JP2009221289A - Heat storage chemical material molded form and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat storage chemical material molded form suppressing the heat storage chemical material's pulverization associated with hydration and dehydration reaction, and capable of fully exhibiting its own ability as a chemical heat storage system, and to provide a method for producing the above molded form. <P>SOLUTION: The heat storage chemical material molded form comprises a skeletal structural part 2 consisting of porous ceramic with many micropores and a heat storage chemical material 3 carried on the outer surface of the skeletal structural part 2 or this outer surface and inside the micropores of the skeletal structural part 2. In this molded form, it is preferable that the skeletal structural part 2 comprises a ceramic obtained by baking a clay mineral, which has preferably a laminar ribbon structure, and the clay mineral is preferably sepiolite and/or palygorskite. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a chemical heat storage material molded body obtained by molding a chemical heat storage material and a method for producing the same.

  Conventionally, a chemical heat storage material has a large amount of heat storage per volume, does not require heat retention, and has a small heat storage loss, and thus can store heat for a long period of time. Therefore, research and development related to a chemical heat storage system that uses a chemical heat storage material has been promoted (Patent Documents 1 to 3).

The invention described in Patent Document 1 relates to a chemical heat storage material and a method for producing the same, and describes means for adjusting the specific surface area after calcining calcium carbonate and converting it to calcium oxide.
The invention described in Patent Document 2 relates to a heat storage device, and the invention described in Patent Document 3 relates to a chemical heat storage material capsule. These inventions are inventions that deal with the above-mentioned pulverization of the chemical heat storage material. There, there is described the suppression of exfoliation and reduction in reactivity due to pulverization by encapsulating a heat storage material in a porous capsule or porous cylinder having a pore size.

JP-A-1-225686 Japanese Patent Publication No. 6-80395 Japanese Patent Publication No. 8-80394

However, the chemical heat storage material described in Patent Document 1 repeats a hydration reaction and a dehydration reaction during operation as a chemical heat storage system. At that time, the powdered chemical heat storage material repeatedly expands and contracts by a volume of several tens of percent, and as a result, the powder breaks down and the particles rub against each other, resulting in a pulverized reaction. There is a problem of lowering.
In the heat storage system, it is also important to perform heat exchange that guides heat to the outside of the system in response to the reaction. However, the heat storage device and the chemical heat storage material capsule described in Patent Documents 2 and 3 generate heat regulation such as increase in heat conduction resistance due to encapsulation of the capsule or cylindrical body and complication of the contact path depending on the distance between particles. To do. Therefore, there exists a problem that sufficient capability cannot be exhibited as a chemical heat storage system.

  The present invention has been made in view of such conventional problems, and can suppress the pulverization of the chemical heat storage material associated with the hydration / dehydration reaction and can sufficiently exhibit the ability as a chemical heat storage system. A chemical heat storage material molded body and a method for producing the same are provided.

  A first invention is a skeleton structure portion made of porous ceramics having a large number of pores, and an outer surface of the skeleton structure portion, or a chemical heat storage material supported on the outer surface of the skeleton structure portion and inside the pores It is in the chemical heat storage material molded object characterized by having (Claim 1).

  The chemical heat storage material molded body has a configuration in which a chemical heat storage material is supported around the specific skeleton structure portion, and the pores of the skeleton structure portion are necessary for heat storage and heat dissipation of the chemical heat storage material. It can be a flow path through which water vapor or the like passes, or can carry a chemical heat storage material. Therefore, the efficiency of the chemical heat storage system can be increased, and the capability as a chemical heat storage system can be sufficiently exhibited. Moreover, pulverization of the chemical heat storage material associated with the hydration / dehydration reaction can be suppressed.

  That is, when a chemical heat storage material is supported on the outer surface of the skeleton structure portion and the pore portion of the skeleton structure portion is hollow, the pore portion mainly becomes a flow path of water vapor or the like, Heat storage and heat dissipation of the chemical heat storage material can be performed particularly well, and the efficiency of the chemical heat storage system can be increased.

Moreover, when the chemical heat storage material is supported on the outer surface and the pores of the skeleton structure portion, the chemical heat storage material molded body can stably support a large number of chemical heat storage materials. Therefore, it is possible to suppress the pulverization of the chemical heat storage material, and to increase the packing density of the chemical heat storage material per volume and the mass in the chemical heat storage material molded body. That is, it becomes the said chemical heat storage material molded object with a large heat storage density. Furthermore, the chemical heat storage material molded body has a larger apparent thermal conductivity than the powder, and has a high heat storage efficiency and a high utilization efficiency of the stored heat.
Thus, according to the present invention, there is provided a chemical heat storage material molded body capable of suppressing the pulverization of the chemical heat storage material associated with the hydration / dehydration reaction and sufficiently exhibiting the ability as a chemical heat storage system. be able to.

