JP5297669B2 - Chemical heat storage material composite and its manufacturing method - Google Patents

Description

  The present invention relates to a chemical heat storage material composite including a chemical heat storage material and a method for producing 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 has been made in view of such conventional problems, and is a chemical heat storage material composite that can suppress pulverization of a chemical heat storage material, secure a heat conduction path, and further improve the structural strength. And a method of manufacturing the same.

A first aspect of the present invention is Ri greens and calcined to particles of chemical thermal storage medium by mixing the clay mineral and structural reinforcing material,
The structural strength improving material is in a chemical heat storage material composite containing one or more selected from aluminum hydroxide, aluminum nitrate, aluminum phosphate and boehmite (Claim 1).

  The chemical heat storage material composite of the present invention is a powdered chemical heat storage material mixed with a clay mineral and a structural strength improving material and fired. Therefore, the chemical heat storage material composite is structured and structured by dispersing and holding the powder chemical heat storage material in the skeleton of the clay mineral and the structural strength improving material. Thereby, the following various effects can be expected.

That is, a gap is formed between the powders of the chemical heat storage material due to the presence of the clay mineral or the like. Therefore, rubbing of the chemical heat storage material due to repeated heat storage and heat dissipation and pulverization associated therewith can be suppressed.
In addition, due to the gap, it is possible to sufficiently secure the introduction / discharge path of the reactant / reaction product accompanying heat storage / heat radiation. Therefore, the movement (diffusion) inhibition of the reactant / reaction product accompanying the heat storage / radiation in the chemical heat storage material complex can be suppressed.

  Moreover, the said chemical heat storage material composite_body | complex turns into a porous structure which has high intensity | strength and a stable structure with the said clay mineral surrounding the said chemical heat storage material, and the said structural strength improvement material. In particular, in the present invention, as described above, in addition to the clay mineral, the structure strength improving material further includes the structural strength improving material, whereby the structural strength improving material strongly stabilizes the structure surrounding the chemical heat storage material by the clay mineral. Alternatively, the structural strength improving material itself may surround the chemical heat storage material together with the clay mineral to form a strong and stable structure, thereby further increasing the structural strength of the entire chemical heat storage material composite. it can.

  Thus, according to the present invention, it is possible to provide a chemical heat storage material composite capable of suppressing the pulverization of the chemical heat storage material, ensuring a heat conduction path, and further improving the structural strength.

The second invention is a mixing step of mixing a powder chemical heat storage material, a clay mineral and a structural strength improving material to obtain a heat storage material mixture;
And firing the heat storage material mixture possess a firing step to obtain a chemical heat storage material complex,
The said structural strength improvement material exists in the manufacturing method of the chemical heat storage material composite characterized by including any 1 or more types chosen from aluminum hydroxide, aluminum nitrate, aluminum phosphate, and boehmite (Claim 15 ).

  In the manufacturing method of the present invention, a chemical storage material mixture is prepared by mixing powder chemical heat storage material, clay mineral and structural strength improving material in the mixing step, and the heat storage material mixture is fired in the baking step. A heat storage material composite is obtained. Therefore, the obtained chemical heat storage material composite is structured and structured by dispersing and holding the powder chemical heat storage material in the skeleton of the clay mineral and the structural strength improving material. Thereby, according to the manufacturing method of the present invention, as described above, the chemical heat storage material composite capable of suppressing the pulverization of the chemical heat storage material and securing the heat conduction path and further improving the structural strength can be obtained. Can be obtained.

  Moreover, in the said mixing process, the thickening effect can be acquired by stirring with a water | moisture content by thixotropy (thixotropic) of the said clay mineral. Therefore, the structure based on the chemical heat storage material can be formed with higher accuracy and higher density. As a result, the obtained chemical heat storage material composite is highly accurate, has a high density, and has an effect that the thermal resistance is low.

In the first and second inventions, the clay mineral is preferably a clay mineral having a layered ribbon structure (Claims 2 and 17 ).
In this case, the clay mineral has a fibrous form that is porous and has a large specific surface area. Therefore, the chemical heat storage material can be well organized and structured by the properties of the clay mineral such as fiber, porosity and plasticity.
Moreover, as a clay mineral which has the said layer ribbon structure, a sepiolite and / or a palygorskite can be used, for example (Claim 3, 18 ).

