WO2016075941A1 - Super-cooling release material and method for producing same - Google Patents

Abstract

A supercooling release material for releasing the supercooled state of a cold-storage material including one or more types of halogenated alkyl ammonium aqueous solution for producing a hydrate by cooling to the hydrate-formation temperature or below, the supercooling release material including an alkyl ammonium ion included in the cold-storage material, and a metal halide ion having as a constituent element a halogen element included in the cold storage material. Using a supercooling release material provided with such a configuration makes it possible to reliably release the supercooled state of a cold-storage material.

Description

Subcool release substance and method for producing the same Cross-reference of related applications

This application is filed on Japanese Patent Application No. 2014-231287 filed on November 14, 2014 and Japanese Patent Application No. 2015-105672 filed on May 25, 2015 and on October 23, 2015. Japanese Patent Application No. 2015-209259, which is incorporated herein by reference.

This disclosure relates to a supercooling release substance that releases supercooling of a regenerator material and a manufacturing method thereof.

Inclusion hydrates such as TBAB hydrate produced by cooling an aqueous solution of TBAB (tetrabutylammonium bromide) have a large heat density and are known to be used as a cold storage material. Such clathrate hydrate can be used alone as a heat storage material, or one kind of clathrate hydrate can be used as a heat storage material by mixing multiple types of clathrate hydrate (patent) Reference 1). However, an aqueous solution that generates clathrate hydrate tends to be in a supercooled state in which no hydrate is generated even when cooled to below the hydrate formation temperature, and is difficult to use stably as a cold storage material.

In contrast, a technique for releasing the supercooled state by applying an electric field to the supercooled TBAB aqueous solution has been reported (see Non-Patent Document 1). In this method, the supercooling release material is generated in the part where the electric field is applied in the TBAB aqueous solution, and the supercooling release material assists the generation of crystal nuclei, and the supercooling is released. It is assumed that TBAB hydrate grows through crystal growth.

However, in the method described in Non-Patent Document 1, the details of the supercooling release substance generated when an electric field is applied to the TBAB aqueous solution are unknown, and what kind of substance causes the supercooling of the TBAB aqueous solution to be released. There are no reported cases.

Japanese Patent Laid-Open No. 2007-161893

This disclosure is intended to provide a supercooling release material that can release supercooling of a regenerator material and a method for manufacturing the same.

1st aspect of this indication WHEREIN: The supercooling cancellation | release which cancels | releases the supercooling state of the cool storage material containing the 1 or more types of alkylammonium halide aqueous solution which produces | generates a hydrate by cooling below hydrate formation temperature The substance includes alkylammonium ions contained in the regenerator material and metal halide ions having a halogen element contained in the regenerator material as a constituent element.

It is possible to reliably release the supercooling state of the regenerator material by using the supercooling release material having such a configuration. By specifying the structure of the supercooling release substance, the supercooling release substance can be generated not only by voltage application but also by organic synthesis.

2nd aspect of this indication WHEREIN: The supercooling cancellation | release which cancels | releases the supercooling state of the cool storage material containing 1 or more types of alkylammonium halide aqueous solution which produces | generates a hydrate by cooling below hydrate formation temperature The method for producing a substance comprises applying a voltage to the alkyl ammonium halide aqueous solution. The supercooling release substance includes alkylammonium ions contained in the cold storage material and metal halide ions having a halogen element contained in the cold storage material as a constituent element.

In the method for producing a supercooling release material having such a configuration, the supercooled state of the regenerator material can be reliably released. By specifying the structure of the supercooling release substance, the supercooling release substance can be generated not only by voltage application but also by organic synthesis.

In the third aspect of the present disclosure, a supercooling release material that releases a supercooled state of a cold storage material containing one or more aqueous alkylammonium halide solutions that form a hydrate by cooling to a hydrate formation temperature or lower The manufacturing method includes adding at least any single metal of Ag, Cu, Fe, or Zn to the cold storage material. The supercooling release substance includes alkylammonium ions contained in the cold storage material and metal halide ions having a halogen element contained in the cold storage material as a constituent element.

In the method for producing a supercooling release material having such a configuration, the supercooled state of the regenerator material can be reliably released. By specifying the structure of the supercooling release substance, the supercooling release substance can be generated not only by voltage application but also by organic synthesis.

The above and other objects, features, and advantages of the present disclosure will become more apparent from the following detailed description with reference to the accompanying drawings. The drawing
FIG. 1 is a conceptual diagram showing the overall configuration of the cold storage device of the first embodiment, FIG. 2 is a conceptual diagram showing the configuration of the electrodes of the voltage application unit, FIG. 3 is a graph showing the relationship between the concentration of an aqueous TBAB solution and the hydrate formation temperature. FIG. 4 is a flowchart showing the supercooling release control process. FIG. 5 is a diagram showing a mass spectrum that is an analysis result of the supercooled release substance, FIG. 6 is a diagram illustrating a supercooling release rate when the electrode material of the voltage application unit is changed in the second embodiment. FIG. 7 is a diagram showing a mass spectrum which is an analysis result of a supercooling release material generated when a Zn electrode is used, FIG. 8 is a diagram showing a mass spectrum which is an analysis result of a supercooling release substance generated when an Ag electrode is used, FIG. 9 is a conceptual diagram showing the overall configuration of the cold storage device of the third embodiment, FIG. 10 is a diagram showing a supercooling release effect when various additives are added to the TBAB aqueous solution in the third embodiment. FIG. 11 is a diagram showing a supercooling release effect when various additives are added to the TBAB aqueous solution in the sixth embodiment.

(First embodiment)
Hereinafter, a first embodiment of the present disclosure will be described with reference to FIGS. 1 to 5.

As shown in FIG. 1, the regenerator 1 of this embodiment includes a supercooling release substance generation unit 10, a regenerator storage unit 15, a cold heat supply unit 22, a control unit 28, and the like.

In the supercooling release substance generation unit 10, a regenerator material is stored. As the cold storage material, an alkylammonium halide aqueous solution that forms a hydrate by cooling to a hydrate formation temperature or lower is used. In this embodiment, a TBAB (tetrabutylammonium bromide) aqueous solution is used as the alkylammonium halide aqueous solution. In this embodiment, a TBAB aqueous solution adjusted to 20 wt% is used as the cold storage material.

