JP5276865B2 - Heat storage device using chemical heat storage material composite and manufacturing method thereof - Google Patents

Description

The present invention relates to a heat storage device using a chemical heat storage material composite including a chemical heat storage material and a method for manufacturing the same.

Conventionally, chemical heat storage materials using chemical heat storage and chemical heat storage systems using the same are known.
For example, in Patent Document 1, a large number of pores are obtained by heating crystalline limestone in the range of 0.3 to 4 mm for a predetermined time in the range of 850 to 1100 ° C. and then heating in the range of 500 to 600 ° C. for a predetermined time. A chemical heat storage material for obtaining quicklime that has produced lime and a method for producing the same are disclosed.
Patent Document 2 discloses a heat storage device in which a powder chemical heat storage material is accommodated in a porous capsule. Patent Document 3 discloses a chemical heat storage capsule obtained by filling a powdered chemical heat storage material into a cylindrical body of a heat-resistant porous body.

JP-A-1-225686 Japanese Patent Publication No. 6-80395 Japanese Patent Publication No. 6-80394

  However, when quick lime with pores formed in Patent Document 1 is used as a chemical heat storage material in powder form, the powder chemical heat storage material has a volume of due to repeated hydration and dehydration reactions during operation. Repeat expansion and contraction. For this reason, there is a problem in that the fine powder is formed by contacting and rubbing with other powder, and the reactivity as the heat storage system is lowered.

  In addition, in the heat storage systems shown in Patent Document 2 and Patent Document 3, although it is possible to suppress the pulverization of the powder, due to the increase in heat conduction resistance and the complexity of the heat transfer path due to encapsulation or cylindrical body encapsulation, There was a problem that heat generated by the exothermic reaction of the chemical heat storage material could not be taken out efficiently, and furthermore heat generated by the heat storage reaction could not be supplied efficiently.

The present invention, such conventional been made in view of the problems, is excellent in heat storage, heat radiation performance and heat transfer performance, and to provide a heat storage device and a manufacturing method thereof using a highly durable chemical heat storage material complex To do.

The reference invention contains a powdered chemical heat storage material and a foam expansion material obtained by subjecting a foam expansion material disposed adjacent to the chemical heat storage material to foam expansion by applying a predetermined foaming start treatment. It is in the characteristic chemical heat storage material composite .

The chemical heat storage material composite according to the reference invention is composed of a chemical heat storage material and a foam expansion material obtained by foaming and expanding a foam expansion material. Therefore, for example, when the chemical heat storage material composite is formed by foaming and expanding the foam-expandable material in a predetermined space, the space in the space is filled by the foam-expanding action of the foam-expandable material. And the said chemical heat storage material arrange | positioned adjacent to the said foam expansible material is firmly hold | maintained in the said space.

Therefore, the chemical heat storage material composite has high adhesion to the outside due to the foamed and expanded foam material. Thereby, heat transfer performance becomes high and heat exchange with the outside can be performed satisfactorily.
In addition, the chemical heat storage material composite is in a state where the chemical heat storage material is firmly held by the foamed and expanded foam material, and has a high strength and a stable structure. Thereby, pulverization of the said chemical heat storage material which had arisen by the expansion | swelling and shrinkage | contraction of the volume accompanying heat storage / heat radiation can be suppressed, and it becomes a durable thing.

Moreover, the said chemical heat storage material composite contains the said foam expansion material which carried out foam expansion of the spring shape, for example. Therefore, volume expansion and contraction of the chemical heat storage material accompanying heat storage and heat dissipation can be mitigated by the foamed expansion material, and the durability becomes high.
Moreover, the said chemical heat storage material composite has the space | gap formed by the foam expansion inside the said foam expansion material. Therefore, it is possible to sufficiently secure the introduction / discharge path of the reactant / reaction product accompanying heat storage / heat radiation. Thereby, the movement (diffusion) inhibition of the reaction product and reaction product accompanying heat storage and heat dissipation can be suppressed, and excellent heat storage. It will have heat dissipation performance.

Thus, according to the reference invention , it is possible to provide a chemical heat storage material composite having excellent heat storage / heat dissipation performance and heat transfer performance and high durability.

1st invention , the wall which divides a thermal storage material accommodating part,
A chemical heat storage material composite housed in the heat storage material housing portion,
The chemical heat storage material composite contains a powder chemical heat storage material and a foam expansion material,
The wall body has a double tube structure composed of an inner tube and an outer tube which are tubular bodies, and the heat storage material accommodation portion is formed between the inner tube and the outer tube,
At least one of the inner tube and the outer tube, in the heat storage apparatus characterized by pores can flow fluid is provided a number (claim 1).

