The present invention relates to a plate-shaped chemical heat storage body.
Background technology
[0002]
A latent heat storage material that utilizes the phase change of a substance is known as one of the heat storage technologies. For example, Patent Document 1 discloses a heat storage body in which a plurality of latent heat storage particles are placed on a sheet, and a paint is applied from the particles to fix the particles to the sheet. This heat storage body is covered with a coating film so that the heat storage material does not leak to the outside when it changes to a liquid or gas due to a phase change.
[0003]
Chemical heat storage material is known as another heat storage technology. In the chemical heat storage material, a working medium of a gas such as water reacts with the chemical heat storage material and utilizes the heat absorption or heat generation at that time. It is said that the chemical heat storage material has a higher heat storage amount per unit mass than the latent heat storage material and the sensible heat storage material.
As a chemical heat storage material, for example, Patent Document 2 discloses a heat storage member obtained by molding a powder of a metal oxide such as calcium oxide and magnesium oxide into a plate shape.
[0004]
Patent Document 3 describes a cage-like structure having a large number of pores obtained by mixing and firing a clay mineral and a flammable granule, and being supported on the outer surface and the inside of the pores of the cage-like structure. Discloses a chemical heat storage material characterized by having a chemical heat storage material.
[0005]
Patent Document 4 describes a skeletal structure made of porous ceramics having a large number of pores, and a chemical heat storage material supported on the outer surface of the skeletal structure, or on the outer surface of the skeletal structure and inside the pores. Discloses a chemical heat storage material molded body characterized by having.
Prior art literature
Patent documents
[0006]
Patent Document 1: Japanese Patent Application Laid-Open No. 8-29081
Patent Document 2: Japanese Unexamined Patent Publication No. 2011-208865
Patent Document 3: Japanese Unexamined Patent Publication No. 2009-256517
Patent Document 4: Japanese Unexamined Patent Publication No. 2009-22128
Outline of the invention
Problems to be solved by the invention
[0007]
An object of the present invention is to provide a plate-shaped chemical heat storage body having excellent durability.
Means to solve problems
[0008]
As a result of studies to solve the above problems, the present invention including the following aspects has been completed.
[0009]
[1] A substrate made of a metal net and
It has a heat storage material composition supported on the substrate, and has
The heat storage material composition comprises a group consisting of magnesium hydroxide or oxide, strontium hydroxide or oxide, barium hydroxide or oxide, calcium hydroxide or oxide, and calcium sulfate. Contains at least one selected,
Plate-shaped chemical heat storage body.
[0010]
[2] The plate-shaped chemical heat storage material according to [1], wherein the heat storage material composition further contains at least one selected from the group consisting of titanium dioxide, silicon dioxide, alumina silicate fiber, E glass fiber, and cellulose.
[3] The plate-shaped chemical heat storage material according to [1] or [2], wherein the net is made of at least one selected from the group consisting of stainless steel, aluminum, aluminum alloy, copper, and copper alloy.
[4] The plate-shaped chemical heat storage material according to any one of [1] to [3], which has a plate thickness of 0.3 mm or more and 2 mm or less.
[0011]
[5] A chemical heat storage structure in which at least one plate-shaped chemical heat storage body according to any one of [1] to [4] is laminated.
[0012]
[6] A chemical heat storage system comprising the plate-shaped chemical heat storage body according to any one of [1] to [4] or the chemical heat storage structure according to [5].
The invention's effect
[0013]
The plate-shaped chemical heat storage material of the present invention has excellent shape retention and quick thermal response. In the plate-shaped chemical heat storage body of the present invention, gas such as water vapor easily penetrates deep inside, so that the efficiency of endothermic reaction and exothermic reaction is high, and the amount of heat storage per unit weight is high. In the plate-shaped chemical heat storage body of the present invention, even if a volume change occurs due to the dehydration / hydration reaction of the heat storage material, the substrate made of a net absorbs it and prevents cracking and pulverization, so that the heat storage / heat dissipation performance is achieved. Can be maintained high and for a long period of time.
A brief description of the drawing
[0014]
FIG. 1 is a diagram showing an example of a plate-shaped chemical heat storage body of the present invention.
FIG. 2 is a diagram showing an example of a plate-shaped chemical heat storage body of the present invention.
FIG. 3 is a diagram showing an example of a plate-shaped chemical heat storage body of the present invention.
FIG. 4 is a diagram showing an example of a substrate used for the plate-shaped chemical heat storage body of the present invention.
FIG. 5 is a diagram showing an example of a substrate used for the plate-shaped chemical heat storage body of the present invention.
