 40 is suppressed from shrinkage due to firing, and it is easy to ensure its dimensional accuracy. In particular, when baking is performed while the chemical heat storage reaction part 40 is restrained in the container, the chemical heat storage reaction part 40 is concerned that the chemical heat storage reaction part 40 may crack due to shrinkage. Therefore, since shrinkage | contraction itself is suppressed, the crack of the chemical heat storage reaction part 40 is suppressed or prevented.

  In addition, in 2nd Embodiment, although the chemical heat storage reaction part 30 showed the example which has the single flow path 32, it replaces with the single flow path 32, for example, as FIG. It is good also as a structure which has the several (two) flow path 34 paralleled in the orthogonal | vertical direction, and as FIG. 6 shows, the multiple (four) flow path paralleled in the flat direction and the orthogonal direction is further shown. 36 may be adopted. In these cases, the thickness tb of the partition wall portion 30B formed between the flow paths 34 or between the flow paths 36 is preferably 8 mm or less, and more preferably 4 mm or less.

  Further, in each of the above-described embodiments, an example is shown in which Turkish or Spanish sepiolite is used for molding the chemical heat storage material composite molded body 10, but the present invention is not limited to this, and for example, Chinese sepiolite. It is also possible to use. However, the sepiolite used for molding the chemical heat storage material composite molded body 10 is most preferably from Turkey, secondly from Spain, and then from China. This is because Turkish sepiolite has few impurities, is fine (the wire diameter is thin, and the length is short), is easy to form a shell structure by kneading and baking with the powder chemical heat storage material 12, and is advantageous in terms of dispersibility. In addition, it is preferable that the amount of impurities is small because the shell structure is easily made brittle and causes firing to be hindered.

  Further, in each of the above-described embodiments, an example is shown in which sepiolite is used as a clay mineral having a layer ribbon structure as the clay mineral, but the present invention is not limited to this, and for example, a clay mineral having a layer ribbon structure is used. A certain palygorskite (attapulgite) or kaolinite (a wire diameter of 5 μm or less, or 1 μm or less) may be used, or bentonite which does not belong to a clay mineral having a layered ribbon structure may be used. In addition, when bentonite is supplemented, bentonite is a clay mineral having a strong adhesive force as compared with a clay mineral having a layered ribbon structure, and a strong porous structure is obtained by itself (even in a configuration not mixed with sepiolite 16). For example, it contributes to improving the bonding strength to the metal wall. The chemical heat storage reaction unit 10 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 10 according to a use etc. in consideration of these merit. Further, a clay mineral obtained by mixing a clay mineral having a layer ribbon structure other than sepiolite 16 and bentonite 42 may be mixed with the powder chemical heat storage material 12.

  Further, the present invention is not limited to a configuration and a manufacturing method in which clay mineral such as sepiolite 16 is kneaded and fired with the powder chemical heat storage material 12. For example, the powder chemical heat storage material 12 is a clay corresponding to sepiolite 16 ( It is good also as a structure which does not have a mineral.

Further, in each of the embodiments described above, 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 limited to this. 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.

It is a front view which shows typically the external shape of the chemical thermal storage reaction part which concerns on the 1st Embodiment of this invention. It is sectional drawing which shows typically the internal structure of the chemical thermal storage reaction part which concerns on the 1st Embodiment of this invention. It is a figure which shows typically the manufacturing method of the chemical thermal storage reaction part which concerns on the 1st Embodiment of this invention, Comprising: (A) is a figure which shows a raw material, (B) is a figure which shows the 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 a baking process. It is a front view which shows typically the external shape of the chemical thermal storage reaction part which concerns on the 2nd Embodiment of this invention. It is a front view which shows typically the external shape of the chemical thermal storage reaction part which concerns on the 1st modification of the 2nd Embodiment of this invention. It is a front view which shows typically the external shape of the chemical thermal storage reaction part which concerns on the 2nd modification of the 2nd Embodiment of this invention. It is a figure which shows typically the manufacturing method of the chemical heat storage reaction part which concerns on the 3rd Embodiment of this invention, Comprising: (A) is a figure which shows a clay mineral raw material, (B) is a chemical heat storage material and a clay mineral raw material. The figure which shows a mixture, (C) is a figure which shows a mixing process.

Explanation of symbols

10 Chemical heat storage reaction part (Chemical heat storage material molding)
10A partition wall (molded body between flow paths)
10C peripheral wall (between the flow path and the molded body surface)
12 Powder chemical heat storage material (chemical heat storage material)
14 pores 15 channels 16 sepiolite (clay mineral)
30.40 Chemical heat storage reaction part (chemical heat storage material molding)
30B partition wall (formed body between flow paths)
32, 34, 36 Channel 42 Bentonite (clay mineral)
S Kneaded material

Claims (33)

