JP6094411B2 - Thermal storage device and thermal storage control method - Google Patents

Description

  The invention disclosed herein relates to a heat storage device that uses a heat storage material that stores a low temperature, and a heat storage control method for controlling the timing of starting heat storage using the heat storage material.

  Patent document 1 discloses the technique which utilizes the aqueous solution containing the thermal storage main agent which cools low temperature as a thermal storage material. This technique discloses adjusting the solidification temperature of the aqueous solution, that is, the melting point, by adding a solid phase material having a similar crystal structure to the heat storage agent in the aqueous solution in order to prevent the supercooled state of the aqueous solution. In this technology, a hydrate of a heat storage main agent grows with an additive as a core.

Japanese Patent No. 5104159

  In the configuration of the prior art, the solidification temperature of the aqueous solution can be adjusted, but the timing for starting the heat storage cannot be controlled. When the supercooling is suppressed, the temperature drop is temporarily suppressed at the solidification temperature. For this reason, in the use etc. of an air conditioner, the fall of blowing temperature is suppressed and the request | requirement of rapid cooling may not be satisfied.

  In order to deal with such a problem, it is possible to adjust the concentration of the heat storage main agent in the aqueous solution so as to lower the solidification temperature. However, it may become impossible to use a concentration having a large heat storage amount such as a harmonic concentration, and it has been difficult to achieve both a solidification temperature and a heat storage amount.

  In the above-mentioned viewpoints or other viewpoints not mentioned, further improvements are required for the heat storage device and the heat storage control method.

  One of the objects of the invention is to provide an improved heat storage device and a heat storage control method.

  One of the objects of the invention is to provide a heat storage device and a heat storage control method capable of controlling the timing for starting heat storage.

  Another object of the invention is to provide a heat storage device and a heat storage control method capable of controlling the solidification temperature of an aqueous solution without relying only on the concentration adjustment of the heat storage main agent.

  Another object of the invention is to allow control of the start time of solidification of an aqueous solution in a supercooled state, thereby allowing supercooling of the aqueous solution and making the low temperature before heat storage available for use such as rapid cooling. And it is providing the thermal storage apparatus which can start thermal storage at the arbitrary time according to a use, and the thermal storage control method.

  The invention disclosed herein employs the following technical means to achieve the above object. Note that the reference numerals in parentheses described in the claims and in this section indicate a corresponding relationship with specific means described in the embodiments described later as one aspect, and limit the technical scope of the invention. Not what you want.

One of the inventions is that in the heat storage device (1) for storing heat by generating the hydrate (34) from the aqueous solution (32) containing the heat storage main agent, the aqueous solution is supercooled below the solidification temperature, and from water. A controller (4) that generates a hydrate from an aqueous solution and initiates heat storage by generating a phase change to ice, a phase change from a solution to a hydrate, and / or a phase change accompanied by a change in hydration number. ) , The control unit (4) includes a phase change generation unit (41) that generates a phase change, and the phase change generation unit (41) includes a liquid phase for generating a phase change in the aqueous solution. comprising adding unit for adding the additive (43), characterized in Rukoto.

  According to this configuration, since the aqueous solution is supercooled, the low temperature can be used before heat storage is started. Furthermore, generation of a hydrate is started by generating a phase change in a state where the aqueous solution is supercooled, and heat storage is started. Therefore, it is possible to control the time when heat storage is started after the aqueous solution is in a supercooled state.