In the heat storage device of the present invention, a chemical heat storage material composite having excellent heat transfer performance and high durability of the reference invention is stored in the heat storage material storage section partitioned by the wall body. Therefore, for example, when the chemical expansion material is formed by foaming and expanding the foam-expandable material in the heat storage material accommodation section partitioned by the wall body, the foam-expandable material has a foam expansion action. The chemical heat storage material disposed adjacent to the foam expandable material is firmly held in the heat storage material storage portion while the gap of the heat storage material storage portion is filled.

Therefore, the chemical heat storage material composite has high adhesion to the wall body due to the foamed and expanded foam material. Thereby, it becomes a thing with high heat-transfer performance, and heat exchange can be performed favorably through the said wall body. As a result, the heat storage device has high performance as a heat storage system.
In addition, the chemical heat storage material composite is in a state where the chemical heat storage material is firmly held by the foamed and expanded foam material, and has a high strength and a stable structure. Thereby, pulverization of the said chemical heat storage material which had arisen by the expansion and contraction of the volume accompanying heat storage / heat radiation can be suppressed. As a result, the heat storage device is highly durable and can obtain a stable heat storage effect over a long period of time.

Moreover, the said chemical heat storage material composite contains the said foam expansion material which carried out foam expansion of the spring shape etc., for example. Therefore, the expansion and contraction of the volume of the chemical heat storage material accompanying heat storage and heat dissipation can be mitigated by the foamed expansion material. Thereby, the said heat storage apparatus becomes a thing with high durability.
Moreover, the said chemical heat storage material composite has the space | gap formed by the foam expansion inside the said foam expansion material. Therefore, it is possible to sufficiently secure the introduction / discharge path of the reactant / reaction product accompanying heat storage / heat radiation. Thereby, the movement (diffusion) inhibition of the reaction product and reaction product accompanying heat storage and heat dissipation can be suppressed, and excellent heat storage and heat dissipation performance can be obtained. As a result, the heat storage device has high performance as a heat storage system.

  Thus, according to the present invention, it is possible to provide a heat storage device that is excellent in heat storage / heat dissipation performance and heat transfer performance and has high durability.

A second invention is a method of manufacturing the heat storage device of the first invention ,
A housing step of housing the chemical heat storage material and the foam expandable material in the heat storage material housing section partitioned by the wall; and
And a fixing step of forming the chemical heat storage material composite by foaming and expanding the foam expandable material by performing a predetermined foaming start treatment, and fixing the chemical heat storage material with the foam expansion material. The method of manufacturing a heat storage device is as follows ( claim 13 ).

  In the method for manufacturing a heat storage device of the present invention, the chemical heat storage material and the foam expandable material are stored in the heat storage material storage section in the storage step, and the foam expandable material is started to be foamed in the fixing step. The chemical heat storage material is fixed by the foam expansion material to form the chemical heat storage material composite. Thereby, according to the manufacturing method of this invention, as above-mentioned, it is excellent in heat storage and heat dissipation performance and heat transfer performance, and can obtain the heat storage apparatus with high durability.

In the first aspect of the present invention, it is preferable that the expanded foam material is expanded by subjecting the expanded foam material disposed adjacent to the chemical heat storage material to a predetermined expansion start process.
Furthermore, the chemical heat storage material composite is preferably made of a two-layer structure and a layer obtained by laminating containing layer and the foam expansion material containing the chemical heat storage material (claim 3).
In this case, the layer of the chemical heat storage material can be firmly held in a predetermined position by the foamed and expanded material. In particular, the heat transfer performance can be enhanced by disposing the chemical heat storage material layer close to the surface to which heat is to be transferred.

Further, the chemical heat storage material composite may have a structure obtained by foaming and expanding the foam expandable material in a mixture of the chemical heat storage material and the foam expandable material ( claim 4 ).
In this case, the chemical heat storage material can be more firmly held by the foamed and expanded foamed material.

The chemical heat storage material composite may be mixed with ceramic fibers such as glass fibers and alumina fibers in order to further improve the durability.
Moreover, the ceramic fibers such as the glass fiber and the alumina fiber may be mixed in a layer containing the foam expansion material (foam expansion material) in the two-layer structure described above, or the chemical heat storage material. You may mix in the mixed layer which consists of a mixture with the said foam expansible material (foam expandable material).

