JP2637381B2 - Method for producing heat storage material composition and method for producing heat storage device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a heat storage material composition and a method for producing a heat storage device.
The present invention relates to a method for producing a heat storage material composition which is excellent in heat storage and heat radiation efficiency and can be used repeatedly for a long period of time, and a method for producing a heat storage device using the heat storage material composition thus obtained.

[0002]

2. Description of the Related Art A heat storage material made of a composition having a large latent heat is widely used as an indoor heating device. For example, an indoor heating device is used in which heat storage material is heated and melted by nighttime electric power at a low electricity rate to store energy, and coagulation heat (latent heat) generated when the heat storage material is solidified is used for daytime indoor heating. I have.

[0003] As such a heat storage material, sodium sulfate decahydrate (bow nitrate) is known, and sodium borate decahydrate as a supercooling inhibitor (nucleating agent) is further added to the sodium sulfate decahydrate. Thermal storage material compositions containing salt (borax, borax) are widely used. The heat storage material composition comprising sodium sulfate decahydrate and sodium borate decahydrate theoretically has a capacity of about 58 kcal /
This heat storage material composition which has a latent heat of kg and is in a molten state emits a large amount of heat in a constant temperature range for a long time when solidified, and can maintain a comfortable temperature in the room.

[0004] However, the heat storage material composed of sodium sulfate decahydrate and sodium borate decahydrate sometimes has a reduced heat storage amount when the heat-melting-solidification is repeated many times. Although the heat storage material has a theoretical latent heat value of about 58 kcal / kg as described above, it is actually 20 to 40 kcal / kg.
There was a problem that only latent heat of about al / kg could be taken out.

The inventor of the present invention has conducted intensive studies on a heat storage material composed of sodium sulfate decahydrate and sodium borate decahydrate in order to extract more latent heat. By doing
Further, they have found that a heat storage material composition obtained by blending each component by a specific method has excellent properties as a heat storage material.

Japanese Patent Publication No. Hei 5-79714 discloses that
"A method for producing a heat storage material, comprising a step of obtaining a viscous composition by batch-mixing and stirring a supercooling inhibitor, anhydrous sodium sulfate, water and calcium sulfate dihydrate" is disclosed. In Example 1, anhydrous sodium sulfate, water, sodium chloride and calcium sulfate 2
A mixture of water salt, borax and finely divided silica is heated at 35 ° C. to 60
It is described that a viscous composition was obtained by stirring for minutes.

Further, Japanese Patent Publication No. Hei 4-22198 discloses that
"Sodium sulfate decahydrate as the main material, supercooling inhibitor,
In a heat storage material composition comprising a solid-liquid separation preventing agent and a thickener, hydrated calcium sulfate is used as a solid-liquid separation preventing agent.
A heat storage material characterized by adding a silica-based thickener as a thickener in an amount of from 15 to 15% by weight (in the heat storage material composition). In Example 1, a mixture comprising anhydrous sodium sulfate, water, α-hemihydrate gypsum, and finely divided silica was stirred at 35 ° C. for 80 minutes, and borax was added to obtain a viscous composition. In Example 8, anhydrous sodium sulfate was added to sulfuric acid under stirring at about 30 ° C., and then a 1: 1 mixture of No. 3 water glass and water was gradually added. After the addition, sodium chloride and α-hemihydrate gypsum were further added and stirred, and borax was added, followed by stirring to obtain a composition.

However, the methods for producing heat storage materials described in these publications have a problem in that the components cannot be uniformly mixed, and thus a heat storage material having sufficiently excellent characteristics cannot be obtained.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above. The components in the heat storage material composition are uniformly mixed, and a large latent heat can be taken out. Further, it is an object of the present invention to provide a method for manufacturing a heat storage material composition and a method for manufacturing a heat storage device that can be used repeatedly for a long period of time.

[0010]

SUMMARY OF THE INVENTION A method for producing a heat storage material composition according to the present invention comprises mixing water, water glass and hydrochloric acid to obtain a uniform pH of 7 to 8.
Is prepared, and anhydrous sodium sulfate (anhydrous borate nitrate), a supercooling inhibitor [eg, sodium borate decahydrate (borax, borax)] and hydratable sulfuric acid are added to the obtained gel. calcium _{(CaSO 4 · 1 / 2H 2} O, CaSO 4)
Are mixed one by one in an arbitrary order.

