JP5680382B2 - Heat storage device and air conditioner equipped with the same - Google Patents

Description

  The present invention relates to a heat storage device using an aqueous solution as a heat storage solution, and an air conditioner including the heat storage device.

  Water is widely used as a heat storage solution (heat storage material, heat storage medium) for heat storage devices because its specific heat capacity is relatively large compared to other substances, is liquid at room temperature, and is low in price. Yes. When water is used as a heat storage solution, it is generally used as a dihydric alcohol aqueous solution to which a dihydric alcohol such as ethylene glycol is added as an “antifreeze”. If the heat storage device using such a heat storage solution is an open air type, a part of the heat storage solution evaporates as the heat storage operation is repeated. Therefore, it is necessary to periodically replenish the heat storage device with the heat storage solution.

  Thus, various techniques for suppressing evaporation of the heat storage solution have been proposed. Specifically, for example, in Patent Document 1, in an open air type heat storage device that is incorporated in a refrigeration cycle of an air conditioner and has a heat storage material mainly composed of water, the heat storage container stores heat. The structure which provided the evaporation suppression means of material is disclosed. Specifically, the heat storage material is exemplified by brine in which water is the main component and 30% ethylene glycol is mixed, and a configuration is disclosed in which an oil film of 1 mm or more is formed on the surface of the heat storage material to serve as an evaporation suppression means. ing.

  Patent Document 2 discloses a configuration in which a moisture evaporation prevention film is provided on the surface of a latent heat storage material in a heat storage device in which a latent heat storage material mainly composed of a hydrated salt is filled in a heat storage tank. . Specifically, what mixed 1 to 2% of xanthan gum as a thickener with sodium acetate trihydrate as a latent heat storage material is illustrated, and paraffin is used as a moisture evaporation prevention film on the surface of the latent heat storage material. Or a polymer film etc. are illustrated. The moisture evaporation prevention film may be basically any material that does not allow moisture to permeate, and may be liquid or solid. However, if there is a gap between the surface of the heat storage material, the moisture will evaporate to some extent. Therefore, it is disclosed that a flexible material is preferable.

  Patent Document 3 discloses a composition containing a moisture evaporation inhibitor, which is a heat storage material composition used for household heating and hot water supply equipment and for cooling electronic components. Specifically, as a heat storage material composition, a supercooling inhibitor, water, a thickener, and a heat transfer promoter are mixed in a predetermined range of composition with a hydrated salt type heat storage material such as sodium acetate trihydrate. What melt | dissolved and stirred is illustrated, Furthermore, what added the liquid paraffin as a water | moisture-content evaporation inhibitor to the said thermal storage material composition is illustrated. The moisture evaporation inhibitor is not limited to liquid paraffin as long as it is insoluble in the heat storage material and has a low specific gravity and a high boiling point. For example, synthetic oils such as animal and vegetable oils and silicone oils, organic solvents and the like are also exemplified. .

  Thus, conventionally, in order to suppress evaporation of the heat storage solution (heat storage material), a heat storage device having a configuration in which an evaporation preventing layer is formed on the upper surface of the heat storage solution is known. A more specific example of such a heat storage device, including a configuration applied to an air conditioner, will be described with reference to FIGS. 6 (a) and 6 (b).

  FIG. 6A shows a cross section of a conventional heat storage device 910 disclosed in Patent Document 1. FIG. In the heat storage device 910, a heat storage container is configured by a metal heat storage tank 901 and a metal lid 902, and a heat storage material 903 is accommodated in the internal space of the heat storage tank 901. As the heat storage material 903, brine in which water is the main component and 30% ethylene glycol is mixed is used in order to prevent freezing at low temperatures. A plurality of heat-dissipating heat exchangers 4 and a plurality of heat-absorbing heat exchangers 5 are provided in the internal space of the heat-storage tank 901 and in positions immersed in the heat-storage material 903.

  The heat storage material 903 stores the heat released from the heat storage heater 906 and the heat dissipation heat exchanger 904 provided outside the heat storage container, and collects the heat by the heat absorption heat exchanger 905. Since a refrigerant (not shown) flows in the heat exchanger for heat absorption 905, heat is recovered from the heat storage material 903, so that the heat is transferred to the refrigerant and becomes a high temperature. The conventional heat storage device 910 improves the heating start-up characteristics in the refrigeration cycle (not shown) disclosed in Patent Document 1 using such heat storage and heat recovery.

  An oil film 907 having a thickness of, for example, 3 mm is provided on the surface of the heat storage material 903, and the oil film 907 is configured to suppress a decrease due to evaporation of the heat storage material 903. Further, since the opening 908 is provided in the lid 902, the internal pressure of the heat storage container is not excessively increased by evaporation or thermal expansion of the heat storage material 903. The opening 908 is provided with a steam suppression means (not shown) so as not to release steam excessively to the atmosphere. Further, an air layer 909 is formed between the oil film 907 and the lid 902. Thereby, it is comprised so that the one part may not overflow outside a thermal storage container via the opening 908 (and vapor | steam suppression means) by the thermal expansion accompanying the temperature rise of the thermal storage material 903. FIG.

  FIG.6 (b) has shown the structure which incorporated the heat storage apparatus 910 of the said structure in the refrigerating cycle of the air conditioner. The air conditioner includes an indoor unit 911, an expansion valve (not shown), an outdoor unit 912, a compressor 913, and a pipe 916 connecting them. The indoor unit 911 includes an indoor heat exchanger (not shown), the outdoor unit 912 includes an outdoor heat exchanger (not shown), and a refrigerant flows inside the pipe. The indoor unit 911, the expansion valve, the outdoor unit 912, and the compressor 913 constitute a heating heat pump.

  Further, a bypass pipe 914 is provided so as to connect the downstream side in the direction in which the refrigerant flows in the pipe 916 connected to the indoor unit 911 and the upstream side in the direction in which the refrigerant flows out of the pipe 916 connected to the compressor 913. ing. The bypass pipe 914 includes an endothermic heat exchanger 905 and is configured such that the refrigerant flows by opening the two-way valve 915.

  According to the said structure, a refrigerant | coolant becomes high temperature / high pressure by the compressor 913, flows through the inside of the piping 916 along arrow m1 (block arrow filled in black) in the figure, and reaches the thermal storage device 910. Then, heat is dissipated from the high-temperature refrigerant by the heat-dissipating heat exchanger 904 and is stored in the heat storage material 903 in the heat storage device 910. At the same time, the heat storage material 903 is further heated by the heat storage heater 906 provided in the heat storage device 910 and is heated to, for example, 93 to 97 ° C. Therefore, the heat from the heat storage heater 906 is also stored in the heat storage material 903.

  The heat storage material 903, which has become high temperature due to the heat storage, opens the two-way valve 915 so that the refrigerant flowing in the bypass pipe 914 along the direction indicated by the arrow m3 (white block arrow) in the figure is exchanged for heat absorption. Heat through vessel 905. The refrigerant warmed by the heat storage material 903 (recovered heat from the heat storage material 903) reaches the compressor 913, and finally flows to the indoor unit 911 including the indoor heat exchanger, and performs heat exchange in the indoor unit 911. Thus, warm air for heating is generated. Note that the refrigerant having a low temperature after the heat exchange flows through the pipe 916 along the direction indicated by the arrow m2 in the drawing, and returns to the compressor 913 through the outdoor unit 912.

  Recently, a novel low melting point polymer (crystalline higher α-olefin copolymer) as disclosed in Patent Document 4 has been developed. This polymer is a polyolefin-based material in which the composition of the molecular weight distribution and the like is made uniform and the side chain crystallinity is improved by controlling the stereoregularity of the main chain, and it melts sharply at a low temperature of 30 to 50 ° C. It has become.

Japanese Patent Laid-Open No. 10-288359 Japanese Patent Laid-Open No. 64-10098 JP 2000-119643 A JP 2005-75908 A

  However, in the conventional configuration, the heat storage solution is stably maintained in the heat storage container regardless of whether the evaporation suppression means such as an oil film or the moisture evaporation prevention film (hereinafter referred to as an evaporation prevention layer) is liquid or solid. It may be insufficient to hold.