According to a second aspect of the present invention, there is provided a chemical heat storage material molded body having a skeleton structure portion made of porous ceramics having a large number of pores, and a chemical heat storage material supported on the outer surface of the skeleton structure portion and inside the pores. A method of manufacturing comprising:
A skeleton firing step for obtaining the skeleton structure portion by firing a ceramic material arranged in a desired shape;
A chemical heat storage material disposing step of disposing a heat storage material slurry, which is a slurry containing the chemical heat storage material, on the outer surface and inside the pores of the skeleton structure;
And a drying step of drying the heat storage material slurry disposed in the skeleton structure. (Claim 16).

The manufacturing method of the chemical heat storage material molded body is made of porous ceramics, and a skeleton structure portion having a desired shape is formed in advance, and the heat storage material slurry is infiltrated into the outer surface and the pores of the skeleton structure portion. Then, excess water in the heat storage material slurry is blown off. As a result, an excellent chemical heat storage material molded body having a skeleton structure portion made of porous ceramics having a large number of pores and a chemical heat storage material supported on the outer surface of the skeleton structure portion and inside the pores is obtained. be able to.
Thus, according to the present invention, a method for producing a chemical heat storage material molded body capable of suppressing the pulverization of the chemical heat storage material associated with the hydration / dehydration reaction and sufficiently exhibiting the ability as a chemical heat storage system. Can be provided.

The third invention is a method for producing a chemical heat storage material molded body having a skeleton structure portion made of porous ceramics having a large number of pores and a chemical heat storage material supported on the outer surface of the skeleton structure portion. And
Using a honeycomb substrate having a large number of cells surrounded by a porous partition wall having a large number of pores, and a ceramic material impregnation step of impregnating the ceramic material into the pores of the partition wall of the substrate;
A chemical heat storage material disposing step of disposing a heat storage material slurry that is a slurry containing the chemical heat storage material in the cell of the base material;
The base material, the ceramic raw material and the chemical heat storage material disposed on the base material are integrally fired to burn down the base material, and the skeleton structure portion obtained by firing the ceramic raw material and the chemical supported on the base material. A chemical heat storage material molded body comprising a calcining step of obtaining a chemical heat storage material molded body made of a heat storage material (claim 21).

The method for producing a chemical heat storage material molded body is as follows: a ceramic material is disposed on the outer surface and pores of a honeycomb substrate having a large number of cells surrounded by a porous partition wall having a large number of pores. The heat storage material slurry is disposed in and around the cells of the honeycomb base material, and then the base material, the ceramic raw material, and the heat storage material slurry are integrally fired and the base material is burned off. Thereby, the outstanding chemical heat storage material molded object which consists of the frame | skeleton structure part of the ceramic in which the part which the base material existed, and the chemical heat storage material carry | supported by the outer peripheral surface can be obtained.
Thus, according to the present invention, a method for producing a chemical heat storage material molded body capable of suppressing the pulverization of the chemical heat storage material associated with the hydration / dehydration reaction and sufficiently exhibiting the ability as a chemical heat storage system. Can be provided.

As described above, the chemical heat storage material molded body of the first invention includes a skeleton structure portion made of porous ceramics having a large number of pores, and an outer surface of the skeleton structure portion or an outer surface of the skeleton structure portion, and And a chemical heat storage material supported inside the pores.
It is preferable that the skeleton structure has an affinity for a chemical heat storage material and is stable at about 500 ° C.
And it is preferable that the said frame | skeleton structure part of the said chemical heat storage material molded object consists of ceramics which bake a clay mineral (Claim 2).

In the first invention, the second invention, and the third invention, the clay mineral constituting the skeleton structure portion is preferably a clay mineral having a layered ribbon structure (Inventions 3 and 26). .
In this case, the clay mineral has a fibrous shape that is porous and has a large specific surface area. Therefore, due to the properties of the clay mineral such as fiber, porosity, plasticity, etc., it is possible to satisfactorily form pores that become a flow path of water vapor or the like into which the chemical heat storage material enters in the skeleton structure portion. it can.
And it is preferable that the clay mineral which shows the said layer ribbon structure is a sepiolite and / or a palygorskite (Claims 4 and 27).

Here, the sepiolite is a clay mineral having a layered ribbon structure. Specifically, the sepiolite is one of clay minerals in which a plurality of single chains resembling pyroxene are combined to form a tetrahedral ribbon. Sepiolite includes, for example, 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. Sepiolite also includes variants of those represented by the above chemical formula.
The clay mineral is preferably bentonite (claims 5 and 28).

The chemical heat storage material is preferably a hydration reaction type chemical heat storage material that absorbs heat in association with a dehydration reaction and releases heat in association with a hydration reaction (claims 6 and 29).
The chemical heat storage material is preferably a hydration reaction type chemical heat storage material that becomes an oxide along with a dehydration reaction and a hydroxide along with a hydration reaction (claims 7 and 30).
In any case, the said chemical heat storage material molded object can perform heat dissipation and heat storage favorably by a 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 is favorably supported by the skeletal structure, so that the chemical heat storage material is finely powdered. It can be sufficiently suppressed.