Moreover, it is preferable that the said foaming start process is heating the said foam expansible material and / or adding hydrogen peroxide water to the said foam expansible material ( Claim 5 ).
In this case, it is possible to easily perform the foaming start process on the foam-expandable material with almost no unnecessary substance remaining after foaming.

Moreover, it is preferable that the said foam expansible material is a vermiculite and / or weathered biotite ( Claim 6 ).
In this case, the foam-expandable material can be foamed and expanded satisfactorily. In particular, since the vermiculite expands to a thickness of about 10 to 100 times, the chemical heat storage material can be held more firmly in a predetermined space by its foam expansion action. Moreover, since it becomes a spring shape after expansion | swelling, it can absorb and relieve | swell the expansion | swelling and shrinkage | contraction of a volume accompanying the thermal storage / radiation of the said chemical thermal storage material.

Furthermore, the chemical heat storage material absorbs heat with the dehydration reaction, it is preferable that the hydration reaction chemical thermal storage medium to the heat radiation with the hydration reaction (Claim 7).
Furthermore, the chemical heat storage material is oxidized with the dehydration reaction, it is preferable that the hydration reaction chemical thermal storage medium that is hydroxylated with the hydration reaction (claim 8).
In any case, the chemical heat storage material composite can perform heat storage and heat dissipation satisfactorily by hydration reaction and dehydration (reverse hydration reaction), and can improve performance as a heat storage system. And since the flow path of the water vapor | steam required in this case can be ensured inside the said foam expansion material, it is optimal for the structure of this invention.

Moreover, it is preferable that the said chemical heat storage material is an inorganic compound ( Claim 9 ).
In this case, the material stability with respect to the heat storage / heat radiation reaction (hydration / dehydration reaction) of the chemical heat storage material is increased. That is, it does not deteriorate due to the heat history during use. Therefore, the chemical heat storage material composite can obtain a stable heat storage effect over a long period of time.

Furthermore, the chemical heat storage material is a nickel compound, an aluminum compound, a cobalt compound, is preferably composed of one or more compounds selected from copper compounds and alkaline earth metal compounds (Claim 10), an alkaline earth metal among them Compounds are more preferred.
In this case, the material stability with respect to the heat storage / heat radiation reaction (hydration / dehydration reaction) of the chemical heat storage material is increased. Therefore, the chemical heat storage material composite can obtain a stable heat storage effect over a long period of time. In addition, by using a safe material with a small environmental load as the chemical heat storage material, it is easy to ensure safety including manufacturing, use, recycling, and the like.

The chemical heat storage material is made of one or more compounds selected from nickel hydroxide, aluminum hydroxide, cobalt hydroxide, copper hydroxide, barium hydroxide, calcium hydroxide, calcium oxide hydrate and magnesium hydroxide. is preferably made (claim 11), more preferably calcium and magnesium hydroxide are among them, the calcium hydroxide is more preferred. In this case, it is possible to further improve the material stability of the chemical heat storage material with respect to heat storage / radiation reaction (hydration / dehydration reaction), and to stabilize the heat storage effect of the chemical heat storage material composite over a long period of time. Can be maintained.

  In addition to the above, the chemical heat storage material is aluminum hydroxide / magnesium (dolomite), strontium hydroxide, alkali metal hydroxide (lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium water). Oxide, cesium hydroxide, etc.), transition metal hydroxide, iron hydroxide, diaspore (AlO (OH)), goethite (FeO (OH)), alkaline earth sulfate hydrate, calcium sulfate hydrate And mixtures or compounds thereof may also be used.

Moreover , it is preferable that the said wall body is comprised with the metal material (Claim 12).
In this case, the chemical heat storage material composite can perform heat exchange more favorably through the wall. Thereby, the performance as a heat storage system of the said heat storage apparatus can further be improved.

The wall body is a tubular body .
In this case, in the heat storage material accommodation section partitioned by the wall body of the tubular body, the foam expansion material expanded and expanded fills the gap of the heat storage material accommodation section and is disposed adjacent to the foam expansion material. The made chemical heat storage material can be firmly held in the heat storage material housing portion.

The wall body has a double-pipe structure composed of an inner tube and an outer tube, and at least one of the inner tube and the outer tube is provided with a large number of pores through which fluid can flow. .
In this case, introduction and discharge of reactants and reaction products accompanying heat storage and heat dissipation are performed through one wall of the inner tube and the outer tube, and the other wall is used. Heat exchange can be performed. Thereby, the performance as a heat storage system of the said heat storage apparatus can be improved.