  In addition, when the clay mineral is porous and has a large specific surface area, due to the adsorptivity of the clay mineral, excessive reactants, such as water vapor, existing during heat storage and heat dissipation reactions are adsorbed in the clay mineral. be able to. Therefore, for example, in the case of a low temperature state where the heat storage system using the chemical heat storage material composite is stopped, the chemical heat storage material prevents water from being absorbed and liquefied in the chemical heat storage material composite. Can do. Thereby, the sintering by reaction with the said chemical heat storage material and liquid water can be suppressed.

As the clay mineral, bentonite can be used in addition to those having the above layer ribbon structure (Claims 4 and 19 ).
In this case, since the adhesive strength of the clay mineral becomes strong, the chemical heat storage material can be well organized and structured.

Moreover, it is preferable that the said clay mineral is exhibiting the fibrous form of a diameter smaller than the particle diameter of the said chemical heat storage material (Claim 5, 20 ).
In this case, since the chemical heat storage material is surrounded by the fibrous clay mineral having a smaller diameter, the chemical heat storage material can be organized and structured using a small amount of the clay mineral. It is. Therefore, the chemical heat storage material composite is obtained by reinforcing a porous structure in which a gap is formed between the chemical heat storage materials with a small amount of the clay mineral. Thereby, the occupation rate of the said chemical heat storage material per mass per volume in the said chemical heat storage material composite can be enlarged. That is, the chemical heat storage material composite having a large heat storage capacity is obtained. Furthermore, since the chemical heat storage material itself has a main structure, the chemical heat storage material composite has a simple heat transfer path, and has high heat storage efficiency and utilization efficiency of the stored heat.

The structural strength improving material is preferably a material that becomes porous after firing (claims 6 and 21 ).
In this case, the chemical heat storage material composite can more sufficiently secure the introduction / discharge path of the reactant / reaction product accompanying heat storage / heat dissipation due to the porosity of the structural strength improving material. Therefore, the chemical heat storage material composite can further suppress the movement (diffusion) inhibition of the reactant / reaction product accompanying the heat storage / radiation in the chemical heat storage material composite, and has excellent heat transfer performance. Become.

Moreover, it is preferable that the said structural strength improvement material contains Al .
In this case, the Al component of the structural strength improving material appropriately reacts with the chemical heat storage material component (alkaline earth metal element (Ca etc.)) or the clay mineral component (Si etc.), − Al-O-Ca-, -Al-O-Si-, etc. are formed, and the structural strength of the chemical heat storage material composite can be further improved.
Moreover, as said structural strength improvement material containing Al, what contains 1 or more types chosen from aluminum hydroxide, aluminum nitrate, aluminum phosphate, and boehmite, for example can be used .

The chemical heat storage material is preferably a hydration reaction-type chemical heat storage material that absorbs heat with a dehydration reaction and dissipates heat with a hydration reaction (Claims 7 and 22 ).
The chemical heat storage material is preferably a hydration reaction type chemical heat storage material that is oxidized with a dehydration reaction and hydroxylated with a hydration reaction (claims 8 and 24 ).
In any case, the chemical heat storage material composite can perform good heat storage and heat dissipation by hydration reaction and dehydration (reverse hydration) reaction, and can improve the performance as a heat storage system. Although the volume of the chemical heat storage material repeatedly expands and contracts with the hydration reaction and dehydration reaction, the chemical heat storage material can be sufficiently prevented from being pulverized by organization and structuring of the chemical heat storage material. it can.

The chemical heat storage material is preferably a hydroxide (claims 9 and 26 ).
In this case, when the chemical heat storage material is mixed with the clay mineral and the structural strength improving material, when a carbonic acid compound is used as the chemical heat storage material, it can be used as a binder for mixing and thickening. Water that could not be used can be used. Thereby, the moldability of the said chemical heat storage material composite can be improved. Moreover, high-temperature baking around 1000 ° C. during the decarbonation step, which is necessary when a carbonic acid compound is used as the chemical heat storage material, is not necessary. Thereby, a calcination temperature can be made low and the freedom degree of a use material and a process can be raised.
In addition, in the said chemical heat storage material composite formed by baking, the said chemical heat storage material exists in the state of an oxide.