  First, if the evaporation prevention layer is composed of a liquid (if it is a liquid layer), the heat storage device is open to the atmosphere, and thus, for example, when the heat storage device is transported, the heat storage solution may leak from the vent hole. There is. Therefore, in order to avoid leakage of the heat storage solution, it is necessary to handle the heat storage device so that it does not shake excessively. That is, from the viewpoint of improving the handleability of the heat storage device, in addition to the function of preventing or suppressing the evaporation of the heat storage solution (hereinafter referred to as the evaporation prevention function), the heat storage solution is added to the evaporation prevention layer. The function of preventing or suppressing the leakage (hereinafter referred to as a leakage prevention function) is required.

  On the other hand, if the evaporation prevention layer is made of a solid (if it is a solid layer), the solid layer can improve the airtightness on the upper surface of the heat storage solution. It can be realized well.

  However, for the evaporation prevention layer, when the pressure of the heat storage solution increases, the function of reducing the increase in the pressure and stably holding the heat storage solution in the heat storage container (hereinafter referred to as a pressure relaxation function). .) Is also required. If the evaporation prevention layer is a solid layer and the airtightness on the upper surface of the heat storage solution is high, it will be difficult to effectively realize the pressure relaxation function, resulting in damage to the heat storage container as a result of long-term intermittent use. It can happen. In this case, since the heat storage solution may leak from the damaged portion, the heat storage solution cannot be stably held. Further, if the air tightness on the upper surface of the heat storage solution is lowered in order to improve the pressure relaxation function in the solid layer, the evaporation prevention function and the leakage prevention function are lowered.

  Here, even if the evaporation prevention layer is a solid layer, the material design of the solid layer used as the evaporation prevention layer should be performed so that the evaporation prevention function, the leakage prevention function, and the pressure relaxation function can be satisfied at the same time. Is possible. For example, the gas (vapor or dissolved oxygen) is improved while improving the flexibility of the solid layer and ensuring the barrier property of the liquid (heat storage solution) by selecting the material to be the solid layer, designing the composition, devising the molding method, etc. Etc.) is expected to be ensured. However, since such material design realizes contradictory functions, the manufacturing conditions of the solid layer, such as material selection, composition design, and ingenuity of the molding processing method, become complicated, and as a result, the evaporation prevention layer Incurs high costs.

  The polyolefin-based low melting point polymer as disclosed in Patent Document 4 is mainly used as a wax, a thermoplastic resin, a lubricating oil, or the like. Therefore, it has not been conventionally known that this low-melting-point polymer is used as an evaporation preventing layer of a heat storage device, and furthermore, the material design is not suitable for use as an evaporation-preventing layer. When used as an evaporation preventing layer, the evaporation preventing function, the leakage preventing function, and the pressure relaxation function could not be satisfied at the same time.

  The present invention has been made to solve such problems, and provides a heat storage device that can stably hold a heat storage solution in a heat storage container and has excellent handling properties, and an air conditioner including the heat storage device. For the purpose.

In order to solve the above-described problems, a heat storage device according to the present invention includes a heat storage container having a vent hole communicating with outside air, and a heat storage solution layer and an evaporation prevention layer are arranged in this order from the bottom in the heat storage container. The upper part of the evaporation preventing layer is communicated with the outside air, the heat storage solution layer is composed of a heat storage solution made of at least water, and the air layer is formed by the outside air flowing in from the vent hole. The evaporation prevention layer is configured to contain at least a crystalline higher α-olefin that satisfies the following conditions (a) and (b).
(A) A polymer in which the α-olefin monomer has 16 to 44 carbon atoms and uses at least one of these monomers.
(B) In a melting behavior measurement using a differential scanning calorimeter (DSC), a polymer whose melting point exceeds at least 35 ° C. and only one peak temperature is observed.

  When the carbon number of the α-olefin monomer is 16 or more, the crystalline higher α-olefin obtained by polymerizing the monomer becomes a composition having high crystallinity and no stickiness and improved strength. On the other hand, if the carbon number of the α-olefin monomer is 44 or less, the crystalline higher α-olefin obtained by polymerizing the monomer has less unreacted monomer and has a homogeneous melting and crystallization temperature range. Composition.

For this reason, the crystalline higher α-olefin obtained by polymerization using any of the α-olefin monomers having 16 to 44 carbon atoms can easily control the melting point and crystallinity (hardness) and has a specific gravity. It is possible to synthesize a uniform highly crystalline composition having a melting point of about 0.9 g / cm ³ and having one melting point of 35 ° C. or higher.

  As a result, the anti-evaporation layer using crystalline poly α-olefin has high crystallinity and thus has an anti-evaporation function, and has a specific gravity smaller than that of water as the heat storage solution, and therefore floats above the heat storage solution. Moreover, since melting | fusing point is higher than normal temperature (20 degreeC +/- 15 degreeC), it is solid in the normal temperature state which does not perform heat storage operation | movement. In this way, since a solid evaporation prevention layer is formed within the range of normal temperature, it is possible to effectively prevent excessive evaporation of the heat storage solution, and the heat storage solution leaks to the outside or is exposed to the air layer during transportation of the heat storage device. Can be suppressed. Further, even if the temperature of the heat storage solution rises during the heat storage operation, the evaporation prevention layer becomes a highly viscous liquid layer, so that not only can the excessive evaporation of the heat storage solution be effectively prevented, but also the pressure increase of the heat storage solution. It can respond enough. As described above, the evaporation prevention layer using the crystalline poly α-olefin can satisfy all of the evaporation prevention function, the leakage prevention function, and the pressure relaxation function at the same time.

  Moreover, according to the said structure, it is preferable that the crystalline higher alpha-olefin which comprises an evaporation prevention layer has the high crystallinity of the side chain part. Since this crystalline higher α-olefin has an isotactic structure in which the hydrocarbons in the side chain portion are regularly arranged on the same side, the crystallinity of the side chain portion is increased. Therefore, the air holes in the liquid layer are extremely small, and the heat storage solution evaporation prevention function, leakage prevention function, etc. are extremely excellent.

  In the heat storage device, at least one sub-evaporation prevention layer is further mixed with the evaporation prevention layer or formed as an independent layer below the evaporation prevention layer in the heat storage container, The sub-evaporation preventing layer is composed of a solvent composition comprising at least one water-insoluble solvent, and the melting point of the solvent composition is preferably less than room temperature.

  According to the above configuration, at least one sub-evaporation preventing layer is mixed with the evaporation preventing layer in the heat storage container, or is formed as an independent layer below the evaporation preventing layer. Therefore, the heat storage solution is protected by a plurality of “evaporation prevention layers”. In addition, during the heat storage operation, the evaporation prevention layer becomes a high viscosity liquid layer, and the sub-evaporation prevention layer is maintained as a relatively low viscosity liquid layer regardless of whether it is used or not used. The degree of adhesion increases. As a result, the vapor passage holes in each of these layers become narrower and the evaporation prevention function is improved compared to the case of using each of them alone, but the vapor of excess heat storage solution is released from each of these layers. Is possible. Further, after the heat storage operation, a crack generated after the evaporation prevention layer is cured can be filled with the sub-evaporation prevention layer. Therefore, the evaporation prevention function, the leakage prevention function, and the pressure relaxation function can be realized even more reliably.

  In the heat storage device, the specific gravity of the crystalline higher α-olefin is more preferably smaller than the specific gravity of the solvent composition.

  According to the above configuration, since the specific gravity of the solvent composition constituting the sub-evaporation prevention layer is large, it is necessary to prevent sub-evaporation regardless of whether the crystalline higher α-olefin as the main component of the evaporation prevention layer is solid or liquid. It will “float” on top of the layer. Therefore, even when the evaporation preventing layer becomes a liquid phase at a high temperature, it is possible to further prevent evaporation of the heat storage solution. In addition to this, the amount of the sub-evaporation preventing layer that is a liquid increases as it is located below the evaporation preventing layer. Therefore, after the heat storage operation, cracks generated after the evaporation prevention layer is cured can be filled with the sub-evaporation prevention layer even more reliably. As a result, it is possible to effectively suppress the heat storage solution from leaking to the air layer side during transportation of the heat storage device.

  In the heat storage device, the melting point of the solvent composition is more preferably lower than the freezing point of the heat storage solution.

