WO2018061990A1 - Heat storage device and heat exchange device - Google Patents

Abstract

The present invention provides: a heat storage device which uses a chemical heat storage material that has high strength and heat conductivity in a processed state; and a heat exchange device. This heat storage device (1) is provided with: a chemical heat storage body (10); and a heat storage body chamber (20) in which the chemical heat storage body (10) is contained. The chemical heat storage body (10) is composed of a chemical heat storage material that contains a group 2 element compound, a boron compound and a silicone polymer; and the heat storage body chamber (20) has a first port (20a) through which a fluid (G1, G2) is able to be introduced. A heat exchange device (100) is provided with this heat storage device (1); and the chemical heat storage body (10) functions as a heat source body in this heat exchange device (100).

Description

Heat storage device and heat exchange device

The present invention relates to a heat storage device and a heat exchange device.

Recently, in order to reduce energy consumption by reducing fossil fuel consumption, the development of heat storage technology that stores and uses waste heat in factories and power plants has been promoted. As such a heat storage technique, for example, a technique (latent heat storage) that stores heat accompanied by a phase transition of a substance, such as a change from water to ice, is known.

In latent heat storage, the time during which heat can be stored generally tends to be short. The latent heat storage tends to have a low amount of heat (heat storage density) that can be stored per unit volume. Therefore, it is difficult to store heat or transport heat for a long time in latent heat storage.
In view of such a situation, among heat storage technologies, chemical heat storage materials that can store heat for a long time and have a high heat storage density have attracted attention.

More specific explanation of chemical heat storage. For example, in the case of calcium oxide / water type chemical heat storage, the heat generated when the calcium oxide in the chemical heat storage material is hydrated can be released, and conversely, the water generated by the hydration of calcium oxide. Heat can be stored in the chemical heat storage material by dehydrating calcium oxide by heating or decompressing. In this way, if a chemical heat storage material is used, it is possible to repeat heat dissipation and heat storage using heat generation and heat absorption associated with chemical changes in substances.

The chemical heat storage material is filled in, for example, a heat exchanger and recovered. When heat recovery is performed with a heat exchanger that uses inorganic powder such as calcium oxide as a chemical heat storage material (hereinafter also referred to as a heat exchange type reactor), the chemical heat storage material is in powder form and has low thermal conductivity. Heat recovery from a place away from the exchange surface is difficult, and heat recovery efficiency tends to be low. In addition, the powdered chemical heat storage material may form a gap during filling, and is difficult to handle.

To solve such a problem, a technique using a pellet-shaped chemical heat storage material that has higher thermal conductivity than powder and is easy to handle has been disclosed (for example, see Patent Document 1). In addition, in order to improve the heat exchange efficiency of the heat exchange type reactor, a technique of forming a layer made of a chemical heat storage material on the heat exchange surface is also known (for example, see Patent Document 2).

JP 2009-227772 A JP 2012-127588 A

By the way, inorganic powders such as calcium oxide used for chemical heat storage materials increase in volume when hydrated, and conversely decrease in volume when dehydrated. The technique disclosed in Patent Document 1 aims to improve the strength of the pellet-shaped chemical heat storage material by containing clay mineral and prevent pulverization due to the increase or decrease in the volume of the chemical heat storage material. However, the technique disclosed in Patent Document 1 is not sufficiently satisfactory as a technique for improving the strength of a chemical heat storage material formed into a pellet. Moreover, in the technique disclosed by patent document 2, the intensity | strength of the chemical heat storage material formed in the heat exchange surface is not considered.

In addition, since the chemical heat storage material molded into pellets does not easily allow water to penetrate inside, it has sufficient heat generation performance (increasing the temperature of water into which the chemical heat storage material is charged) compared to the content of the inorganic powder. May not have the ability).

Thus, the present situation is that no chemical heat storage material having high strength and high thermal conductivity in a state of being processed into a pellet or the like has been found.

This invention is made | formed in view of the said subject, and it aims at providing the thermal storage apparatus and heat exchange apparatus which have a chemical thermal storage material with the high intensity | strength and heat conductivity in the processed state.

A heat storage device according to the present invention includes a chemical heat storage body, and a heat storage chamber containing the chemical heat storage body, wherein the chemical heat storage body includes a Group 2 element compound, a boron compound, and a silicone polymer. It consists of the chemical heat storage material to contain, The said thermal storage body chamber has a 1st port which can introduce | transduce a fluid.

The Group 2 element compound is calcium oxide, and the chemical heat storage material has a calcium atom content of 13 to 59% by mass and a boron atom content of 0.4 to 11.3% by mass. The silicon atom content is preferably 4.8 to 33.2% by mass.

The Group 2 element compound is magnesium oxide, and the chemical heat storage material has a magnesium atom content of 8.3 to 46.5% by mass, and a boron atom content of 0.5 to 11%. The content of silicon atoms is preferably 6.2 to 35.1% by mass.

The heat storage chamber may be a flow-through chamber having a second port that can discharge the fluid.

The heat storage chamber may be a sealed chamber that forms a closed space that communicates with the first port.

A heat exchange device according to the present invention includes the above heat storage device, and the chemical heat storage body is a heat source body.

According to the present invention, it is possible to provide a heat storage device and a heat exchange device having a chemical heat storage material having high strength and thermal conductivity in a processed state.

It is a schematic cross section which shows the heat storage apparatus which concerns on 1st Embodiment of this invention, and the heat exchange apparatus which concerns on 1st Embodiment of this invention. It is a schematic cross section which shows the heat storage apparatus which concerns on 1st Embodiment of this invention, and the heat exchange apparatus which concerns on 2nd Embodiment of this invention. It is a schematic cross section which shows the heat storage apparatus which concerns on 2nd Embodiment of this invention, and 3rd Embodiment of this invention. It is the top view which shows an example of the chemical heat storage body which can be used for the heat storage apparatus and heat exchange apparatus of this invention, and a perspective perspective view of the said chemical heat storage body.

Hereinafter, various embodiments of the present invention will be described with reference to the drawings.

<Heat storage device and heat exchange device>
In FIG. 1, the code | symbol 1 is the thermal storage apparatus based on 1st Embodiment of this invention. As will be described later, the heat storage device 1 can also function as the heat exchange device 100 according to the first embodiment of the present invention.

Reference numeral 10 denotes a chemical heat storage body. The chemical heat accumulator 10 reacts with water molecules H ₂ O to generate heat, and after the reaction is completed, the heat generation performance is restored by separating the water molecules H ₂ O by heating or decompression, allowing reversible operation. It consists of a simple chemical heat storage material. As will be described later, the chemical heat storage material contains a Group 2 element compound, a boron compound, and a silicone polymer.

Reference numeral 20 denotes a heat storage chamber containing the chemical heat storage body 10. In the present embodiment, the heat accumulator chamber 20 is disposed in the tubular member 21 having an internal passage and the internal passage of the tubular member 21 and is spaced from each other in the axial direction of the tubular member 21. It consists of two partition walls 22. Each of the two partition walls 22 is made of a member having air permeability such as a metal mesh. In the present embodiment, a plurality of chemical heat storage bodies 10 are filled in a heat storage body chamber 20 constituted by a cylindrical member 21 and two partition walls 22.