The chemical heat storage material is preferably an inorganic compound (claims 10 and 27 ).
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.

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 compound (claim 11, 28), alkaline earth among them A metal group compound is more preferable.
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. Further, by using a safe material having 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 preferably composed of one or more compounds selected from nickel hydroxide, aluminum hydroxide, cobalt hydroxide, copper hydroxide, barium hydroxide, calcium hydroxide, and magnesium hydroxide. Item 12, 29 ) Among them, calcium hydroxide and magnesium hydroxide are more preferable, and calcium hydroxide is more preferable.
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, lithium hydroxide or the like can also be used as the chemical heat storage material.

Moreover, it is preferable that the total content of the clay mineral and the structural strength improving material with respect to 100% by mass of the chemical heat storage material composite is 0.1 to 20% by mass (Claims 13 and 30 ).
In this case, the structural strength of the chemical heat storage material composite can be sufficiently improved by the clay mineral and the structural strength improver.
When the total content of the clay mineral and the structural strength improving material is less than 0.1% by mass, the structural strength of the chemical heat storage material composite may not be sufficiently improved. On the other hand, when it exceeds 20 mass%, there exists a possibility that the effect as a thermal storage system in the said chemical thermal storage material composite body may fall.

The chemical heat storage material composite is preferably fired at a temperature of 350 to 500 ° C. (Claims 14 and 31 ).
In this case, the crystallization of the clay mineral and the dehydration reaction of the chemical heat storage material can proceed simultaneously. Thereby, structuring of the chemical heat storage material and an increase in specific surface area of the chemical heat storage material composite formed as a porous structure can be achieved simultaneously.

The firing temperature is preferably close to the dehydration temperature of the chemical heat storage material. As such a combination, for example, sepiolite (firing temperature: 350 ° C. or higher) and an alkaline earth metal compound (dehydration temperature: 400 to 450). (° C.).
Moreover, in the said baking process, after shape | molding the said thermal storage mixture in a predetermined shape and obtaining a molded object, the molded object can be baked, for example.

In the second aspect of the invention, the mixing step includes a first mixing step of mixing the clay mineral and the structural strength improving material to obtain an additive mixture,
It is preferable to include a second mixing step of mixing the chemical heat storage material with the additive mixture to obtain the heat storage material mixture (claim 16 ).
In this case, the chemical heat storage material in powder can be firmly surrounded by the clay mineral and the structural strength improving material, and the chemical heat storage material can be well organized and structured.

In the mixing step (second mixing step), it is preferable that the clay mineral and the structural strength improving material (additive mixture) are mixed with the chemical heat storage material in a hydrated state (claim 23 ).
Further, in the mixing step (second mixing step), it is preferable to mix the above-mentioned chemical heat storage material of the hydroxide state said clay mineral and said structural reinforcing material (the additive mixture) (Claim 25).
In any case, the chemical heat storage material does not react with water unlike the case where the dehydrated chemical heat storage material is used. Therefore, when the clay mineral and the structural strength improving material (addition mixture) are mixed with the chemical heat storage material, water can be used as a binder, and the above steps can be easily performed.

Example 1
A chemical heat storage material composite according to an embodiment of the present invention and a manufacturing method thereof will be described with reference to the drawings.
As shown in FIG. 1, the chemical heat storage material composite 1 of this example is obtained by mixing a powdered chemical heat storage material 11 with a clay mineral 12 and a structural strength improving material 13 and firing the mixture.
FIG. 1 schematically shows the relationship between the chemical heat storage material 11, the clay mineral 12 and the structural strength improving material 13.

  Specifically, as shown in the figure, the chemical heat storage material composite 1 is a structure in which a large number of chemical heat storage materials 11 are organized and structured, and there are gaps (pores) between the chemical heat storage materials 11. Is formed. Therefore, the chemical heat storage material composite 1 of this example is grasped as a porous structure (porous body).