In the present invention, an inorganic salt as a melting point modifier is mixed with water, water glass and hydrochloric acid to form a uniform p-type salt.
It is desirable to prepare a gel of H7-8. The method for manufacturing a heat storage device according to the present invention comprises: [A]: a step of filling a bottom portion and / or an inner peripheral surface of a cylindrical container with a supercooling inhibitor; [B]: a process of filling water, water glass, hydrochloric acid, A homogeneous gel (solution) is prepared by mixing with a cooling inhibitor (eg, sodium borate decahydrate), and the obtained gel is mixed with anhydrous sodium sulfate, a supercooling inhibitor and a hydrating agent. Filling a heat storage material composition obtained by mixing calcium sulfate one by one in an arbitrary order into the cylindrical container.

In the heat storage material composition obtained by the present invention, the components in the composition are uniformly mixed.
Even if heat storage and heat release are repeated, no phase separation occurs, no supercooling phenomenon occurs, large latent heat can be taken out, and the device can be used repeatedly for a long period of time.

Further, the heat storage device manufactured as described above can extract a large amount of latent heat and can be used repeatedly for a long time.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for producing a heat storage material composition and a method for producing a heat storage device according to the present invention will be specifically described. [Method of Manufacturing Heat Storage Material Composition] In the method of manufacturing the heat storage material composition according to the present invention, first, water and water glass (Na ₂ O · nSi) are used.
O _2, n = 2~4) and a mixture of hydrochloric acid (HCl) in a uniform pH7~8 preferably prepared gel of pH7.1~7.6 (solution).

In preparing such a uniform gel (solution), usually at a temperature of 10 to 60 ° C. for 1 minute to 1 hour,
Preferably, stirring is performed at a temperature of 20 to 50 ° C. for 1 minute to 1/2 hour.

The water used at this time combines with, for example, anhydrous sodium sulfate described later and contributes to the formation of sodium sulfate decahydrate (boat salt, Na ₂ SO ₄ .10H ₂ O). 20 to 70% by weight, preferably 40 to 60% by weight, and more preferably 4 to 70% by weight in the material composition.
It is desirable to use it in such an amount that it becomes 5 to 55% by weight.

The water glass contributes to the increase in the viscosity of the heat storage material composition and the content of the water glass in the heat storage material composition is usually 0.2 to 2%.
0% by weight, preferably 1 to 10% by weight, more preferably 2 to 7% by weight, in other words, SiO ₂
In terms of amount, the content in the heat storage material composition is 0.0
It is desirable to use it in such an amount that it becomes 6 to 6% by weight. However, in this specification, the amount of water glass is a value converted to the amount of Na ₂ O · 2SiO ₂ having a concentration of 44%.

Hydrochloric acid may be used in an amount capable of contributing to the neutralization of the water glass and neutralizing the basic component of the water glass. More specifically, the content in the obtained heat storage material composition is reduced. , 35% hydrochloric acid, usually 0.1 to 10% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 5% by weight.
Preferably, it is used in such an amount that it becomes ~ 3.5% by weight.

In the present invention, a uniform gel (solution) having a pH of 7 to 8 is prepared by mixing water, water glass, and hydrochloric acid as described above. At this time, a melting point modifier is added and mixed. And may be added to and mixed with a gel obtained as described below. As such a melting point regulator,
Examples thereof include inorganic salts such as NaCl, KCl, NH ₄ Cl, and NaNO _{3. In} the present invention, one or more of such melting point regulators may be blended. The content of such a melting point regulator in the heat storage material composition is usually 0.1%.
It is preferably used in such an amount that it becomes -5% by weight, preferably 0.5-3% by weight.

In the present invention, the gel (solution) obtained as described above is then added to anhydrous sodium sulfate (anhydrous borate), a supercooling inhibitor, and a hydrated calcium sulfate (CaSO ₄ .1). / 2H ₂ O, CaSO ₄ ) are mixed one by one in an arbitrary order. In other words, in the present invention,
After mixing anhydrous sodium sulfate (anhydrous borate salt), a supercooling inhibitor, and any one of hydrated calcium sulfate, and the gel (solution) obtained as described above, Mix with any one of the remaining two, then mix with the last remaining one.

As described above, anhydrous sodium sulfate, a supercooling inhibitor (eg, sodium borate decahydrate), and any one of hydrated calcium sulfate, for example, anhydrous sodium sulfate, (Solution) is usually mixed at a temperature of 10 to 60 ° C. for 1 minute to 1 hour, preferably 2 minutes to 1 hour.
It is desirable to stir at a temperature of 0 to 50 ° C for 1 minute to 1/2 hour.

Next, a mixture of the above-mentioned uniform gel-like substance and anhydrous sodium sulfate is mixed with, for example, sodium borate decahydrate as a supercooling inhibitor, usually in 10 to 10 minutes.
1 minute to 1 hour at a temperature of 60 ° C, preferably 20 to 50 ° C
It is desirable to stir at a temperature of 1 minute to 1/2 hour.