2nd invention WHEREIN: In the said accommodation process, both may be accommodated in the said thermal storage material accommodating part so that it may become a two-layer structure which laminated | stacked the said layer of the chemical thermal storage material and the said layer of the foam expansible material. Preferred ( claim 14 ).
In this case, in the subsequent fixing step, the layer of the chemical heat storage material can be firmly held at a predetermined position by the foamed and expanded material. And especially heat transfer performance can be improved by arrange | positioning the layer of the said chemical heat storage material close to the surface (wall body which performs heat exchange) which should transfer heat.

Moreover, it is preferable to accommodate in the said thermal storage material accommodating part in the said accommodation process in the state which mixed the said chemical thermal storage material and the said foam expansible material ( Claim 15 ).
In this case, in the subsequent fixing step, the chemical heat storage material can be more firmly held by the foamed and expanded material.

Further, foaming starts processing in the fixing step is preferably the addition of hydrogen peroxide solution and / or the expandable intumescent material to heat the foamed intumescent material (claim 16).
In this case, it is possible to easily perform the foaming start process on the foam-expandable material with almost no unnecessary substance remaining after foaming.

Moreover, it is preferable to perform the said heating at the temperature of 400-800 degreeC ( Claim 17 ).
In this case, foaming of the foam expandable material can be reliably started. In addition, the foam-expandable material can be foamed and expanded satisfactorily.

Example 1
A chemical heat storage material composite according to an embodiment of the present invention, a heat storage device using the same, and a manufacturing method thereof will be described with reference to the drawings.
As shown in FIG. 1, the heat storage device 10 of this example includes a chemical heat storage material complex 1 and a heat exchanger body 2 for performing heat exchange with the chemical heat storage material complex 1. The heat exchanger main body 2 includes a wall body 20 having a double tube structure including an inner tube 21 and an outer tube 22, and an outer wall 23 surrounding the outer tube 22. The inner tube 21, the outer tube 22, and the outer wall 23 are made of a metal material such as stainless steel or aluminum.

As shown in the figure, a space between the inner tube 21 and the outer tube 22 is configured as a heat storage material storage portion 32 that stores the chemical heat storage material composite 1. In the heat storage material storage portion 32, the chemical heat storage material composite 1 is stored.
Further, the inside of the inner pipe 21 is configured as a reaction flow path 31 through which water vapor as a reactant and a reaction product accompanying heat storage and heat dissipation of the chemical heat storage material complex 1 flows. The inner tube 21 has a mesh shape through which fluid (water vapor) can flow. That is, water vapor can flow between the heat storage material accommodation portion 32 and the reaction flow path 31 via the inner pipe 21.
In addition, a space between the outer tube 22 and the outer wall 23 is configured as a heat exchange flow path 33 through which a fluid (a gas in this example) as a heat exchange medium that exchanges heat with the chemical heat storage material composite 1 flows. ing.

  Moreover, as shown to the same figure, the chemical thermal storage material composite body 1 accommodated in the thermal storage material accommodating part 32 contains the chemical thermal storage material 11 and the foam expansion material 12 of a powder. The chemical heat storage material composite 1 includes a chemical heat storage material layer 111 containing the chemical heat storage material 11 arranged close to the outer tube 22 and a foam expansion material layer containing the foam expansion material 12 arranged in other areas. It has a two-layer structure in which 121 is laminated.

In this example, the chemical heat storage material 11 is calcium hydroxide (Ca (OH) ₂ ), stores heat (endothermic) with dehydration, and dissipates heat (exothermic) with hydration (restoration to calcium hydroxide). To do. That is, the chemical heat storage material 11 reversibly repeats heat storage and heat dissipation by the following reactions.
Ca (OH) ₂ ⇔CaO + H ₂ O
Further, when the heat storage amount and the heat generation amount Q are shown together in the above formula, the following is obtained.
Ca (OH) ₂ + Q → CaO + H ₂ O
CaO + H ₂ O → Ca (OH) ₂ + Q

  The expanded foam material 12 is obtained by expanding and expanding a foam expandable material by performing a predetermined foam start process. The expanded foam material 12 of this example is obtained by adding hydrogen peroxide water as a foam start process to vermiculite as a foam expandable material, and expanding and expanding it into a spring shape about 10 to 100 times in thickness. It is. Moreover, the foam expansion material 12 has the space | gap formed by foam expansion inside.