The heat accumulator chamber 20 has a first port 20a through which a fluid can be introduced. In the present embodiment, the first port 20a is configured as a part of the cylindrical member 21 (one end portion of the cylindrical member 21). As the fluid, in addition to a first fluid (a gas containing water molecules H ₂ O, for example, water vapor) G1 that causes a chemical reaction of the chemical heat storage body 10 (the chemical heat storage material), the chemical heat storage body 10 (the chemical heat storage material). The second fluid (for example, indoor or outdoor air or dry air) G2 in which heat exchange (heating) is actually performed according to the amount of heat (reaction heat) from is included. Switching of introduction (supply) of the first fluid G1 or the second fluid G2 to the heat accumulator chamber 20 can be performed by, for example, a switching valve.

Furthermore, in this embodiment, the thermal storage chamber 20 is a flow-through chamber having a second port 20b that can discharge the fluid. In the present embodiment, the second port 20b is configured as a part of the cylindrical member 21 (the other end of the cylindrical member 21). The 2nd port 20b can discharge | emit the 1st fluid G1 or the 2nd fluid G2 which passed the chemical thermal storage body 10 and heat-exchanged as the fluid G3 by which heat exchange was carried out.

Next, operations of the heat storage device 1 and the heat exchange device 100 according to the present embodiment will be described.

[Heat dissipation mode]
In the heat storage device 1 according to this embodiment, first, the first fluid G1 is supplied to the heat storage chamber 20 from the first port 20a. The first fluid G1 is a gas containing water molecules H ₂ O. The temperature of the first fluid G1 may be high or low. Examples of the first fluid G1 include water vapor such as factory steam. When the first fluid G1 is introduced from the first port 20a into the heat storage chamber 20, the chemical heat storage material constituting the chemical heat storage body 10 starts to react with the first fluid G1.

The first fluid G1 has, for example, water molecules H ₂ 0 necessary for the reaction in the chemical heat storage body 10 to reach a criticality (here, “when the heat release in the chemical heat storage body 10 is maximized”). Until the chemical heat storage body 10 is supplied. In the present embodiment, the first fluid G1 is supplied from the start of supply of the first fluid G1 until a predetermined time t1. In the present embodiment, the predetermined time t1 is a time required for supplying the first fluid G1 required until the reaction in the chemical heat storage body 10 reaches the criticality. The predetermined time t1 can be obtained in advance according to the type and amount of the chemical heat storage body 10 and the first fluid G1. The supply time of the first fluid G1 can be longer than the predetermined time t1, or can be shorter than the predetermined time t1.

After the predetermined time t1 has elapsed, the supply of the first fluid G1 is stopped and the reaction in the chemical heat storage body 10 is continued. The supply of new fluid from the first port 20a is stopped, for example, until the reaction in the chemical heat storage body 10 reaches a critical value. In the present embodiment, the supply of new fluid from the first port 20a is performed by, for example, detecting the temperature of the chemical heat storage body 10, specifically the temperature in the heat storage body chamber 20, by a temperature detector such as a thermometer or a temperature sensor. And the temperature is stopped until the temperature reaches a predetermined temperature, for example, the temperature when the temperature in the heat storage chamber 20 reaches a critical point. However, the timing for supplying a new fluid from the first port 20a is not limited to this. In the present embodiment, the supply of new fluid from the first port 20a can be performed regardless of the predetermined time t1.

After reaching the predetermined temperature, the heat storage device 1 according to the present embodiment supplies the second fluid G2 from the first port 20a to the heat storage body chamber 20. Switching between the first fluid G1 and the second fluid G2 can be performed by, for example, a switching valve. Thereby, the 2nd fluid G2 is discharged | emitted as the fluid G3 which passed the chemical heat storage body 10, and was heat-exchanged.

Thus, the heat storage device 1 according to the present embodiment starts the reaction in the chemical heat storage body 10 by the first fluid G1 supplied from the first port 20a, so that the chemical heat storage body 10 becomes a heat source. It generates heat as a body. For this reason, in the heat storage device 1, if the first fluid G1 supplied from the first port 20a is switched to the second fluid G2, the second fluid G2 discharged from the second port 20b is heated by the chemical heat storage body 10. It can be used as the exchanged fluid G3. That is, the chemical heat storage device 1 also functions as a heat exchange device 100 using the chemical heat storage body 10 as a heat source. Furthermore, in the heat storage device 1 according to the present embodiment, it is possible to continue supplying the first fluid G1 to the first port 20a without changing the first fluid G1 supplied from the first port 20a to the second fluid G2. It is. In this case, the first fluid G1 discharged from the second port 20b can be used as the fluid G3 exchanged by the chemical heat storage body 10.

[Heat storage mode]
In the heat storage device 1 according to the present embodiment, the heat generation performance of the chemical heat storage body 10 is restored by heating or depressurizing and dehydrating the chemical heat storage body 10 after completion of the reaction. The chemical heat storage body 10 is heated by, for example, heating the chemical heat storage body 10 using a heating wire or an electric furnace in which electric energy is converted into heat energy, or a high temperature gas is supplied to the heat storage body chamber 20. It introduce | transduces into any one of the 1st port 20a and the 2nd port 20b, and is performed by heating the chemical thermal storage body 10. FIG. The decompression of the chemical heat storage body 10 is performed, for example, by sealing one of the first port 20a and the second port 20b of the heat storage body chamber 20 and in the heat storage body chamber 20 from the other first port 20a or second port 20b. This is done by sucking air. Thereby, the heat generation performance of the chemical heat storage body 10 is restored.

As described above, the heat storage device 1 according to the present embodiment is a heat storage device capable of reversible operation of heat dissipation and heat storage, and gives heat to the fluid (G1 and / or G2) from the first port 20a. Thus, the fluid (G1 and / or G2) can be made to function as the heat exchange device 100 that discharges the fluid G3 that has undergone heat exchange.

Next, in FIG. 2, reference numeral 200 denotes a heat exchange device according to the second embodiment of the present invention. The heat exchange device 200 has the same heat storage device 1 as in FIG. 1, and the chemical heat storage body 10 is a heat source body. In the following description, parts substantially the same as those of the heat storage device 1 in FIG. 1 have the same reference numerals and description thereof is omitted.

The heat exchange device 200 according to the present embodiment includes an inlet port P1 that can introduce the first fluid G1, an outlet port P2 that can discharge the fluid G3, and another inlet port P3 that can introduce the second fluid G2. A chemical heat storage body 10, a heat storage body chamber 20 having a first port 20a and a second port 20b and containing the chemical heat storage body 10, an on-off valve V1 for opening and closing the second port 20b, and an inlet 30a. A heating chamber 30 having a built-in heat storage chamber 20 and a distribution mechanism D for introducing the fluid (G1) into at least one of the inlet 30a of the heating chamber 30 and the first port 20a of the heat storage chamber 20. It is equipped with.

In this embodiment, the heating chamber 30 is a space formed between the heat storage body chamber 20 and a preheating fluid can be supplied to the space through the introduction port 30a. The distribution mechanism D includes an inlet port P1 into which the first fluid G1 is introduced, a heating chamber side path R1 in which the inlet port P1 and the inlet 30a of the heating chamber 30 communicate with each other, an inlet port P1 and the heat storage chamber 20 A heat storage chamber side path R2 communicating with the first port 20a and at least one switching valve (V2, V3) for opening and closing the heating chamber side path R1 and the heat storage body chamber side path R2 are provided.