  According to the above configuration, even if the temperature is decreased until the heat storage solution is solidified, the solvent composition constituting the sub-evaporation prevention layer can maintain fluidity, and thus effectively prevents evaporation of the heat storage solution even at a low temperature. Can be realized. In addition, since the solvent composition is not solidified even when the heat storage solution is solidified, it is possible to relieve the volume expansion associated with the solidification of the heat storage solution, thereby further reducing the pressure increase in the heat storage solution. It can be certain.

  In the heat storage device, it is more preferable that the solvent composition contains at least one of hydrocarbons having a carbon number in the range of 24 to 44 as the water-insoluble solvent.

  According to the said structure, since the solvent composition which comprises the said sub-evaporation prevention layer contains the hydrocarbon which has a carbon number in the range of 24-44 as a water-insoluble solvent, fluidity maintenance at low temperature is carried out. It can be made even more reliable.

  In the said heat storage apparatus, although the specific structure of the said heat storage solution is not specifically limited, The example whose heat storage solution is the aqueous solution containing a bihydric alcohol can be mentioned preferably.

  According to the above configuration, since the heat storage solution is an aqueous solution containing not only water but also a dihydric alcohol, freezing can be avoided even when the heat storage solution is below the freezing point.

  The heat storage device may further include a heat source that heats the heat storage solution and a heat storage heat exchanger that recovers heat stored in the heat storage solution. Moreover, it is preferable that the heating source is provided outside the heat storage solution layer, and the heat storage heat exchanger is provided at a position immersed in the heat storage solution inside the heat storage container.

  According to the said structure, while providing a heat source, more suitable heat storage is attained, and by providing the heat exchanger for heat storage, the heat which stored heat can be collect | recovered suitably, and as a heat source, for example, heat storage If equipment having a function other than the heating function, such as a compressor located outside the solution layer, is used, the waste heat can be effectively stored and recovered.

  In the heat storage device, it is preferable that the heat storage container is provided so as to surround the heating source.

  According to the said structure, since the thermal storage container is located around a heating source, the heat from a heating source can be stored efficiently.

  In the heat storage device, it is preferable that the heat storage container is in contact with the heating source via a heat conductive member.

  According to the said structure, since the thermal storage container and the heating source are contacting via the heat conductive member, the heat from a heating source can be efficiently conducted to a thermal storage container.

  The heat storage device according to the present invention can be suitably used in any field for storing heat, but a typical example is an air conditioner. That is, the present invention includes an air conditioner including the heat storage device having the above-described configuration.

  As described above, according to the present invention, it is possible to provide a heat storage device that can stably hold a heat storage solution in a heat storage container and is excellent in handleability, and an air conditioner including the heat storage device.

(A) is typical sectional drawing which shows an example of a structure of the thermal storage apparatus which concerns on Embodiment 1 of this invention, (b) is the thermal storage solution layer formed in the inside of the thermal storage apparatus shown to (a). FIG. 5 is a schematic diagram showing a change in phase state accompanying a temperature change in the evaporation prevention layer. It is the melting curve which analyzed the crystalline higher alpha-olefin used for the evaporation prevention layer of the thermal storage apparatus shown to Fig.1 (a) using the differential scanning calorimeter. (A) is typical sectional drawing which shows an example of a structure of the thermal storage apparatus which concerns on Embodiment 2 of this invention, (b) is the thermal storage solution layer formed in the inside of the thermal storage apparatus shown to (a). FIG. 5 is a schematic diagram showing a change in phase state accompanying a temperature change in the evaporation prevention layer. (A) is a cross-sectional view which shows an example of a structure of the heat storage apparatus which concerns on Embodiment 3 of this invention, (b) is a longitudinal cross-sectional view of the heat storage apparatus shown to (a). It is a block diagram which shows an example of a structure of the air conditioning apparatus which concerns on Embodiment 4 of this invention. (A) is sectional drawing which shows an example of a structure of the conventional heat storage apparatus, (b) is a block diagram which shows an example of a structure of an air conditioning apparatus provided with the heat storage apparatus shown to (a).

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. In the following description, the same or corresponding elements are denoted by the same reference symbols throughout the drawings, and redundant description thereof is omitted.

(Embodiment 1)
[Configuration of heat storage device]
First, a specific configuration of the heat storage device according to the present embodiment will be specifically described with reference to FIG.

  As shown to Fig.1 (a), the thermal storage apparatus 20A which concerns on this Embodiment is provided with the thermal storage container 21 and the heat exchanger 22 for thermal storage, and the thermal storage solution is stored in the thermal storage container 21 by storing a thermal storage solution. A layer 11 is formed, and an evaporation preventing layer 13 and an air layer 12 are formed above the heat storage solution 11.

  The heat storage container 21 includes a box part 211 and a lid part 212. The box part 211 is a main body of the heat storage container 21, has a substantially rectangular parallelepiped shape, and has an upper opening 213 on its upper surface. The internal space of the box part 211 is configured to be able to store the heat storage solution 11, and the internal space is connected to the external space via the upper opening 213. The lid portion 212 is provided so as to cover the upper opening 213 of the box portion 211, and a ventilation hole 214 connected to the internal space of the box portion 211 is provided in a part thereof. Therefore, the internal space of the heat storage container 21 communicates with the outside air through the vent hole 214 even when the upper opening 213 of the box portion 211 is closed by the lid portion 212.

  The box part 211 and the cover part 212 may be made of a material and a shape that can stably hold the heat storage solution 11 in the internal space. Generally, the material is stainless steel (SUS) or fiber reinforced plastic ( FRP) is used, and the shape generally includes a rectangular parallelepiped shape or a cubic shape. Moreover, it does not specifically limit about the internal volume of the box part 211, What is necessary is just to design so that it may become an appropriate volume according to the use conditions etc. of 20 A of heat storage apparatuses.

  The vent hole 214 provided in the lid portion 212 causes the internal air forming the air layer 12 to flow out of the heat storage container 21 or the steam generated from the heat storage solution in order to alleviate the pressure increase inside the heat storage container 21. It is configured to release dissolved air or the like to the outside. In addition, it is possible to prevent the air constituting the air layer 12 from flowing inside or outside the heat storage container 21 more than necessary, or the steam generated from the heat storage container 21 being released more than necessary to reduce the heat storage solution or the like. The opening area only needs to be optimized. The specific configuration such as the position, shape, and number of the vent holes 214 is not particularly limited as long as the configuration can realize relaxation of the pressure increase and suppression of decrease in the heat storage solution and the like. The vent hole 214 may be provided not on the lid portion 212 but on the upper portion of the box portion 211 or on both sides.

  As shown in FIG. 1, the heat storage heat exchanger 22 has a pipe-like configuration provided so as to spread over the entire interior of the heat storage container 21, and a heat medium for heat exchange (referred to as a heat exchange medium for convenience) inside. .) Is configured to be flowable. Further, the position where the heat storage heat exchanger 22 is provided is a position where the heat storage solution 21 is immersed in the heat storage container 21.

  The inlet part 221 and the outlet part 222 which are both ends of the heat storage heat exchanger 22 pass through the lid part 212 and are exposed to the outside from above the heat storage container 21, and these inlet part 221 and outlet part An external pipe for flowing the heat exchange medium is connected to 222. Moreover, the main body piping part 223 which constitutes most of the heat storage heat exchanger 22 is configured to be folded in a large part, and the main body piping part 223 extends from the inlet part 221 to the outlet part 222. The shape is unicursal. Most of the main body piping part 223 is immersed in the heat storage solution layer 11. Then, the heat exchange medium flows through the inside of the main body piping part 223 from the inlet part 221 toward the outlet part 222, whereby heat exchange is performed between the heat storage solution layer 11 and the heat exchange medium. The specific configuration of the heat storage heat exchanger 22 is not particularly limited, and a known configuration can be suitably used.

  The method of heat storage and heat recovery by the heat storage heat exchanger 22 is not particularly limited. For example, the following two methods can be used.