Moreover, it is preferable that the said chemical heat storage material consists of hydroxides (Claims 8 and 31).
In this case, as described later, when the chemical heat storage material and the clay mineral are mixed to form a chemical heat storage material molded body, a carbonate compound is used as the chemical heat storage material as a binder for mixing and thickening. In this case, water that could not be used can be used. Thereby, the moldability of the said chemical heat storage material molded object can be improved. Moreover, high-temperature baking at around 1000 ° C. during the decarbonation step, which was necessary when a carbonic acid compound was used as the chemical heat storage material, becomes unnecessary. Thereby, a calcination temperature can be made low and the freedom degree of a use material and a process can be raised.

The hydroxide is preferably an inorganic compound (claims 9 and 32).
From the viewpoint of heat storage density, long-term heat storage stability, release rate, and safety, an inorganic system is preferable.
In this case, the material stability with respect to the heat storage / heat radiation reaction (dehydration / hydration reaction) of the chemical heat storage material is increased. Therefore, the said chemical heat storage material molded object can acquire the stable heat storage effect over a long period of time.

The inorganic compound is preferably an alkaline earth metal hydroxide (claims 10 and 33).
In this case, the material stability with respect to the heat storage / heat radiation reaction (dehydration / hydration reaction) of the chemical heat storage material is increased. Therefore, the said chemical heat storage material molded object can acquire the 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 alkaline earth metal hydroxide is preferably one or more of calcium hydroxide, magnesium hydroxide, and barium hydroxide (claims 11 and 34).
In this case, it is possible to further improve the material stability of the chemical heat storage material against heat storage / heat radiation reaction (dehydration / hydration reaction), and to stabilize the heat storage effect of the chemical heat storage material molded body over a long period of time. Can be maintained.
A mixture of magnesium hydroxide and calcium hydroxide can also be used.

  Moreover, the said inorganic compound can also use 1 type (s) or 2 or more types among nickel hydroxide, aluminum hydroxide, cobalt hydroxide, and copper hydroxide other than alkaline-earth metal hydroxide. 12, 35).

In the first invention, it is preferable that the chemical heat storage material is supported on the skeletal structure in a composite material formed by mixing with at least a clay mineral.
In this case, due to the properties of the clay mineral such as fiber, porosity and plasticity, the chemical heat storage material is supported on the skeletal structure in a state of being dispersed and held in the porous clay mineral. become. Therefore, compared with the case of only a chemical heat storage material, impact resistance can be improved significantly.
Moreover, it is preferable that the said composite material containing the said chemical heat storage material and the said clay mineral is baked (Claim 14). In this case, the clay mineral around the chemical heat storage material becomes structurally strong, and a more stable chemical heat storage material molded body can be obtained.

Moreover, it is preferable that the said chemical heat storage material molded object has the hollow part formed by penetration (Claim 15).
In this case, since the said hollow part becomes a flow path into and out of water vapor | steam, the reactivity of a chemical heat storage material can be ensured, and heat storage and heat dissipation can be performed favorably.

In addition, the method for producing a chemical heat storage material molded body according to the second aspect of the invention is a skeleton firing in which a skeletal structure portion made of porous ceramics having a large number of pores is obtained by firing a ceramic material arranged in a desired shape. Process.
The ceramic raw material can be adjusted to a desired shape by, for example, extrusion molding, compression molding, or a method using a support material as described later.
Moreover, it is preferable that the skeleton firing step is performed in a temperature range of 900 ° C. to 1100 ° C.

Moreover, the said manufacturing method has a chemical heat storage material arrangement | positioning process which arrange | positions the heat storage material slurry which is a slurry containing the said chemical heat storage material on the outer surface and the inside of a pore of the said frame | skeleton structure part.
The heat storage material slurry can be disposed on the outer surface of the skeleton structure portion and inside the pores by, for example, a method of immersing the skeleton structure portion in the heat storage material slurry.
The heat storage material slurry only needs to contain a chemical heat storage material, and may be a slurry containing only a chemical heat storage material or a slurry containing a clay mineral as described later.

Moreover, the said manufacturing method has a drying process which dries the said thermal storage material slurry arrange | positioned in the said frame | skeleton structure part.
It is preferable to perform the said drying process in the temperature range of 80 to 110 degreeC.
Moreover, since the mixing | blending, the optimal value of a viscosity, etc. of the said ceramic raw material and a thermal storage material slurry are fluctuate | varied with manufacturing environments etc., it is preferable to derive | lead-out suitably by experiment.

  Prior to the skeleton firing step, the method for producing the chemical heat storage material molded body is a ceramic slurry which is a slurry containing the ceramic raw material on a support material made of a fiber or a porous material that can be burned down by firing in the skeleton firing step. It is preferable to have a shaping step of shaping the substrate into a desired shape in a state where it is supported, and in the skeleton firing step, the support material is burned down.

  In this case, a skeletal structure having a desired shape can be produced efficiently, and cavities can be formed uniformly by burning out the support material. Thereby, the heat storage material slurry can be satisfactorily penetrated into the pores of the skeleton structure portion.

  As the support material, any material can be used as long as it is a fiber or a porous material that is easily infiltrated with the ceramic raw material and burns away by firing in the firing step. And in order to fully infiltrate the said ceramic raw material, the said support material should just have the clearance gap of a micro order.