The TBAB aqueous solution can be suitably used as a cold storage material that cools heat by generating TBAB hydrate in the aqueous solution by cooling. The supercooling release substance generation unit 10 is provided to generate a supercooling release substance for releasing supercooling of the TBAB aqueous solution. The supercooling release substance will be described later in detail.

The supercooling release substance generation unit 10 is provided with a voltage application unit 12. The voltage application part 12 is provided in order to apply a voltage to a cool storage material, For example, it can be set as the structure which sends an electric current between a pair of electrodes provided at predetermined intervals. By applying a voltage to the regenerator material by the voltage application unit 12, a subcool release material is generated in the regenerator material of the subcool release material generation unit 10. The voltage application unit 12 of this embodiment includes an electrode interval adjustment mechanism.

As shown in FIG. 2, the voltage application unit 12 includes a pair of electrodes 12a and 12b, a fixing member 12c, and a motor 12d. The pair of electrodes 12a and 12b is composed of a fixed electrode 12a and a movable electrode 12b, and these tips are provided so that their tips are opposed to each other. A male screw portion is formed on the shaft portion of the movable electrode 12b, and a female screw portion corresponding to the male screw portion of the movable electrode 12b is formed on the fixed member 12c.

In this embodiment, the movable electrode 12b is an electrode connected to the positive side of a DC power source (not shown), and the fixed electrode 12a is an electrode connected to the negative side of the DC power source. Further, a metal is used as an electrode material constituting the electrodes 12a and 12b, and a metal electrode made of Cu is used in this embodiment.

The movable electrode 12b is rotated by operating the motor 12d, and the movable electrode 12b can be moved in a direction toward or away from the fixed electrode 12a. Thereby, the voltage application part 12 can adjust the space | interval of the fixed electrode 12a and the movable electrode 12b. Further, the distance between the fixed electrode 12a and the movable electrode 12b can be detected, for example, by measuring the resistance between the electrodes 12a and 12b.

Referring back to FIG. 1, the cool storage material storage unit 15 stores the cool storage material therein. The cold storage material storage unit 15 communicates with the supercooling release material generation unit 10 via the cold storage material pipe 14, and the cold storage material can flow between the supercooling release material generation unit 10 and the cold storage material storage unit 15. It has become. Moreover, the cool storage material storage part 15 is arrange | positioned isolated from the supercooling cancellation | release substance production | generation part 10, and suppresses the influence of the heat which mutually gives as much as possible.

The cold storage material storage unit 15 is configured to store cold by cooling the cold storage material and generating a hydrate. The cold energy stored in the cold storage material in the cold storage material storage unit 15 can be used for cooling the air conditioner, for example.

The cold storage material storage unit 15 includes a plurality (three in this embodiment) of storage units 15a, 15b, and 15c. Each storage part 15a, 15b, 15c is connected with the supercooling release substance production | generation part 10 via the cool storage material piping 14, respectively.

Each of the storage units 15a, 15b, 15c is provided with temperature sensors 16, 17, 18 for detecting the temperature of the internal cold storage material. Each of the storage units 15a, 15b, and 15c is provided with supercooling detection units 19, 20, and 21 for detecting the occurrence of a supercooling state in the internal regenerator material.

For example, the supercooling detection units 19, 20, and 21 include a light emitting element and a light receiving element, and a configuration for detecting the transmittance of light reaching the light receiving element from the light emitting element, and a structure for detecting scattered light by the light receiving element. can do. When the regenerator material is cooled and the proportion of hydrate increases, the light transmittance decreases. Therefore, if the light transmittance exceeds the reference value at a temperature lower than the hydrate formation temperature, it is in a supercooled state. If the light transmittance is below the reference value, it can be determined that the supercooling state is not established. In addition, when the regenerator material is cooled and the hydrate ratio increases, light from the light-emitting element scatters. Therefore, if the scattered light cannot be detected at a temperature lower than the hydrate formation temperature, it is determined that the supercooled state is reached. If the scattered light can be detected, it can be determined that the supercooling state is not established.

Or, since the viscosity of the regenerator material increases when the regenerator material is cooled and the proportion of hydrate increases, the supercooling detectors 19, 20, and 21 may detect the viscosity of the regenerator material. In this case, if the viscosity of the regenerator material is lower than the reference value at a temperature lower than the hydrate formation temperature, it can be determined that the supercooled state is present, and if the viscosity of the regenerator material exceeds the reference value, the subcoolant is It can be determined that it is not in a state.

Alternatively, when the regenerator material is cooled and hydrates are generated, the amount of heat changes due to the phase change. Therefore, for example, thermocouples may be used as the subcooling detection units 19, 20, and 21 to detect the differential heat. In this case, if the differential heat detected by the supercooling detectors 19, 20, and 21 is below the reference value, it can be determined that the supercooling state is present, and the differential heat detected by the supercooling detectors 19, 20, and 21 is detected. If the value exceeds the reference value, it can be determined that the supercooling state has not occurred.

The cold heat supply unit 22 is configured to supply a low-temperature refrigerant to the first heat exchanger 24 via the refrigerant pipe 23 to cool the cold storage material storage unit 15. The cold heat supply unit 22 is configured as a known refrigeration cycle including, for example, a compressor, a condenser, an expansion valve, and the like, and the first heat exchanger 24 can be an evaporator of the refrigeration cycle. The first heat exchanger 24 is in thermal contact with the cold storage material storage unit 15, and exchanges heat between the low-temperature refrigerant supplied from the cold heat supply unit 22 and the cold storage material storage unit 15, thereby the cold storage material. The regenerator material stored in the storage unit 15 can be cooled. That is, the cold heat supply part 22, the 1st heat exchanger 24, and the refrigerant | coolant piping 23 comprise the "cooling device."