One of the inventions is that in the heat storage device (1) for storing heat by generating the hydrate (34) from the aqueous solution (32) containing the heat storage main agent, the aqueous solution is supercooled below the solidification temperature, and from water. A controller (4) that generates a hydrate from an aqueous solution and initiates heat storage by generating a phase change to ice, a phase change from a solution to a hydrate, and / or a phase change accompanied by a change in hydration number. ), The control unit (4) includes a phase change generation unit (41) that generates a phase change, and the phase change generation unit (41) includes a water mass for generating a phase change in the aqueous solution or An addition unit (43) for adding an ice block, and an ultrasonic supply unit (44) for generating a phase change from water to ice by applying ultrasonic waves to at least the water block or the water block generated by melting the ice block. It is characterized by providing.
One of the inventions is a heat storage method (1) for storing heat by generating a hydrate (34) from an aqueous solution (32) containing a heat storage main agent, and a supercooling step for supercooling the aqueous solution below the solidification temperature, By generating a phase change from water to ice, a solution to a hydrate, and / or a phase change with a change in hydration number in a supercooled state below the freezing temperature, to generate a hydrate, have a phase change step of starting the thermal storage, phase change step, in an aqueous solution, characterized in that it comprises the addition step of adding an additive liquid phase to generate a phase change And
One of the inventions is a heat storage control method (1) for storing heat by generating a hydrate (34) from an aqueous solution (32) of a heat storage main agent. By generating a phase change from water to ice, a solution to a hydrate, and / or a phase change with a change in hydration number in a supercooled state below the freezing temperature, A phase change step for generating a hydrate and initiating heat storage, the phase change step comprising adding an aqueous phase or ice block for generating a phase change in the aqueous solution (43), and at least And an ultrasonic supply step of generating a phase change from water to ice by applying ultrasonic waves to the water mass generated by melting the water mass or ice mass.

  According to this method, since the aqueous solution is supercooled, the low temperature can be used before heat storage is started. Furthermore, generation of a hydrate is started by generating a phase change in a state where the aqueous solution is supercooled, and heat storage is started. Therefore, it is possible to control the time when heat storage is started after the aqueous solution is in a supercooled state.

It is a block diagram of the thermal storage apparatus which concerns on 1st Embodiment of invention. It is the transition diagram which showed the state change in the aqueous solution of 1st Embodiment. It is the transition diagram which showed the state change in the aqueous solution of 2nd Embodiment of invention. It is a table | surface which contrasts an Example and a comparative example.

  Hereinafter, a plurality of embodiments for carrying out the invention will be described with reference to the drawings. In each embodiment, portions corresponding to the matters described in the preceding embodiment may be denoted by the same reference numerals and redundant description may be omitted. In each embodiment, when only a part of the configuration is described, the other configurations described above can be applied to other portions of the configuration. Further, in the following embodiments, the correspondence corresponding to the matters corresponding to the matters described in the preceding embodiments is indicated by adding reference numerals that differ only by one hundred or more, and redundant description may be omitted. .

(First embodiment)
In FIG. 1, the heat storage device 1 includes a refrigeration cycle 2, a heat storage device 3, and a control unit 4. The heat storage device 1 provides, for example, a device that cools use air in an air conditioner. For example, even after the refrigeration cycle 2 stops, the heat storage device 1 cools the use air with the low temperature stored in the heat storage device 3. In this embodiment, since the low temperature is stored in the heat accumulator 3, the term heat storage can be replaced with cold storage.

  The refrigeration cycle 2 is a heat source machine and supplies a low temperature to be stored in the heat accumulator 3. The refrigeration cycle 2 includes an evaporator 21, a compressor 22, a radiator 23, and a decompressor 24. The evaporator 21 is provided on the suction side of the compressor 22 and supplies a low temperature as the refrigerant evaporates inside. The evaporator 21 is, for example, an air cooler in an air conditioner. The compressor 22 sucks and compresses the refrigerant evaporated in the evaporator 21, and discharges the high-pressure refrigerant. The radiator 23 receives the high-pressure refrigerant supplied from the compressor 22 and cools the high-pressure refrigerant. The decompressor 24 decompresses the high-pressure refrigerant cooled in the radiator 23 and supplies the low-pressure refrigerant to the evaporator 21. The refrigeration cycle 2 can intermittently generate a low temperature in the evaporator 21 by switching the compressor 22 to an operating state or a stopped state, for example.

  The heat accumulator 3 has a container 31 that is thermally coupled to the evaporator 21. The container 31 can be provided in mechanical contact with the evaporator 21. The container 31 contains an aqueous solution 32.