  Moreover, as shown in the figure, the chemical heat storage material composite 1 surrounds a large number of chemical heat storage materials 11 so that the clay mineral 12 and the structural strength improving material 13 are entangled. That is, the chemical heat storage material composite 1 is grasped as a structure in which the chemical heat storage material 11 is dispersed and held in the skeleton of the porous clay mineral 12 and the structural strength improvement material 13. In the chemical heat storage material composite 1, the structure as a porous structure in which pores are formed between a large number of chemical heat storage materials 11 is held (reinforced) by the clay mineral 12 and the structural strength improving material 13. It has become.

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
In addition, the chemical heat storage material 11 shown by FIG. 1 is the state after baking. Therefore, calcium hydroxide (Ca (OH) ₂ ) as the chemical heat storage material 11 exists as calcium oxide (CaO).

The clay mineral 12 is sepiolite, which is a clay mineral having a layer ribbon structure. Specifically, one of the clay minerals formed by combining a plurality of single chains resembling pyroxene to form a tetrahedral ribbon. It is. Sepiolite is, for example, 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. Sepiolite itself is porous and has a fibrous shape with a large specific surface area. Note that sepiolite includes variants of those represented by the above chemical formula.

The structural strength improving material 13 is aluminum hydroxide (Al (OH) ₃ ).
The structural strength improving material 13 shown in FIG. 1 is in a state after firing. Therefore, aluminum hydroxide (Al (OH) ₃ ) as the structural strength improving material 13 exists as porous alumina (Al ₂ O ₃ ).

Next, the manufacturing method of a chemical heat storage material composite is demonstrated.
The manufacturing method of this example includes a mixing step of mixing the powdered chemical heat storage material 11, the clay mineral 12 and the structural strength improving material 13 to obtain the heat storage material mixture M1, and a chemical heat storage material composite by firing the heat storage material mixture M1. And a firing step for obtaining the body 1.
The mixing step is a first mixing step of mixing the clay mineral 12 and the structural strength improving material 13 to obtain the additive mixture M0, and a mixing step of mixing the additive mixture M0 with the chemical heat storage material 11 to obtain the heat storage material mixture M1. 2 mixing steps.
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, as the clay mineral 12, sepiolite (Mg ₈ Si ₁₂ O ₃₀ (OH)) is a clay mineral having a fiber shape in which the fiber diameter when suspended in water is smaller than the average particle diameter D of the chemical heat storage material 11. ₄ (OH ₂ ) ₄ · 8H ₂ O) was prepared. Specifically, it is desirable that sepiolite has a wire diameter (fiber diameter) of 1 μm or less and a length (fiber length) of 200 μm or less. In this example, Turkish sepiolite having a wire diameter of about 0.01 μm and a length of about several tens of μm was prepared.
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, as the structural strength improving material 13, aluminum hydroxide (Al (OH) ₃ ) that becomes porous after firing was prepared.

  Next, in the first mixing step in the mixing step, as shown in FIGS. 2A and 2B, sepiolite 12 as a clay mineral and aluminum hydroxide 13 as a structural strength improving material are put in a mixing vessel 21 and uniform. Then, as shown in FIG. 2 (c), the mixture was put into a kneader 22 and kneaded while gradually adding water as a binder to increase the viscosity. As a result, an additive mixture M0 which is a kneaded mixture of sepiolite 12 and aluminum hydroxide 13 was obtained.

  Next, in the second mixing step in the mixing step, as shown in FIG. 2 (d), calcium hydroxide 11 as a chemical heat storage material is placed in the kneader 22 containing the additive mixture M0, and water as a binder is gradually added. While kneading, the mixture was thickened. Thereby, the heat storage material mixture M1 which is a kneaded material of the calcium hydroxide 11 and the addition mixture M0 was obtained.

  Next, as shown in FIG. 2 (e), the heat storage material mixture M <b> 1 obtained in the mixing step was placed in the extrusion mold 23 and extruded. Thereby, the heat storage material mixture M <b> 1 was formed in a predetermined shape corresponding to the shape of the extrusion die 23. In this example, it was formed as a pellet (molded body) P having a size of several mm. The pellet P can be formed into, for example, a substantially cylindrical shape with a diameter of about 3 mm and a length of about 3 to 5 mm, a prismatic shape with an equivalent size, or the like. Moreover, you may make it form the pellet P by cut | disconnecting the thermal storage material mixture M1 extruded from the extrusion type | mold 23 as needed.