As shown in FIG. 1, the first heat exchanger 24 is disposed on the upper part of the cold storage material storage unit 15. Since the heat storage material that has not solidified in the cold storage material storage unit 15 is considered to gather above the inside of the cold storage material storage unit 15, the heat storage material is efficiently condensed by cooling from the upper part of the cold storage material storage unit 15. Can be made.

The apparatus for supplying cold from the cold supply unit 22 to the first heat exchanger 24 may be performed using the refrigerant pipe 23 described above, or a fluid such as wind having cold from the cold supply unit 22. May be directly introduced into the first heat exchanger 24.

The cold energy stored in the cold storage material of the cold storage material storage unit 15 is supplied to the cold energy utilization unit 25 via a heat medium. The cold heat utilization unit 25 can be an air conditioner, for example, and water can be used as the heat medium, for example. The 2nd heat exchanger 26 is provided in the downward direction of the cool storage material storage part 15 so that it may contact thermally, and the 2nd heat exchanger 26 heat-exchanges between the cool storage material storage part 15 and a heat medium. . The heat medium that has received the cold flows to the cold energy utilization unit 25 through the heat medium pipe 27, whereby the cold energy stored in the cold storage material of the cold storage material storage unit 15 can be supplied to the cold energy utilization unit 25. The cold energy utilization unit 25, the second heat exchanger 26, and the heat medium pipe 27 correspond to the “cold energy utilization device”.

Moreover, since the hydrate crystals of the heat storage material have a higher specific gravity than water, it is considered that the heat storage material gathers below in the cold storage material storage unit 15. For this reason, by providing the 2nd heat exchanger 26 under the cool storage material storage part 15, the cold energy stored in the cool storage material of the cool storage material storage part 15 can be utilized efficiently.

The apparatus for supplying cold from the second heat exchanger 26 to the cold heat utilization unit 25 may be performed using the heat medium pipe 27 described above, or the wind having cold from the second heat exchanger 26 may be used. Such a fluid may be directly introduced into the cold heat utilization unit 25.

The control unit 28 includes a known microcomputer including a CPU, a ROM, a RAM, and the like and its peripheral circuits, and performs various calculations and processes based on an air conditioning control program stored in the ROM. Sensor signals from the temperature sensors 13, 16, 17, 18 and the supercooling detection units 19, 20, 21 are input to the control unit 28, and control signals are sent to the temperature adjustment unit 11, the voltage application unit 12, and the cooling / heating supply unit 22. Is configured to output.

Here, the TBAB aqueous solution used as a cold storage material in this embodiment will be described. As shown in FIG. 3, two types of typical TBAB hydrates, a first hydrate having a hydration degree of about 26 and a second hydrate having a hydration degree of about 38, have been reported. Yes. The hydrate formation temperature varies depending on the type of hydrate and the concentration of the TBAB aqueous solution. In the TBAB aqueous solution adjusted to 20 wt%, both the first hydrate and the second hydrate may be formed, and the hydrate formation temperature is about 8 ° C. in either case. In the TBAB aqueous solution adjusted to 40 wt%, the first hydrate is formed, and the hydrate formation temperature is about 12 ° C.

As described in the above-mentioned section of the prior art, the TBAB aqueous solution has a property that even when cooled to a temperature lower than the hydrate formation temperature, it tends to be in a supercooled state in which TBAB hydrate is not generated. For this reason, in the cool storage device 1 of the present embodiment, the supercooling release substance is generated, and the supercooling release substance is uniformly supplied to the desired portion, thereby suppressing the TBAB aqueous solution from being supercooled. Yes.

In the present embodiment, the supercooling release material generated by the supercooling release material generation unit 10 is supplied in a branched manner to each of the plurality of storage units 15a, 15b, and 15c via the cold storage material pipe 14. It is configured. As a result, the supercooling release material generated in the supercooling release material generation unit 10 is uniformly diffused and supplied to each of the storage units 15 a, 15 b, and 15 c without being biased toward a specific location of the cold storage material storage unit 15. be able to.

Next, the supercooling release control process by the regenerator 1 having the above configuration will be described based on the flowchart of FIG.

As shown in FIG. 4, first, a voltage is applied to the regenerator material of the supercooling release substance generating unit 10 by the voltage applying unit 12 (S10). Thereby, the supercooling release substance is generated inside the supercooling release substance generation unit 10. Then, the supercooling release material is supplied to the cold storage material of the cold storage material storage unit 15 via the cold storage material pipe 14.

Next, the cold storage material storage unit 15 is cooled by supplying a low-temperature refrigerant from the cold heat supply unit 22 to the first heat exchanger 24 (S11). Then, based on the sensor signals from the temperature sensors 16 to 18, it is determined whether or not the cold storage material temperature of the cold storage material storage unit 15 is lower than the hydrate generation temperature (S12).

As a result, when it is determined that the regenerator temperature is not lower than the hydrate formation temperature (S12: NO), the process returns to S11. On the other hand, when it is determined that the temperature of the regenerator material is equal to or lower than the hydrate formation temperature (S12: YES), the regenerator material storage unit 15 stores the regenerator based on the sensor signals from the supercooling detectors 19, 20, and 21. It is determined whether or not the material is in a supercooled state (S13).

As a result, when it is determined that the regenerator material is in a supercooled state (S13: YES), the voltage application unit 12 applies a voltage to the regenerator material of the subcool release material generating unit 10 (S14). Thereby, the supercooling release substance is generated inside the supercooling release substance generation unit 10. Then, the supercooling release material is supplied to the cold storage material of the cold storage material storage unit 15 via the cold storage material pipe 14.

Further, as a result of the determination process of S13, when it is determined that the regenerator material is not in the supercooled state (S13: NO), the supercooling release control process is terminated.

Here, the supercooling cancellation | release substance produced | generated in the supercooling cancellation | release substance production | generation part 10 of this embodiment is demonstrated. In the present embodiment, the supercooling release substance is extracted from the TBAB aqueous solution containing the supercooling release substance generated by the supercooling release substance generation unit 10 by voltage application by the voltage application unit 12 in the following steps.