FIG. 6 is a diagram showing an example of the chemical heat storage structure of the present invention.
FIG. 7 is a diagram showing an example of the chemical heat storage structure of the present invention.
FIG. 8 is a diagram showing an example of the chemical heat storage structure of the present invention.
FIG. 9 is a diagram showing an example of the chemical heat storage structure of the present invention.
Embodiment for carrying out the invention
[0015]
The plate-shaped chemical heat storage body 1 of the present invention has a substrate 3 and a heat storage material composition 2 supported on the substrate 3.
[0016]
The substrate 3 used in the present invention is a metal net. The net may be any of knitted wire, cut and stretched plate (expanded metal), and perforated plate (punching metal).
The material of the net is not particularly limited as long as it is a metal, but a metal having a higher thermal conductivity than the heat storage material composition is preferable, and stainless steel, aluminum, an aluminum alloy, copper, or a copper alloy is preferable.
[0017]
The mesh opening of the mesh is not particularly limited, but is preferably 10 μm or more, more preferably 100 μm or more, because the heat storage material composition is difficult to peel off from the substrate and the thermal conductivity between the heat storage material composition and the substrate is enhanced. More preferably, it is 1 mm or more and 5 mm or less.
The net is a flat net with a flat main surface, a hump net with bump-like ridges on the main surface, a corrugated net with wavy ridges on the main surface, and a rib net with protrusions on the main surface. And so on. Since the heat storage material composition enters the mesh and exerts an anchor effect, it exhibits sufficient strength even with a flat mesh. The bumps, waves or ribs can be expected to further enhance the anchoring effect of the bumps, waves or ribs.
[0018]
The heat storage material composition used in the present invention contains a chemical heat storage material. The chemical heat storage material is selected from the group consisting of magnesium hydroxide or oxide, strontium hydroxide or oxide, barium hydroxide or oxide, calcium hydroxide or oxide, and calcium sulfate. Use at least one of them.
[0019]
Magnesium hydroxides or oxides utilize chemical heat storage that utilizes heat storage when magnesium hydroxide dehydrates and changes to magnesium oxide, and heat dissipation when magnesium oxide hydrates and changes to magnesium hydroxide. It is a material. The heat storage operating temperature of magnesium hydroxide or oxide is around 350 ° C.
A hydroxide or oxide of strontium is a chemical heat storage that utilizes heat storage when strontium hydroxide is dehydrated and converted to strontium oxide and heat dissipation when strontium oxide is hydrated and converted to strontium hydroxide. It is a material.
Hydroxides or oxides of barium utilize chemical heat storage that utilizes heat storage when barium hydroxide dehydrates and changes to barium oxide, and heat dissipation when barium oxide hydrates and changes to barium hydroxide. It is a material.
A hydroxide or oxide of calcium utilizes chemical heat storage that utilizes heat storage when calcium hydroxide dehydrates and changes to calcium oxide, and heat dissipation when calcium oxide hydrates and changes to calcium hydroxide. It is a material. The heat storage operating temperature of calcium hydroxide or oxide is around 500 ° C.
Calcium sulfate stores heat when calcium sulfate 0.5 hydrate dehydrates and changes to anhydrous calcium sulfate, and dissipates heat when anhydrous calcium sulfate hydrates and changes to calcium sulfate 0.5 hydrate. It is a chemical heat storage material that utilizes. The heat storage operating temperature of calcium sulfate is around 90 ° C.
[0020]
The heat storage material composition used in the present invention may contain additives such as a heat conductive filler, reinforcing fibers, and binder in addition to the above chemical heat storage material.
[0021]
Examples of the heat conductive filler include molten silica, aluminum oxide, boron nitride, alumnium nitride, silicon nitride, magnesium carbonate, carbon nanotubes, boron nitride nanotubes, and beryllium oxide.
Examples of the reinforcing fiber include carbon fiber, glass fiber, alumina silicate fiber, E glass fiber, aramid fiber, polyolefin fiber, vinylon fiber, steel fiber and the like.
Other fillers include titanium dioxide, zeolite, activated clay, sepiolite, bentonite, parigolstite, hydrotalcite, zinc oxide, iron oxide, barium sulfate, calcium carbonate, talc, aluminum hydroxide, antimony oxide, graphite, ferrite, etc. be able to. Of these, a filler in which the heat storage material composition supported on the substrate is porous is preferably used.
[0022]
Binders include silica sol, silicate, phosphate, cement, silicone and other inorganic binders; cellulose acetate, nitrile cellulose, cellulose, polyvinylidene fluoride, polyvinyl alcohol, styrene butadiene rubber, nitrile rubber, polytetrafluoroethylene, Examples thereof include organic binders such as polypropylene, polyethylene, acrylic resin, and epoxy resin.