  First, the first method is a method of using the heat storage heat exchanger 22 as a heat radiation source. Specifically, the heat stored in the heat exchange medium is radiated to the heat storage solution layer 11 while a high-temperature heat exchange medium (for example, hot water or a high-temperature refrigerant) is circulated in the main body piping part 223. Thus, heat is stored in the heat storage solution layer 11. Although not shown in FIG. 1, a heat exchanger is provided separately from the heat storage heat exchanger 22, and a low-temperature heat exchange medium (for example, cold water or a low-temperature refrigerant) is circulated in the heat exchanger. Thus, heat is recovered from the heat storage solution layer 11.

  Next, in the second method, a heat supply device (a heat exchanger other than the heat storage heat exchanger 22 or a heat source) not shown in FIG. It is. Specifically, heat is stored in the heat storage solution layer 11 from the heat supply device, and a low-temperature heat exchange medium is circulated in the heat storage heat exchanger 22, thereby recovering heat from the heat storage solution layer 11 and storing heat. This is transmitted to a heat utilization device (not shown) connected to the outlet part 222 of the heat exchanger 22.

[Layer structure in heat storage container]
Next, the configuration of each layer formed in the heat storage container 21 will be specifically described with reference to FIG. As described above, the heat storage solution 11 is formed inside the heat storage container 21 by storing the heat storage solution. The heat storage solution layer 11 is stacked above the heat storage solution layer 11. Thus, the evaporation preventing layer 13 is formed. Further, the air layer 12 is formed above the evaporation preventing layer 13 by the outside air flowing from the vent holes 214. Therefore, the heat storage solution layer 11, the evaporation prevention layer 13, and the air layer 12 are formed in this order from the lower side inside the heat storage container 21.

  The layer thicknesses of the heat storage solution layer 11 and the air layer 12 are not particularly limited, and are appropriate depending on various conditions such as the shape of the heat storage container 21, the volume of the internal space, and the volume increase of the heat storage solution due to thermal expansion. May be set. In other words, what is the value of the layer thickness of the heat storage solution layer 11 and the air layer 12 as long as a spatial margin (air layer 12) is formed so that the heat storage solution does not leak from the vent hole 214 due to thermal expansion? Also good.

  The heat storage solution constituting the heat storage solution layer 11 may be a heat-storage medium composed of at least water. The heat storage solution may be composed only of water, but may contain various additives that can be dissolved or dispersed in water. In particular, in the present embodiment, it is preferable that a dihydric alcohol is contained as an antifreezing agent (antifreeze). If the heat storage solution is an aqueous solution containing a dihydric alcohol, freezing of the heat storage solution can be avoided even if it is below the freezing point (0 ° C. at normal temperature and normal pressure).

  The dihydric alcohol is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, butanediol, neopentyl glycol, 3-methylpentadiol, 1,4-hexanediol, 1,6-hexanediol, and the like. Can be mentioned. Among these, ethylene glycol or propylene glycol is preferably used from the viewpoints of cost and actual use as an antifreezing agent. These dihydric alcohols may be used alone or in combination of two or more. Furthermore, the antifreezing agent is not limited to the dihydric alcohol, and may be a compound or composition other than the dihydric alcohol.

  Further, the specific type of additive added to the heat storage solution is not particularly limited, and besides the antifreezing agent, a supercooling inhibitor, a thickener, a heat transfer accelerator, a moisture evaporation inhibitor, and a corrosion inhibitor. Various additives known in the field of the heat storage material composition such as a rust preventive (when the heat storage container 21 is made of metal) can be used. The addition amount and addition method of these additives are not particularly limited, and a known range or method can be suitably used.

  The evaporation prevention layer 13 is laminated on the heat storage solution layer 11 and prevents or suppresses evaporation of the heat storage solution. The evaporation preventing composition constituting the evaporation preventing layer 13 is composed of at least a crystalline poly α-olefin having a heat distortion temperature of normal temperature or higher.

  Further, the evaporation preventing layer 13 imparts preferable physical properties for realizing an evaporation preventing function, a leakage preventing function, and a pressure relaxation function, which will be described later, or the evaporation preventing layer 13 is stably held in the heat storage container 21. In addition to the crystalline poly α-olefin, other components known in the art may be included. Specifically, for example, antioxidants, corrosion inhibitors, rust inhibitors, pour point depressants, antifoaming agents, viscosity modifiers and the like can be exemplified. The addition amount and addition method of these additives are not particularly limited, and a known range or method can be suitably used.

  Therefore, both the heat storage solution layer 11 and the evaporation prevention layer 13 may be a composition prepared by preparing a plurality of components with a specific composition.

[Composition of crystalline poly α-olefin]
Next, a specific configuration of the crystalline poly α-olefin included as the main component of the evaporation preventing layer 13 will be specifically described.

In the present embodiment, the crystalline poly-α-olefin used as the evaporation preventing layer 13 satisfies the following conditions (a) and (b).
(A) The number of carbon atoms of the α-olefin monomer is in the range of 16 to 44, and a polymer (b) a differential scanning calorimeter (DSC) using at least one of these monomers was used. Polymer in which melting point is at least 35 ° C. or more and only one peak temperature is observed in melting behavior measurement Crystals obtained by polymerizing α-olefin monomer having 16 or more carbon atoms The high-grade α-olefin has a high crystallinity and is non-sticky and has improved strength. On the other hand, if the carbon number of the α-olefin monomer is 44 or less, the crystalline higher α-olefin obtained by polymerizing the monomer has less unreacted monomer and has a homogeneous melting and crystallization temperature range. Composition.

For this reason, the crystalline higher α-olefin obtained by polymerization using any of the α-olefin monomers having 16 to 44 carbon atoms can easily control the melting point and crystallinity (hardness) and has a specific gravity. A uniform highly crystalline composition having a melting point of about 0.9 g / cm ³ and one melting point of 35 ° C. or higher can be easily synthesized. As a result, the evaporation prevention layer 13 using the crystalline poly-α-olefin has high crystallinity and thus has an excellent evaporation prevention function. Since the specific gravity is lighter than that of the water as the heat storage solution layer 11, it floats on the upper part and has a melting point of room temperature Since it is higher than (20 ° C. ± 15 ° C.), it is solid at room temperature when no heat storage operation is performed.

  Therefore, since the solid evaporation prevention layer 13 is formed within the range of normal temperature, excessive evaporation of the heat storage solution layer 11 can be effectively prevented, and the heat storage solution layer 11 leaks to the outside during transportation of the heat storage device. Exposure to the air layer can be suppressed. Further, even if the temperature of the heat storage solution layer 11 rises during the heat storage operation, the evaporation prevention layer 13 becomes a high-viscosity liquid layer, so that not only excessive evaporation of the heat storage solution layer 11 can be effectively prevented, but also the heat storage solution layer. 11 can sufficiently cope with the pressure increase. By these things, the evaporation prevention layer 13 using this crystalline poly α-olefin can satisfy all of the evaporation prevention function, the leakage prevention function, and the pressure relaxation function at the same time.

  Now, since the thermal storage solution layer 11 consists of at least water, the boiling point maximum value is about 100 degreeC. Considering the function of the evaporation preventing layer 13, the maximum melting point is preferably lower than the boiling point of the heat storage solution layer 11, and 80 ° C. is particularly favorable.

  On the other hand, when the α-olefin monomer had less than 16 carbon atoms, the polymer was a non-crystalline, sticky but strong composition with low strength. Further, when the α-olefin monomer has 45 or more carbon atoms, the polymer was a non-homogeneous composition with a large amount of unreacted monomers and a wide temperature range for melting and crystallization. Therefore, the evaporation prevention layer 13 of these crystalline poly α-olefins using α-olefin monomers of less than 16 carbon atoms or 45 or more should satisfy the evaporation prevention function, the leakage prevention function, and the pressure relaxation function at the same time. I could not.

  Furthermore, it is preferable that the crystalline higher α-olefin as the evaporation preventing layer has high crystallinity in the side chain portion. Since this crystalline higher α-olefin has an isotactic structure in which the hydrocarbons in the side chain portion are regularly arranged on the same side, the crystallinity of the side chain portion is increased. Therefore, the air holes in the liquid layer are extremely small, and the evaporation preventing layer 13 using the crystalline poly α-olefin is extremely excellent in the function of preventing the evaporation of the heat storage solution and the function of preventing leakage.