  The aqueous solution 32 is an aqueous solution containing a heat storage main agent. The aqueous solution 32 is prepared by dissolving a heat storage main agent in water. The aqueous solution 32 can additionally contain an additive such as a rust inhibitor. The aqueous solution 32 is adjusted to a concentration in the vicinity of a concentration having a large amount of heat storage, such as a harmonic concentration. The aqueous solution 32 generates a hydrate of the heat storage agent and water at a solidification temperature, that is, below the melting point. The solidification temperature of the aqueous solution 32 is a solidification temperature of water, that is, a temperature exceeding 0 ° C. under atmospheric pressure.

  The solidification temperature of the aqueous solution 32 is higher than the low temperature that the evaporator 21 can provide. When used for air conditioning, the temperature of the evaporator 21 is slightly higher than 0 ° C. under atmospheric pressure, for example, about 3 ° C., in order to suppress blockage of the air passage due to frost growth. The solidification temperature of the aqueous solution 32 is around 10 ° C. Therefore, the aqueous solution 32 may be supercooled by the refrigeration cycle 2. However, the supercooled state of the aqueous solution 32 does not fall below the solidification temperature of water. Therefore, the supercooled state of the aqueous solution 32 is provided above the solidification temperature of water.

  The main heat storage agent is a quaternary alkyl ammonium salt. The aqueous solution 32 of a quaternary alkyl ammonium salt forms a quaternary alkyl ammonium salt hydrate at a solidification temperature or lower. The heat storage main agent is tetrabutylammonium bromide or tetrabutylammonium fluoride.

  The control unit 4 controls the time when heat storage is started, that is, the time when heat storage is started. The control unit 4 includes a phase change generation unit 41 and a control device 42.

  The phase change generation unit 41 generates a phase change for the hydrate 34 to start growing in the aqueous solution 32 in a supercooled state. A phase change is a phase change with a phase change from water to ice, a phase change from an aqueous solution to a hydrate, and / or a hydrate number change of the hydrate. In the figure, as an example of the phase change, an ice nucleus 33 provided by a phase change from water to ice is shown. In the aqueous solution 32 in a supercooled state, the hydrate 34 starts to grow with the generation of ice nuclei 33 as a trigger. The phase change generation unit 41 gives an external stimulus to the aqueous solution 32 in order to generate a phase change. The external stimulus is given to the whole or a part of the aqueous solution 32. The external stimulus is provided by vibration, sound, ultrasonic wave, light, electromagnetic wave, electric field, magnetic field, discharge, partial temperature change, partial pressure change and the like.

  The control device 42 controls the phase change generator 41. The control device 42 activates the phase change generation unit 41 at a time when heat storage should be started, and generates a phase change in the aqueous solution 32. The control device 42 waits until the aqueous solution 32 is subcooled below the solidification temperature, and then causes the phase change generator 41 to generate a phase change in a state where the aqueous solution 32 is subcooled below the solidification temperature. Thereby, a hydrate grows in the aqueous solution 32 in a supercooled state starting from the phase change. Therefore, the progress of supercooling can be suppressed. Moreover, heat storage is started.

  The control device 42 is an electronic control device. The control device has at least one arithmetic processing unit (CPU) and at least one memory device (MMR) as a storage medium for storing programs and data. The control device is provided by a microcomputer including a computer-readable storage medium. The storage medium stores a computer-readable program non-temporarily. The storage medium can be provided by a semiconductor memory or a magnetic disk. The controller can be provided by a computer or a set of computer resources linked by a data communication device. The program is executed by the control device to cause the control device to function as the device described in this specification and to cause the control device to perform the method described in this specification. The control device provides various elements. At least some of those elements can be referred to as a means for performing functions, and in another aspect, at least some of those elements can be referred to as constituent blocks or modules.

  In one example, the phase change generator 41 is configured as a means for generating a phase change from water to ice in the aqueous solution 32. The phase change generation unit 41 includes a water mass addition unit 43 and an ultrasonic wave supply unit 44.