In order to mix a mixture of the above homogeneous gel, anhydrous sodium sulfate, and sodium borate decahydrate as a supercooling inhibitor with the last remaining hydrated calcium sulfate, usually 10 It is desirable to stir at a temperature of ６０60 ° C. for 10 minutes to 2 hours, preferably at a temperature of 20〜50 ° C. for 20 minutes to 1 hour.

In the case where sodium sulfate decahydrate (boat salt) has already been added to the above gel-like material, hydrated calcium sulfate (calcium sulfate 1/2 hydrate, ie, baked gypsum and / or When calcium sulfate anhydrous (anhydrous gypsum) is further added and stirred for about 1/2 hour, the clay of the resulting mixture rises. Therefore, if other salts (eg, sodium borate decahydrate (Bolux), NaCl) are added after the addition of sodium sulfate decahydrate (boat salt) and hydrated calcium sulfate, it becomes difficult to uniformly disperse. Become. Therefore, the order of adding and mixing the salts to the gel-like material is not particularly limited, but it is preferable to stir for about 1/2 hour after adding all the salts.

In the present invention, the order of adding anhydrous sodium sulfate, a supercooling inhibitor, and hydrated calcium sulfate to the gel (solution) can be changed as appropriate. Also, the above conditions corresponding to the compounds to be added and mixed can be adopted. Also,
The above mixing operation is usually performed under normal pressure, but is not particularly limited.

The anhydrous sodium sulfate contributes to heat storage and heat radiation as a main component of the heat storage material composition, and its content in the heat storage material composition is usually 15 to 50% by weight, preferably 2 to 50% by weight.
It is desirably used in such an amount as to be 0 to 45% by weight, more preferably 25 to 40% by weight. In the present invention, the above-mentioned water and this anhydrous sodium sulfate have a weight ratio [water / anhydrous sodium sulfate] of usually 1.
It is used in such an amount as to be 27 to 2 (10 to 15 in molar ratio). Further, in the present invention, sodium sulfate decahydrate (boat salt, Na ₂ S
O ₄ · 10H ₂ O) may be used, if so,
The amount of water described above can be reduced.

Examples of the supercooling inhibitor include sodium borate decahydrate (borax, borax), anhydrous sodium borate and the like. Such a supercooling inhibitor acts as a nucleus (nucleating agent) for crystallization during cooling of the obtained heat storage material composition, promotes fine crystallization of sodium sulfate decahydrate, and contributes to prevention of supercooling, It is desirable to use the heat storage material composition in such an amount that its content Z is usually 0.1 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight. . In the present invention, anhydrous sodium borate and water can be used instead of sodium borate decahydrate as described above. In this case, the amount of the water may be increased. .

As will be described later, a part X (eg, 5 to 45% by weight of Z) of the supercooling inhibitor used is unevenly distributed at the bottom or the like in the cylindrical container, and the remaining portion Y of the supercooling inhibitor is used. [Example:
95 to 55% by weight of the total amount Z of the supercooling inhibitor in the heat storage container]
May be mixed with other components to be filled as a heat storage material composition in a portion other than the bottom or the like in the cylindrical container. In such a case, the content of the supercooling inhibitor in the heat storage material composition filled in a portion other than the bottom in the cylindrical container is determined based on the total amount Z of the supercooling inhibitor from the bottom in the cylindrical container. The supercooling inhibitor is used at the time of preparing the heat storage material composition in such an amount that the amount (ZX) obtained by subtracting the amount X unevenly distributed in the heat storage material is used.

As an example, the total amount of sodium borate decahydrate as a supercooling inhibitor in the obtained heat storage container is 10% by weight of the total amount of the heat storage material filled in the heat storage container.
When 20% by weight (corresponding to 2% by weight in the total amount of the heat storage material) of the total amount of sodium borate decahydrate is unevenly distributed at the bottom of the cylindrical container, the sodium borate 10 water in the heat storage material composition Sodium borate decahydrate may be used in preparing the heat storage material composition such that the amount of the salt is 8% by weight of the total amount of the heat storage material.

Hydrating calcium sulfate (calcium sulfate 1 /
The dihydrate and / or calcium sulfate anhydrous) contribute to the prevention of solid-liquid phase separation of the obtained heat storage material composition, and the content in the heat storage material composition (calcium sulfate 1/2 hydrate and sulfuric acid) (Total amount of anhydrous calcium salt) is usually less than 2% by weight, preferably 0.5 to 1.5% by weight, more preferably 0.7 to 1.3% by weight. . When the amount of the hydrated calcium sulfate is 2% by weight or more, the durability of the obtained heat storage material composition may decrease.