In the present embodiment, at least one of the switching valves in the distribution mechanism D is two switching valves, that is, an opening / closing valve V2 provided in the heating chamber side path R1 and an opening / closing valve V3 provided in the heat storage body chamber side path R2. . The on-off valve V2 opens and closes the heating chamber side path R1, and the on-off valve V3 opens and closes the heat accumulator chamber side path R2. By providing the opening / closing valve V2 or the opening / closing valve V3 in the heating chamber side path R1 and the heat storage body chamber side path R2, respectively, the supply of the first fluid G1 from the heating chamber side path R1 and the heat storage body chamber side path R2 The first fluid G1 can be independently controlled.

Note that at least one of the switching valves in the distribution mechanism D may be a single electric control valve. As such an electric control valve, for example, a valve provided with one input port, two output ports, and one plunger that can be electrically controlled by an electromagnetic solenoid or the like can be cited. The electric control valve can switch a path from the input port to the two output ports and close a path from the input port to the two output ports by operating a plunger. Reference sign V4 is an open / close valve that opens and closes the inlet port P1. The on-off valve V4 is an arbitrary switching valve provided as an auxiliary to the distribution mechanism D. In the present embodiment, the on-off valve V4 can be arbitrarily provided with respect to the distribution mechanism D, and functions as a fail-safe switching valve in the present embodiment.

The heat exchange device 200 according to the present embodiment includes a scavenging medium path R3 connected to the first port 20a of the heat storage chamber 20 having another inlet port P3 into which the scavenging medium is introduced. In the present embodiment, the scavenging medium is the second fluid G2.

In the present embodiment, the scavenging medium path R3 includes a decarboxylation device 40. In the decarboxylation device 40, a decarboxylation process using a chemical adsorption method, lithium silicate, or the like is performed, and carbon dioxide CO2 is removed from the scavenging medium. When the carbon dioxide CO2 contained in the scavenging medium is removed, for example, the carbon dioxide CO2 is combined with calcium oxide CaO contained in the chemical heat storage material, thereby changing to calcium carbonate CaCO3 and heating the chemical heat storage body 10. However, the phenomenon that the heat generation performance cannot be completely restored is suppressed.

In the present embodiment, the scavenging medium path R3 has an on-off valve V5 between the decarboxylation device 40 and the first port 20a of the heat storage chamber 20. The on-off valve V5 opens and closes the scavenging medium path R3 between the decarboxylation device 40 and the first port 20a.

The heating chamber 30 is a chamber for preheating the heat accumulator chamber 20. In the present embodiment, for example, the steam in the factory is used as the first fluid G1, and the heating chamber 30 is heated by being introduced from the inlet port P1 into the heating chamber 30 via the inlet 30a. Preheat chamber 20. Thereby, the water molecule H ₂ O contained in the first fluid G1 also supplied to the heat storage chamber 20 is liquefied in the heat storage chamber 20 due to the low temperature of the heat storage chamber 20. A decrease in the heat generation performance of the heat storage body 10 can be suppressed.

Furthermore, in this embodiment, the heating chamber 30 has a drain port P4. The drain port P4 communicates with the heating chamber 30 and discharges the excessive first fluid G1 accumulated in the heating chamber 30 to the outside. In the present embodiment, the drain port P <b> 4 communicates with the drain chamber 50. As a result, the excessive first fluid G1 accumulated in the heating chamber 30 can be liquefied and discarded or recovered.

Furthermore, in this embodiment, the drain port P4 has an on-off valve V6. In the present embodiment, by closing the on-off valve V6, the discharge of the first fluid from the heating chamber 30 can be stopped and the temperature in the heating chamber 30 can be maintained.

Next, the operation of the heat exchange device 200 according to this embodiment will be described.

[Heat dissipation mode]
In the heat exchanging device 200 according to the present embodiment, first, the steam in the factory opens the on-off valves V4 and V2, and is supplied to the heating chamber 30 as the first fluid G1. At this time, the on-off valves V1, V3 and V5 other than the on-off valve V6 of the drain port P4 are in a closed state. Thereby, the heating chamber 30 is heated by the 1st fluid G1, and the thermal storage body chamber 20 of the thermal storage apparatus 1 is pre-heated.

Next, when the preheating of the heat accumulator chamber 20 is completed, the first fluid G1 is supplied into the heat accumulator chamber 20 by opening the on-off valves V1 and V3, and the reaction in the chemical heat accumulator 10 is started. The timing for opening the on-off valves V1 and V3 is controlled based on, for example, temperature detection means in the heat storage body chamber 20.

The on-off valve V3 is opened until, for example, water molecules H ₂ 0 necessary for the reaction in the chemical heat storage body 10 to reach the criticality are supplied to the chemical heat storage body 10. In the present embodiment, the on-off valve V3 is supplied until a predetermined time t1 after the on-off valve V3 is opened and the supply of the first fluid G1 to the heat storage chamber 20 is started.

On the other hand, for example, when the temperature of the heat storage chamber 20 reaches a predetermined temperature, the second fluid G2 is supplied from the first port 20a to the heat storage chamber 20 by closing the on-off valve V3 and opening the on-off valve V5. Thereby, the 2nd fluid G2 passes through the exit port P2 of the heat exchange apparatus 200 from the 2nd port 20b, passes through the chemical heat storage body 10, and is discharged | emitted as the fluid G3.

Thus, in the heat exchange device 200 according to the present embodiment, the chemical heat storage body 10 is started by the reaction of the chemical heat storage body 10 by the first fluid G1 supplied from the first port 20a. It generates heat as a heat source. For this reason, in the heat exchange device 200, the first fluid G1 supplied from the first port 20a is switched to the second fluid G2, so that the second fluid G2 discharged from the second port 20b is supplied by the chemical heat storage body 10. It can be used as the heat exchanged fluid G3. Furthermore, in the heat exchange device 200 according to the present embodiment, the first fluid G1 may be continuously supplied to the first port 20a without changing the first fluid G1 supplied from the first port 20a to the second fluid G2. Is possible. In this case, the first fluid G1 discharged from the second port 20b can be used as the fluid G3 exchanged by the chemical heat storage body 10.

[Heat storage mode]
In the heat exchange device 200 according to the present embodiment, the heat generation performance of the chemical heat storage body 10 is restored by heating or depressurizing the chemical heat storage body 10 after completion of the reaction. In the present embodiment, the chemical heat storage body 10 is heated by, for example, opening at least the on-off valves V1, V3, and V4 or the on-off valves V1 and V5 and starting from the outlet port P2 of the heat exchange device 200. This can be done by introducing a high-temperature gas into the 2-port 20b and heating the chemical heat storage body 10. Alternatively, the chemical heat storage body 10 can be depressurized by, for example, opening the on-off valve V1 and closing the on-off valve V3 or on-off valve V5, or opening the on-off valve V3 or on-off valve V5 and closing the on-off valve V1. Either one of the first port 20a and the second port 20b of the chamber 20 is sealed, and the air in the heat accumulator chamber 20 is removed from the other first port 20a or the second port 20b via any of the ports P1 to P3. This can be done by aspiration. Thereby, the heat generating performance of the chemical heat storage body 10 is restored by heating or depressurizing and dehydrating the chemical heat storage body 10 after completion of the reaction.

As described above, the heat exchange device 200 according to the present embodiment applies heat to the fluid (G1 and / or G2) from the first port 20a, and the fluid (G1 and / or G2) is heat-exchanged. The fluid G3 can be discharged.

Furthermore, in FIG. 3, the code | symbol 300 is the heat exchange apparatus based on 3rd Embodiment of this invention. In the heat exchange device 300, the heat source body is the heat storage device 2 according to the second embodiment of the present invention. In the following description, parts substantially the same as those of the heat storage device 1 in FIG.