  The water mass adding unit 43 adds a liquid phase additive for generating a phase change that starts the growth of the hydrate 34 into the aqueous solution 32. The water mass adding unit 43 adds a water mass that easily causes a phase change from water to ice due to an external stimulus in the aqueous solution 32. The water mass adding unit 43 supplies the water mass only to a part of the aqueous solution 32. The water mass adding unit 43 can also be referred to as a water droplet adding unit that supplies small water droplets. The water mass addition unit 43 can also be referred to as a supply unit that supplies water mass into the aqueous solution 32. It can be said that the water mass adding unit 43 is adding water as a liquid phase additive to the aqueous solution 32.

  The water mass adding unit 43 supplies the water mass generated by melting the ice mass in the aqueous solution 32 by supplying the ice mass in the aqueous solution 32. Therefore, the water mass adding unit 43 can also be called the ice mass adding unit 43. The ice block supplied by the ice block adding unit 43 is melted in the aqueous solution 32 in a supercooled state but higher than the solidification temperature of water, and provides a water block around the ice core.

  The ultrasonic supply unit 44 is an example of an external stimulus supply unit that applies an external stimulus to the aqueous solution 32. The ultrasonic supply unit 44 irradiates the water mass supplied into the aqueous solution 32 with ultrasonic waves. Ultrasound generates local high pressure and low pressure portions in the aqueous solution 32 and water mass. As a result, a phase change from water to ice occurs in the water mass. The ice block supplied by the water block adding unit 43 contributes to maintaining the temperature of the water block in the vicinity of the solidification temperature of water. For this reason, the phase change from water to ice is promoted by supplying the ice block. Starting from the phase change from water to ice, the growth of the hydrate 34 is started in the aqueous solution 32. It can also be seen that the hydrate 34 grows in the aqueous solution 32 with the fine ice nuclei 33 generated by the phase change from water to ice as nuclei. As a result, the progress of supercooling is suppressed and heat storage is started.

  FIG. 2 shows the state transition of the aqueous solution 32. First, as illustrated in the state (0), the ice block 35 is supplied into the aqueous solution 32 by the water block adding unit 43. The ice block 35 is gradually melted in a supercooled state at a temperature lower than the solidification temperature of the aqueous solution 32 but higher than the solidification temperature of water. Eventually, as shown in state (1), a water mass 36 is formed around the reduced ice mass 35.

  Next, as illustrated in the state (2), at least the water mass 36 is irradiated with ultrasonic waves by the ultrasonic wave supply unit 44. The ultrasonic waves generate a high pressure portion and a low pressure portion in the water mass 36. The temperature of the water mass 36 is relatively low because the water mass 36 is caused by the ice mass 35. For this reason, a phase change from water to ice occurs in the water mass 36 due to pressure fluctuations caused by the ultrasonic waves. Due to this phase change, small ice nuclei 33 are generated. This phase change initiates hydrate formation of the aqueous solution 32 in a supercooled state. As a result, as shown in the state (3), hydrates grow rapidly with the ice nucleus 33 as the nucleus. Thereby, heat storage is started.

  Accordingly, in this embodiment, after allowing the aqueous solution 32 to be supercooled, a step of causing a phase change from water to ice in the aqueous solution 32 is performed. As a result, the aqueous solution 32 in a supercooled state rapidly forms a hydrate and starts storing heat. The step of generating the phase change is performed by supplying a water mass 36 into the aqueous solution 32 and applying an external stimulus to the water mass 36. The supply of the water mass 36 is performed by supplying the ice mass 35 into the aqueous solution 32. External stimulation is given by ultrasound. As a result, the heat storage start time can be controlled. In addition, since the supercooling of the aqueous solution 32 is allowed before the heat storage is started, the heat storage device 3 can be lowered. Thereby, for example, rapid cooling in air conditioning becomes possible.

  When the refrigeration cycle 2 is activated and starts operation, the control device 42 controls the phase change generator 41 so as to allow the aqueous solution 32 to be supercooled. That is, the control device 42 controls the phase change generation unit 41 so that the phase change generation unit 41 does not generate a phase change in the aqueous solution 32 so that the aqueous solution 32 is supercooled. This provides a supercooling stage in which the aqueous solution 32 is supercooled below the solidification temperature.