In the present invention, examples of such hydrated calcium sulfate include calcium sulfate 1/2 hydrate and calcium sulfate anhydrous, and a combination of calcium sulfate 1/2 hydrate and calcium sulfate anhydrous is used. Either calcium sulfate 1/2 hydrate or calcium sulfate anhydrous may be used, but it is preferable to use calcium sulfate 1/2 hydrate. When calcium sulphate 1/2 hydrate and calcium sulphate anhydrous are used in combination as hydrated calcium sulphate, the amount ratio is not particularly limited, but the weight ratio (calcium sulphate 1/2 hydrate: calcium sulphate anhydrous) salt)
And usually 1-99: 99-1, preferably 50-99:
Used in amounts of 50-1.

The heat storage material composition thus obtained is
Each of the above amounts of water and water glass (Na ₂ O · nS)
iO ₂ , n = 2 to 4), hydrochloric acid (HCl) and a supercooling inhibitor [Example: sodium borate decahydrate (borax, borax,
Na ₂ B ₄ O ₇ .10H ₂ O)], anhydrous sodium sulfate (anhydrous borate, Na ₂ SO ₄ ) and hydratable calcium sulfate (Ca
SO ₄ .1 / 2H ₂ O, CaSO ₄ ). Usually, water: 20 to 70% by weight, water glass: 44% N
in terms of a ₂ O · 2SiO ₂ weight 0.2 to 20 wt%, hydrochloric acid: in terms of 35% hydrochloric acid 0.1 to 10 wt%, anhydrous sodium sulfate: 15 to 50 wt%, a supercooling inhibitor : 0.
1 to 20% by weight, hydrated calcium sulfate: less than 2% by weight (total is 100% by weight).

In the present invention, when preparing the heat storage material composition, a melting point modifier can be used. Such a melting point modifier is prepared by mixing water, water glass and hydrochloric acid as described above. It may be used when preparing a gel having a uniform pH of 7 to 8, may be added to and mixed with the obtained gel, and further divided into both during the preparation of the gel and after the preparation of the gel. May be added and mixed. When the melting point regulator is added to and mixed with the obtained gel, the anhydrous sodium sulfate, the supercooling inhibitor, the hydratable calcium sulfate and the melting point modifier are added to the gel in any order. What is necessary is just to mix one kind at a time. The content of such a melting point regulator in the heat storage material composition is usually 0.1 to 5% by weight, preferably 0.5 to 5% by weight.
%, More preferably 0.5 to 3% by weight.

In the heat storage material composition thus obtained, each component, ie, water, water glass, hydrochloric acid, a supercooling inhibitor, anhydrous sodium sulfate and hydrated calcium sulfate (and a melting point regulator used as necessary) Are homogeneously mixed, so that even if heat storage and heat radiation are repeatedly performed, no phase separation occurs, no supercooling phenomenon occurs, a large latent heat can be taken out, and the device can be used repeatedly for a long period of time. [Method of Manufacturing Heat Storage Device] Next, a method of manufacturing the heat storage device according to the present invention will be specifically described with reference to the drawings.
In the drawings, the same reference numerals indicate the same members.

FIGS. 1 and 3 are longitudinal sectional views of a heat storage device obtained by one embodiment of the present invention. FIG.
FIG. 4 shows [A] − of the heat storage device shown in FIGS. 1 and 3, respectively.
[A] FIG.

In the heat storage device 1 shown in FIG. 1, sodium borate decahydrate (borax) is unevenly distributed at the bottom (end face) 6 in the cylindrical container 2 and the remaining space in the cylindrical container 2 is Is filled with the heat storage material composition 3 obtained by the production method described above. In FIG. 1, sodium borate decahydrate also contained in the composition is placed in a cylindrical container 2
Although the embodiment in which the one side surface is unevenly distributed on one end surface 6 is shown, the sodium borate decahydrate may be unevenly distributed on the other end surface 6A or the inner peripheral surface 9 in the cylindrical container.

In the method for manufacturing a heat storage device according to the present invention, the above-described heat storage device 1 is manufactured as follows. That is, in the method for manufacturing a heat storage device according to the present invention, [A]: the bottom portion 6 and / or the inner peripheral surface 9 of the cylindrical container 2
A step of filling a supercooling inhibitor [eg: sodium borate decahydrate (borax, borax)]; [B]: mixing water, water glass and hydrochloric acid to obtain a uniform pH of 7 to
8. A gel (solution) was prepared, and the obtained gel was
Anhydrous sodium sulfate (anhydrous borate), a supercooling inhibitor, and a hydratable calcium sulfate ((CaSO ₄ .1 / 2H ₂ O, C
aSO ₄ ) in the cylindrical container 2 with the heat storage material composition 3 obtained by mixing one kind at a time in any order.