[0023]
Of these additives, at least one selected from the group consisting of titanium dioxide, silicon dioxide, alumina silicate fiber, E glass fiber, and cellulose can be preferably contained in the heat storage material composition.
[0024]
The total amount of additives is preferably 1% by weight or more and 40% by weight or less with respect to the total amount of chemical heat storage materials.
[0025]
In the plate-shaped chemical heat storage material of the present invention, the heat storage material composition is supported on the substrate, more specifically, on the outer surface of the net constituting the substrate, and in the mesh of the net.
The support can be carried out by applying a slurry or paste of the heat storage material composition to the substrate and drying it, by compacting the powder of the heat storage material composition together with the substrate, or by another supporting method.
[0026]
The plate-shaped chemical heat storage body of the present invention has a plate thickness t of preferably 0.3 mm or more and 2 mm or less, more preferably 0.5 mm or more and 1 mm or less.
The surface of the plate-shaped chemical heat storage material of the present invention may be completely covered with the heat storage material composition, or a part of the substrate may be exposed.
The main surface of the plate-shaped chemical heat storage body of the present invention may be a smooth surface or a rough surface. When the surface is rough, a slight gap is formed when the plate-shaped chemical heat storage material of the present invention is laminated, so that water, which is an operating medium for the chemical heat storage material, easily penetrates to the depth. From such a viewpoint, the surface roughness of the main surface is preferably several μm to several hundred μm.
[0027]
The plate-shaped chemical heat storage material of the present invention may be cut into chips, bent into a cylinder or a box, or embossed to be wavy (for example, shown in FIGS. 2 and 3) depending on the purpose. It can be shaped). Further, a plurality of plate-shaped chemical heat storage bodies of the present invention can be laminated or laminated with other plate-shaped materials.
[0028]
The chemical heat storage structure of the present invention is formed by laminating at least one plate-shaped chemical heat storage structure of the present invention.
FIG. 6 shows a chemical heat storage structure 4 in which a large number of plate-shaped chemical heat storage bodies 1a of the present invention are laminated. When there is a gap between adjacent plate-shaped chemical heat storage bodies 1a, water vapor, which is an operating medium, easily passes through this gap. The chemical heat storage structure 4 has a high packing density of the chemical heat storage material per unit volume, can exhibit higher heat storage / heat dissipation performance, and can stably maintain its shape for a long period of time.
[0029]
FIG. 7 shows a chemical heat storage structure 5 in which a plate-shaped chemical heat storage body 1a of the present invention and another plate-shaped material 3 are alternately laminated. The other plate-like material 3 is not particularly limited, and may be, for example, a substrate 3-a made of a metal net that does not support the heat storage material composition. In the chemical heat storage structure 5, the plate-shaped material 3 acts as a spacer and the flow path to the plate-shaped chemical heat storage body 1 is expanded, so that water vapor, which is an operating medium, easily flows, and dehydration / hydration occurs. The reaction is promoted.
[0030]
FIG. 8 shows a plate-like chemical storage in which ridges and flat portions are alternately formed at predetermined intervals as shown in FIG.
The structure in which the hot body 1c is laminated is shown.
FIG. 9 shows a corrugated honeycomb-shaped structure in which a plate-shaped chemical heat storage body 1a and a plate-shaped chemical heat storage body 1b are alternately laminated as shown in FIG.
The stacking height h at this time is not particularly limited, but is preferably set to 2 mm or more and 4 mm or less.
[0031]
In the structure of the present invention, since the substrate functions as an aggregate, it is possible to maintain high strength and shape retention for a long period of time. In addition, as long as it is a form in which the action and effect in the present invention are exhibited, it is not limited to the above, and other shapes may be used.
[0032]
Hereinafter, examples of the present invention will be shown, and the present invention will be described in more detail. It should be noted that these are merely examples for explanation, and the present invention is not limited thereto.
[0033]
[Example 1]
Kneading with kneader while adding water to 10 kg of magnesium hydroxide powder. 4 kg of silica-alumina fiber was added thereto, and the mixture was further kneaded to obtain a paste-like chemical heat storage material composition having a water content of about 40%. Using a pair of rolling rollers, a paste-like chemical heat storage is applied to an expanded metal substrate (metal lath plate, P 1 = 4.5 mm, P 2 = 3.0 mm) made of SUS430 with a width of 500 mm so as to fill the gaps between the lath eyes. The material composition was applied. Then, it was cut to a length of 500 mm with a cutting machine. This was dried at 120 ° C. for 2 hours. Then, it was cut into small pieces of 50 × 50 mm to obtain a plate-shaped chemical heat storage body having a thickness of 0.7 mm. The density of the heat storage material composition supported on the plate-shaped chemical heat storage body was 0.95 g / cm 3.