  For the measurement of melting point and latent heat of fusion using a differential scanning calorimeter, a known method can be used, but in this embodiment, in accordance with Japanese Industrial Standard JIS K 7121, as a differential scanning calorimeter, DSC-7 (trade name, manufactured by Perkin Elmer) was used to measure the melting point and latent heat of fusion.

  Specifically, the sample was heated from room temperature to 150 ° C. at 100 ° C./min, held at 150 ° C. for 5 minutes, then cooled to −30 ° C. at 10 ° C./min, and at −30 ° C. for 5 minutes. After being held, by raising the temperature to 150 ° C. at 10 ° C./min, a melting curve showing an endothermic peak, for example, a melting curve shown in FIG. 2 can be obtained. As shown in FIG. 2, the peak top temperature in this melting curve is the melting point (Tm), and the latent heat of fusion is the shaded region shown in FIG. The melting latent heat will be specifically described. A straight line obtained by extending the high-temperature side base line to the low-temperature side is represented by k, and the temperature at which the straight line k and the melting curve intersect at the low-temperature side is represented by (Tl). Is (Th), the endothermic amount (unit: J / g) in the temperature Tl to Th range is the latent heat of fusion (ΔH).

  The production of the crystalline poly α-olefin as the main component of the evaporation preventing layer 13 is based on a novel low melting point polymer (crystalline higher α-olefin copolymer) described in Patent Document 4. Specifically, for example, a monomer having 16 to 44 carbon atoms is used as the α-olefin, and two or more of these monomers having one or more carbon atoms and one kind of olefin having 2 to 30 carbon atoms are used. The example obtained by superposing | polymerizing combining the above is mentioned. Moreover, it is not limited to this example, It is also possible to superpose | polymerize using 1 type of a C16-44 monomer as an alpha olefin. These polymers are obtained by copolymerization using a metallocene catalyst having a unique structure and devising reaction conditions. Examples of the types and physical properties of α-olefin monomers used for copolymerization are shown in Prototype Examples 1 to 4.

  In addition, the manufacturing method of crystalline poly α-olefin according to the following prototype is described in Patent Document 4, and in the present embodiment, various conditions and the like are appropriately changed within the scope disclosed in Patent Document 4. Or the crystalline poly (alpha) -olefin of the following trial examples is obtained by modifying. Note that the contents described in Patent Document 4 are made a part of the description of the present specification by referring to the present specification.

  The crystalline poly α-olefin of Prototype Example 1 is a polymer obtained from a mixture of α-olefin monomers having 20, 22, and 24 carbon atoms, and its physical properties are [1] containing α-olefin unit. Rate was 100%, [2] melting point was 49 ° C., [3] latent heat at melting was 82 J / g, [4] weight average molecular weight (Mw) was 48000, and [5] measured by wide-angle X-ray scattering intensity distribution method. The single peak angle X1 is 21 °, and the intensity ratio is 100%.

  The crystalline poly α-olefin of Prototype Example 2 is a polymer obtained by mixing a small amount of an olefin having 2 carbon atoms with an α-olefin monomer having 18 carbon atoms, and the physical properties thereof are [1] α-olefin. Unit content of 92%, [2] melting point of 40 ° C., [3] latent heat at melting of 88 J / g, [4] weight average molecular weight (Mw) of 110000, [5] wide angle X-ray scattering intensity distribution method The single peak angle X1 measured in (1) is 21 °, and the intensity ratio is 100%.

  The crystalline poly α-olefin of Prototype Example 3 is a polymer obtained by mixing a small amount of an olefin having 4 carbon atoms with a mixture of α-olefin monomers having 20, 22 and 24 carbon atoms, and its physical properties are [1] Unit content of α-olefin is 60%, [2] Melting point is 39 ° C., [3] Latent heat at melting is 57 J / g, [4] Weight average molecular weight (Mw) is 92000, [5] The single peak angle X1 measured by the wide-angle X-ray scattering intensity distribution method is 21 °, and the intensity ratio is 100%.

  The crystalline poly α-olefin of Prototype Example 4 is a polymer obtained by mixing a small amount of an olefin having 4 carbon atoms with a mixture of α-olefin monomers having 20, 22 and 24 carbon atoms, and its physical properties are [1] unit content of α-olefin is 76%, [2] melting point is 43 ° C., [3] latent heat at melting is 62 J / g, [4] weight average molecular weight (Mw) is 84000, [5] The single peak angle X1 measured by the wide-angle X-ray scattering intensity distribution method is 21 °, and the intensity ratio is 100%.

  In addition to the above-described prototype examples 1 to 4, the crystalline higher α-olefin can be synthesized with various polymers by devising the type of α-olefin, the metallocene catalyst for synthesis, and the reaction conditions. The unit content of the α-olefin of the monomer having 16 to 44 carbon atoms is preferably 50% or more. The melting point is measured using a differential scanning calorimeter, for example, by the above-described method. When the melting point is at least 35 ° C., only one peak temperature is observed, and the latent heat at the time of melting is at least 57 J / g or more. Polymers are desirable.

The crystallinity of the side chain part is measured using, for example, the wide-angle X-ray scattering intensity distribution method, and when a single peak X1 is observed at 15 deg <2θ <30 deg, it is determined that there is side chain crystallization. Can do. That is, in the present invention, when a single peak is observed at 15 deg <2θ <30 deg in the wide-angle X-ray scattering intensity distribution, it is determined that the side chain portion has high crystallinity. The molecular weight is measured by a gel permeation chromatograph (GPC) method, and the weight average molecular weight (Mw) in terms of polystyrene is preferably 1,000 to 1,000,000, and more preferably 10,000 to 10,000. 000,000. An example of the conditions for crystallinity measurement and molecular weight measurement by the wide-angle X-ray scattering intensity distribution method is shown below, but it goes without saying that the crystallinity and molecular weight measurement methods are not limited to the following conditions.
(Wide-angle X-ray scattering measurement)
In the crystalline poly α-olefin used in the present embodiment, a single peak X1 derived from side chain crystallization observed at 15 deg <2θ <30 deg is observed in the wide-angle X-ray scattering intensity distribution. An example of a wide-angle X-ray scattering intensity distribution measurement method and measurement conditions are as follows.

That is, using a counter cathode type rotor flex RU-200 manufactured by Rigaku Corporation, collimated monochromatic light of CuKα ray (wavelength = 1.542Å) of 30 kV, 100 mA output with a 1.5 mm pinhole, and position sensitive proportional counting Using a tube, wide-angle X-ray scattering (WAXS) intensity distribution was measured at an exposure time of 1 minute.
(Molecular weight measurement)
The crystalline poly α-olefin used in the present embodiment is measured for average molecular weight (Mw) in terms of polystyrene weight by gel permeation chromatography (GPC). An example of the conditions is as follows.
GPC measuring device column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)
[Function of evaporation prevention layer]
Next, a specific function of the evaporation preventing layer 13 containing the crystalline poly α-olefin will be specifically described with reference to FIG.

  In the present embodiment, since the evaporation preventing layer 13 contains the crystalline poly α-olefin, the crystallinity is high and the specific gravity is lighter than that of water. The evaporation preventing layer 13 has a melting point of 35 ° C. or higher, and the maximum melting point is preferably lower than the boiling point of the heat storage solution layer 11, and 80 ° C. is particularly good considering the evaporation preventing function. Therefore, it is solid at room temperature where no heat storage operation is performed.

  Regarding the heat storage solution layer 11 and the evaporation prevention layer 13, the change in the phase state from the solid phase to the liquid phase accompanying the temperature change is compared. As shown in FIG. 1B, if the temperature is low, all the layers are solid (shaded area in the figure), but if the temperature is gradually increased, the heat storage solution layer 11 has a freezing point Tf. The phase changes from solid to liquid and is maintained in liquid until the boiling point Tb is reached. On the other hand, the evaporation preventing layer 13 is solid at the freezing point Tf of the heat storage solution, and further remains solid even in the range of room temperature (a region sandwiched by a chain line in the figure).