More specifically, in the present invention, [A]: the bottom 6 and / or the inner peripheral surface 9 of the cylindrical container is filled with a supercooling inhibitor, and then [B]: the heat storage material composition The remaining space may be filled with the heat storage material composition 3 obtained by the production method of the above, or the step [A] may be performed after the step [B], and the steps [A] and [B] may be performed. May be performed simultaneously.
In order to perform the [A] step and the [B] step at the same time, for example, the bottom 6 of the cylindrical container is filled with a supercooling preventing agent from one end side, and the above-described production is performed from the other end 6A side. What is necessary is just to fill the heat storage material composition 3 obtained by the method. The heat storage material composition used in the step [B] is obtained by the method for producing a heat storage material composition.

In the present invention, the cylindrical container 2
A part X of the supercooling preventive agent filled in the inside is unevenly distributed on the inner bottom part 6 of the cylindrical container, and the remaining part is contained in the heat storage material composition 3, but the heat storage device shown in FIG. In [1], the above [A] is such that 5 to 45% by weight, preferably 10 to 40% by weight, of the total amount Z of the supercooling inhibitor filled in the cylindrical container 2 is unevenly distributed on the bottom 6 of the cylindrical container 2. It is preferable to fill the remaining part Y (= ZX) of the supercooling inhibitor together with other components as the heat storage material composition 3 in the above step [B].

As shown in FIG. 1, a part of the supercooling inhibitor is unevenly distributed on one end face 6 in the cylindrical container 2, and the rest of the supercooling inhibitor is made of other materials such as anhydrous sodium sulfate. When the heat storage material composition 3 is uniformly mixed with the components of the formula (1) and filled as the heat storage material composition 3, the crystals of the supercooling inhibitor serve as nuclei when sodium sulfate combines with water and solidifies as sodium sulfate decahydrate, The entire heat storage material composition can be rapidly crystallized (solidified). Such a heat storage device 1
Thus, large latent heat can be taken out and can be used repeatedly for a long time.

In the above description, as shown in FIG. 1, a part of the supercooling inhibitor, for example, sodium borate decahydrate is unevenly distributed on one end face 6 of the cylindrical container 2 and the sodium borate decahydrate is partially dispersed. In the embodiment, the remainder of the salt is filled into the remaining space in the cylindrical container 2 as the heat storage material composition 3 together with the other compounding components. The material composition 3 may be filled (not shown). When the heat storage material composition 3 obtained by the present invention is filled in the entire cylindrical container 2 as described above, the entire amount of the supercooling inhibitor such as sodium borate decahydrate is used as the heat storage material composition. May be used at the time of preparation.

The cylindrical container 2 used in the present invention may have a cylindrical shape whose both ends are sealed as shown in FIG. 1, or may have a cylindrical shape as shown in FIG. Inside, a cylindrical hollow core material 15 having substantially the same length as the cylindrical container 2 is provided.
It may be arranged concentrically with the cylindrical container 2. In the heat storage device 1 shown in FIG. 3, the heat storage material composition 3 is filled in the gap 11 between the cylindrical container 2 having a circular cross section and the cylindrical hollow core material 15. The radial distance D between the inner peripheral surface 9 of the cylindrical container and the outer peripheral surface of the hollow cylindrical core material is 5 to 25 mm, preferably 10 to 25 mm.
It is desirably about 20 mm.

The material for the cylindrical container 2 preferably has durability and flexibility, and also has corrosion resistance so that it can be used by being embedded in a floor or the like. Examples of such a material include polyethylene and polypropylene. (PP), acrylic resin, vinyl chloride, aluminum, copper, iron, stainless steel and the like.
P) is preferred. Such a material for the cylindrical container 2 is also used as a material for the cylindrical hollow core material 15. In addition, the cylindrical container and the cylindrical hollow core material 1 used in the present invention
5 may have an elliptical cross section. The outer peripheral surface 7 including the end surface of the cylindrical container 2 is roughened by a method such as applying a ceramic material-containing paint to the outer peripheral surface of the cylindrical container made of polypropylene (PP) or the like. The heat transfer area is preferably large, and a heat sink may be provided on the outer peripheral surface 7.

In the heat storage device 1 shown in FIG. 3, the respective components in the heat storage material composition are uniformly mixed as described above.
Moreover, since the heat storage material composition 3 is filled in a cylindrical shape and does not exist in the cylindrical hollow core portion (that is, the center portion of the cylindrical container 2), the heat storage material composition 3 does not undergo phase separation or the like.
Solidifies efficiently and can extract a large latent heat stored in the heat storage device 1. In addition, in the heat storage device 1, it is possible to pass a heat medium such as a liquid (eg, water) or a heater 13 through the space 12 in the cylindrical hollow core material 15. The heat storage material composition was efficiently solidified without phase separation or the like from both directions of the outer peripheral surface direction of the cylindrical hollow core material and the center of the cylindrical container 2 and stored in the heat storage device 1. Latent heat can be extracted.