First, a TBAB aqueous solution containing a supercooling release substance generated by applying a voltage is taken out from the supercooling release substance generating unit 10, and suction filtered using an omnipore membrane filter (manufactured by Merck Millipore, pore size: 0.45 μm). Insoluble material was obtained. The material was dried using a vacuum dryer at 25 ° C. for 12 hours. Here, AVO-200NB manufactured by AS ONE was used as the dryer, and GLD-051 manufactured by ULVAC was used as the vacuum pump.

Next, after the dried material was mixed and stirred with chloroform, it was suction filtered again using an omnipore membrane filter (manufactured by Merck Millipore, pore size: 0.45 μm) to obtain a substance insoluble in chloroform. This material was dried using a vacuum dryer at 25 ° C. for 12 hours to obtain the desired supercooling release material.

The chemical structure of the supercooled release material obtained in the above extraction process was identified by mass spectrometry using matrix-assisted laser desorption / ionization as follows.

As an analyzer, MALDI-TOF MASS (BRUKER DALTONICS, autoflex) was used. Measurement conditions were such that an N ₂ laser (wavelength: 337 nm) was used as the laser light source, the measurement mass range was 20-3000 (m / z), and the number of integrations was 1000 times.

As a result of the analysis, the mass spectrum of the cation shown in the upper part of FIG. 5 and the mass spectrum of the anion shown in the lower part of FIG. 5 were obtained.

From the mass spectrum in the upper part of FIG. 5, it can be seen that the supercooling release substance contains tetrabutylammonium ion (TBA ⁺ ) represented by the general formula (1) as a cation. This tetrabutylammonium ion is derived from TBAB (tetrabutylammonium bromide) which is a cold storage material.

The cation contained in the supercooling release material may be an alkylammonium ion having at least 4 hydrocarbon groups having 1 to 7 carbon atoms. The four hydrocarbon groups may be the same or different. Hydrocarbon groups include methyl (n = 1), ethyl (n = 2), n-propyl (n = 3), iso-propyl (n = 3), n-butyl (n = 4), iso-butyl (N = 4), n-pentyl (n = 5), iso-pentyl (n = 5), n-hexyl (n = 6), iso-hexyl (n = 6), n-heptyl (n = 7) , Iso-heptyl (n = 7).

Further, from the mass spectrum in the lower part of FIG. 5, it is found that the supercooling release material contains at least a copper bromide ion represented by the general formula (2) as an anion.

The anions contained in the supercooling release substance are [Br ⁻ , Cu ⁺ ], [Br ⁻ , Cu ²⁺ ].
Or the copper bromide ion containing at least any combination of [Br ^{< -} >, Cu ^{< +} >, Cu ^{< 2+} >] should just be included. Cu contained in these copper bromide ions is derived from the Cu electrode, and Br contained in the copper bromide ions is derived from TBAB (tetrabutylammonium bromide) which is a cold storage material. Hereinafter, anions made of combinations of these metal ions and halide ions are collectively referred to as metal halide ions. However, the valence and number of ions constituting them and the valence of the whole anion are not limited.

From the above, it can be specified that the supercooling release substance contains the substance represented by the general formula (3).

In the present embodiment described above, a voltage is applied to the cold storage material of the supercooling release substance generation unit 10 by the voltage application unit 12. Thereby, the supercooling release material generating unit 10 can generate the supercooling release material as necessary, and the cold storage material storage unit 15 communicating with the supercooling release material generating unit 10 hydrates the cold storage material. When cooled below the product generation temperature, it is possible to effectively suppress overcooling of the regenerator material.

In the present embodiment, the chemical structure of a substance that is one of a plurality of constituent components of the supercooled release substance that is generated by applying a voltage to the TBAB aqueous solution can be specified. As a result, it was possible to clarify what kind of substance can cancel the supercooling of the TBAB aqueous solution.

Moreover, in this embodiment, the 1st heat exchanger 24 for cooling the heat storage material of the cool storage material storage part 15 is arrange | positioned in the upper part of the cool storage material storage part 15. FIG. Thereby, the heat storage material gathered upward without solidifying in the cold storage material storage part 15 can be cooled from the upper part of the cold storage material storage part 15, and can be condensed efficiently.

Moreover, in this embodiment, the 2nd heat exchanger 26 for receiving the cold of the heat storage material of the cool storage material storage part 15 is arrange | positioned in the lower part of the cool storage material storage part 15. FIG. Thereby, the cold energy of the heat storage material solidified in the cold storage material storage unit 15 and gathered downward can be efficiently received from the lower part of the cold storage material storage unit 15.

(Second Embodiment)
Next, a second embodiment of the present disclosure will be described. In the second embodiment, description of the same parts as in the first embodiment will be omitted, and only different parts will be described.

In the second embodiment, a plurality of types of materials are used as the electrode material of the voltage application unit 12, and the supercooling release processing of the TBAB aqueous solution is repeatedly performed on each electrode material. The supercooling release processing was performed according to the procedure described with reference to the flowchart of FIG. 4 in the first embodiment. And the frequency | count that the TBAB aqueous solution solidified by the subcooling cancellation | release process for every electrode material was measured, and the subcooling cancellation | release rate for every electrode material was computed. In the second embodiment, Cu, Zn, Ag, and C are used as the electrode material of the voltage application unit 12. Moreover, the cooling temperature of a cool storage material is 5 degreeC.

As shown in FIG. 6, the supercooling release rate when the Cu electrode is used is 97%, the supercooling release rate when the Zn electrode is used is 100%, and the supercooling when the Ag electrode is used. The release rate was 100%. That is, when any metal electrode of Cu, Zn, or Ag was used, a high supercooling release effect was obtained. On the other hand, when the C electrode, which is a non-metallic electrode, was used, the overcooling release rate was 20%, and the overcooling release effect was low.

The analysis result of the substance generated in the TBAB aqueous solution by the voltage application by the Cu electrode has been described in the first embodiment with reference to FIG. 5. Therefore, in the second embodiment, the TBAB aqueous solution is applied by the voltage application by the Zn electrode and the Ag electrode. The analysis result of the substance produced in the inside will be described. Mass spectrometry is performed in the same procedure as in the first embodiment.