Next, in the firing step, as shown in FIG. 2 (f), the pellet P was placed in the firing furnace 24 and fired at about 450 ° C. for a predetermined time. Thereby, the chemical heat storage material composite 1 was obtained.
In addition, this baking temperature is more than the dehydration temperature of calcium hydroxide and aluminum hydroxide. Therefore, the dehydration reaction of calcium hydroxide and aluminum hydroxide proceeds simultaneously by firing in the firing step. Therefore, in the chemical heat storage material composite 1 immediately after manufacture, the chemical heat storage material 11 exists in the state of calcium oxide. Moreover, the structural strength improving material 13 exists in the state of porous alumina.

  The chemical heat storage material composite 1 manufactured as described above may be used as it is in the heat storage system as the chemical heat storage material composite 1, or may be used as a raw material (intermediate) for manufacturing a larger heat storage material. Well, you may form in a shaping | molding process in the shape according to the application used. When forming as a raw material (intermediate) for producing a large heat storage material, the firing temperature is lower than the dehydration temperature of calcium hydroxide (eg, 350 ° C. or lower), Baking is preferably performed at a temperature higher than the dehydration temperature.

Next, the effect in the chemical heat storage material composite 1 of this example is demonstrated.
The chemical heat storage material composite 1 of this example is a powdered chemical heat storage material 11 mixed with a clay mineral 12 and a structural strength improving material 13 and fired. Therefore, the chemical heat storage material composite 1 is organized and structured by dispersing and holding the powder chemical heat storage material 11 in the skeleton of the clay mineral 12 and the structural strength improving material 13. Thereby, the following various effects can be expected.

That is, a gap is formed between the powders of the chemical heat storage material 11 due to the presence of the clay mineral 12 and the like. Therefore, rubbing of the chemical heat storage material 11 due to repeated heat storage and heat dissipation and pulverization associated therewith can be suppressed.
In addition, due to the gap, it is possible to sufficiently secure the introduction / discharge path of the reactant / reaction product accompanying heat storage / heat radiation. Therefore, the movement (diffusion) inhibition of the reactant / reaction product accompanying the heat storage / radiation in the chemical heat storage material composite 1 can be suppressed.

  The chemical heat storage material composite 1 becomes a porous structure having a high strength and a stable structure by the clay mineral 12 and the structural strength improving material 13 surrounding the chemical heat storage material 11. In particular, in this example, as described above, in addition to the clay mineral 12, the structural strength improving material 13 further includes the structural strength improving material 13, thereby firmly stabilizing the structure surrounding the chemical heat storage material 11 by the clay mineral 12. Alternatively, the structural strength improving material 13 itself surrounds the chemical heat storage material 11 together with the clay mineral 12 to form a strong and stable structure, thereby further increasing the structural strength of the entire chemical heat storage material composite 1. it can.

  As the clay mineral 12, sepiolite, which is a clay mineral having a layered ribbon structure, is used. That is, a porous material having a fibrous form with a large specific surface area is used. Therefore, the chemical heat storage material 11 can be well organized and structured by the properties of the clay mineral 12 such as fiber, porosity, and plasticity.

  Further, due to the adsorptivity of the porous clay mineral 12 having a large specific surface area, it is possible to adsorb excessive water vapor present during the heat storage / heat dissipation reaction into the clay mineral 12. Therefore, for example, in the case of a low temperature state where the heat storage system using the chemical heat storage material complex 1 is stopped, the chemical heat storage material 11 is prevented from absorbing water and becoming liquid in the chemical heat storage material complex 1. be able to. Thereby, the sintering by reaction with the chemical heat storage material 11 and liquid water can be suppressed.

  Moreover, as the clay mineral 12, what has a fibrous form with a diameter smaller than the particle diameter of the chemical heat storage material 11 is used. Therefore, since the chemical heat storage material 11 is surrounded by the fibrous clay mineral 12 having a smaller diameter, the chemical heat storage material 11 can be organized and structured using a small amount of the clay mineral 12. Specifically, the chemical heat storage material composite 1 is obtained by reinforcing a porous structure in which pores are formed between the chemical heat storage materials 11 with a small amount of clay mineral 12. Thereby, the occupation rate of the chemical heat storage material 11 per volume in the chemical heat storage material complex 1 per volume can be increased. That is, the chemical heat storage material composite 1 having a large heat storage capacity is obtained. Furthermore, since the chemical heat storage material complex 1 itself has a main structure, the chemical heat storage material complex 1 has a simple heat transfer path, and has high heat storage efficiency and utilization efficiency of the stored heat.