The heat storage device 1 thus obtained is set, for example, under a floor indoors.

[0046]

According to the method for producing a heat storage material composition of the present invention, water, water glass, hydrochloric acid, anhydrous sodium sulfate, supercooling inhibitor, and hydrated calcium sulfate can be uniformly mixed. Therefore, even if heat storage and heat radiation are repeatedly performed, the obtained heat storage material composition does not undergo phase separation, does not cause a supercooling phenomenon, can extract large latent heat, and can be used repeatedly for a long period of time.

Further, in the heat storage device obtained by the method of manufacturing a heat storage device according to the present invention, a large latent heat can be taken out and can be used repeatedly for a long time.

[0048]

EXAMPLES Hereinafter, the method for producing a heat storage material composition and the method for producing a heat storage device according to the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples. Not something.

[0049]

Example 1 (Melting point controlling agent-free type) Each of the following amounts of water, water glass and hydrochloric acid was added to 40 parts.
The mixture was mixed at ° C. for 時間 hour to prepare a uniform gel (solution) having a pH of 7.5.

To the obtained gel, the following amount of anhydrous sodium sulfate (anhydrous nitrate) was added and mixed at 40 ° C. for 0.1 hour, and then sodium borate decahydrate (Vorax) was added. The mixture was mixed at 0.1 ° C. for 0.1 hour, hydrated calcium sulfate (calcium sulfate 1/2 hydrate) was further added, and mixed at 40 ° C. for 1/2 hour to produce a heat storage material composition.

[Composition of heat storage material composition] Water (H ₂ O): 50.02 parts by weight Anhydrous sodium sulfate (anhydrous sodium sulfate, Na ₂ SO ₄ ) 36.81 parts by weight Calcium sulfate (calcium sulfate 1/2 hydrate) ··· 0.84 parts by weight Sodium borate decahydrate (Bolux, Na ₂ B ₄ O ₇ · 10H ₂ O) ··· 3.0 parts by weight Water glass (44% Na ₂ O · 2SiO ₂ ) 6.2 parts by weight Hydrochloric acid (35% HCl) 3.13 parts by weight (total 100 parts by weight of heat storage material composition) , A cylindrical container having an outer surface roughened (inner diameter D: 15 mm, wall thickness: 2.5 mm, length L: 12
00 mm) to produce a heat storage device. After the temperature of the heat storage material composition in the heat storage device was raised from room temperature (25 ° C.) to 28 ° C., the temperature was lowered to the original temperature 5000 times, and the occurrence of phase separation, heat storage, and heat release were measured.

As a result, when the temperature was raised from room temperature (25 ° C.) to 28 ° C., heat absorption (latent heat storage) was started, and after a lapse of 160 minutes, an endotherm of 246 KJ / Kg was recognized.
When the temperature was lowered to ° C., heat release (solidification) was started, and at a point of time 160 minutes after the heat release, heat release of 224 KJ / Kg was observed.

In the heat storage device filled with the heat storage material composition, even if the above-described heat storage and heat release are repeatedly performed, phase separation does not occur, a supercooling phenomenon does not occur, and large latent heat can be taken out. Moreover, it was confirmed that it could be used repeatedly for a long time.

[0054]

EXAMPLE 2 Each of the following amounts of water, water glass, hydrochloric acid and NaCl as a melting point regulator was halved at 40 ° C.
The mixture was mixed for a period of time to prepare a uniform gel (solution) having a pH of 7.5.

To the obtained gel, the following amount of anhydrous sodium sulfate (anhydrous borate) is added and mixed at 40 ° C. for 0.1 hour, and then sodium borate decahydrate (borax, borax) is added. In addition, mix at 40 ° C for 0.1 hour,
Further, hydrated calcium sulfate (calcium sulfate 1/2 hydrate) was added and mixed at 40 ° C. for 1/2 hour to produce a heat storage material composition.

[Blending composition of heat storage material composition] Water (H ₂ O) ··· 50.02 parts by weight Anhydrous sodium sulfate (anhydrous sodium nitrate, Na ₂ SO ₄ ) · · 36.57 parts by weight calcium sulfate sodium borate (1/2 hydrate calcium sulphate) ... 0.84 parts by weight of acid decahydrate _{(borax, Na 2 B 4 O 7 ·} 10H 2 O) ···· 3.0 parts by weight of water glass (44% Na ₂ O.2SiO ₂ ) 6.2 parts by weight Hydrochloric acid (35% HCl) 3.13 parts by weight Salt (NaCl) 0.24 parts by weight (heat storage material) Using this heat storage material composition, a heat storage device was manufactured in the same manner as in Example 1, and the same test as in Example 1 was performed.