In the shaping step, for example, a desired shape can be obtained by, for example, filling a support material in a state where the ceramic slurry is supported in a mold material made of, for example, a resin or the like that is burned down in the skeleton firing step. .
The shape of the support material may be a bellows shape or a flat shape, and these support materials may be stacked, draped, bent, or the like to have a desired shape. Obtainable.
Moreover, it is preferable that the said support material consists of a cloth-like material which interwoven the fiber (Claim 18). As this cloth-like material, for example, a material having a relatively coarse weave such as a lace is more preferable.

Further, the skeleton structure part has a hollow part formed through, and a core material is inserted into the hollow part in the chemical heat storage material arranging step and the drying step, and the core material is removed after the drying step. Preferred (claim 19).
The said hollow part becomes a flow path where reaction fluid, such as water vapor | steam comes in and out, and can perform heat storage and heat dissipation of a chemical heat storage material favorably.
The core material is preferably a metal member, but is not necessarily a metal, and may be ceramics of clay mineral (such as sepiolite) after firing.

Further, after the drying step, there may be a secondary firing step of integrally firing the skeleton structure portion and the chemical heat storage material supported on the skeleton structure portion (claim 20).
When hydroxide is used as the chemical heat storage material, the chemical heat storage material molded body obtained in this case is a composite of oxide and clay mineral.
Moreover, it is preferable that the calcination temperature in the said secondary calcination process is 350-500 degreeC.

As described above, the method for producing a chemical heat storage material molded body of the third invention uses a honeycomb substrate having a large number of cells surrounded by a porous partition wall having a large number of pores. A ceramic material impregnation step of impregnating the pores of the partition wall with the ceramic material.
Since the inside of the cells of the honeycomb-shaped base material after the ceramic raw material impregnation step is preferably hollow, the ceramic raw material soaks into the base material, stays in the pores of the base material, and has a surface tension. It is preferable that the viscosity is low to some extent so as to remain on the outer surface.
The ceramic raw material constituting the skeleton structure is preferably a mixture of clay mineral and water (claim 25). And since the mixing | blending of the said ceramic raw material, the optimal value of a viscosity, etc. change with manufacturing environments etc., it is preferable to derive | lead-out suitably by experiment.
Moreover, the said honeycomb-like base material can maintain a structure before baking, and any thing can be used if it consists of the material burned down in a baking process.

Moreover, the said manufacturing method has a chemical heat storage material arrangement | positioning process which arrange | positions the heat storage material slurry which is a slurry containing the said chemical heat storage material in the cell of the said base material.
It is preferable to use a material having a high viscosity so that the heat storage material slurry can be filled in the cells of the honeycomb-shaped substrate.
And it is preferable to arrange | position so that a heat storage material slurry with a high clay may be pushed in said cell.
In addition, since the blending of the heat storage material slurry, the optimum value of the viscosity, and the like vary depending on the manufacturing environment and the like, it is preferable to derive from experiments as appropriate.

In addition, the manufacturing method includes a skeletal structure portion in which the base material, the ceramic raw material and the chemical heat storage material disposed on the base material are integrally fired to burn off the base material, and the ceramic raw material is fired. And a calcining step of obtaining a chemical heat storage material molded body comprising the chemical heat storage material carried on the substrate.
The firing process is preferably performed in a temperature range of 400 ° C to 500 ° C.

In the method for producing the chemical heat storage material molded body, the base material is preferably made of a porous resin.
The base material may be formed of a resin mesh formed in a mesh shape.
A base material made of these resins can be easily burned off in the above baking step, and is suitable as a base material.

Moreover, it is preferable that the said base material has the bulk part which burns down in the said baking process and becomes a hollow part (Claim 24).
In this case, the formed hollow portion becomes a passage through which water vapor enters and exits, and heat storage and heat dissipation of the chemical heat storage material can be performed satisfactorily.
The bulk portion can be provided by forming a lump made of resin at a desired position when forming the skeleton.

In the second and third inventions, it is preferable that the heat storage material slurry is formed by kneading a chemical heat storage material, a clay mineral, and water (Claim 36).
In this case, due to the properties of the clay mineral such as fiber, porosity and plasticity, the chemical heat storage material is supported on the skeletal structure in a state of being dispersed and held in the porous clay mineral. become. Therefore, compared with the case of only a chemical heat storage material, impact resistance can be improved significantly.
From the viewpoint of affinity, it is preferable to use the same clay mineral as the clay mineral constituting the heat storage material slurry as the ceramic raw material constituting the skeleton structure portion.

Moreover, it is preferable that the clay mineral which comprises the said thermal storage material slurry is a clay mineral which has a layer ribbon structure (Claim 37).
In this case, the clay mineral has a fibrous shape of a layer ribbon structure which 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, it is preferable that the clay mineral which shows the layer ribbon structure which comprises the said thermal storage material slurry is a sepiolite and / or a palygorskite (Claim 38).