Moreover, as shown in the figure, in the chemical heat storage material composite 1, the chemical heat storage material layer 111 is pressed against the outer tube 22 by the foam expansion material 12 expanded and expanded in the foam expansion material layer 121. It is comprised by.
On the other hand, the foam expansion material layer 121 is composed of a foam expansion material 12 formed by foaming and expanding a foam expansion material.

Moreover, as shown in the figure, in the heat storage device 10, when the chemical heat storage material 11 is supplied with heat in the state of calcium hydroxide, the chemical heat storage material 11 is oxidized using the heat as reaction heat. . That is, the heat storage device 10 is configured such that the chemical heat storage material 11 discharges water vapor to the reaction channel 31 through the inner tube 21 and becomes calcium oxide by a dehydration reaction to store heat corresponding to the reaction heat.
On the other hand, the heat storage device 10 is configured such that water vapor is supplied from the reaction flow path 31 through the inner tube 21 to the chemical heat storage material 11 in a calcium oxide state and becomes calcium hydroxide by a hydration reaction to dissipate heat. .

Further, as shown in the figure, the heat storage device 10 is configured such that the heat supply during the heat storage in the chemical heat storage material complex 1 is performed by heat exchange via the outer tube 22 from the fluid (gas) flowing through the heat exchange flow path 33. Heat is supplied to the heat storage material composite.
On the other hand, the heat radiation at the time of heat radiation in the chemical heat storage material complex 1 is radiated from the chemical heat storage material complex 1 to the fluid (gas) flowing through the heat exchange flow path 33 by heat exchange via the outer tube 22. It is configured as follows.

Next, a method for manufacturing the heat storage device 10 will be described.
As shown in FIG. 2 and FIG. 3, the manufacturing method of the heat storage device 10 of this example includes a storage step of storing the chemical heat storage material 11 and the foam expandable material 120 in the heat storage material storage section 32 partitioned by the wall, And a fixing step of forming the chemical heat storage material composite 1 formed by expanding and expanding the expandable material 120 by performing a predetermined foaming start process and fixing the chemical heat storage material 11 with the foam expansion material 12.
This will be described in detail below.

First, as the chemical heat storage material 11, calcium hydroxide (Ca (OH) ₂ ) having an average particle diameter D = 10 μm (laser diffraction measurement method, using SALD-2000A manufactured by Shimadzu Corporation) was prepared.
Further, vermiculite (palmite) was prepared as the foam expandable material 120. Specifically, South African vermiculite, which is a plate-like particle having a thickness of 0.2 to 0.5 mm, was prepared.

Next, in the housing process, as shown in FIG. 2A, calcium hydroxide as the chemical heat storage material 11 was applied to the inner wall surface of the outer tube 22 in the wall body 20.
Specifically, 8 g of calcium hydroxide powder having an average particle diameter of about 1 μm and 1 g of glass fibers (fiber diameter of about 10 μm, average fiber length of 5 mm) were mixed in a dry manner using a pestle in an alumina mortar. Thereafter, a suspension in which 1 g of Turkish sepiolite was dispersed in 10 cc of water was added and sufficiently kneaded with a pestle to prepare a paste mainly composed of calcium hydroxide. This paste was uniformly applied to the inner wall surface of the outer tube 22 using a polyethylene spoon and a round bar having a diameter of about 10 mm.

  Then, as shown in FIG. 2 (b), a rubber plug (not shown) was provided at the lower end of the heat storage material accommodation portion 32, and then the heat storage material accommodation portion 32 was filled with vermiculite as the foam expandable material 120. In this example, vermiculite corresponding to about 1/5 of the volume of the heat storage material accommodation portion 32 was filled.

  Next, in the fixing step, as shown in FIG. 2 (c), 35 mass% hydrogen peroxide water W was added to the extent that the vermiculite was immersed in the heat storage material accommodation portion 32. Thereafter, a brass plate (not shown) having a thickness of 10 mm was placed so as to cover the upper end of the heat storage material accommodation unit 32 and left at room temperature for about 5 hours. As a result, the plate-like vermiculite having a thickness of about 0.2 to 0.5 mm expanded and expanded into a spring shape to a thickness of about 10 cm.

Thereby, as shown in FIG. 1, the chemical heat storage material composite 1 formed by fixing calcium hydroxide as the chemical heat storage material 11 to the outer tube 22 side by vermiculite as the foam expansion material 12 expanded and expanded was formed. That is, in the heat storage material accommodating part 32, the foam expansion material containing the chemical heat storage material layer 111 containing the chemical heat storage material 11 arranged close to the outer tube 22 and the foam expansion material 12 arranged in other regions. The chemical heat storage composite 1 having a two-layer structure in which the layer 121 was laminated was formed.
Thus, the heat storage device 10 was obtained.