  Since the crystalline poly α-olefin constituting the evaporation preventing layer 13 is a polymer in comparison with the heat storage solution (aqueous solution) constituting the heat storage solution layer 11, it reaches the melting point Tm and is liquefied as a highly viscous liquid. In the present embodiment, the room temperature range is defined as a range of 20 ° C. ± 15 ° C. (5 ° C. or more and 35 ° C. or less) in accordance with Japanese Industrial Standard JIS Z 8703. Therefore, the melting point Tm of the crystalline poly α-olefin only needs to exceed 35 ° C.

  If the temperature of the heat storage solution layer 11 further increases, when the boiling point Tb is reached, the heat storage solution boils and vaporization starts, but the evaporation prevention layer 13 is maintained as a highly viscous liquid. Since the crystalline poly-α-olefin constituting the evaporation preventing layer 13 is thermally decomposed without being vaporized when the temperature becomes sufficiently high, the thermal decomposition start temperature Tt is also shown in FIG.

  Thus, since the evaporation prevention layer 13 becomes a solid within the range of normal temperature, excessive evaporation of the heat storage solution can be effectively prevented (realization of the evaporation prevention function), and the heat storage solution layer 11 is transported when the heat storage device 20A is transported. Can be prevented from leaking out of the heat storage container 21 or exposed to the air layer 12 (realization of a leakage prevention function). Even if the temperature of the heat storage solution rises during the heat storage operation, the evaporation preventing layer 13 becomes a high-viscosity liquid layer, so that excessive evaporation of the heat storage solution can be effectively prevented.

  Furthermore, even if the vapor pressure rises due to evaporation of the heat storage solution or a gas such as dissolved oxygen contained in the heat storage solution is liberated, the evaporation prevention layer 13 is a highly viscous liquid. Even if the swell expands, the upper surface thereof is satisfactorily covered with the evaporation preventing layer 13. Moreover, even if the pressure rises greatly, a part of the vapor or free gas escapes from the liquid evaporation preventing layer 13 to the air layer 12, so that the pressure does not rise excessively and is sufficient for increasing the pressure of the heat storage solution. It can respond (realization of pressure relief function). Therefore, any of the evaporation prevention function, the leakage prevention function, and the pressure relaxation function can be realized satisfactorily. As a result, the heat storage solution can be stably held in the heat storage container 21, and the heat storage device 20 </ b> A excellent in handleability can be obtained.

  Further, the melting point Tm of the crystalline poly-α-olefin used as the evaporation preventing layer 13 may be normal temperature or higher as described above, but as shown in FIG. 1B, it should be lower than the boiling point Tb of the heat storage solution. Is preferred. In the present embodiment, since the aqueous solution is used as the heat storage solution, the boiling point Tb is substantially 100 ° C. Therefore, the melting point Tm of the crystalline poly α-olefin is preferably 35 ° C. or higher and lower than 100 ° C. In consideration of the evaporation preventing function, it is more preferable that the temperature is 35 ° C. or more and 80 ° C. or less. Thereby, since crystalline poly (alpha) -olefin has melting | fusing point Tm lower than boiling point Tb of a thermal storage solution, it can melt | dissolve reliably within the temperature range in which thermal storage operation | movement is performed. Therefore, any of the evaporation prevention function, the leakage prevention function, and the pressure relaxation function can be realized satisfactorily.

  Further, if the evaporation preventing layer 13 is composed of the above-mentioned crystalline poly α-olefin as a main component, the evaporation preventing layer 13 can be formed only by being laminated on the heat storage solution layer 11, and It is possible to suppress the possibility that a large amount of organic acid is generated and the quality of the heat storage solution is deteriorated. Therefore, it is possible to avoid an increase in manufacturing cost or maintenance cost of the heat storage device 20A.

(Embodiment 2)
The heat storage device 20A in the first embodiment has a configuration in which three layers of the heat storage solution layer 11, the evaporation prevention layer 13, and the air layer 12 are formed in order from the bottom in the heat storage container 21. In the present embodiment, one or more sub-evaporation preventing layers 14 are further provided above the heat storage solution layer 11 and below the evaporation preventing layer 13. And this sub-evaporation prevention layer 14 is comprised from the solvent composition which consists of an at least 1 sort (s) of water-insoluble solvent, and melting | fusing point of a solvent composition is less than normal temperature. This configuration will be specifically described with reference to FIGS. 3 (a) and 3 (b).

[Layer structure in heat storage container]
As shown in FIG. 3A, the heat storage device 20B according to the present embodiment has the same configuration as the heat storage device 20A according to the first embodiment. The four layers of the heat storage solution layer 11, the sub-evaporation prevention layer 14, the evaporation prevention layer 13, and the air layer 12 are formed in order.

  The sub-evaporation prevention layer 14 is a layer that prevents or suppresses evaporation of the heat storage solution that constitutes the heat storage solution layer 11 together with the evaporation prevention layer 13 (implements an evaporation prevention function). In this embodiment, the evaporation prevention layer 13 is used. Is formed as an independent layer below. For this reason, the evaporation preventing layer 13 is always disposed above at room temperature, and has a leakage preventing function.

  Although not shown in FIG. 3A, the sub-evaporation preventing layer 14 may be mixed with the evaporation preventing layer 13 to be substantially one layer. In this case, if both are laminated and kept at a high temperature, the evaporation preventing layer 13 and the sub-evaporation preventing layer 14 become a liquid mixture. Even if the temperature is lowered to room temperature, this mixed state is maintained in a gel state, so that the solid evaporation prevention layer 13 is formed on the upper side and a large amount of crystalline poly-α-olefin is exposed. Therefore, it has a leakage prevention function.

  The sub-evaporation preventing layer 14 is composed of a solvent composition composed of at least one water-insoluble solvent. The sub-evaporation preventing layer 14 is a solvent composition composed of at least one water-insoluble solvent, 85% to slightly less than 100% (% by weight), and the balance is composed of a mixture of additives such as antioxidants. The examples can be preferably used.

  The solvent composition constituting the sub-evaporation preventing layer 14 has a melting point Tp of less than room temperature. The melting point Tp is a temperature at which a solid changes to a liquid, but does not exhibit a melting point when it is a multi-component mixture like a solvent composition comprising at least one water-insoluble solvent. Therefore, when the sub-evaporation preventing layer 14 is composed of a multi-component solvent composition, the temperature (pour point) at which the sub-evaporation prevention layer 14 stops flowing under a certain condition is obtained, and the pour point is used as an alternative display of the melting point. In the present embodiment, the pour point employs a value measured in accordance with Japanese Industrial Standard (JIS) K2269, and the measurement method is as follows. In other words, after the sample taken in the test tube is preheated to 46 ° C, it is cooled by the specified method, and the measurement is started from a temperature 10 ° C higher than the expected pour point, and the test tube is cooled every time the temperature drops by 2.5 ° C. Remove from bath and observe. In this way, a temperature at which the test tube does not move at all for 5 seconds even when it is placed sideways is obtained, and a temperature higher by 2.5 ° C. is set as a pour point.

  When two or more sub-evaporation prevention layers 14 are formed, each of the sub-evaporation prevention layers 14 may be composed of a solvent composition having a different composition and may be formed independently without being mixed with each other. Alternatively, the sub-evaporation preventing layers 14 may be mixed with each other or may be mixed with the evaporation preventing layer 13.

  One or more water-insoluble solvents used to constitute the solvent composition are nonpolar solvents that are substantially non-polar, a single layer that is substantially free of water and mixed with water at room temperature. A low-polarity solvent or the like having a low degree of polarity may be used, and the liquid may be shown at least within the range of normal temperature.

  Specific examples of the water-insoluble solvent include saturated alkanes such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, and cyclohexane; toluene, xylene, Aromatic alkanes such as benzene; haloalkanes such as 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, carbon tetrachloride, methylene chloride (dichloromethane); methyl acetate, ethyl acetate, acetic acid Esters such as isopropyl; Ethers such as diethyl ether, isopropyl ether, ethyl tert-butyl ether, furan; Mineral oils such as polyalphaolefin wax, paraffin wax, silicone oil; Oil, soybean oil, sesame oil, rapeseed oil, rice oil, coconut oil, safflower oil, palm kernel oil, coconut oil, cottonseed oil, sunflower oil, sesame oil, olive oil, peanut oil, almond oil, grape seed oil, mustard oil, fish oil, etc. Edible oils and fats; industrial fats and oils such as castor oil and oilseed oil; but not limited thereto. These water-insoluble solvents may be used alone or in combination of two or more. Moreover, when a solvent composition contains multiple types of water-insoluble solvent, if the effective evaporation prevention function is realizable, the composition of each solvent will not be specifically limited, either.