Moreover, it is preferable that the clay mineral which comprises the said thermal storage material slurry is exhibiting the fibrous form of a diameter smaller than the particle diameter of the said chemical thermal storage material (Claim 39).
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 said chemical heat storage material molded object becomes what reinforce | strengthened the porous structure body which made the clearance gap between the said chemical heat storage materials with a small amount of the said clay mineral. Thereby, the filling density of the said chemical heat storage material per mass per volume in the said chemical heat storage material molded object can be enlarged. That is, it becomes the said chemical heat storage material molded object with a large heat storage density. Furthermore, since the said chemical heat storage material molded object has a large apparent thermal conductivity compared with powder, the thermal storage efficiency and the utilization efficiency of the stored heat become high.

Moreover, it is preferable that the clay mineral which comprises the said thermal storage material slurry is a bentonite (Claim 40).
Since the bentonite is a clay mineral with strong adhesive strength, the chemical heat storage material can be well organized and structured by this adhesive strength.

Example 1
This example demonstrates the chemical heat storage material molded object and its manufacturing method concerning the Example of this invention using FIGS. 1-8.
As shown in FIG. 8, the chemical heat storage material molded body 1 of this example includes a skeleton structure portion 2 made of porous ceramics having a large number of pores, and the outer surface of the skeleton structure portion 2 or the skeleton structure portion. And the chemical heat storage material 3 supported on the inside of the pores.
This will be described in detail below.

First, a ceramic raw material 21 for forming the skeleton structure portion 2 was prepared by mixing and stirring clay mineral and water.
Sepiolite (Mg ₈ Si ₁₂ O ₃₀ (OH) ₄ (OH ₂ ) ₄ · 8H ₂ O), which is a clay mineral having a layer ribbon structure, was prepared as the clay mineral constituting the ceramic raw material 21.
The sepiolite exhibits a fiber shape having a fiber diameter smaller than the average particle diameter of the chemical heat storage material when suspended in water.
Specifically, the sepiolite preferably 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 approximately 0.01 μm and a length of approximately several tens of μm is prepared.
Instead of Turkish sepiolite, for example, Spanish sepiolite having a wire diameter of 0.1 μm and a length of approximately 100 μm can be used.

Moreover, the heat storage material slurry 31 was prepared by mixing and stirring the chemical heat storage material 3, the clay mineral, and water.
As the chemical heat storage material 3 constituting the heat storage material slurry 31, an alkaline earth metal Ca hydroxide Ca (OH) ₂ was prepared. The average particle diameter D of the chemical heat storage material is 10 μm (by laser diffraction measurement method, SALD-2000A manufactured by Shimadzu Corporation).
Further, the chemical heat storage material reversibly repeats heat storage and heat dissipation by the following reactions.
Ca (OH) ₂ Ｃａ 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

Moreover, the same sepiolite as the sepiolite used for the said ceramic raw material 21 was prepared as the said clay mineral which comprises the thermal storage material slurry 31. FIG.
The mixing ratio of the chemical heat storage material and the clay mineral was 9: 1.

Next, a manufacturing method will be described.
In the manufacturing method of this example, a skeleton firing step for obtaining the skeleton structure portion 2 by firing a ceramic material arranged in a desired shape, and a heat storage material slurry 31 that is a slurry containing the chemical heat storage material 3 are used as the skeleton structure. A chemical heat storage material disposing step disposed on the outer surface of the portion 2 and inside the pores, and a drying step of drying the heat storage material slurry 31 disposed on the skeleton structure portion 2.

First, as shown in FIG. 1, before the skeleton firing step, a support material 4 made of fibers that can be burned down by firing in the skeleton firing step was prepared. The support material 4 was obtained by cutting a lace, which is a cloth-like material in which fibers are interwoven, into a predetermined shape.
After that, as shown in FIG. 2, the support material 4 was immersed in the ceramic raw material 21 so that the ceramic raw material 21 was sufficiently immersed in the support material 4.

Then, as shown in FIG. 3, the mold 5 (H = 10 mm, W = 40 mm, L = 50 to 100 mm, D1 to D3 = 5 mm) made of a resin with the ceramic material 21 supported on the support material 4. , W2 = 32 to 34 mm, D4 = 2 to 4 mm), and a shaping step for shaping into a desired shape was performed.
Subsequently, as shown in FIG. 4, the resin mold 5 and the support material 4 are burned out by firing the ceramic raw material 21 arranged in a desired shape in the furnace 6 at a temperature of 1000 ° C. in the furnace 6. I let you. Thereby, as shown in FIG. 5, the skeleton structure portion 2 including a hollow portion 22 made of a clay mineral and penetratingly formed was obtained.

  Next, as shown in FIG. 6, in the chemical heat storage material arrangement step, the skeleton structure portion 2 is immersed in the heat storage material slurry 31, and the heat storage material slurry is placed on the outer surface of the skeleton structure portion 2 and inside the pores. 31 was infiltrated. At this time, the core material 7 (size that fits into the hollow portion 22 formed in the skeleton structure portion 2) is inserted into the hollow portion 22 that becomes a passage for water vapor or the like when used as a chemical heat storage system, and the hollow portion 22 is secured did.