Next, the effect in this example is demonstrated.
In the heat storage device 10 of this example, the chemical heat storage material composite 1 is stored in the heat storage material storage portion 32 partitioned by the wall body 20. The chemical heat storage material composite 1 is composed of a chemical heat storage material 11 and a foam expansion material 12 formed by expanding and expanding the foam expansion material 120. Therefore, as in this example, the chemical heat storage material composite 1 is formed by foaming and expanding the foam expansion material 120 in the heat storage material accommodation portion 32 partitioned by the wall body 20 (the inner tube 21 and the outer tube 22). The expansion of the foam expandable material 120 fills the gap between the heat storage material accommodation portion 32 and the chemical heat storage material 11 disposed adjacent to the foam expansion material 120 is firmly contained in the heat storage material accommodation portion 32. Retained.

Therefore, the chemical heat storage material composite 1 has high adhesion to the wall body 20 (outer tube 22) due to the expanded foam material 12 expanded and expanded. Thereby, it becomes a thing with high heat transfer performance, and heat exchange with the fluid (gas) which distribute | circulates the heat exchange flow path 33 via the wall 20 (outer tube 22) can be performed favorably. As a result, the heat storage device 10 has high performance as a heat storage system.
In addition, the chemical heat storage material composite 1 is in a state where the chemical heat storage material 11 is firmly held by the expanded foam material 12 expanded and expanded, and has a high strength and a stable structure. Thereby, the pulverization of the chemical heat storage material 11 caused by the expansion and contraction of the volume accompanying heat storage and heat dissipation can be suppressed. As a result, the heat storage device 10 is highly durable and can obtain a stable heat storage effect over a long period of time.

In addition, the chemical heat storage material composite 1 contains a foam expansion material 12 that is expanded in a spring shape. Therefore, the expansion and contraction of the volume of the chemical heat storage material 11 accompanying heat storage and heat dissipation can be mitigated by the foamed expansion material 12. Thereby, the heat storage device 10 becomes highly durable.
Further, the chemical heat storage material composite 1 has voids formed by foam expansion inside the foam expansion material 12. Therefore, it is possible to sufficiently secure the introduction / discharge path of the reactant / reaction product accompanying heat storage / heat radiation. Thereby, the movement (diffusion) inhibition of the reaction product and reaction product accompanying heat storage and heat dissipation can be suppressed, and excellent heat storage and heat dissipation performance can be obtained. As a result, the heat storage device 10 has high performance as a heat storage system.

  In this example, the chemical heat storage material composite 1 has a two-layer structure in which a chemical heat storage material layer 111 containing the chemical heat storage material 11 and a foam expansion material layer 121 containing the foam expansion material 12 are laminated. Therefore, the chemical heat storage material layer 111 can be firmly held at a predetermined position by the expanded foam material 12 expanded and expanded. And heat transfer performance can be improved by arrange | positioning the chemical heat storage material layer 111 close to the surface (outer tube 22 of the wall body 20) which should heat-transfer like this example.

Further, the foaming start processing of the foam expandable material 120 is to add the hydrogen peroxide solution W to the foam expandable material 120. Therefore, it is possible to easily perform the foaming start process on the foamable expansible material 120 with almost no unnecessary substance remaining after foaming.
In addition, the foam start process of the foam expansible material 120 can be performed also by heating at the temperature of 400-800 degreeC. In this case, it is possible to simultaneously perform the foaming start treatment and the heating for dehydrating the hydroxide (calcium hydroxide in this example). Thereby, shortening of a process is realizable.
Moreover, the foaming start process of the foam expandable material 120 can be performed by both the process of adding hydrogen peroxide and heating.

  Moreover, vermiculite is used as the foam expandable material 120. Therefore, the foam expandable material 120 can be foamed and expanded satisfactorily. In particular, vermiculite expands about 10 to 100 times in thickness, so that the chemical heat storage material 11 can be held more firmly in the heat storage material accommodation portion 32 by its foam expansion action. Moreover, since it becomes a spring shape after expansion | swelling, it can absorb and relieve | swell the expansion | swelling and shrinkage | contraction of the volume accompanying the thermal storage / radiation of the chemical heat storage material 11.