  As an example of a particularly preferable water-insoluble solvent in the present embodiment, among the hydrocarbons such as the saturated alkanes and aromatic alkanes, at least one of the hydrocarbons having a carbon number in the range of 24 to 44 is used. Can be mentioned. More specifically, polyalphaolefin wax or paraffin wax containing a component having a carbon number within the above range can be exemplified.

  The fact that the solvent composition contains such a water-insoluble solvent means that the solvent composition contains a hydrocarbon having a specific range of molecular weight. Therefore, as will be described later, the fluidity retention of the sub-evaporation preventing layer 14 at a low temperature can be made more reliable. More desirably, the sub-evaporation preventing layer 14 retains fluidity at a low temperature if the water-insoluble solvent constituting the main component of the solvent composition contains a hydrocarbon having a carbon number in the range of 24 to 44. Can be made even more reliable.

  The carbon structure of the water-insoluble solvent constituting the solvent composition will be described. Generally speaking, saturated alkanes (also called saturated hydrocarbons) are gases at room temperature when the carbon number is 4 or less, liquid at room temperature with 5 to about 18 carbon atoms, and room temperature when the carbon number exceeds about 18 It is solid. The regularity of this general theory is a story that consists of saturated alkanes of straight-chain structure in which the carbon is arranged in a straight line and has no branches. When saturated alkanes with branches are used, the carbon number exceeds about 18. Also becomes liquid at room temperature. Therefore, for example, when an α-olefin having 8 to 10 carbon atoms (unsaturated alkene having a double bond at the terminal and others having a single bond structure) is subjected to a hydrogenation treatment, the number of carbon atoms is in the range of 24 to 44. Saturated alkanes (or hydrocarbons close to saturated alkanes) containing at least one of the hydrocarbons in (1) are produced. Moreover, since this saturated alkane is a saturated alkane having many branches by devising a polymerization reaction, it is liquid at room temperature. Synthetic oils and semi-synthetic oils can be obtained using this process, but mineral oils obtained by refining crude oil contain this water-insoluble solvent composed of hydrocarbons with such characteristics. A water-soluble solvent is used.

  Such hydrocarbons with a carbon number in the numerical range are often left to the control because it is difficult to control the carbon number with current technology. Therefore, when it becomes a hydrocarbon having less than 24 carbon atoms, it is likely to be a saturated alkane having a linear structure, so that a highly volatile liquid is generated, which is immediately volatilized and has a short life. On the other hand, when the hydrocarbon number exceeds 44, it becomes difficult to handle because it tends to be solid at room temperature, and it becomes even more difficult when the carbon number exceeds 50. As described above, the water-insoluble solvent contains at least one of hydrocarbons having a carbon number in the range of 24 to 44 because it is difficult to volatilize and has a long life, is difficult to be solid at room temperature, and is easy to handle. It was set as the composition which was supposed to be.

  In addition to this, hydrocarbons having a carbon number in the range of 24 to 44 are difficult to produce organic acids and are highly airtight, so that evaporation of the heat storage solution is prevented or suppressed and oxygen in the air is stored in the heat storage solution. There is also an advantage that it is difficult to enter.

  Furthermore, the solvent composition may contain other known components in addition to the water-insoluble solvent. Specifically, an antioxidant, a corrosion inhibitor, a rust inhibitor, an antifoaming agent, etc. can be illustrated, for example. The addition amount and addition method of these additives are not particularly limited, and a known range or method can be suitably used.

  Although the specific composition of the sub-evaporation preventing layer 14 is not particularly limited, in the present embodiment, as described above, at least one water-insoluble solvent is within a range of 85 to 100% by weight, The structure which the mixture containing the said additive is remainder (within the range of slightly 0%-15 weight%) can be mentioned preferably. Of course, it goes without saying that the composition can be appropriately designed according to various conditions such as the performance required for the sub-evaporation prevention layer 14 and the usage environment of the heat storage device 20A.

  The temperature condition of the solvent composition is not particularly limited, but it is preferable that the solvent composition is liquid within the range of normal temperature, and therefore the melting point is preferably less than normal temperature. Further, as will be described later, the melting point Tp of the solvent composition constituting the sub-evaporation preventing layer 14 is preferably lower than the freezing point Tf of the heat storage solution. With this configuration, even if the temperature is lowered until the heat storage solution is solidified, the solvent composition can maintain fluidity, so that prevention of evaporation of the heat storage solution can be effectively realized even at a low temperature. In addition, since the solvent composition is not solidified even when the heat storage solution is solidified, it is possible to relieve the volume expansion associated with the solidification of the heat storage solution, thereby further reducing the pressure increase in the heat storage solution. It can be certain.

[Function of sub-evaporation prevention layer]
Next, a specific function of the sub-evaporation preventing layer 14 containing the water-insoluble solvent will be specifically described with reference to FIG.

  Regarding the heat storage solution layer 11, the evaporation prevention layer 13, and the sub-evaporation prevention layer 14, a change in phase state from a solid phase to a liquid phase accompanying a temperature change is compared. As shown in FIG. 3 (b), the phase change of the heat storage solution layer 11 and the evaporation preventing layer 13 is as described in the first embodiment, but the sub-evaporation preventing layer 14 is shown in FIG. 3 (b). In the example shown, even if it is within the range of normal temperature or exceeds normal temperature, it remains substantially liquid.

  As described above, the sub-evaporation preventing layer 14 is a liquid in the range of normal temperature, but the evaporation preventing layer 13 disposed on the upper side thereof is a solid, so that the evaporation preventing layer 13 realizes an evaporation preventing function for the heat storage solution. In addition, the leakage preventing function can be realized for the heat storage solution and the sub-evaporation prevention layer 14. Further, when the temperature of the heat storage solution rises during the heat storage operation, the evaporation prevention layer 13 becomes a high viscosity liquid layer, and the sub-evaporation prevention layer 14 is maintained as a relatively low viscosity liquid layer regardless of use or non-use. Therefore, the heat storage solution is protected by the two liquid layers, and the adhesion between the liquid layers increases.

  As a result, in these layers, the vapor passage holes are narrowed and the function of preventing evaporation is improved, but the excess heat storage solution vapor or dissolved oxygen is released in these layers as compared with the case where each is used alone. (Improvement of pressure relaxation function). In addition, after the heat storage operation, a crack generated after the evaporation prevention layer 13 is cured can be filled with the sub-evaporation prevention layer 14 (improvement of the evaporation prevention function and the leakage prevention function).

  Moreover, as shown in FIG.3 (b), melting | fusing point Tp of the solvent composition which comprises the sub-evaporation prevention layer 14 is lower than the freezing point Tf of a thermal storage solution. Thereby, even if the temperature of the heat storage device 20B is lowered until the heat storage solution is solidified, the evaporation preventing layer 14 made of the solvent composition can maintain fluidity, so that the evaporation preventing function can be effectively realized even in a low temperature state. Can do. In addition, since the solvent composition of the sub-evaporation prevention layer 14 formed from the solidification of the heat storage solution layer 11 is not solidified, the volume expansion associated with the solidification of the heat storage solution can be relaxed, and the pressure relaxation function is further enhanced. It can be certain. In particular, if the solvent composition contains a hydrocarbon water-insoluble solvent having a carbon number in the range of 24 to 44, the sub-evaporation preventing layer 14 can be better maintained in fluidity at low temperatures. .

  As described above, the sub-evaporation prevention layer 14 is formed in the heat storage container 21 in addition to the evaporation prevention layer 13, so that any of the evaporation prevention function, the leakage prevention function, and the pressure relaxation function by the evaporation prevention layer 13 is good. In addition, the functions can be further improved. Therefore, the heat storage solution can be stably held in the heat storage container 21, and the heat storage device 20B excellent in handleability can be obtained.