First, the result of analyzing a substance generated in a TBAB aqueous solution by applying voltage with a Zn electrode by mass spectrometry will be described with reference to FIG.

From the mass spectrum in the upper part of FIG. 7, it is understood that the supercooling release substance contains tetrabutylammonium ion (TBA ⁺ ) represented by the above general formula (1) as a cation. Moreover, it can be seen from the mass spectrum in the lower part of FIG. 7 that the supercooling release material contains zinc bromide ions represented by [Zn ²⁺ , Br ⁻ , Br ⁻ , Br ⁻ ] as anions.
From these combinations, it can be seen that the supercooled release material contains a Zn complex.

Next, the result of analyzing the substance generated in the TBAB aqueous solution by applying voltage with the Ag electrode by mass spectrometry will be described with reference to FIG.

From the mass spectrum in the upper part of FIG. 8, the supercooled release substance includes tetrabutylammonium ion (TBA ⁺ ) represented by the above general formula (1) as a cation and Ag ⁺ (or [Ag ⁺ , Br ⁻ ,. .., Ag ⁺ ]) is included. Further, it can be seen from the mass spectrum in the lower part of FIG. 8 that the supercooling release substance contains Br ⁻ (or [Br ⁻ , Ag ⁺ ,..., Br ⁻ ]) as anions. From the combination of silver bromide ions in which the cation is tetrabutylammonium ion (TBA ⁺ ) and the anion is [Br ⁻ , Ag ⁺ ,..., Br ⁻ ], the supercooling release substance contains an Ag complex. You can see that

According to the second embodiment described above, when any metal of Cu, Zn, and Ag is used as the electrode material of the voltage application unit 12, a high overcooling release effect can be obtained.

Moreover, in this 2nd Embodiment, it was shown by changing the electrode material of the voltage application part 12 that the structure of the subcooling cancellation | release substance to produce | generate changes. For example, when a Cu electrode was used, a supercooling release material containing tetrabutylammonium ions (TBA ⁺ ) as cations and copper bromide ions as anions was generated. In addition, when a Zn electrode was used, a supercooling release material containing TBA ⁺ as a cation and zinc bromide ion as an anion was generated. In addition, when an Ag electrode was used, a supercooling release material containing TBA ⁺ as a cation and silver bromide ion as an anion was generated.

That is, in the first embodiment, the supercooling release material containing TBA ⁺ as a cation and copper bromide ion as an anion has been described. However, according to the second embodiment, silver bromide as an anion. It was shown that even when metal bromide ions other than copper bromide ions such as ions and zinc bromide ions are contained, the effect of releasing the supercooling of the TBAB aqueous solution may be obtained.

In addition, as described above, when any one of Cu, Zn, and Ag is used as the electrode material of the voltage applying unit 12, the substance generated in the TBAB aqueous solution is analyzed by mass spectrometry. A mass peak derived from bromide was confirmed. Further, from the cation, TBA ⁺ which is an ammonium ion contained in the TBAB aqueous solution was detected. From this result, it is conceivable that the compound composed of metal bromide ions and alkylammonium ions generated by voltage application at the voltage application unit 12 has a supercooling release effect on the TBAB aqueous solution.

Generally, the d-orbital state of a metal element in a complex is called structure selection energy and is known to be closely related to the coordination structure of the complex. Therefore, materials with similar d-orbital states often have similar physical and chemical properties.

In the second embodiment, the metal element that has been confirmed to form a complex having a subcooling release effect may become a closed shell state in which the d orbital is filled with 10 electrons when it becomes an ion. There is a feature that there is. Such elements include Cd and Au in addition to Cu, Ag and Zn.

Also, the state in which five electrons enter the d orbit is called a semi-closed shell, and it is known that it has characteristics very similar to the closed shell state. Such elements include Fe, Cr, Mn, Co, Ni, Mo, Tc, Ru, Rh, Re, Os, Ir, and Pt. Therefore, in addition to the complex confirmed this time, a complex composed of bromide ions and tetrabutylammonium ions of these metal elements is highly likely to have a supercooling release effect on the TBAB aqueous solution.

From the above, as a metal element constituting the supercooling release material, a metal whose d orbital can be in a closed shell state when it becomes an ion, or a metal whose d orbital can be in a semi-closed shell state when it becomes an ion. Can be used. Specifically, Cu, Ag, Zn, Cd, Au, Cr, Mn, Fe, Co, Ni, Mo, Tc, Ru, Rh, Re, Os, Ir, At least one metal element of Pt can be used.

In the second embodiment, the voltage application unit 12 applies a voltage to the TBAB aqueous solution and inputs electric energy from the outside, thereby promoting the chemical reaction that generates the supercooling release substance. That is, even if no voltage is applied to the TBAB aqueous solution, it is considered that the target substance can be obtained by adding a simple metal constituting the supercooling release substance to the cold storage material in advance.

Moreover, in this 2nd Embodiment, as a result of applying a voltage with respect to the cool storage material containing tetrabutylammonium ion (TBA ^<+> ), the compound containing tetrabutylammonium ion was obtained. When the same operation is performed on a regenerator material containing ammonium ions different from tetrabutylammonium ions, a compound containing the ammonium ions is generated, and it is considered that the substance has a supercooling release effect.

(Third embodiment)
Next, a third embodiment of the present disclosure will be described. In the third embodiment, the description of the same parts as those in the above embodiments will be omitted, and only different parts will be described.

The regenerator 1 according to the first embodiment is configured to generate a supercooling release substance inside the supercooling release substance generation unit 10 by applying a voltage to the TBAB aqueous solution in the supercooling release substance generation unit 10. . On the other hand, in the third embodiment, the supercooling release substance is generated in advance outside the regenerator 1.

As shown in FIG. 9, the cool storage device 1 of the third embodiment includes a cool storage material storage unit 15, a cold energy supply unit 22, a control unit 28, and the like. The supercooling release substance generation unit 10 is not provided in the regenerator 1 of the third embodiment. The cool storage material storage part 15 of this 3rd Embodiment is comprised as one container, and is filled with TBAB aqueous solution as a cool storage material inside. The supercooling release substance produced | generated outside the cool storage apparatus 1 is added to the cool storage material.