  The chemical heat storage material 11 is a hydration reaction type chemical heat storage material that absorbs heat with a dehydration reaction and dissipates heat with a hydration reaction. The chemical heat storage material 11 is oxidized with a dehydration reaction and water with a hydration reaction. Calcium hydroxide, which is a hydration reaction type chemical heat storage material that is oxidized, is used. Therefore, the chemical heat storage material composite 1 can favorably store and release heat by hydration reaction and dehydration (reverse hydration reaction), and can improve the performance as a heat storage system. And since the flow path of the water vapor | steam required in this case can be ensured inside the foam expansion material 12, it is optimal for the structure like this example.

  Moreover, as the chemical heat storage material 11, calcium hydroxide which is an inorganic compound is used. Therefore, the material stability with respect to the heat storage / heat radiation reaction (hydration / dehydration reaction) of the chemical heat storage material 11 is increased. That is, it does not deteriorate due to the heat history during use. Therefore, the chemical heat storage material composite 1 can obtain a stable heat storage effect over a long period of time.

  Moreover, as the chemical heat storage material 11, calcium hydroxide which is an alkaline earth metal compound is used. That is, a safe material with a small environmental load is used as the chemical heat storage material 11. Therefore, it becomes easy to ensure safety including the manufacture, use, recycling, and the like of the chemical heat storage material composite 1.

  Moreover, in the heat storage apparatus 10 of this example, the wall body 20 is comprised with the metal material. Therefore, the chemical heat storage material composite 1 can perform heat exchange more favorably through the wall body 20 (outer tube 22). Thereby, the performance as a heat storage system of the heat storage apparatus 10 can further be improved.

  The wall body 20 is a tubular body. Therefore, in the heat storage material accommodating portion 32 partitioned into the tubular wall body 20 (the inner tube 21 and the outer tube 22), the gap between the heat storage material accommodating portions 32 is filled with the foam expansion material 12 expanded and expanded, and the foam expansion property is achieved. The chemical heat storage material 11 disposed adjacent to the material 120 can be firmly held in the heat storage material accommodation portion 32.

  Further, the wall body 20 has a double tube structure including an inner tube 21 and an outer tube 22, and the inner tube 21 has a mesh shape through which a fluid (water vapor) can flow. Therefore, it is possible to introduce and discharge reactants and reaction products that accompany heat storage and heat dissipation via the inner tube 21, and to perform heat exchange via the outer tube 22. Thereby, the performance as a thermal storage system of the thermal storage apparatus 10 can be improved.

  Thus, according to this example, it is possible to obtain the chemical heat storage material composite 1 having excellent heat storage / heat dissipation performance and heat transfer performance and high durability, and the heat storage device 10 using the same.

In this example, calcium hydroxide is used as the chemical heat storage material 11, but it can be replaced with magnesium hydroxide or a mixture of calcium hydroxide and magnesium hydroxide.
Further, although vermiculite is used as the foam expandable material 120, it can be changed to weathered biotite or a mixture of vermiculite and weathered biotite. In addition, generally weathered biotite may be marketed as vermiculite.
Moreover, although the hydrogen peroxide solution was added as the foaming start processing of the foam expandable material 120, this can be changed to heating at 400 to 800 ° C., or both processing can be performed.

  In this example, the wall body 20 has a double pipe structure composed of the inner tube 21 and the outer tube 22, and the inner tube 21 is used as the reaction flow path 31. For example, as shown in FIG. 3, the inner tube 21 of the wall body 20 is eliminated and only the outer tube 22 is formed, and the center of the outer tube 22 is formed. A portion (inside the original inner pipe 31) is filled with the foam expansion material 12, and the foam expansion material layer 121 and the reaction channel 31 can be integrated. FIG. 3 shows the chemical heat storage material 1 and the wall body 20.

(Example 2)
In this example, the configuration of the chemical heat storage material composite 1 is changed.
In this example, as shown in FIG. 4, in the heat storage device 10, the chemical heat storage material composite 1 is composed of a mixture 13 in a state where the chemical heat storage material and the foam expansion material are mixed. That is, the chemical heat storage material composite 1 of this example is stored in the heat storage material storage portion 32 in a state where the chemical heat storage material and the foam expandable material are mixed, and hydrogen peroxide is added to expand the foam expandable material. And formed.
Other configurations are the same as those in the first embodiment.