  Thereafter, as shown in FIG. 7, in the drying step, after excess moisture in the heat storage material slurry 31 disposed in the skeleton structure portion 2 is dried under a low temperature condition (temperature 80 ° C., 96 hours), The heartwood 7 was extracted. As a result, as shown in FIG. 8, the skeleton structure portion 2 made of porous ceramics having the hollow portion 22 and having a large number of pores, and the outer surface of the skeleton structure portion 2 and the inside of the pores are supported. A chemical heat storage material molded body 1 having the chemical heat storage material 3 was obtained.

  The obtained chemical heat storage material molded body 1 has a configuration in which a chemical heat storage material 3 is supported around a skeleton structure portion 2 made of porous ceramics having a large number of pores. Moreover, since the chemical heat storage material 3 is supported on the outer surface of the skeleton structure portion 2 and inside the pores, many chemical heat storage materials 3 can be stably supported. Therefore, the pulverization of the chemical heat storage material 3 can be suppressed, and the filling density of the chemical heat storage material 3 per volume per mass in the chemical heat storage material molded body 1 can be increased. That is, it becomes the said chemical heat storage material molded object 1 with a large heat storage density. Furthermore, since the said chemical heat storage material molded object 1 becomes larger in apparent heat conductivity compared with powder, the thermal storage efficiency and the utilization efficiency of the stored heat become high.

Thus, according to this example, while suppressing the pulverization of the chemical heat storage material associated with the hydration / dehydration reaction, the chemical heat storage material molded body 1 capable of exhibiting sufficient capability as a chemical heat storage system and its It can be seen that a manufacturing method can be provided.
Moreover, the obtained chemical heat storage material molded object 1 can comprise a chemical heat storage material reactor by loading a molded object in the metal container comprised so that heat exchange is possible.

In this example, sepiolite was used as the clay mineral, but palygorskite, bentonite, or the like can be used instead of sepiolite.
In this example, calcium hydroxide is used as the chemical heat storage material. However, magnesium hydroxide or a mixture of magnesium hydroxide and calcium hydroxide can be used instead.

(Example 2)
In this example, a chemical heat storage material molded body and a manufacturing method thereof according to an example of the present invention will be described with reference to FIGS.
As shown in FIG. 13, the chemical heat storage material molded body 12 of this example includes a skeleton structure portion 2 made of porous ceramics having a large number of pores, and the outer surface of the skeleton structure portion 2 or the skeleton structure portion. And a chemical heat storage material 3 supported on the outer surface of the material.
This will be described in detail below.

First, a ceramic raw material 23 for forming a skeletal structure was prepared by mixing and stirring clay minerals and water.
As the clay mineral constituting the ceramic raw material 23, the same sepiolite as the sepiolite used for the ceramic raw material in Example 1 was prepared.

Moreover, the chemical heat storage material 3, the clay mineral, and water were mixed and stirred, and the heat storage material slurry 32 was prepared.
As the chemical heat storage material 3 constituting the heat storage material slurry 32, the same Ca (OH) ₂ as the alkaline earth metal Ca hydroxide Ca (OH) ₂ used in the heat storage material slurry in the first embodiment is used. Prepared.
Moreover, the same sepiolite as the sepiolite used for the said ceramic raw material was prepared as the said clay mineral which comprises the thermal storage material slurry 32. FIG.
The mixing ratio of the chemical heat storage material 3 and the clay mineral was 9: 1.

Next, a manufacturing method will be described.
The manufacturing method of this example uses a honeycomb substrate 8 having a large number of cells surrounded by a porous partition wall having a large number of pores, and the ceramic raw material 23 is placed in the pores of the partition wall of the substrate 8. A ceramic raw material impregnation step for impregnation, a chemical heat storage material disposing step for disposing a heat storage material slurry 32 which is a slurry containing the chemical heat storage material 3 in a cell of the base material 8, and the base material 8 and the above-described base material disposed thereon. The ceramic raw material 23 and the chemical heat storage material 32 are integrally fired to burn out the base material 8 and the skeleton structure portion 2 formed by firing the ceramic raw material 23 and the chemical heat storage material 3 supported thereon. And a firing step for obtaining a chemical heat storage material molded body 12 made of

First, as shown in FIG. 9, a honeycomb substrate 8 having a large number of cells surrounded by a porous partition wall having a large number of pores (H2 = 30 mm, W3 = 58 mm, L2 = 50 to 100 mm, D5 -D8 = 2mm, W4, 5 = 5mm).
The honeycomb substrate 8 is formed by assembling a resin mesh.

Next, as shown in FIG. 10, in the ceramic raw material impregnation step, the honeycomb base material 8 was immersed in the ceramic raw material 23, and the ceramic raw material 23 was impregnated in the pores of the partition walls of the base material 8.
Then, as shown in FIG. 11, in the chemical heat storage material arrangement step, the cells of the base material 8 are filled with the heat storage material slurry 32 and subjected to pressure molding, whereby the cells of the base material 8 are filled with the above. The heat storage material slurry 32 which is a slurry containing the chemical heat storage material 3 was disposed.