The supercooling release substance is generated by an external voltage application device (not shown). The external voltage application device has the same configuration as the supercooling release substance generation unit 10 provided in the cold storage device 1 of the first and second embodiments. The voltage application device is provided with an electrode for applying a voltage to the cold storage material. By applying voltage to the regenerator material with the voltage application device, the supercooling release substance is generated.

In the third embodiment, the supercooling release effect was evaluated when an externally generated supercooling release substance was added to the regenerator material. As the cold storage material, a TBAB aqueous solution adjusted to 40 wt% was used. The hydrate formation temperature of the aqueous TBAB solution adjusted to 40 wt% is about 12 ° C. As an additive to the regenerator material, each product in the case of using Cu, Ag, Zn as an electrode material with an external voltage application device was used. The product by voltage application was extracted by the procedure described in the first and second embodiments. In FIG. 10, the product when the voltage is applied by the Cu electrode is “Cu product”, the product when the voltage is applied by the Ag electrode is “Ag product”, and the product when the voltage is applied by the Zn electrode is “Zn product”. Product ".

A solution obtained by adding 0.01 wt% of the above additive to the cold storage material was allowed to stand in a thermostatic bath set at 5 ° C. to evaluate the effect of releasing the supercooling. In FIG. 10, the case where the hydrate crystals can be visually observed within 24 hours after the start of cooling is indicated by “◯”, and the case where the crystals are not visually observed is indicated by “X”.

As shown in FIG. 10, when a Cu product, an Ag product, and a Zn product are added to the cold storage material, the cold storage material is solidified, and when no product is added, the cold storage material is solidified. I did not. For this reason, it has confirmed that the substance produced | generated by the voltage application to TBAB aqueous solution had a supercooling cancellation | release effect.

According to the configuration of the third embodiment, when the regenerator material becomes supercooled by adding a subcool release material that has been generated in advance by applying voltage to the regenerator material, The generation of nuclei larger than the critical crystal nucleus diameter can be expected in a short time. As a result, the supercooled state of the regenerator material can be reliably released.

Further, in the third embodiment, the supercooling release substance generated by voltage application outside the cold storage device 1 is added to the cold storage material in advance. For this reason, in the cool storage apparatus 1 of this 3rd Embodiment, it is not necessary to provide the voltage application part 12 like the said 1st Embodiment, and it can cancel | release the supercooled state of a cool storage material reliably with a simple structure. .

(Fourth embodiment)
Next, a fourth embodiment of the present disclosure will be described. In the fourth embodiment, the description of the same parts as those in the above embodiments will be omitted, and only different parts will be described.

The fourth embodiment is different from the third embodiment in that the supercooling release substance is generated by organic synthesis or the like. The cool storage device 1 of the fourth embodiment has the same configuration as the cool storage device 1 of the third embodiment shown in FIG.

In the fourth embodiment, the supercooling release material generated in advance by organic synthesis or the like is added to the cold storage material of the cold storage material storage unit 15. The supercooling release substance of the fourth embodiment is a substance having a chemical structure represented by the general formula (3) of the first embodiment (that is, a compound composed of copper bromide ions and tetrabutylammonium ions). Acta Chemica Scandinavica B37 (1983), p.57-62 ”.

In the fourth embodiment, the supercooling release substance having the above chemical structure was organically synthesized by the method described in “Acta Chemica Scandinavica B36 (1982), p. 125-126”. It was confirmed by mass spectrometry that the target substance was obtained.

Also, a TBAB aqueous solution adjusted to 20 wt% was used as a cold storage material. The hydrate formation temperature of the aqueous TBAB solution adjusted to 20 wt% is about 8 ° C. A solution obtained by adding 0.01 wt% of the supercooling release material obtained by synthesis to the cold storage material was allowed to stand in a thermostat set to 1 ° C., and the supercooling release effect was evaluated. Hydrate crystals were visible within 24 hours after the start of cooling. On the other hand, when no compound was added, hydrate crystals could not be confirmed. As a result, it was confirmed that the synthesized compound had a supercooling release effect.

According to the configuration of the fourth embodiment, when the supercooling release material having the chemical structure represented by the general formula (3) is added to the cold storage material in advance, the cold storage material is in a supercooled state. The supercooling release material helps to generate crystal nuclei and can be expected to generate nuclei larger than the critical crystal nucleus diameter in a short time. As a result, the supercooled state of the regenerator material can be reliably released.

In the fourth embodiment, the supercooling release substance generated by organic synthesis or the like is added to the cold storage material in advance. For this reason, in the cool storage apparatus 1 of this 4th Embodiment, it is not necessary to provide the voltage application part 12 like the said 1st Embodiment, and it can cancel | release the supercooled state of a cool storage material reliably with a simple structure. .

(Fifth embodiment)
Next, a fifth embodiment of the present disclosure will be described. In the fifth embodiment, the description of the same parts as those of the above embodiments will be omitted, and only different parts will be described.

The fifth embodiment is different from the fourth embodiment in the type of supercooling release material to be synthesized. In the fifth embodiment, a compound composed of silver bromide ions and tetrabutylammonium ions was synthesized by the following procedure.

First, 0.36 g (that is, 3 mmol) of KBr was added to 90 mL of DMF (dimethylformamide) and stirred. To this, 0.56 g (that is, 3 mmol) of AgBr was added in a dark room and stirred for 30 minutes. Insoluble matter was filtered through a 0.5 μm membrane filter to obtain a filtrate. A solution prepared by dissolving 1.93 g (that is, 6 mmol) of TBAB in 100 mL of EtOH was separately prepared. These filtrates and solutions were mixed.

The precipitated single yellow powder was filtered through a 0.5 μm membrane filter and washed with EtOH to obtain 245 mg of a single yellow powder (yield: 9.8%). It was confirmed by mass spectrometry that the target substance was obtained.