In this case, the chemical heat storage material composite 1 is in a state where the chemical heat storage material is more firmly held by the foamed and expanded foam expansion material, and has a high strength and a stable structure. Thereby, the thermal storage apparatus 10 becomes a highly durable thing which can acquire the stable thermal storage effect over a long period of time.
In other respects, the same effects as those of the first embodiment can be obtained.

Explanatory drawing which shows the structure of the thermal storage apparatus in Example 1. FIG. Explanatory drawing which shows the manufacturing method of the thermal storage apparatus in Example 1. FIG. The photograph which shows the chemical heat storage material composite_body | complex formed in the heat storage material accommodating part in Example 1. FIG. Explanatory drawing which shows the structure of the thermal storage apparatus in Example 2. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Chemical thermal storage material composite body 10 Thermal storage apparatus 11 Chemical thermal storage material 12 Foam expansion material 20 Wall body 32 Thermal storage material accommodating part

Claims (17)

A wall body that partitions the heat storage material accommodation section;
A chemical heat storage material composite housed in the heat storage material housing portion,
The chemical heat storage material composite contains a powder chemical heat storage material and a foam expansion material,
The wall body has a double tube structure composed of an inner tube and an outer tube which are tubular bodies, and the heat storage material accommodation portion is formed between the inner tube and the outer tube,
At least one of the inner pipe and the outer pipe is provided with a large number of pores through which fluid can flow. 2. The heat storage device according to claim 1, wherein the foam expansion material is foamed and expanded by subjecting a foam expansion material disposed adjacent to the chemical heat storage material to a predetermined foam start process. 3. 3. The heat storage device according to claim 2, wherein the chemical heat storage material composite has a two-layer structure in which a layer containing the chemical heat storage material and a layer containing the foam expansion material are laminated. 3. The heat storage device according to claim 2, wherein the chemical heat storage material composite is obtained by foaming and expanding the foam expandable material in a mixture of the chemical heat storage material and the foam expandable material. 5. The foaming start treatment according to claim 2, wherein the foaming start treatment is heating the foaming expansible material and / or adding hydrogen peroxide water to the foaming expansible material. Heat storage device. 6. The heat storage device according to claim 5, wherein the foam expandable material is vermiculite and / or weathered biotite. The heat storage device according to any one of claims 1 to 6, wherein the chemical heat storage material is a hydration reaction type chemical heat storage material that absorbs heat with a dehydration reaction and dissipates heat with a hydration reaction. . The chemical heat storage material according to any one of claims 1 to 7, wherein the chemical heat storage material is a hydration reaction type chemical heat storage material that is oxidized in association with a dehydration reaction and hydroxylated in association with a hydration reaction. Thermal storage device. The heat storage device according to any one of claims 1 to 8, wherein the chemical heat storage material is an inorganic compound. In any 1 item | term of Claims 1-9, the said chemical heat storage material consists of 1 or more types of compounds chosen from a nickel compound, an aluminum compound, a cobalt compound, a copper compound, and an alkaline-earth metal compound, It is characterized by the above-mentioned. Thermal storage device. The chemical heat storage material according to claim 1, wherein the chemical heat storage material is nickel hydroxide, aluminum hydroxide, cobalt hydroxide, copper hydroxide, barium hydroxide, calcium hydroxide, calcium oxide hydrate, and hydroxide. A heat storage device comprising one or more compounds selected from magnesium. The heat storage device according to claim 1, wherein the wall body is made of a metal material. A method for manufacturing the heat storage device according to any one of claims 1 to 12,
A housing step of housing the chemical heat storage material and the foam expandable material in the heat storage material housing section partitioned by the wall; and
And a fixing step of forming the chemical heat storage material composite by foaming and expanding the foam expandable material by performing a predetermined foaming start treatment, and fixing the chemical heat storage material with the foam expansion material. A method for manufacturing a heat storage device. In Claim 13, in the said accommodation process, both are accommodated in the said thermal storage material accommodating part so that it may become a two-layer structure which laminated | stacked the said layer of the chemical thermal storage material and the layer of the said foam expansible material. A method for manufacturing a heat storage device. 14. The method of manufacturing a heat storage device according to claim 13, wherein in the storage step, the chemical heat storage material and the foam expandable material are mixed and stored in the heat storage material storage portion. The foaming start process in the fixing step according to any one of claims 13 to 15, wherein the foaming expansible material is heated and / or hydrogen peroxide water is added to the foaming expansible material. A method for manufacturing a heat storage device. The method of manufacturing a heat storage device according to claim 16, wherein the heating is performed at a temperature of 400 to 800 ° C.