In FIG. 3, reference numeral 60 denotes a heat accumulator chamber that houses the chemical heat accumulator 10. The heat accumulator chamber 60 has a first port 60a through which a fluid can be introduced. In the present embodiment, the first port 60a has an on-off valve V7 and communicates with the steam tank 70 through the on-off valve V7. Thereby, the steam from the steam tank 70 is supplied to the heat accumulator chamber 60 as the first fluid G1 by opening the on-off valve V7.

The thermal storage chamber 60 is a sealed chamber that forms a closed space that communicates with the first port 60a. The heat storage device 2 according to the present embodiment includes a chemical heat storage body 10 and a heat storage body chamber 60 having a first port 60a.

On the other hand, the heat exchange device 300 includes an on-off valve V7, a steam tank 70, the heat storage device 2, and a heat exchange circuit 80. In the present embodiment, the heat exchange circuit 80 is disposed in the heat accumulator chamber 60. The heat exchanging circuit 80 has a first port 80a into which a second fluid G2 that requires heat exchange is introduced, and a second port 80b through which the fluid is discharged as a fluid G3 heat exchanged by the chemical heat storage body 10. is doing. The heat exchange circuit 80 does not communicate with the space in the heat storage chamber 60. In the present embodiment, gas or liquid can be used as the second fluid G2 supplied to the heat exchange circuit 80.

Next, the operation of the heat exchange device 300 according to the present embodiment will be described together with the operation of the heat storage device 2.

[Heat dissipation mode]
In the heat exchange device 300 according to the present embodiment, first, the on-off valve V7 is opened, and the first fluid G1 is supplied from the first port 60a of the heat storage device 2 to the heat storage chamber 60. When the first fluid G1 is introduced into the heat storage chamber 60, the reaction in the chemical heat storage body 10 is started by the first fluid G1. In the present embodiment, the on-off valve V7 may be closed when the reaction in the chemical heat storage body 10 reaches a critical value, or may be left open as it is.

Next, when the second fluid G2 is caused to flow through the heat exchanging circuit 80, the second fluid G2 is discharged as the fluid G3 that has undergone heat exchange via the heat exchanging circuit 80.

[Heat storage mode]
In the heat exchange apparatus 300 according to the present embodiment, the heat generation performance of the chemical heat storage body 10 is restored by heating and dehydrating the chemical heat storage body 10 housed in the heat storage apparatus 2 after completion of the reaction. The chemical heat storage body 10 is heated using, for example, a heating wire or an electric furnace provided in the heat storage chamber 60. Alternatively, the chemical heat storage body 10 is heated by introducing a high temperature gas or a high temperature liquid into one of the first port 80a and the second port 80b of the heat exchange circuit 80 and heating the chemical heat storage body 10. It can also be done. The heat generation performance can be restored by, for example, reducing the pressure of the heat storage chamber 60 from the first port 60a. Thereby, the heat generation performance of the chemical heat storage body 10 is restored.

<Chemical heat storage material>
The chemical heat storage material that can be used in each embodiment described above contains a Group 2 element compound, a boron compound, and a silicone polymer.

The group 2 element compound contained in the chemical heat storage material is not particularly limited as long as it can perform a reversible chemical reaction. The group 2 element compound is a compound containing any metal selected from beryllium, magnesium, calcium, strontium, barium and radium which are group 2 elements. The Group 2 element compound preferably generates heat when hydrated, and stores heat by dehydration after hydration.
Examples of the Group 2 element compound that generates heat by hydration and stores heat by dehydration after hydration can include the compounds listed in Table 1. “Heat storage operation temperature” in Table 1 is the temperature at which the indicated compound undergoes an exothermic reaction, and “heat storage density” is the amount of heat energy released per unit volume of the indicated compound.

Among the Group 2 element compounds listed in Table 1, it is preferable that at least one of calcium oxide and magnesium oxide is contained in the chemical heat storage material because the heat storage operation temperature and the heat storage density are high. Further, calcium oxide and magnesium oxide can be obtained at low cost. Strontium oxide and barium oxide can also be preferably used as the Group 2 element compound.

The boron compound contained in the chemical heat storage material is boron oxide derived from the boron-containing compound contained in the chemical heat storage material forming composition described later. The chemical heat storage material contains a boron compound, whereby the strength in a state of being formed into a pellet is improved. The reason why the chemical heat storage material contains the boron compound is not necessarily clear, but the inclusion of boron atoms in the silicone polymer described later makes the silicone polymer melting point lower and makes it easier to expand and contract ( This is thought to be due to increased flexibility.

The silicone polymer contained in the chemical heat storage material is at least one selected from the group consisting of an alkoxysilane, a hydrolyzate thereof, and a condensate thereof contained in a composition for forming a chemical heat storage material described later (hereinafter referred to as alkoxysilane and the like). Is a condensed silicone polymer. The silicone polymer condensed with alkoxysilane or the like preferably has a structure in which all alkoxy groups bonded to silicon are eliminated in the baking step described later. The silicone polymer forms a dense three-dimensional structure and prevents the chemical heat storage material from collapsing. Further, the silicone polymer can hold the Group 2 element compound inside a dense three-dimensional structure.

As the silicone polymer, a silicone polymer in which at least one selected from the group consisting of at least one of triethoxysilane and tetraethoxysilane, a hydrolyzate thereof, and a condensate thereof is condensed to form a denser three-dimensional structure. Is preferable.
Further, the content of the silicone polymer in the chemical heat storage material is preferably 12 to 83% by mass. If the content of the silicone polymer in the chemical heat storage material is less than 12% by mass, the chemical heat storage material tends to be easily collapsed. If the content is more than 83% by mass, the amount of heat that can be released from the chemical heat storage material is small. It tends to become.

When the Group 2 element compound is calcium oxide, the chemical heat storage material has a calcium atom content of 13 to 59% by mass and a boron atom content of 0.4 to 11.3% by mass, The silicon atom content is preferably 4.8 to 33.2% by mass. The chemical heat storage material contains calcium atoms derived from calcium oxide, boron atoms derived from boron compounds, and silicon atoms derived from silicone polymers.

When the content of calcium atoms in the chemical heat storage material is less than 13% by mass, the amount of heat that can be released from the chemical heat storage material tends to decrease due to the small amount of calcium oxide. When the content of calcium atoms in the chemical heat storage material is more than 59% by mass, the chemical heat storage material tends to collapse because the silicone polymer decreases.

When the content of boron atoms in the chemical heat storage material is less than 0.4% by mass, the strength of the chemical heat storage material tends to decrease. When the content of boron atoms in the chemical heat storage material is more than 11.3% by mass, the chemical heat storage material tends to be easily collapsed due to the decrease in the silicone polymer.

When the content of silicon atoms in the chemical heat storage material is less than 4.8% by mass, the chemical heat storage material tends to collapse because the silicone polymer is small. When the content of silicon atoms in the chemical heat storage material is more than 33.2% by mass, the amount of heat that can be released from the chemical heat storage material tends to decrease due to a decrease in calcium oxide.

For the same reason as when the Group 2 element compound is calcium oxide, when the Group 2 element compound is beryllium oxide, the content of beryllium atoms in the chemical heat storage material is 3.2 to 24.4 mass%. The boron atom content is preferably 0.7 to 12.6% by mass, and the silicon atom content is preferably 8.7 to 37.1% by mass.