  Moreover, as the structural strength improving material 13, aluminum hydroxide is used and becomes porous after firing. Therefore, the chemical heat storage material composite 1 can more sufficiently secure the introduction / discharge path of the reactant / reaction product accompanying the heat storage / heat dissipation due to the porosity of the structural strength improving material 13. Therefore, the chemical heat storage material composite 1 can further suppress the movement (diffusion) inhibition of the reactant / reaction product accompanying the heat storage / radiation in the chemical heat storage material composite 1 and has excellent heat transfer performance. It becomes.

  Moreover, as the structural strength improving material 13, aluminum hydroxide containing Al is used. Therefore, when the Al component of the structural strength improving material 13 reacts appropriately with the Ca component, which is an alkaline earth metal element of the chemical heat storage material 11, the Si component of the clay mineral 12, and the like, -Al-O-Ca-,- Al—O—Si— or the like is formed, and the structural strength of the chemical heat storage material composite 1 can be further improved.

  The chemical heat storage material 11 is a hydration reaction-type chemical heat storage material that absorbs heat with the dehydration reaction and dissipates heat with the hydration reaction, and is oxidized with the dehydration reaction and water with the 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 perform heat storage and heat dissipation satisfactorily by a hydration reaction and a dehydration (reverse hydration) reaction, and can improve performance as a heat storage system.

  Moreover, as the chemical heat storage material 11, calcium hydroxide which is a hydroxide is used. Therefore, when mixing the powder chemical heat storage material 11 and the additive mixture M0 in the second mixing step in the mixing step, when a carbonic acid compound is used as the chemical heat storage material 11, it is used as a binder for mixing and thickening. Water that could not be used can be used. Thereby, the moldability of the chemical heat storage material composite 1 can be improved. Moreover, high-temperature baking around 1000 ° C. in the decarbonation step, which is necessary when a carbonic acid compound is used as the chemical heat storage material 11, becomes unnecessary. Thereby, a calcination temperature can be made low and the freedom degree of a use material and a process can be raised.

  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 and heat dissipation reaction (hydration / dehydration reaction) of the chemical heat storage material is increased. In particular, since the reversibility of calcium hydroxide is high, 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 manufacturing method of this example, in the 2nd mixing process in a mixing process, the additive mixture M0 is mixed with the chemical heat storage material 11 of a hydration state and a hydroxide state. Therefore, unlike the case where the dehydrated chemical heat storage material 11 is used, the chemical heat storage material 11 does not react with water. Therefore, when the additive mixture M0 is mixed with the chemical heat storage material 11, water can be used as a binder, and the above steps can be easily performed.

  Moreover, in the 2nd mixing process in a mixing process, the thickening effect can be acquired by stirring with a water | moisture content by thixotropy (thixotropy) of the clay mineral 12. FIG. Therefore, the structure based on the chemical heat storage material 11 can be formed with higher accuracy and higher density. Thereby, the obtained chemical heat storage material composite 1 has high accuracy and high density and low thermal resistance.

  In the firing step, firing is performed at a temperature of 350 to 500 ° C. Therefore, the crystallization of the clay mineral 12 and the dehydration reaction of the chemical heat storage material 11 can proceed simultaneously. Thereby, the structuring of the chemical heat storage material 11 of the chemical heat storage material composite 1 formed as a porous structure and the increase of the specific surface area can be achieved simultaneously.

  Thus, according to this example, it is possible to obtain the chemical heat storage material composite 1 capable of suppressing the pulverization of the chemical heat storage material 11 and securing the heat conduction path and further improving the structural strength. .

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 aluminum hydroxide is used as the structural strength improving material 13, aluminum nitrate, aluminum phosphate, boehmite, or the like can also be used.