  Eventually, when the aqueous solution 32 is supercooled and a predetermined effect is obtained after the refrigeration cycle 2 is started, the control device 42 causes the phase change generator 41 to generate a phase change in the aqueous solution 32. The generator 41 is controlled. That is, when it is time to start heat storage, the control device 42 controls the phase change generator 41 so that the phase change generator 41 generates a phase change in the aqueous solution 32. That is, by generating a phase change, a phase change stage is provided in which a hydrate 34 is generated from the aqueous solution 32 and heat storage is initiated.

  Specifically, the ice block 35 is supplied into the aqueous solution 32 by the water block adding unit 43. That is, the phase change step includes an addition step of adding liquid phase additives 35 and 36 for generating a phase change to the aqueous solution 32. The phase change stage includes an external stimulus stage that generates a phase change by applying an external stimulus to the aqueous solution 32. Here, ultrasonic waves are supplied by the ultrasonic wave supply unit 44. Therefore, the phase change step can include an ultrasonic supply step of generating a phase change from water to ice by applying ultrasonic waves to the water mass generated by melting the water mass or ice mass at least. As a result, a phase change from water to ice occurs in the aqueous solution 32. Furthermore, due to the phase change, a hydrate 34 grows in the aqueous solution 32, the supercooling is released, and heat storage is started.

  According to the embodiment described above, the aqueous solution of the heat storage main agent that produces a hydrate is used as the heat storage material. An apparatus and a method capable of controlling the heat storage start temperature of the heat storage material are provided. In this apparatus and method, when the aqueous solution containing the heat storage agent is at a temperature below the solidification temperature, the phase change from water to ice, the phase change from solution to hydrate, in the aqueous solution containing the heat storage agent, Alternatively, it is possible to release the supercooling of the aqueous solution by generating a phase change accompanied by a hydration number change, and to control the start time of heat storage. Specifically, a quaternary alkyl ammonium salt hydrate is generated and used for heat storage. The phase change may occur in the whole aqueous solution, a part of the aqueous solution, or an additive added to the aqueous solution. The phase change is generated by an external stimulus such as ultrasonic wave, light, electric field, and local temperature control at a temperature lower than the solidification temperature of the aqueous solution. More specifically, at a temperature not higher than the solidification temperature of the aqueous solution, water or ice is added to the aqueous solution, and irradiation with ultrasonic waves is performed to release the supercooling at 0 ° C. or higher, which is the solidification temperature of water. The start time of heat storage can be controlled.

(Second Embodiment)
This embodiment is a modification based on the preceding embodiment. In the above embodiment, the water mass adding unit 43 supplies the ice mass 35 into the aqueous solution 32. Instead, the water mass adding unit 43 may be configured to supply a water mass not caused by ice into the aqueous solution 32.

  As illustrated in the state (1) of FIG. 3, the water mass adding unit 43 supplies the water mass 236 into the aqueous solution 32. As illustrated in the state (2), at least the water mass 236 is irradiated with ultrasonic waves by the ultrasonic wave supply unit 44. The ultrasonic waves generate a high pressure portion and a low pressure portion in the water mass 236. Due to pressure fluctuations caused by the ultrasonic waves, a phase change from water to ice occurs in the water mass 236. Due to this phase change, small ice nuclei 33 are generated. This phase change initiates hydrate formation of the aqueous solution 32 in a supercooled state. As a result, as shown in the state (3), hydrates grow rapidly with the ice nucleus 33 as the nucleus. Thereby, heat storage is started.

Example 1
First, 40.8 wt% of tetrabutylammonium bromide (TBAB) aqueous solution was prepared. This aqueous solution has a melting point, that is, a solidification temperature of 11.6 ° C. The aqueous solution has a latent heat of 190 J / g. Only 90 ml of this aqueous solution was placed in a container and cooled. Further, in the cooling process, when the aqueous solution was supercooled to + 7.0 ° C., ice blocks were supplied and ultrasonic waves were applied. Here, about 10 mg of ice block was supplied. The ultrasonic oscillation frequency was 42 kHz, and the output was 70 W.