For the same reason, when the Group 2 element compound is magnesium oxide, the content of magnesium atoms in the chemical heat storage material is 8.3 to 46.5% by mass, and the content of boron atoms is 0. The silicon atom content is preferably 6.2 to 35.1% by mass.

For the same reason, when the Group 2 element compound is strontium oxide, the content of strontium atoms in the chemical heat storage material is 24.5 to 75.8% by mass, and the content of boron atoms is 0. The silicon atom content is preferably 2.8 to 28.6% by mass.

For the same reason, when the Group 2 element compound is barium oxide, the content of barium atoms in the chemical heat storage material is 33.7 to 83.1% by mass, and the content of boron atoms is 0. The silicon atom content is preferably 2.0 to 25.0% by mass.

Thus, when the Group 2 element compound is calcium oxide, magnesium oxide, strontium oxide, and barium oxide, the preferable content in terms of mass of each component is different. However, if these are the contents in terms of substance amount, they are equivalent. Further, as the second element compound, two or more kinds selected from calcium oxide, magnesium oxide, strontium oxide and barium oxide may be used in combination.

In addition, content of these atoms (Ca etc., B, Si, and O) in a chemical heat storage material can be calculated | required by the composition analysis by a fluorescent X ray analyzer (XRF) etc.
The chemical heat storage material may contain components other than the Group 2 element compound, the boron compound, and the silicone polymer as necessary.

The chemical heat storage material becomes a porous material by being formed using a chemical heat storage material forming composition described later as a raw material.
The chemical heat storage material can be processed into an arbitrary shape using a chemical heat storage material forming composition described later as a raw material. The heat released from the chemical heat storage material can be used by being transferred to the outside by the heat exchanged fluid G3 or the heat exchange device, for example.

Subsequently, the operation of the chemical heat storage material will be described. The chemical heat storage material can repeat heat generation and heat storage.
First, in the heat generation process in which heat is generated from the chemical heat storage material, water vapor is brought into contact with the chemical heat storage material. In this case, it is preferable to contact water (water vapor) in a molar amount not more than 1.2 times the molar amount of the Group 2 element compound such as calcium oxide contained in the chemical heat storage material. The water that has come into contact with the chemical heat storage material penetrates into the pores formed in the chemical heat storage material, and heat is generated well inside the chemical heat storage material. If too much water is brought into contact with the chemical heat storage material, the water itself consumes heat and reduces the total calorific value. The heat generated from the chemical heat storage material is recovered by the heat medium of the heat exchange device. The method of bringing water vapor into contact with the chemical heat storage material is not limited, and any of ventilation of water vapor to the chemical heat storage material, immersion of the chemical heat storage material in liquid water, addition of liquid water to the chemical heat storage material (dropping, spraying, etc.) It may be. Especially, since it is easy to make it contact with a chemical heat storage material uniformly, it is preferable to make water vapor contact a chemical heat storage material by ventilation | gas_flowing of water vapor | steam.

On the other hand, in the heat storage process in which heat is stored in the chemical heat storage material, the chemical heat storage material containing a Group 2 element compound such as calcium hydroxide generated by hydration of calcium oxide or the like is heated. By heating the chemical heat storage material, the hydroxide of the Group 2 element compound in the chemical heat storage material is dehydrated and returns to the state before the exothermic process (for example, calcium oxide). Water vapor generated in the heat storage process is recovered as necessary.

In the exothermic process, the volume of the chemical heat storage material increases. More specifically, the volume of the Group 2 element compound in the chemical heat storage material increases by about 20% as the chemical heat storage material hydrates and generates heat. Conversely, in the heat storage process, the volume of the Group 2 element compound in the chemical heat storage material decreases as it dehydrates and stores heat. The repeated increase and decrease in the volume of the chemical heat storage material causes the chemical heat storage material formed in a desired shape to collapse and become fine powder.
Since the chemical heat storage material that can be used in each of the embodiments described above is porous, the chemical heat storage material itself can absorb the shape distortion caused by the increase and decrease in volume. Moreover, the chemical heat storage material according to the present embodiment is considered to increase flexibility by containing a boron compound. Therefore, the chemical heat storage material that can be used in each of the above-described embodiments is difficult to collapse even when heat generation and heat storage are repeated, and has high strength.

<Composition for forming chemical heat storage material>
The chemical heat storage material forming composition for forming the chemical heat storage material that can be used in each embodiment described above includes a Group 2 element compound, a boron-containing compound, alkoxysilane, a hydrolyzate thereof, and It contains at least one selected from the group consisting of the condensate and a resin. Said chemical heat storage material is formed using the composition for chemical heat storage material formation which can be used for each embodiment mentioned above.

The Group 2 element compound contained in the chemical heat storage material forming composition is the same as the Group 2 element compound contained in the chemical heat storage material.
However, it is preferable to use a hydrated Group 2 element compound as the Group 2 element compound contained in the chemical heat storage material forming composition. If the hydrated Group 2 element compound is contained in the chemical heat storage material forming composition, the Group 2 element compound is dehydrated and the volume is reduced in the firing step in the formation of the chemical heat storage material described later. Therefore, if the chemical heat storage material is formed by using the chemical composition for forming a chemical heat storage material containing the hydrated Group 2 element compound in this way, even if the volume is expanded, it is difficult for distortion to occur. It tends to be difficult. Examples of the Group 2 element compound contained in the chemical heat storage material forming composition include calcium hydroxide, magnesium hydroxide, strontium hydroxide, and barium hydroxide.

In particular, it is more preferable that the chemical heat storage material forming composition contains at least one of calcium hydroxide and magnesium hydroxide as the Group 2 element compound. As shown in Table 1, calcium hydroxide and magnesium hydroxide have high heat storage operation temperature and heat storage density.

Further, the chemical heat storage material forming composition preferably contains at least one selected from the group consisting of boric acid, trialkyl borates and triaryl borates as the boron-containing compound. When the chemical heat storage material forming composition contains these boron-containing compounds, the flexibility of the silicone polymer in the chemical heat storage material is improved. More preferably, the chemical heat storage material forming composition contains a trialkyl borate as the boron-containing compound. Examples of the trialkyl borate include trimethyl borate and triethyl borate. Trialkyl borate has high reactivity with alkoxysilane and the like described later, and improves the flexibility of the silicone polymer in the chemical heat storage material. It is considered that the strength of the chemical heat storage material in the processed state is improved by improving the flexibility of the silicone polymer in the chemical heat storage material.

At least one selected from the group consisting of an alkoxysilane, a hydrolyzate thereof, and a condensate thereof contained in the chemical heat storage material forming composition becomes a silicone polymer in the chemical heat storage material to form a dense three-dimensional structure.
Examples of the alkoxysilane include tetraalkoxysilane, alkyltrialkoxysilane, dialkylalkoxysilane, and partial condensates thereof. More specifically, as the partial condensate of tetraalkylsilane, MKC silicate MS51 (condensate of tetraalkoxysilane manufactured by Mitsubishi Chemical Corporation), ethyl silicate 40 (condensate of tetraethoxysilane manufactured by Colcoat Co., Ltd.), etc. Can be mentioned.

As the alkoxysilane contained in the composition for forming a chemical heat storage material, since the silicone polymer can form a dense three-dimensional structure, at least one of triethoxysilane and tetraethoxysilane, its hydrolyzate and its condensation It is preferably at least one selected from the group consisting of products.