  A molded chemical heat storage material, which is formed by molding a chemical heat storage material in powder form, and in which a flow path for supplying a reactant or discharging a reaction product is formed.   The chemical heat storage material molded body according to claim 1, wherein a representative dimension of the flow path is larger than a particle size of the chemical heat storage material.   The chemical heat storage material molded body according to claim 1 or 2, wherein a plurality of the flow paths are formed.   The chemical heat storage material molded body according to any one of claims 1 to 3, wherein a thickness between the flow path and the surface of the molded body is 4 mm or less.   The chemical heat storage material molded body according to any one of claims 1 to 4, wherein a thickness between the flow path and the molded body surface is 2 mm or less. A plurality of the flow paths are formed in parallel,
The chemical heat storage material molded body according to any one of claims 1 to 5, wherein a thickness of the molded body between the flow paths is 8 mm or less. A plurality of the flow paths are formed in parallel,
The chemical heat storage material molded body according to any one of claims 1 to 6, wherein a thickness of the molded body between the flow paths is 4 mm or less.   The chemical heat storage material molded body according to any one of claims 1 to 7, wherein the chemical heat storage material is formed by being dispersed and held in a clay mineral.   The chemical heat storage material molded body according to claim 8, wherein a clay mineral having a layer ribbon structure is used as the clay mineral.   The chemical heat storage material molded body according to claim 8, wherein a clay mineral having a layered ribbon structure and bentonite having a plate-like structure are used as the clay mineral.   The chemical heat storage material molded body according to claim 9 or 10, wherein sepiolite, palygorskite, or kaolinite is used as the clay mineral having the layer ribbon structure.   The chemical heat storage material molded body according to claim 8, wherein bentonite is used as the clay mineral.   The chemical heat storage material molded body according to any one of claims 8 to 12, wherein the clay mineral has a fiber shape smaller than a particle diameter of the chemical heat storage material.   The chemical heat storage material molded body according to any one of claims 1 to 13, wherein the chemical heat storage material has fine cracks.   The chemical heat storage material molding according to any one of claims 1 to 14, 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. body.   The chemical heat storage material according to any one of claims 1 to 15, wherein a hydration reaction type chemical heat storage material that is oxidized with a dehydration reaction and hydroxylated with a hydration reaction is used as the chemical heat storage material. Material molded body.   The chemical heat storage material molded body according to claim 16, wherein the hydration reaction type chemical heat storage material is an inorganic compound.   The chemical heat storage material molded body according to claim 17, wherein the inorganic compound is an alkaline earth metal compound.   The powder hydration reaction type chemical heat storage material and sepiolite as the clay mineral are kneaded and molded into a predetermined shape and fired at a temperature of 350 ° C to 500 ° C. Item 20. The chemical heat storage material molded article according to any one of Items 18 above. A kneading step for obtaining a kneaded product having a high viscosity using a powder chemical heat storage material;
A molding step of molding the kneaded product so that a flow path is formed therein;
A firing step of firing the molded body of the kneaded product molded in the molding step;
The manufacturing method of the chemical heat storage material molded object containing this.   The method for producing a chemical heat storage material molded body according to claim 20, wherein the molding step is performed by extrusion molding of the kneaded product.   The method for producing a chemical heat storage material molded body according to claim 20 or 21, wherein in the kneading step, a kneaded product of a kneaded material in which a clay mineral is kneaded with the chemical heat storage material at a predetermined ratio is obtained.   The method for producing a chemical heat storage material molded body according to claim 22, wherein a clay mineral having a layer ribbon structure is used as the clay mineral.   The method for producing a chemical heat storage material molded body according to claim 22, wherein a clay mineral having a layered ribbon structure and bentonite having a plate-like structure are used as the clay mineral.   The method for producing a chemical heat storage material molded body according to claim 23 or 24, wherein sepiolite, palygorskite, or kaolinite is used as the clay mineral having the layer ribbon structure.   The method for producing a chemical heat storage material molded body according to claim 22, wherein bentonite is used as the clay mineral.   27. The method for producing a chemical heat storage material molded body according to any one of claims 22 to 26, wherein in the kneading step, the clay mineral having a fiber shape smaller than a particle diameter of the chemical heat storage material is used. As the 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,
28. The method for producing a chemical heat storage material molded body according to any one of claims 22 to 27, wherein in the kneading step, the chemical heat storage material in a hydrated state is kneaded with the clay mineral. As the 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 producing a chemical heat storage material molded body according to any one of claims 22 to 28, wherein in the kneading step, the chemical heat storage material in a hydroxide state is kneaded with the clay mineral.   The method for producing a chemical heat storage material molded body according to claim 29, wherein the hydration reaction type chemical heat storage material is an inorganic compound.   The method for producing a chemical heat storage material molded body according to claim 30, wherein the inorganic compound is an alkaline earth metal compound.   32. The method for producing a chemical heat storage material molded body according to any one of claims 29 to 31, wherein in the firing step, the kneaded product is fired at a temperature at which the hydrated chemical heat storage material is dehydrated.   33. The method for producing a chemical heat storage material molded body according to claim 32, wherein the chemical heat storage material is fired at a temperature at which fine cracks are formed in the chemical heat storage material.