A TBAB aqueous solution adjusted to 40 wt% was used as a cold storage material. The hydrate formation temperature of the aqueous TBAB solution adjusted to 40 wt% is about 12 ° C. A solution obtained by adding 0.01 wt% of a substance synthesized with respect to the cold storage material was allowed to stand in a thermostat set to 9 ° C., and the effect of canceling the supercooling was evaluated. Hydrate crystals were visible within 24 hours after the start of cooling. On the other hand, when no compound was added, hydrate crystals could not be confirmed. As a result, it was confirmed that the synthesized compound had a supercooling release effect.

In the fifth embodiment described above, the same effects as in the fourth embodiment can be obtained.

(Sixth embodiment)
Next, a sixth embodiment of the present disclosure will be described. In the sixth embodiment, description of the same parts as those in the above embodiments will be omitted, and only different parts will be described.

The cool storage device 1 of the sixth embodiment has the same configuration as the cool storage device of the third embodiment shown in FIG. In the sixth embodiment, a supercooling release material made of any single metal of Zn, Fe, Cu, or Ag is added to the regenerator material of the regenerator material storage unit 15.

In the sixth embodiment, these simple metals and, as comparative examples, SiO ₂ and zeolite were added to the regenerator material, and the supercooling release effect was evaluated. As the cold storage material, a TBAB aqueous solution adjusted to 20 wt% was used. The hydrate formation temperature of the aqueous TBAB solution adjusted to 20 wt% is about 8 ° C. Additives to the regenerator material include Zn with a particle size of less than 75 μm and 75 to 150 μm, Fe with a particle size of 45 μm, Cu with a particle size of 350 nm, Ag with a particle size of 150 nm, SiO _{2 with} a particle size of 5 to 15 nm, and a particle size of 75 μm. Zeolite) was used.

The result of having left the solution which added 0.01 wt% of the said additive with respect to the cool storage material in the thermostat set to 1 degreeC is shown in FIG. In FIG. 11, the case where the hydrate crystals were visible within 24 hours after the start of cooling was indicated by “◯”, and the case where the crystals were not visible was indicated by “X”.

As shown in FIG. 11, in the case of Zn, Fe, Cu, and Ag, even when a single metal was added to the cold storage material, the effect of canceling the supercooling was confirmed. It should be noted that SiO ₂ and zeolite having the same particle size as these metals did not show the effect of releasing the supercooling, so that it is clear that the effect is not due to the addition of simple fine particles.

In the first and second embodiments, by analogy with the case where a voltage is applied by the voltage application unit 12, when these single metals are added, a reaction that generates a supercooling release substance proceeds in the solution. It is considered that the cooling release effect was obtained. That is, it is considered that the single metal becomes a metal bromide ion together with Br contained in the TBAB aqueous solution serving as the cold storage material, and this metal bromide ion functions as a supercooling release material together with TBA ⁺ contained in the TBAB aqueous solution serving as the cold storage material.

According to the configuration of the sixth embodiment described above, the cool storage material is supercooled by adding in advance to the cool storage material a supercool release material made of any single metal of Cu, Ag, Zn, or Fe. In this state, it can be expected that the supercooling release material helps the generation of crystal nuclei and that nuclei having a critical crystal nucleus diameter or more are generated in a short time. As a result, it is possible to reliably release the supercooled state of the regenerator material by using the easily obtained supercooling release material made of a single metal.

(Seventh embodiment)
Next, a seventh embodiment of the present disclosure will be described. In the seventh embodiment, the description of the same parts as those in the above embodiments will be omitted, and only different parts will be described.

In each of the above embodiments, an aqueous solution of alkylammonium halide made of TBAB (tetrabutylammonium bromide) is used alone as the heat storage material. However, in the seventh embodiment, a plurality of types of aqueous solutions of alkylammonium halide are mixed. It is used as a heat storage material (hereinafter also referred to as a mixed cold storage material).

When a plurality of types of alkylammonium halide aqueous solutions are mixed and used as a mixed heat storage material, a portion of the alkylammonium halide hydrate contained in the mixed heat storage material crystallizes in advance, It is believed that crystallization of other alkyl ammonium halides is induced and the entire mixed regenerator is solidified.

However, when the alkylammonium halide hydrate, which is expected to be crystallized in advance in the mixed regenerator material, is in a supercooled state, the supercooling release effect is not exhibited, and the entire mixed regenerator material is in a supercooled state. there is a possibility. In this case, a situation may occur in which the performance of the regenerator material cannot be exhibited at all. Therefore, in the seventh embodiment, the supercooling release material is added to the mixed regenerator material to release the supercooled state of the mixed regenerator material.

The supercooling release material used for the mixed regenerator material only needs to have a supercooling release effect with respect to at least one alkylammonium halide aqueous solution contained in the mixed regenerator material. If the supercooled state of a part of the alkylammonium halide aqueous solution contained in the mixed regenerator material can be released and solidified, the solidified alkylammonium halide hydrate induces solidification of other alkylammonium halide aqueous solutions. It is considered that the entire mixed regenerator material can be solidified.

The cool storage device 1 of the seventh embodiment has the same configuration as the cool storage device of the third embodiment shown in FIG. In the seventh embodiment, a tri-n-butyl-n-pentylammonium bromide (TBPAB) aqueous solution adjusted to 34 wt% and a tetrabutylammonium bromide (TBAB) aqueous solution adjusted to 40 wt% are prepared as cold storage materials. did.

The hydrate formation temperature of the TBPAB aqueous solution adjusted to 34 wt% is about 6 ° C., and the hydrate generation temperature of the TBAB aqueous solution adjusted to 40 wt% is about 12 ° C. Therefore, the hydrate formation temperature of the cold storage material can be adjusted by mixing these two types of aqueous solutions.

In the seventh embodiment, an aqueous solution in which the above-described TBPAB aqueous solution and TBAB aqueous solution are mixed at a weight ratio of 9: 1 is used as a mixed cold storage material. Moreover, the Ag product described in the third embodiment was used as an additive. The Ag product is a product obtained by applying a voltage using an Ag electrode.