The resin contained in the chemical heat storage material forming composition serves as a thickener and is necessary for maintaining the shape of the chemical heat storage material.
The resin contained in the composition for forming a chemical heat storage material is not limited as long as it plays the above-described role, and may be any of natural resins and synthetic resins. Polysaccharides such as cellulose, proteins, polyphenols, One type can be selected from a polyester resin, a polyether resin, an acrylic resin, a polyurethane resin, a fluororesin, an epoxy resin, or a plurality of types can be used in combination. The composition for forming a chemical heat storage material preferably contains, as a resin, at least one selected from the group consisting of polyvinyl alcohol, modified polyvinyl alcohol, polyethylene glycol, polyethylene oxide, a hydroxyl group-containing acrylic resin, and a butyral resin. Since these resins are hydroxyl group-containing resins, they have a high affinity with Group 2 element compounds and alkoxysilanes. In addition, from the viewpoint of stabilizing the shape of the chemical heat storage material, the chemical heat storage material forming composition preferably contains a hydroxyl group-containing acrylic resin or butyral resin.
The resin contained in the chemical heat storage material forming composition preferably has a volume average molecular weight of 100 to 5,000,000. The volume average molecular weight of the resin contained in the chemical heat storage material forming composition can be measured by gel permeation chromatography (GPC) using a polystyrene standard sample standard.

More specifically, examples of the butyral resin include ESREC B series and K series (both manufactured by Sekisui Chemical Co., Ltd.). Further, as the hydroxyl group-containing acrylic resin, more specifically, a secondary hydroxyl monomer such as 2-hydroxybutyl (meth) acrylate, a tertiary hydroxyl monomer such as 2-hydroxy-2-methylpropyl (meth) acrylate, The polymer which can be obtained by superposing | polymerizing the monomer liquid mixture containing another monomer by a conventional method can be mentioned.
In addition, resin which the composition for chemical heat storage material formation contains is removed in the baking process of the formation method of the chemical heat storage material mentioned later.

Also, the chemical heat storage material forming composition preferably contains glass fiber. When the chemical heat storage material forming composition contains glass fiber, the strength of the chemical heat storage material in the processed state is improved.

Furthermore, the chemical heat storage material forming composition may contain at least one of a substance made of carbon and a hydrocarbon. The chemical heat storage material forming composition contains at least one of a carbon substance and a hydrocarbon, so that more pores are formed inside and on the surface of the chemical heat storage material, thereby stabilizing the shape of the chemical heat storage material. be able to.
Examples of the carbon material include carbon black, graphite, and carbon nanofiber. Examples of the hydrocarbon include paraffin, olefin, and cycloalkane.

More preferably, finer pores are formed in the surface or inside of the chemical heat storage material, and the shape of the chemical heat storage material can be further stabilized. Therefore, the composition for forming a chemical heat storage material includes carbon black and hydrocarbon. It is preferable to contain.
In addition, the substance and hydrocarbon which consist of carbon which the composition for chemical heat storage material formation contains are removed in the baking process of the formation method of the chemical heat storage material mentioned later.

The chemical heat storage material forming composition preferably contains a solvent in order to disperse the above components. As the solvent, at least one of an organic solvent and water can be used. Examples of the organic solvent include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, cellosolve acetate and butylcellosolve, alcohols and the like.

The composition for forming a chemical heat storage material may contain components other than the above components as necessary.

<Chemical heat storage>
In the present invention, as the chemical heat storage body 10, for example, powder, pulverized material, molded product, heat storage device 1 or heat storage chambers 20 of the heat exchange devices 100 and 200, partition walls 22, and heat of the heat exchange device 300 are used. For example, a chemical heat storage material forming composition is applied to the exchange surface (for example, the heat exchange circuit 80) and then baked. In particular, as such a chemical heat storage body 10, for example, a granular body having a particle size larger than a powdery material having a particle size larger than 0 mm and not larger than 0.05 mm, the size of which is one chemical heat storage body 10. It is preferable that the maximum diagonal length DLmax, which is the distance between the farthest vertices, is a size exceeding 0.05 mm. When the maximum diagonal length DLmax of one chemical heat storage element 10 is smaller than 0.05 mm, the pressure loss in ventilation becomes too large, and the ventilation function tends to be greatly impaired. In addition, since dusting starts to occur, the handling tends to be impaired. Here, “powdering” refers to a state in which the powder rises and the suspension in the air can be visually confirmed.

The chemical heat storage body as the molded product can be classified according to the difference in the manufacturing method of the molding process (hereinafter referred to as “molding process” widely refers to a “process to form a certain shape”). For example, “granule” formed by granulation or “pellet” formed by molding (herein, “molding” refers to “molding using a mold”) can be mentioned. “Pellets” also include those obtained by further molding powders and granules. Moreover, the manufacturing method of the chemical heat storage body 10 is not limited to these two types. In particular, the chemical heat storage body that can be used in each embodiment described above has high strength in a processed state by containing a Group 2 element compound, a boron compound, and a silicone polymer. Thus, when the chemical heat storage body is a granule or a pellet, pulverization due to an increase or decrease in the volume of the chemical heat storage material is prevented, and it can withstand repeated heat generation and heat storage.

An example of a method for forming a chemical heat storage body according to the present embodiment will be described. The chemical heat storage body forming method according to the present embodiment includes, for example, a processing method including a forming step and a firing step. The molding step is a step of molding a chemical heat storage material forming composition in which the above components are mixed by an arbitrary method. For example, if the chemical heat storage material is a “granule”, it is a manufacturing method by granulation. If it is “pellet”, it is a production method by molding using a mold.

Here, the manufacturing method of the granule type chemical heat storage body 10 will be described.

Examples of the granule type production method include the following granulation methods, such as rolling granulation, fluidized bed granulation, stirring granulation, compression granulation, extrusion granulation, crush granulation, and the like. However, the granule type production method may be a granulation method other than these, or may be processed by combining two or more granulation methods. When the particle size of the granule-type chemical heat storage element 10 is 5 mm or more, rolling granulation or crushing granulation is suitably used as the granulation method.

In the firing step, the molded chemical heat storage material forming composition is fired after the molding step. The firing step can be performed with an electric furnace or the like, but the firing apparatus is not particularly limited.
When the chemical heat storage material forming composition is fired in the firing step, the resin, the substance made of carbon, and the hydrocarbon are vaporized and removed from the chemical heat storage material. The chemical heat storage material has pores formed by removing a resin, a substance made of carbon, hydrocarbons, and the like.

In the firing step, the molded chemical heat storage material forming composition is preferably fired at 200 to 1200 ° C., more preferably 300 to 1000 ° C. In the firing step, when the molded composition for forming a chemical heat storage material is fired at a temperature of less than 200 ° C., the chemical heat storage material tends to collapse due to insufficient firing, and the temperature is higher than 1200 ° C. When it is fired, the Group 2 element compound cannot maintain the oxide state, and the heat storage performance of the chemical heat storage material tends to be lowered.

In the firing step, the formed chemical heat storage material forming composition is preferably fired for 30 to 120 minutes. As long as the function of the chemical heat storage material is not hindered, the resin, the substance made of carbon, and the hydrocarbon may remain in the chemical heat storage material after the firing step. In the firing process, when the firing time is less than 30 minutes, the chemical heat storage material tends to collapse due to insufficient firing, and when longer than 120 minutes, bubbles are generated inside the chemical heat storage material. After all, chemical heat storage materials tend to collapse easily.