[0034]
[Example 2]
A plate in the same manner as in Example 1 except that the expanded metal substrate made of SUS430 used in Example 1 was changed to an expanded metal substrate made of aluminum (metal lath plate, P 1 = 4.5 mm, P 2 = 3.0 mm). A state chemical heat storage material was obtained. The density of the heat storage material composition supported on the plate-shaped chemical heat storage body was 0.92 g / cm 3.
[0035]
[Comparative Example 1]
Magnesium hydroxide powder (manufactured by Kishida Chemical Co., Ltd.) was placed in a tableting molding machine, and a pressure of 700 kg / cm 2 was applied for 10 seconds to obtain a pellet-shaped heat storage body having a diameter of 13 mm and a thickness of 2.4 mm. The density of the pellet-shaped heat storage body was 0.94 g / cm 3.
[0036]
[test]
A durability test was conducted with dehydration treatment and hydration treatment as one cycle under the conditions shown in Table 1.
The shape, dehydration rate and water content of the heat storage body were recorded for each cycle. The results are shown in Table 2.
The dehydration rate was calculated assuming that the initial magnesium hydroxide was completely converted to magnesium oxide.
The hydration rate was calculated assuming that all magnesium oxide was reconverted to the initial magnesium hydroxide weight as 100%.
[0037]
The pellet-shaped heat storage body of Comparative Example 1 was in a state where cracks were generated in the second cycle, cracks were generated on the entire surface of the pellets in the fifth cycle, and magnesium powder was attached to the hands when touched.
On the other hand, in the plate-shaped chemical heat storage bodies of Examples 1 and 2, slight cracks were confirmed in a part of the heat storage material composition in the 5th cycle, but no detachment or peeling from the substrate was observed. The magnesium powder did not stick to my hands when I touched it.
As shown in Table 2, the plate-shaped chemical heat storage bodies of Examples 1 and 2 had higher dehydration rates and hydration rates than the pellet-shaped heat storage bodies of Comparative Example 1, and were excellent in heat storage performance.
[0038]
As is clear from the above results, the plate-shaped chemical heat storage body of the present invention has high strength and high dehydration / hydration reaction efficiency. By using the plate-shaped chemical heat storage body of the present invention, it is possible to construct a high-performance and highly durable chemical heat storage system as compared with the case of using the conventional powder-shaped or pellet-shaped heat storage body.
[0039]
[table 1]

[0040]
[Table 2]

Description of the sign
[0041]
1a, 1b, 1: Plate-shaped chemical heat storage
2: Heat storage material composition
3: Board
3-a: Wire mesh board
3-b: Expanded metal substrate
4: Heat storage structure
5: Heat storage structure
The scope of the claims
[Claim 1]
A board made of metal net and
It has a heat storage material composition supported on the substrate, and has
The heat storage material composition contains a chemical heat storage material.
Plate-shaped chemical heat storage body.
[Claim 2]
A board made of metal net and
It has a heat storage material composition supported on the substrate, and has
The heat storage material composition comprises a group consisting of magnesium hydroxide or oxide, strontium hydroxide or oxide, barium hydroxide or oxide, calcium hydroxide or oxide, and calcium sulfate. Contains at least one selected,
Plate-shaped chemical heat storage body.
[Claim 3]
The plate-shaped chemical heat storage body according to claim 1 or 2, further comprising a heat conductive filler, reinforcing fibers or binder.
[Claim 4]
The plate-shaped chemical heat storage body according to claim 1 or 2, further comprising at least one selected from the group consisting of titanium dioxide, silicon dioxide, alumina silicate fiber, E glass fiber, and cellulose as the heat storage material composition.
[Claim 5]
The plate-shaped chemical heat storage material according to any one of claims 1 to 4, wherein the net consists of at least one selected from the group consisting of stainless steel, aluminum, aluminum alloy, copper, and copper alloy.
[Claim 6]
The plate-shaped chemical heat storage body according to any one of claims 1 to 5, wherein the plate thickness is 0.3 mm or more and 2 mm or less.
[Claim 7]
A chemical heat storage structure in which at least one plate-shaped chemical heat storage according to any one of claims 1 to 6 is laminated.
[Claim 8]
A chemical heat storage system comprising the plate-shaped chemical heat storage body according to any one of claims 1 to 6 or the chemical heat storage structure according to claim 7.