Evaluation was performed by allowing a solution obtained by adding 0.01 wt% of the above additive to the mixed regenerator material to stand in a thermostatic bath set at 5 ° C. When the Ag product was added to the mixed cold storage material, the entire sample solidified within 24 hours after the start of cooling. On the other hand, when the Ag product was not added to the mixed cold storage material, hydrate crystals could not be confirmed even after 24 hours had passed since the start of cooling. Since the Ag product has a supercooling release effect on the TBAB aqueous solution, the crystallization of TBAB hydrate induces the crystallization of TBPAB hydrate. As a result, the mixed regenerator material is solidified. Conceivable.

(Other embodiments)
For example, in the first to sixth embodiments, the TBAB aqueous solution is used as the heat storage material, and in the seventh embodiment, the TBAB aqueous solution and the TBPAB aqueous solution are mixed and used as the heat storage material, but other than the TBAB aqueous solution and the TBPAB aqueous solution are used. Alkyl ammonium halide aqueous solution can be used as a heat storage material. Each of these alkylammonium halide aqueous solutions may be used alone as a heat storage material, or a plurality of types of alkylammonium halide aqueous solutions may be mixed and used as a heat storage material.

Moreover, in the said 1st Embodiment, although the voltage application part 12 has been arrange | positioned in the supercooling cancellation | release substance production | generation part 10 provided apart from the thermal storage material storage part 15, it is not restricted to this, The supercooling cancellation | release substance production | generation part 10 The voltage application unit 12 may be disposed in the heat storage material storage unit 15 without providing the above.

In the third to seventh embodiments, the supercooling release substance is added to the cold storage material of the cold storage material storage unit 15. However, the present invention is not limited to this. A supercooling release material may be provided, and then the cold storage material may be put into the cold storage material storage unit 15.

Moreover, although the said 2nd Embodiment demonstrated the example using any metal of Cu, Zn, or Ag as an electrode material of the voltage application part 12, metal other than these was used as an electrode material of the voltage application part 12 It may be used.

Further, in each of the above embodiments, the example in which the pair of electrodes 12a and 12b of the voltage application unit 12 is configured by the same type of metal electrode has been described. However, the present invention is not limited thereto, and at least the metal electrode may be used as the movable electrode 12b. Hereinafter, this point will be described.

When a voltage is applied to the TBAB aqueous solution by the voltage application unit 12, an oxidation-reduction reaction occurs at the electrodes 12a and 12b. Among these electrodes 12a and 12b, an oxidation reaction occurs at the movable electrode 12b connected to the positive side of the DC power supply. When a metal is used as the electrode material of the movable electrode 12b, the metal becomes ions and dissolves in the aqueous solution. Since this metal ion is a constituent element of the supercooling release substance, it is necessary to use metal for at least the movable electrode 12b in order to generate the supercooling release substance by applying a voltage. On the other hand, the fixed electrode 12a connected to the negative side of the DC power source does not need to be a metal electrode because ionization of the metal constituting the electrode does not occur.

Here, the flowchart described in this application or the process of the flowchart is configured by a plurality of sections (or referred to as steps), and each section is expressed as S10, for example. Further, each section can be divided into a plurality of subsections, while a plurality of sections can be combined into one section. Further, each section configured in this manner can be referred to as a device, module, or means.

Although the present disclosure has been described based on the embodiments, it is understood that the present disclosure is not limited to the embodiments and structures. The present disclosure includes various modifications and modifications within the equivalent range. In addition, various combinations and forms, as well as other combinations and forms including only one element, more or less, are within the scope and spirit of the present disclosure.

Claims (11)

1. A supercooling release material that releases a supercooling state of a regenerator material containing one or more alkylammonium halide aqueous solutions that form a hydrate by cooling to a hydrate formation temperature or below,
   Alkylammonium ions contained in the cold storage material;
   A metal halide ion comprising a halogen element contained in the cold storage material as a constituent element;
   Containing supercooling release material.
2. The metal element contained in the metal halide ion is at least one of Cu, Ag, Zn, Cd, Au, Cr, Mn, Fe, Co, Ni, Mo, Tc, Ru, Rh, Re, Os, Ir, and Pt. The supercooling release material according to claim 1.
3. The alkylammonium ion is represented by the general formula is represented by _{[N (C n H 2n +} 1) 4] +, n is supercooling release material according to claim 1 or 2 is either from 1 to 7.
4. The supercooling release substance according to any one of claims 1 to 3, wherein the halogen element constituting the metal halide ion is Br.
5. The supercooling release material according to any one of claims 1 to 4, wherein the alkylammonium halide contains tetrabutylammonium bromide.
6. A method for producing a supercooling release material for releasing a supercooling state of a cold storage material containing one or more alkylammonium halide aqueous solutions that form a hydrate by cooling to a hydrate formation temperature or below,
   The supercooling release material includes alkylammonium ions contained in the regenerator material, and metal halide ions having a halogen element contained in the regenerator material as a constituent element,
   A method for producing a supercooling release material, comprising applying a voltage to the alkylammonium halide aqueous solution.
7. In the application of the voltage, a voltage is applied to the aqueous alkylammonium halide solution by a pair of electrodes,
   The electrode material is any one of Cu, Ag, Zn, Cd, Au, Cr, Mn, Fe, Co, Ni, Mo, Tc, Ru, Rh, Re, Os, Ir, and Pt. Of producing a supercooling release substance.
8. A method for producing a supercooling release material for releasing a supercooling state of a cold storage material containing one or more alkylammonium halide aqueous solutions that form a hydrate by cooling to a hydrate formation temperature or below,
   The supercooling release material includes alkylammonium ions contained in the regenerator material, and metal halide ions having a halogen element contained in the regenerator material as a constituent element,
   A method for producing a supercooling release material comprising adding at least a single metal of Ag, Cu, Fe, or Zn to the cold storage material.
9. The alkylammonium ion is represented by the general formula [N (C _n H _{2n + 1} ) ₄ ] ⁺ , and n is any one of 1 to 7, A method for producing a cooling release substance.
10. The method for producing a supercooling release material according to any one of claims 6 to 9, wherein the halogen element constituting the metal halide ion is Br.
11. The method for producing a supercooling release substance according to any one of claims 6 to 10, wherein the alkylammonium halide contains tetrabutylammonium bromide.

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