Thus, the chemical heat storage body 10 used in each embodiment of the present invention can be manufactured through a granulation step and a firing step. The “particle size” of the chemical heat storage element 10 is less than 3 mm by using a laser diffraction type particle size distribution measuring device (for example, SALD-3100 manufactured by Shimadzu Corporation), etc. Can be measured. A granule type chemical heat storage body 10 having a particle size exceeding 3 mm can be measured by arbitrarily extracting 100 chemical heat storage bodies 10 and measuring the maximum diagonal length with a micro gauge. Unless otherwise specified in this specification, the particle size of the granule-type chemical heat storage element 10 is the median diameter. In addition, the chemical heat storage body 10 accommodated in the heat storage body chamber is not limited to the granules obtained by the same granulation, but may be a mixture of two or more kinds of granules obtained by different granulations.

Next, the shape of the granule type chemical heat storage body 10 will be described.

In the granule-type chemical heat storage body 10 that can be used in each embodiment described above, the minimum diameter (particle diameter) of the chemical heat storage body 10 measured in the particle size measurement method is preferably, It is 0.05 mm or more, desirably 0.1 mm or more, and more desirably 0.5 mm or more. The maximum diameter (particle size) of the granule type chemical heat storage element 10 is preferably 100 mm or less, desirably 10 mm or less, and more desirably 8 mm or less. However, the maximum diameter (particle diameter) of the granule-type chemical heat storage element 10 may be larger than 100 mm. However, if productivity is considered, the pellet type chemical heat storage body 10 mentioned later is preferable.

Here, the manufacturing method of the pellet type chemical heat storage body 10 will be described.

The pellet-type molding process uses the plasticity of the chemical heat storage material according to the present invention to perform extrusion molding, compression molding with a mold or tableting, injection molding, sheet molding and subsequent die-cutting process, etc. (hereinafter referred to as “extrusion molding”). It is also preferable to use extrusion molding. In the case of extrusion molding, compared with other moldings, the penetration rate as equipment is high, and it is excellent in both economical efficiency and productivity.

After the molding process is performed, the same baking process as that for producing the granule type is performed, and the pellet type chemical heat storage body 10 is obtained through this baking process.

Next, the shape of the pellet type chemical heat storage body 10 will be described.

The shape of the chemical heat storage body 10 is not limited as long as the shape of the pellet type chemical heat storage body 10 is a solid obtained by the above-described extrusion molding or the like. However, the shape of the chemical heat storage element 10 is desirably a hollow shape, for example, a cylindrical shape as shown in FIG. 4 from the viewpoint of air permeability. The term “hollow” as used herein means that “thickening” is provided inside. “Meat removal” includes not only a cylindrical shape shown in FIG. 4 but also a hollow in which one of them is opened, a space in which the periphery is closed, or the like. The dimensions of the pellet-type chemical heat storage element 10 are shown using symbols attached to FIG.

In the pellet type chemical heat storage body 10 shown in FIG. 4, the cylinder height (hereinafter, also simply referred to as “cylindrical height”) is L, the inner radius is r1, the outer radius is r2, and the inner radius r1. Is expressed as k (= r1 / r2) (0 ≦ k <1). The specific surface area of the pellet type chemical heat storage body 10 shown in FIG. 4 is obtained after determining the volume and surface area of the cylinder from the cylinder height L, the inner peripheral radius r1 and the outer peripheral radius r2 as the volume V and the surface area S of the chemical heat storage body 10. Furthermore, the ratio of the volume V and the surface area S can be obtained. From this calculation result, it can be seen that the pellet-type chemical heat storage body 10 shown in FIG. 4 is more advantageous for ventilation because k becomes closer to 1 and L becomes smaller as L becomes smaller.

On the other hand, the strength of the pellet type chemical heat storage body 10 is maximized when k = 0, that is, when the chemical heat storage body 10 is not in a hollow shape and L = 2 · r2.

Here, the range of desirable dimensions is shown using the cylinder height L, the outer radius r2, and the ratio k. However, in the present invention, desirable dimensions described later do not limit the shape of the pellet type chemical heat storage body 10 shown in FIG.

First, if the cylinder height L is 0.1 mm or more, the pellet type chemical heat storage element 10 shown in FIG. 4 can be molded without any trouble. However, from the viewpoint of the strength of the chemical heat storage element 10, it is preferable to use a dimension close to L = 2 · r2 as the cylinder height L.

Next, the outer radius r2 is 3 mm to 300 mm. In this range, the pellet type chemical heat storage body 10 shown in FIG. 4 is suitable for production by extrusion molding. If the outer peripheral radius r2 is 3 mm or less, the granular-type chemical heat storage body 10 is preferable in terms of productivity. If the ratio k is 0.1 or less, the air permeability tends to be poor, and if it is 0.95 or more, it tends to be difficult to mold the chemical heat storage element 10 having strength.

The above description merely discloses an embodiment of the present invention, and various modifications are possible according to the scope of the claims. For example, the configurations of the heat storage device and the heat exchange device according to each of the above-described embodiments can be appropriately replaced with each other or used in combination.

Next, various examples of the chemical heat storage material that can be used in the heat storage device and the heat exchange device according to the present invention will be described in more detail. However, the examples of the chemical heat storage material are limited to the following examples. It is not something.

[Example 1]
Polyethylene glycol resin (manufactured by Meisei Chemical Industry Co., Ltd., trade name “Alcox”), butyral resin (trade name “Mowital B20H”, trade name “Mowital B20H”) and ethyl silicate in the amounts (unit: parts by mass) shown in Table 2 Low condensate (Corcoat Co., Ltd., trade name “ethyl silicate 28”), organic solvent (Nippon Emulsifier Co., Ltd., trade name “MPG-130”, polyethylene glycol methyl ether), and trimethyl borate (Tokyo Chemical Industry) A trade name “Trimethyl Borate” manufactured by Co., Ltd.) was mixed. To this mixture, the amount of calcium hydroxide shown in Table 2 was further added and mixed well to obtain a composition for forming a chemical heat storage material. This chemical heat storage material forming composition was formed into a pellet (cylindrical, about 5 mm in diameter, about 10 mm in height). The molded chemical heat storage material forming composition was put in an electric furnace and baked at 1000 ° C. for 1 hour to obtain a pellet-shaped chemical heat storage material. In addition, calcium hydroxide dehydrates by being fired, and becomes calcium oxide.

[Examples 2 to 13 and Comparative Examples 1 to 4]
A chemical heat storage material forming composition and a chemical heat storage material were obtained by the same process as in Example 1 except that the components of the chemical heat storage material forming composition were changed to the amounts shown in Tables 2 to 4.
In Example 5, glass fiber (manufactured by Central Glass Fiber Co., Ltd., trade name “milled fiber”) was further added to a mixture of butyral resin, ethyl silicate low condensate, organic solvent, and trimethyl borate. added. In Example 6, boric acid was used in place of trimethyl borate. In Examples 7 to 13, magnesium hydroxide, strontium hydroxide, and barium hydroxide were used in place of calcium hydroxide.

[Atom content of chemical heat storage materials]
Table 2 to Table 2 show the content (mass%) of each atom in the total of calcium atoms, boron atoms, silicon atoms, and oxygen atoms contained in chemical heat storage materials as "Atom content in chemical heat storage materials". This is shown in FIG. The “atom content in the chemical heat storage material” was determined by elemental analysis of the chemical heat storage material with a fluorescent X-ray analyzer (XRF).