(Example 2)
In this example, the reaction rate and crushing strength of the chemical heat storage material composite of the present invention are measured.
In this example, as shown in Table 1, the composition ratio of chemical heat storage material (calcium hydroxide (Ca (OH) ₂ ), clay mineral (sepiolite) and structural strength improver (aluminum hydroxide (Al (OH) ₃ )) A chemical heat storage material composite was produced by changing the present invention products (E1 to E3 of the present invention), and as a comparison, a chemical heat storage material composite (comparative product) without addition of a structural strength improver (aluminum hydroxide (Al (OH) ₃ )). C1) was produced.
And the reaction rate and crushing strength were measured about this invention products E1-E3 and the comparative product C1.

Here, the reaction rate is a value obtained by determining the amount of change in weight between dehydration and hydration by thermogravimetric analysis and determining the rate of change from calcium oxide to calcium hydroxide in the sample.
Specifically, about 20 mg of a sample was collected, heated to 450 ° C., and the weight of the sample was measured at a temperature of 450 ° C. under a nitrogen gas flow. At this time, most of the calcium component is calcium oxide. Thereafter, the temperature was lowered to 200 ° C., and the weight change amount to calcium hydroxide was measured by exposing to 200 ° C. and nitrogen gas containing water vapor. This dehydration and hydration was repeated three times, and the third weight change was converted to the weight of the calcium hydroxide charged to obtain the reaction rate.

  The crushing strength is obtained by preparing a pellet-shaped sample, dropping it from a position 20 cm high from the bottom of a 1 L glass beaker, and qualitatively evaluating the scattering state of the sample after dropping. And what crushed many debris was made into crushing strength (small), the thing in which scattering was hardly seen was made into crushing strength (large), and the crushing strength (medium) between these.

Next, the measurement results of reaction rate and crushing strength will be described.
As shown in Table 1, it can be seen that the inventive products E1 to E3 containing the structural strength improving material have a higher reaction rate than the comparative product C1 not containing the structural strength improving material.
In addition, as shown in the table, it can be seen that the inventive products E1 to E3 containing the structural strength improving material have higher crushing strength than the comparative product C1 not containing the structural strength improving material.

  From such a result, the chemical heat storage material composite of the present invention can perform heat storage and heat dissipation well by the hydration reaction and dehydration (reverse hydration) reaction due to the presence of the structural strength improving material. It can be seen that the performance is high. It can also be seen that the structure is structured and structured with high structural strength.

Explanatory drawing which shows the structure of the chemical heat storage material composite_body | complex in Example 1. FIG. Explanatory drawing which shows the manufacturing method of the chemical heat storage material composite_body | complex in Example 1. FIG.

Explanation of symbols

1 Chemical Heat Storage Material Complex 11 Chemical Heat Storage Material 12 Clay Mineral 13 Structural Strength Improvement Material

Claims (31)