As a result, the same result as in Example 1 was obtained.

[0058]

Example 3 In Example 2, water, water glass, and hydrochloric acid were mixed at 40 ° C. for を hour to prepare a uniform gel (solution) having a pH of 7.5, and the obtained gel was obtained. After adding anhydrous sodium sulfate (anhydrous sodium nitrate) to the mixture and mixing at 40 ° C. for 0.1 hour, adding sodium borate decahydrate (Bolux) and mixing at 40 ° C. for 0.1 hour, and then adding hydrated sulfuric acid Calcium (calcium sulfate 1/2 hydrate) was added and mixed at 40 ° C. for 0.1 hour.
Cl) was added and mixed at 40 ° C. for １ hour to produce a heat storage material composition. A heat storage device was manufactured in the same manner as in Example 1, and the same test as in Example 1 was performed.

As a result, the same result as in Example 2 was obtained.

[0060]

Example 4 A heat storage device was manufactured in the same manner as in Example 1 except that the amounts of the components in the heat storage material composition were changed as described below. The test was performed.

As a result, an effect superior to Example 2 in terms of durability was obtained. Other points are the same as in the second embodiment. [Blending composition of heat storage material composition] Water (H ₂ O) ··· 47.04 parts by weight Anhydrous sodium sulfate (anhydrous sodium sulfate, Na ₂ SO ₄ ) · · 36.09 parts by weight Water-soluble calcium sulfate ( 0.84 parts by weight Sodium borate decahydrate (borax, Na ₂ B ₄ O ₇ .10H ₂ O) 3.0 parts by weight Water glass (44% _{Na 2 O · 2SiO 2) ····} 8.62 parts by weight of hydrochloric acid (35% HCl) ···· 4.35 parts by weight sodium chloride (NaCl) · · · · 0.06 parts by weight (heat storage material composition total 100 parts by weight)

[0062]

Example 5 A heat storage device was manufactured in the same manner as in Example 3, except that the amounts of the components in the heat storage material composition were changed as described below. The test was performed.

As a result, an effect superior to Example 3 in terms of durability was obtained. Other points are the same as the third embodiment. [Combined composition of heat storage material composition] Water (H ₂ O) ··· 47.04 parts by weight Anhydrous sodium sulfate (anhydrous bowel nitrate) · · 36.09 parts by weight Hydrating calcium sulfate (calcium sulfate 1/2 monohydrate) ... 0.84 parts by weight of sodium borate decahydrate (borax) ... 3.0 parts by weight water glass _{(44% Na 2 O · 2SiO} 2) ···· 8.62 parts by weight Hydrochloric acid (35% HCl) ··· 4.35 parts by weight Salt (NaCl) ··· 0.06 parts by weight (total 100 parts by weight of heat storage material composition)

[0064]

Example 6 The following amounts of water, water glass, hydrochloric acid, and NaCl as a melting point modifier were mixed at 40 ° C. for 1/2 hour to prepare a uniform gel (solution) having a pH of 7.5. .

The obtained gel was mixed with the following amount of anhydrous sodium sulfate (anhydrous sodium sulfate) at 40 ° C. for 0.1 hour, and then hydrated calcium sulfate (calcium sulfate 1 /
Dihydrate) and mixed at 40 ° C. for 0.1 hour,
The following amount of 2/3 (2.0 parts by weight) of sodium borate decahydrate (Bolux) was added and mixed at 40 ° C. for 時間 hour to prepare a heat storage material composition [b-1].

On the other hand, the remaining bottom (1.0 part by weight) of sodium borate decahydrate (borax) was filled in the bottom of the same cylindrical container as in Example 1. In the obtained cylindrical container containing sodium borate decahydrate, the heat storage material composition [b-1] was added.
To produce a heat storage device.

The same test as in Example 1 was performed using this heat storage device. As a result, crystallization progressed more rapidly than in Example 2. [Combined composition of heat storage material] Water (H ₂ O) ··· 47.04 parts by weight Anhydrous sodium sulfate (anhydrous sodium sulfate, Na ₂ SO ₄ ) · · 36.09 parts by weight Water-soluble calcium sulfate (calcium sulfate) 0.84 parts by weight Sodium borate decahydrate (Borac, Na ₂ B ₄ O ₇ .10H ₂ O) 3.0 parts by weight (1. 0 Mashimashi parts polarized, 2.0 parts by weight remain, are mixed with other ingredients and uniformity.) water glass _{(44% Na 2 O · 2SiO} 2) ···· 8.62 parts by weight of hydrochloric acid ( 4.35 parts by weight Salt (NaCl) 0.06 parts by weight (total 100 parts by weight of heat storage material)

[0068]

Example 7 The same amount of water, water glass and hydrochloric acid as in Example 6 were mixed at 40 ° C. for 1/2 hour to obtain a uniform pH.
A gel (solution) of 7.5 was prepared.