  FIG. 4 shows the result of repeating the experiment of Example 1 three times. The circles indicate that hydrate growth has started and heat storage has begun in response to the supply of ice blocks and the irradiation of ultrasonic waves. From this, it can be seen that when ice blocks are added and ultrasonic irradiation is performed, the supercooled state of the TBAB aqueous solution is released at 0 ° C. or higher, and heat storage can be started at that time.

  Further, FIG. 4 shows the results of Comparative Example 1, Comparative Example 2, and Comparative Example 3. In the figure, the X mark indicates that no hydrate growth was observed, the supercooled state continued, and heat storage was not started. Comparative Example 1 is a case where about 10 mg of ice block is supplied and no ultrasonic wave is irradiated. In Comparative Example 1, the heat storage was not started and the supercooled state was maintained even after 5 minutes. Comparative Example 2 is a case where alumina fine particles prepared to 50 nm or less are added and irradiated with ultrasonic waves. Comparative Example 3 is a case where only the irradiation of ultrasonic waves was performed without adding anything. Also in these comparative examples, heat storage was not started in the supercooled state.

  From the comparison between Example 1 and Comparative Example 1-3, it can be seen that the phase change in the aqueous solution 32 plays an important role in the start of hydrate growth, that is, the start of heat storage.

(Example 2)
First, 8.0 wt% of tetrabutylammonium fluoride (TBAF) aqueous solution was prepared. This aqueous solution has a melting point, that is, a solidification temperature of 10.9 ° C. The aqueous solution has a latent heat of 23 J / g. Only 90 ml of this aqueous solution was placed in a container and cooled. Furthermore, in the cooling process, when the aqueous solution was supercooled to + 8.0 ° C., ice blocks were supplied and ultrasonic waves were applied. Here, about 10 mg of ice block was supplied. The ultrasonic oscillation frequency was 42 kHz, and the output was 70 W.

  FIG. 4 shows the result of repeating the experiment of Example 2 three times. It can be seen that when an ice block is added and ultrasonic irradiation is performed, the supercooled state of the TBAF aqueous solution is released at 0 ° C. or higher, and heat storage can be started at that time.

  Further, FIG. 4 shows the results of Comparative Example 4 and Comparative Example 5. Comparative Example 4 is a case where about 10 mg of ice mass is supplied and no ultrasonic wave is irradiated. Comparative Example 5 is a case where only ultrasonic irradiation was performed without adding anything. Also in these comparative examples, heat storage was not started in the supercooled state.

  From the comparison between Example 2 and Comparative Example 4-5, it can be seen that the phase change in the aqueous solution 32 plays an important role in the start of hydrate growth, that is, the start of heat storage.

(Other embodiments)
In the above embodiment, ultrasonic waves are used as an external stimulus for generating a phase change from water to ice. Alternatively, a phase change from water to ice may be generated using a means for generating a partial pressure change, for example, partial pressurization of an aqueous solution by a mechanical movable part, or reduced pressure. Further, a partial temperature change may be generated in the aqueous solution. Moreover, you may give an external stimulus combining the several means disclosed by the said embodiment.

  The present invention is not limited to the above-described embodiment, and can be implemented with various modifications. The invention is not limited to the combinations shown in the embodiments, and can be implemented in various combinations. Each embodiment may have additional parts. The part of each embodiment may be omitted. The parts of the embodiments can be replaced or combined with the parts of the other embodiments. The structure, operation, and effect of the above embodiment are merely examples. The technical scope of the invention is not limited to the scope of these descriptions. Some technical scope of the invention is indicated by the description of the scope of claims, and should be understood to include all modifications within the meaning and scope equivalent to the description of the scope of claims.

1 heat storage device,
2 refrigeration cycle,
3 heat storage,
31 containers, 32 aqueous solutions, 33 ice nuclei, 34 hydrates,
35 ice blocks, 36 water blocks,
4 control unit,
41 phase change generator, 42 controller,
43 Water (ice) lump addition unit, 44 Ultrasonic supply unit.