  And in the baking process, as shown in FIG. 12, the said base material 8, the said ceramic raw material 23 arrange | positioned to this, and the said chemical heat storage material 32 were integrally baked. The firing step was performed at 450 ° C. As a result, as shown in FIG. 13, the base material 8 is burned away, and the chemical heat storage material molded body composed of the skeleton structure portion 2 formed by firing the ceramic raw material 23 and the chemical heat storage material 3 supported on the structure portion 2. 12 was obtained.

The obtained chemical heat storage material molded body 12 has a structure in which the chemical heat storage material 3 is supported around the skeleton structure portion 2 made of porous ceramics having a large number of pores. Therefore, the pulverization of the chemical heat storage material 3 can be suppressed.
Moreover, since the said chemical heat storage material molded object 12 carry | supports the chemical heat storage material 3 on the outer surface of the said frame | skeleton structure part 2, and the pore part of the said frame | skeleton structure part 2 is hollow, the said pore part is The flow path is mainly made of water vapor and the like, and the heat storage and heat dissipation of the chemical heat storage material 3 can be performed particularly well, and the efficiency of the chemical heat storage system can be increased.

  Thus, according to this example, while suppressing the pulverization of the chemical heat storage material associated with the hydration / dehydration reaction, the chemical heat storage material molded body 12 capable of exhibiting sufficient capability as a chemical heat storage system and its It can be seen that a manufacturing method can be provided.

FIG. 3 is an explanatory view showing a support material in Example 1. FIG. 3 is an explanatory diagram illustrating a process of impregnating a support material with a ceramic material in Example 1. (A) Explanatory drawing which shows a formation process in Example 1, (b) AA sectional view taken on the line AA of Fig.3 (a). FIG. 3 is an explanatory view showing a skeleton firing step in Example 1. (A) Explanatory drawing which shows a skeleton structure part in Example 1, (b) BB sectional view taken on the line in FIG. 5 (a). Explanatory drawing which shows the chemical heat storage material arrangement | positioning process in Example 1. FIG. FIG. 3 is an explanatory diagram showing a drying process in Example 1. (A) Explanatory drawing which shows a chemical heat storage material molded object in Example 1, (b) CC sectional view taken on the line of FIG. 8 (a). FIG. 3 is an explanatory view showing a honeycomb-shaped substrate in Example 2. FIG. 5 is an explanatory view showing a ceramic material impregnation step in Example 2. Explanatory drawing which shows the chemical thermal storage material arrangement | positioning process in Example 2. FIG. Explanatory drawing which shows the baking process in Example 2. FIG. Explanatory drawing which shows the chemical heat storage material molded object in Example 2. FIG.

Explanation of symbols

1 Chemical Heat Storage Material Molded Body 2 Skeletal Structure 3 Chemical Heat Storage Material

Claims (40)