The obtained gel and the same amount of anhydrous sodium sulfate (anhydrous nitrate) as in Example 6 were added to
For 0.1 hour, then add hydrated calcium sulfate (calcium sulfate 1/2 hydrate) and mix at 40 ° C. for 0.1 hour, and then add a melting point modifier (NaCl) for 4 hours.
The mixture was mixed at 0 ° C. for 0.1 hour, and 2.0 parts by weight of sodium borate decahydrate (borax, borax) was further added and mixed at 40 ° C. for 時間 hour to obtain a heat storage material composition [b- 2] was prepared.

On the other hand, the remaining bottom (1.0 parts by weight) of sodium borate decahydrate (borax, borax) was filled in the bottom of the same cylindrical container as in Example 1. The heat storage material composition [b-2] was filled in the obtained cylindrical container containing sodium borate decahydrate to produce a heat storage device.

When a test similar to that of Example 1 was performed using this heat storage device, crystallization progressed more rapidly than in Example 3.

[0072]

Example 8 A heat storage device was manufactured in the same manner as in Example 6, except that the amounts of the components in the heat storage material were the same as in Example 4.

When a test similar to that of Example 1 was performed using this heat storage device, crystallization progressed more rapidly than in Example 4, and the durability was excellent.

[0074]

Example 9 A heat storage device was manufactured in the same manner as in Example 7, except that the amounts of the components in the heat storage material were the same as in Example 5.

The same test as in Example 1 was performed using this heat storage device. As a result, crystallization progressed more rapidly than in Example 5, and the durability was excellent.

[0076]

Examples 10 to 13 In Examples 2 to 5, the order of adding and mixing anhydrous sodium sulfate (anhydrous borate nitrate) and sodium borate decahydrate (borax) to the obtained gel was determined by controlling the temperature and time. Except having replaced with a condition, the heat storage apparatus was manufactured like Example 2-5, respectively.

The same tests as in Example 1 were performed using this heat storage device, and the same results as in Examples 2 to 5 were obtained.

[0078]

Examples 14 to 17 In Examples 6 to 9, the order of addition and mixing of anhydrous sodium sulfate (anhydrous borate salt) and sodium borate decahydrate (borax) to the obtained gel was determined by controlling the temperature, time and the like. Except having replaced with a condition, the heat storage apparatus was manufactured similarly to Examples 6-9, respectively.

The same test as in Example 1 was performed using this heat storage device, and the same results as in Examples 6 to 9 were obtained.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a heat storage device according to one embodiment of the present invention.

2] [A]-[A] of the heat storage device shown in FIG. 1. [FIG.
FIG.

FIG. 3 is a longitudinal sectional view of a heat storage device according to a second embodiment of the present invention.

FIG. 4 is [A]-[A] of the heat storage device shown in FIG.
FIG.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Thermal storage device 2 ... Cylindrical container 3 ... Thermal storage material composition 6,6A ... Inner end part (bottom surface) of cylindrical container 7. ..... Outer peripheral surface of cylindrical container 9 ... Inner peripheral surface of cylindrical container 11 ... Gap between cylindrical container and cylindrical hollow core material 12 .... Void in cylindrical hollow core material 13 Heater 15 Cylindrical hollow core material D Between cylindrical container inner peripheral surface and cylindrical hollow core outer peripheral surface Radial distance S: Inside diameter of cylindrical container.

Claims (3)

(57) [Claims] 1. Mixing water, water glass and hydrochloric acid to form a uniform p
A heat storage material characterized in that a gel material of H7 to 8 is prepared, and anhydrous sodium sulfate, a supercooling inhibitor and a hydrated calcium sulfate are mixed one by one in an arbitrary order with the obtained gel material. A method for producing the composition. 2. The heat storage material composition according to claim 1, wherein an inorganic salt as a melting point modifier is mixed with water, water glass and hydrochloric acid to prepare a uniform gel having a pH of 7 to 8. Method of manufacturing a product. 3. [A]: a step of filling the bottom and / or the inner peripheral surface of the cylindrical container with a supercooling inhibitor, [B]: mixing water, water glass and hydrochloric acid to obtain a uniform pH of 7. ~
The heat storage material composition obtained by mixing the obtained gel-like material with anhydrous sodium sulfate, a supercooling inhibitor and hydratable calcium sulfate one by one in an arbitrary order is prepared in the above-mentioned manner. Filling the inside of the container with the heat storage device.