Claims (13)

In the heat storage device (1) for storing heat by generating the hydrate (34) from the aqueous solution (32) containing the heat storage main agent,
By causing a phase change from water to ice, a phase change from a solution to a hydrate, and / or a phase change accompanied by a hydration number change in a state where the aqueous solution is supercooled below the solidification temperature, A controller (4) for generating a hydrate from the aqueous solution and starting heat storage ;
The control unit (4)
A phase change generator (41) for generating the phase change;
The phase change generator (41)
In the aqueous solution, the heat storage device according to claim Rukoto an addition unit (43) for adding an additive liquid phase for generating the phase change. The additive part (43)
The heat storage device according to claim 1 , wherein a water mass is supplied as the additive. The additive part (43)
The heat storage device according to claim 2 , wherein an ice block is supplied as the additive, and a water block generated by melting of the ice block is supplied. In the heat storage device (1) for storing heat by generating the hydrate (34) from the aqueous solution (32) containing the heat storage main agent,
By causing a phase change from water to ice, a phase change from a solution to a hydrate, and / or a phase change accompanied by a hydration number change in a state where the aqueous solution is supercooled below the solidification temperature, A controller (4) for generating a hydrate from the aqueous solution and starting heat storage ;
The control unit (4)
A phase change generator (41) for generating the phase change;
The phase change generator (41)
An addition unit (43) for adding a water mass or an ice mass for generating the phase change in the aqueous solution;
By applying ultrasonic to the water mass generated by at least said water mass or the ice mass melts, ultrasound supply section for generating a phase change to ice water (44) and heat storage, characterized in Rukoto provided with apparatus. The control unit (4)
5. The control device according to claim 1 , further comprising: a control device that generates the phase change by the phase change generation unit in a state where the aqueous solution is supercooled to a solidification temperature or lower. The heat storage device described. The heat storage device according to any one of claims 1 to 5, wherein the heat storage main agent is a quaternary alkyl ammonium salt. The heat storage device according to claim 6 , wherein the heat storage main agent is tetrabutylammonium bromide or tetrabutylammonium fluoride. In the heat storage control method (1) for storing heat by generating the hydrate (34) from the aqueous solution (32) of the heat storage main agent,
A supercooling step of supercooling the aqueous solution below the solidification temperature;
By causing a phase change from water to ice, a phase change from a solution to a hydrate, and / or a phase change accompanied by a hydration number change in a state where the aqueous solution is supercooled below the solidification temperature, to produce a hydrate from the aqueous solution, it has a phase change step of starting the thermal storage,
The phase change step includes an addition step of adding a liquid phase additive for generating the phase change to the aqueous solution . The heat storage control method according to claim 8 , wherein in the addition step, a water mass is supplied as the additive. The heat storage control method according to claim 9 , wherein in the addition step, an ice block is supplied as the additive, and a water block generated by melting the ice block is supplied. In the heat storage control method (1) for storing heat by generating the hydrate (34) from the aqueous solution (32) of the heat storage main agent,
A supercooling step of supercooling the aqueous solution below the solidification temperature;
By causing a phase change from water to ice, a phase change from a solution to a hydrate, and / or a phase change accompanied by a hydration number change in a state where the aqueous solution is supercooled below the solidification temperature, to produce a hydrate from the aqueous solution, it has a phase change step of starting the thermal storage,
The phase change step includes:
An addition step (43) of adding a water mass or an ice mass for generating the phase change in the aqueous solution;
An ultrasonic supply step of generating a phase change from water to ice by applying ultrasonic waves to at least the water mass or the water mass generated by melting the ice mass, and a heat storage control method. The heat storage control method according to any one of claims 8 to 11, wherein the heat storage main agent is a quaternary alkyl ammonium salt. The heat storage control method according to claim 12 , wherein the heat storage main agent is tetrabutylammonium bromide or tetrabutylammonium fluoride.

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