Ri chemical heat storage material powder greens and fired by mixing clay mineral and structural reinforcing material,
The said structural strength improvement material contains 1 or more types chosen from aluminum hydroxide, aluminum nitrate, aluminum phosphate, and boehmite, The chemical heat storage material composite characterized by the above-mentioned .   2. The chemical heat storage material composite according to claim 1, wherein the clay mineral is a clay mineral having a layer ribbon structure.   3. The chemical heat storage material composite according to claim 2, wherein the clay mineral having the layer ribbon structure is sepiolite and / or palygorskite.   2. The chemical heat storage material composite according to claim 1, wherein the clay mineral is bentonite.   5. The chemical heat storage material composite according to claim 1, wherein the clay mineral has a fibrous shape having a diameter smaller than a particle diameter of the chemical heat storage material.   The chemical heat storage material composite according to any one of claims 1 to 5, wherein the structural strength improving material is a material that becomes porous after firing. The chemical heat storage material 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. Material composite. 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. Chemical heat storage material composite. 9. The chemical heat storage material composite according to claim 1, wherein the chemical heat storage material is a hydroxide. The chemical heat storage material composite according to any one of claims 1 to 9, wherein the chemical heat storage material is an inorganic compound. 11. The chemical heat storage material according to claim 1, wherein the chemical heat storage material includes one or more compounds selected from a nickel compound, an aluminum compound, a cobalt compound, a copper compound, and an alkaline earth metal compound. Chemical heat storage material composite. 12. The chemical heat storage material according to claim 1, wherein the chemical heat storage material is selected from nickel hydroxide, aluminum hydroxide, cobalt hydroxide, copper hydroxide, barium hydroxide, calcium hydroxide, and magnesium hydroxide. A chemical heat storage material composite comprising the above compound. In any 1 item | term of Claims 1-12, The total content of the said clay mineral and the said structural strength improvement material with respect to 100 mass% of said chemical heat storage material composites is 0.1-20 mass%, It is characterized by the above-mentioned. Chemical heat storage material composite. 14. The chemical heat storage material composite according to claim 1, wherein the chemical heat storage material composite is fired at a temperature of 350 to 500 ° C. 15. A mixing step of mixing a powder chemical heat storage material, a clay mineral and a structural strength improvement material to obtain a heat storage material mixture;
And firing the heat storage material mixture possess a firing step to obtain a chemical heat storage material complex,
The said structural strength improvement material contains any 1 or more types chosen from aluminum hydroxide, aluminum nitrate, aluminum phosphate, and boehmite , The manufacturing method of the chemical heat storage material composite characterized by the above-mentioned . In Claim 15, the said mixing process mixes the above-mentioned clay mineral and the above-mentioned structural strength improvement material, and the 1st mixing process which obtains an addition mixture,
A method for producing a chemical heat storage material composite, comprising: a second mixing step of mixing the chemical heat storage material with the additive mixture to obtain the heat storage material mixture. The method for producing a chemical heat storage material composite according to claim 15 or 16, wherein the clay mineral is a clay mineral having a layered ribbon structure. 18. The method for producing a chemical heat storage material composite according to claim 17, wherein the clay mineral having the layer ribbon structure is sepiolite and / or palygorskite. The method for producing a chemical heat storage material composite according to claim 15 or 16, wherein the clay mineral is bentonite. The method for producing a chemical heat storage material composite according to any one of claims 15 to 19, wherein the clay mineral has a fibrous shape having a diameter smaller than the particle diameter of the chemical heat storage material. The method for producing a chemical heat storage material composite according to any one of claims 15 to 20, wherein the structural strength improving material is a material that becomes porous after firing. The chemical heat storage material according to any one of claims 15 to 21, 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. A method for producing a composite material. 23. The method for producing a chemical heat storage material composite according to claim 22, wherein , in the mixing step, the clay mineral and the structural strength improving material are mixed with the chemical heat storage material in a hydrated state. The chemical heat storage material according to any one of claims 15 to 23, wherein the chemical heat storage material is a hydration reaction type chemical heat storage material that is oxidized with a dehydration reaction and hydroxylated with a hydration reaction. A method for producing a chemical heat storage material composite. 25. The method for producing a chemical heat storage material composite according to claim 24, wherein , in the mixing step, the clay mineral and the structural strength improving material are mixed with the chemical heat storage material in a hydroxide state. The method for producing a chemical heat storage material composite according to any one of claims 15 to 25, wherein the chemical heat storage material is a hydroxide. 27. The method for producing a chemical heat storage material composite according to any one of claims 15 to 26, wherein the chemical heat storage material is an inorganic compound. 28. The chemical heat storage material according to claim 15, wherein the chemical heat storage material is composed of one or more compounds selected from a nickel compound, an aluminum compound, a cobalt compound, a copper compound, and an alkaline earth metal compound. A method for producing a chemical heat storage material composite. The chemical heat storage material according to any one of claims 15 to 28, wherein the chemical heat storage material is selected from nickel hydroxide, aluminum hydroxide, cobalt hydroxide, copper hydroxide, barium hydroxide, calcium hydroxide, and magnesium hydroxide. A method for producing a chemical heat storage material composite comprising the above compound. 30. In any one of Claims 15-29, the said mixing process is performed so that the total content of the said addition mixture with respect to 100 mass% of said chemical heat storage material composites may finally be set to 0.1-20 mass%. A method for producing a chemical heat storage material composite. The method for producing a chemical heat storage material composite according to any one of claims 15 to 30, wherein , in the firing step, the molded body is fired at a temperature of 350 to 500 ° C.