  It has a skeleton structure part made of porous ceramics having a large number of pores, and an outer surface of the skeleton structure part, or a chemical heat storage material supported on the outer surface of the skeleton structure part and inside the pores Chemical heat storage material molded body.   The chemical heat storage material molded body according to claim 1, wherein the skeleton structure portion is made of ceramics obtained by firing clay minerals.   The chemical heat storage material molded body according to claim 2, wherein the clay mineral is a clay mineral having a layered ribbon structure.   The chemical heat storage material molded body according to claim 3, wherein the clay mineral showing the layer ribbon structure is sepiolite and / or palygorskite.   The chemical heat storage material molded body according to claim 2, wherein the clay mineral is bentonite.   The chemical heat storage material according to any one of claims 1 to 5, 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 molded body.   The chemical heat storage material according to any one of claims 1 to 6, wherein the chemical heat storage material is an hydration reaction type chemical heat storage material that becomes an oxide along with a dehydration reaction and becomes a hydroxide along with a hydration reaction. Characteristic chemical heat storage material molded body.   In any 1 item | term of the Claims 1-7, the said chemical heat storage material consists of hydroxides, The chemical heat storage material molded object characterized by the above-mentioned.   9. The chemical heat storage material molded body according to claim 8, wherein the hydroxide is an inorganic compound.   The chemical heat storage material molded body according to claim 9, wherein the inorganic compound is an alkaline earth metal hydroxide.   11. The chemical heat storage material molded body according to claim 10, wherein the alkaline earth metal hydroxide is one or more of calcium hydroxide, magnesium hydroxide, and barium hydroxide.   The chemical heat storage material molded body according to claim 9, wherein the inorganic compound is one or more of nickel hydroxide, aluminum hydroxide, cobalt hydroxide, and copper hydroxide.   The chemical heat storage material molded body according to any one of claims 1 to 12, wherein the chemical heat storage material is supported on the skeleton structure portion in a state of a composite material mixed with at least a clay mineral. .   14. The chemical heat storage material molded body according to claim 13, wherein the composite material including the chemical heat storage material and the clay mineral is fired.   15. The chemical heat storage material molded body according to any one of claims 1 to 14, wherein the chemical heat storage material molded body has a hollow portion formed therethrough. A method for producing a chemical heat storage material molded body having a skeleton structure portion made of porous ceramics having a large number of pores, and a chemical heat storage material supported on the outer surface of the skeleton structure portion and inside the pores. ,
A skeleton firing step for obtaining the skeleton structure portion by firing a ceramic material arranged in a desired shape;
A chemical heat storage material disposing step of disposing a heat storage material slurry, which is a slurry containing the chemical heat storage material, on the outer surface and inside the pores of the skeleton structure;
And a drying step of drying the heat storage material slurry disposed in the skeleton structure part.   In Claim 16, before the said skeleton baking process, in the state which carry | supported the ceramic slurry which is a slurry containing the said ceramic raw material on the support material which consists of the fiber or porous material which can be burned down by baking of this skeleton baking process. A method for producing a chemical heat storage material molded body, comprising: a shaping step for shaping into a desired shape, wherein the support material is burned off in the skeleton firing step.   The method of manufacturing a chemical heat storage material molded body according to claim 17, wherein the support material is made of a cloth-like material in which fibers are interwoven.   In any 1 item | term of Claims 16-18, the said frame | skeleton structure part has the hollow part formed by penetration, and inserts a core material into the said hollow part in the said chemical heat storage material arrangement | positioning process and a drying process, The said drying The manufacturing method of the chemical heat storage material molded object characterized by removing the said core material after a process.   20. The method according to claim 16, further comprising a secondary firing step of integrally firing the skeleton structure portion and the chemical heat storage material supported thereon after the drying step. Manufacturing method of chemical heat storage material molded body. A method for producing a chemical heat storage material molded body having a skeleton structure portion made of porous ceramics having a large number of pores and a chemical heat storage material supported on the outer surface of the skeleton structure portion,
Using a honeycomb substrate having a large number of cells surrounded by a porous partition wall having a large number of pores, and a ceramic material impregnation step of impregnating the ceramic material into the pores of the partition wall of the substrate;
A chemical heat storage material disposing step of disposing a heat storage material slurry that is a slurry containing the chemical heat storage material in the cell of the base material;
The base material, the ceramic raw material and the chemical heat storage material disposed on the base material are integrally fired to burn down the base material, and the skeleton structure portion obtained by firing the ceramic raw material and the chemical supported on the base material. A method for producing a chemical heat storage material molded body, comprising a firing step of obtaining a chemical heat storage material molded body made of a heat storage material.   The method for producing a chemical heat storage material molded body according to claim 21, wherein the base material is made of a porous resin.   The method of manufacturing a chemical heat storage material molded body according to claim 21, wherein the base material is formed of a resin mesh formed in a mesh shape.   24. The method for producing a chemical heat storage material molded body according to any one of claims 21 to 23, wherein the base material has a bulk portion that is burned down and becomes a hollow portion in the firing step.   25. The method for producing a chemical heat storage material molded body according to any one of claims 16 to 24, wherein the ceramic raw material constituting the skeleton structure portion is a mixture of a clay mineral and water.   26. The method for producing a chemical heat storage material molded body according to claim 25, wherein the clay mineral is a clay mineral having a layered ribbon structure.   27. The method for producing a chemical heat storage material molded body according to claim 26, wherein the clay mineral showing the layer ribbon structure is sepiolite and / or palygorskite.   26. The method for producing a chemical heat storage material molded body according to claim 25, wherein the clay mineral is bentonite.   29. The chemical heat storage material according to any one of claims 16 to 28, 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 molded material.   The chemical heat storage material according to any one of claims 16 to 29, wherein the chemical heat storage material is a hydration reaction type chemical heat storage material that becomes an oxide along with a dehydration reaction and becomes a hydroxide along with a hydration reaction. The manufacturing method of the chemical heat storage material molded object characterized.   The method for producing a chemical heat storage material molded body according to any one of claims 16 to 30, wherein the chemical heat storage material is made of hydroxide.   32. The method for producing a chemical heat storage material molded body according to claim 31, wherein the hydroxide is an inorganic compound.   33. The method for producing a chemical heat storage material molded body according to claim 32, wherein the inorganic compound is an alkaline earth metal hydroxide.   34. The method for producing a chemical heat storage material molded body according to claim 33, wherein the alkaline earth metal hydroxide is one or more of calcium hydroxide, magnesium hydroxide, and barium hydroxide. .   33. The chemical heat storage material molded body according to claim 32, wherein the inorganic compound is one or more of nickel hydroxide, aluminum hydroxide, cobalt hydroxide, and copper hydroxide.   36. The method for producing a chemical heat storage material molded body according to any one of claims 16 to 35, wherein the heat storage material slurry is obtained by kneading a chemical heat storage material, a clay mineral, and water.   37. The method for producing a chemical heat storage material molded body according to claim 36, wherein the clay mineral constituting the heat storage material slurry is a clay mineral having a layered ribbon structure.   38. The method for producing a chemical heat storage material molded body according to claim 37, wherein the clay mineral showing the layer ribbon structure constituting the heat storage material slurry is sepiolite and / or palygorskite.   The chemical heat storage material molding according to any one of claims 36 to 38, wherein the clay mineral constituting the heat storage material slurry has a fiber shape having a diameter smaller than a particle diameter of the chemical heat storage material. Body manufacturing method.   37. The method for producing a chemical heat storage material molded body according to claim 36, wherein the clay mineral constituting the heat storage material slurry is bentonite.

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