[Shape evaluation]
The shape of the chemical heat storage material immediately after being formed by firing in an electric furnace ("after firing" in Tables 2 to 4) and the shape of the chemical heat storage material after being heated by infiltrating into water (Tables 2 to 4) The “after heat generation” in Table 4) was evaluated visually. When the shape of the pellet is maintained and no cracks are generated, “A”, fine cracks are generated, but when the shape of the pellets is maintained, “B”, when significant cracks occur, When it became, it was set as “C”. The results are shown in Tables 2-4. Note that the chemical heat storage materials according to Comparative Examples 2 to 4 failed to maintain the shape of the pellet because the shape collapsed after heat generation. Therefore, in Table 4, the evaluation of the shape of the chemical heat storage material according to Comparative Examples 2 to 4 after heat generation was “not evaluated”.

[Strength evaluation]
A chemical heat storage material immediately after being formed by firing in an electric furnace ("after firing" in Tables 2 to 4) and a chemical heat storage material after being heated by infiltrating into water ("Table 2 to Table 4" About "after heat generation"), strength was evaluated using a tension compression testing machine (Technograph, manufactured by Minebea Co., Ltd.). Specifically, the force (unit: N) to be crushed by loads from above and below was measured with a tensile and compression tester for each pellet-shaped chemical heat storage material after firing and after heat generation. If the crushing force of the chemical heat storage material after firing and after heat generation is both 10 N or more, it can be determined that the chemical heat storage material has a strength that can withstand repeated heat generation and heat storage. In addition, the chemical heat storage materials according to Comparative Examples 2 to 4 could not stably hold the shape, and the strength could not be evaluated with a tensile and compression tester. Therefore, in Table 4, the evaluation of the strength of the chemical heat storage material according to Comparative Examples 2 to 4 was set as “not evaluated”.

[Heat generation performance evaluation]
For the pellet-like chemical heat storage materials of Examples 1 to 8, the calorific value was measured. The calorific value was measured according to the following procedure.
First, a predetermined amount of water was put into a container covered with a heat insulating material, and a predetermined amount (for example, 5 g) of a chemical heat storage material was put into the water. The water in the container was stirred by a magnetic stirrer, and the temperature rise was followed by a sheathed thermocouple. The temperature measured by the sheath-type thermocouple of the water charged with the chemical heat storage material of the example greatly increased. The calorific value Q (unit: J) of the chemical heat storage material can be obtained by the following equation (1). ΔT in the formula (1) is a value (unit: K) obtained by subtracting the temperature of water immediately before the chemical heat storage material is added from the maximum temperature of the water after the chemical heat storage material is charged. W is the mass (unit: g) of water in the cup, and Cp is the specific heat of water (J / g · K).
[Equation 1]
Q = ΔT × W × Cp (1)

From the comparison between Examples 1 to 4 in Table 2 and Comparative Example 1 in Table 4, the chemical heat storage materials of Examples 1 to 4 and 6 to 8 are comparative examples 1 for both “after heat generation” and “after firing”. It was found that the strength evaluation result was better than the chemical heat storage material. From this result, the chemical heat storage material formed using the chemical heat storage material forming composition containing the Group 2 element compound, the butyral resin, the boron-containing compound, and the low condensate of ethyl silicate is boron. It was confirmed that the strength in the molded state was higher than that of the chemical heat storage material formed using the chemical heat storage material forming composition not containing the contained compound.

Further, from the comparison between Examples 1 to 4 in Table 2 and Examples 7 to 13 in Table 3, the chemical heat storage materials of Examples 7 to 13 are also examples 1 to 4 for both “after heat generation” and “after firing”. It was found to have a strength comparable to that of chemical heat storage materials. From these results, it was confirmed that a compound comprising a Group 2 element other than calcium can also be used for a chemical heat storage material that can be used in the heat storage device and the heat exchange device according to the present invention.

Also, from the results of Comparative Examples 2 to 4, it was found that the chemical heat storage materials formed using the chemical heat storage material forming compositions of Comparative Examples 2 to 4 had poor shape evaluation results. From these results, it was confirmed that the shape of the pellet cannot be maintained when the composition for forming a chemical heat storage material does not contain any of the Group 2 element compound, alkoxysilane, and the resin.

Further, as described above, the temperature of the water in which the chemical heat storage materials of Examples 1 to 13 were added rose greatly. From this result, it was confirmed that the pellet-shaped chemical heat storage materials of Examples 1 to 13 have heat generation performance. The calorific value Q of the pellet-shaped chemical heat storage materials of Examples 1 to 13 was equivalent to the theoretical value of the calorific value obtained from the amount of calcium oxide contained in each chemical heat storage material.

In addition, as for the chemical heat storage material formed using the chemical heat storage material formation composition containing a group 2 element compound, a boron containing compound, alkoxysilane etc., and resin, particles are as mentioned above. Since it is bound, water (water vapor) is immersed into the inside of the pellet as compared to the pellet-shaped chemical heat storage material containing the clay mineral (for example, the chemical heat storage material described in Patent Document 1 above). It is considered easy. The chemical heat storage material of the example in which water (water vapor) is easily immersed to the inside is expected to have high heat generation performance (ability to raise the temperature of water in the above “heat generation performance evaluation”). Moreover, the place mentioned above is considered to be the same also about the chemical heat storage body of a granule other than a pellet.

Therefore, according to the present invention, it is possible to provide a heat storage device and a heat exchange device using a chemical heat storage material having high strength and high thermal conductivity in a processed state.

DESCRIPTION OF SYMBOLS 1; Heat storage apparatus, 2; Heat storage apparatus, 10; Chemical heat storage body, 20; Heat storage body chamber (circulation type chamber), 20a; First port, 20b; Second port, 30; Heating chamber (circulation type chamber), 40 Decarbonation device, 50; drain chamber, 60; heat storage chamber (sealed chamber), 60a; first port, 70; steam tank, 80; heat exchange circuit, 100; heat exchange device, 200; heat exchange device , 300; heat exchange device, D; distribution mechanism, G1; first fluid, G2; second fluid, G3; heat exchanged fluid, P1; inlet port, P2; outlet port, P3; other inlet port, P4 ; Drain port, R1; heating chamber side path, R2; heat storage chamber side path, R3; scavenging medium path, V1 to V6; on-off valve

Claims (6)

1. A chemical heat storage,
   A thermal storage chamber containing the chemical thermal storage;
   With
   The chemical heat storage body is composed of a chemical heat storage material containing a Group 2 element compound, a boron compound, and a silicone polymer,
   The heat storage chamber has a first port through which a fluid can be introduced.
2. The Group 2 element compound is calcium oxide,
   The chemical heat storage material has a calcium atom content of 13 to 59% by mass, a boron atom content of 0.4 to 11.3% by mass, and a silicon atom content of 4.8 to 33.3%. The heat storage device according to claim 1, which is 2 mass%.
3. The Group 2 element compound is magnesium oxide,
   In the chemical heat storage material, the magnesium atom content is 8.3 to 46.5 mass%, the boron atom content is 0.5 to 11.9 mass%, and the silicon atom content is 6. The heat storage device according to claim 1, wherein the amount is 2 to 35.1 mass%.
4. The heat storage device according to any one of claims 1 to 3, wherein the heat storage body chamber is a flow-through chamber having a second port capable of discharging the fluid.
5. The heat storage device according to any one of claims 1 to 3, wherein the heat storage body chamber is a sealed chamber forming a closed space communicating with the first port.
6. A heat exchange device comprising the heat storage device according to any one of claims 1 to 5, wherein the chemical heat storage body is a heat source body.

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