The crystalline poly α-olefin constituting the evaporation preventing layer 13 has a specific gravity of about 0.90 g / cm ³ . The specific gravity of the solvent composition constituting the sub-evaporation preventing layer 14 is about 0.83 to 0.87 g / cm ³ in the case of hydrocarbon. When both are laminated and kept at a high temperature, the evaporation preventing layer 13 and the sub-evaporation preventing layer 14 become a liquid mixture. Even if the temperature is lowered to room temperature, this mixed state is maintained in a gel state, so that the solid evaporation prevention layer 13 is formed on the upper side and a large amount of crystalline poly-α-olefin is exposed. Therefore, it has a leakage prevention function.

On the other hand, for example, when an organic silicone type of about 0.93 to 0.97 g / cm ³ is used as the sub-evaporation prevention layer 14, the crystalline poly α-olefin type evaporation prevention layer 13 has a specific gravity relationship. On the upper side, the organic silicone-based sub-evaporation preventing layer 14 is on the lower side, and the leakage preventing function can be satisfactorily exhibited. Therefore, it is preferable that the specific gravity of the crystalline poly α-olefin (or the evaporation preventing composition containing the same) constituting the evaporation preventing layer 13 is smaller than the specific gravity of the solvent composition constituting the sub-evaporation preventing layer 14. As a result, the evaporation preventing layer 13 is lighter than the sub-evaporation preventing layer 14 even if the crystalline poly α-olefin as a main component is solid, so that the evaporation preventing layer 13 is always on the upper layer of the sub-evaporation preventing layer 14. It will “float”. Therefore, even if the evaporation preventing layer 13 becomes a liquid phase at a high temperature, the evaporation preventing function can be further ensured.

  In addition to this, the amount of the sub-evaporation prevention layer 14 that is a liquid increases as it is located below the evaporation prevention layer 13. Therefore, after the heat storage operation, cracks that occur after the evaporation preventing layer 13 is cured can be more reliably filled with the sub-evaporation preventing layer 14. As a result, the evaporation prevention function and the leakage prevention function can be further improved. Furthermore, both the evaporation preventing layer 13 and the sub-evaporation preventing layer 14 can be easily formed by simply laminating on the heat storage solution layer 11, and the evaporation preventing layer 13 contains crystalline poly α-olefin as described above. Since it is made into the main component, possibility that an organic acid will produce | generate in large quantities and degrade the quality of a thermal storage solution can be suppressed. Therefore, an increase in manufacturing cost or maintenance cost of the heat storage device 20B can be avoided.

  Needless to say, even if the vertical positional relationship between the evaporation preventing layer 13 and the sub-evaporation preventing layer 14 is reversed, the leakage preventing function can be exhibited. That is, even when a crack occurs after the evaporation prevention layer 13 is cured, the sub-evaporation prevention layer is liquid, so that the crack can be filled.

(Embodiment 3)
The heat storage device 20A according to the first embodiment or the heat storage device 20B according to the second embodiment each includes the heat storage container 21 and the heat exchanger 22 for heat storage, but the heat storage according to the present embodiment. The apparatus further includes a heating source, and is configured to be able to store the waste heat of the heating source. This configuration will be specifically described with reference to FIGS. 4 (a) and 4 (b).

  As shown in FIGS. 4A and 4B, the heat storage device 20C according to the present embodiment includes a heat conductive member 25 and a compression as a heating source in addition to the heat storage container 23 and the heat storage heat exchanger 24. A machine 26 is provided. In addition, the V1-V1 arrow cross section in Fig.4 (a) is equivalent to the longitudinal cross-sectional view of 20 C of heat storage apparatuses shown in FIG.4 (b), and the V2-V2 arrow cross section in FIG.4 (b) is FIG.4 (a). This corresponds to a cross-sectional view of the heat storage device 20C shown in FIG.

  Like the heat storage container 21 in the first embodiment, the heat storage container 23 includes a box portion 231 and a lid portion 232, and a lid portion 232 is attached so as to close the upper opening 233 of the box portion 231. The shape of the box portion 231 is substantially a rectangular parallelepiped shape, similar to the box portion 211 in the first or second embodiment, but the shape of the internal space for storing the heat storage solution is the same as that of the box portion 211. In contrast, as shown in FIG. 4A, it has a substantially U-shaped cross section so as to surround the side surface of the compressor 26. As shown in FIG. 4B, a heat storage heat exchanger 24 is provided inside the box portion 231, and the heat storage solution layer 11 is formed so as to immerse most of this. Further, the sub-evaporation prevention layer 14 and the evaporation prevention layer 13 are laminated in this order above the heat storage solution layer 11, and further, above the evaporation prevention layer 13, through a vent hole 234 provided in the lid 232. An air layer 12 is formed by the outside air flowing in.

  The compressor 26 compresses the refrigerant used in the air conditioner, and a compressor having a known configuration is used. In FIGS. 4A and 4B, for convenience of explanation, the compressor 26 schematically shows only the outer shape. In the present embodiment, the compressor 26 has an approximately rectangular parallelepiped shape as shown in FIGS. 4A and 4B, and surrounds three of the four side surfaces of the rectangular parallelepiped shape. The heat storage container 23 is located in the area. Since the internal space of the heat storage container 23 (box portion 211) has a substantially U-shaped cross section as described above, the compressor 26 is positioned in a region where the recessed portion is located in the U-shaped cross section. As a result, at least a part of the periphery of the compressor 26 is surrounded by the heat storage container 23.

  Thus, if the heat storage container 23 is located around the compressor 26, the compressor 26 is substantially integrated with the heat storage container 23, so that the waste heat generated in the compressor 26 is stored in the heat storage container 23. Almost no escape to the outside is transmitted to the heat storage solution layer 11 in the heat storage container 23. Therefore, the compressor 26 which is an external device can be used as a heating source, and waste heat from the compressor 26 can be efficiently stored.

  Here, it is particularly preferable that a layered heat conductive member 25 is provided between the side surface of the compressor 26 and the heat storage container 23. The compressor 26 may be in direct contact with the heat storage solution layer 11 in the heat storage container 23, but in this case, it is necessary to waterproof the side surface of the compressor 26. On the other hand, the shape of the heat storage container 23 may be configured to match the compressor 26 and have a substantially U-shaped cross section, but in addition to the processing of the heat storage container 23 becoming complicated and the cost rising, It becomes difficult to improve the adhesion between the outer surface of the heat storage container 23 and the side surface of the compressor 26. Therefore, it is preferable to provide the heat conductive member 25 as in the present embodiment.

  The specific configuration of the heat conductive member 25 is not particularly limited as long as it can cover the periphery of the compressor 26 and can transfer the heat from the compressor 26 to the heat storage solution layer 11 in a good manner. . Specifically, for example, a metal sheet formed of copper, silver, aluminum, or an alloy thereof; a heat conductive sheet in which graphite or metal particles are dispersed in a resin composition; a graphite or metal particle in a gel composition Heat conductive grease dispersed in the material.

  Thus, the heat storage container 23 is in contact with the compressor 26 via the heat conductive member 25, so that the heat from the compressor 26 can be recovered well by the heat storage device 20C. In particular, if the heat conductive member 25 is a heat conductive sheet, if a flexible material, for example, an elastomer material such as EPDM (ethylene-propylene-diene rubber) or silicone rubber is selected as the resin composition, the compressor 26 Even if unevenness is present on the side surface, the contact between the compressor 26 and the heat storage container 23 can be improved, so that the heat conduction from the compressor 26 to the heat storage container 23 is made even smoother. Can do.

  Also in the present embodiment, the evaporation preventing layer 13 and the sub-evaporation preventing layer 14 described in the first and second embodiments are formed in the heat storage container 23. Therefore, the evaporation prevention function, the leakage prevention function, and the pressure relaxation function are all realized well by these layers, so that the heat storage solution can be stably held in the heat storage container 23, and the handling property is excellent. The heat storage device 20C can be obtained.

  In addition, in this Embodiment, although the compressor 26 was illustrated as a heating source, it is not limited to this, It is not limited to this, It is another heating source with which the apparatus with which heat storage apparatus 20C which concerns on this invention is applied, such as an air conditioning apparatus. There may be. Moreover, the heat source should just be provided in the exterior of the thermal storage solution layer 11, and does not necessarily need to be the exterior of the thermal storage container 23. FIG. Further, the heat source may not be surrounded by the heat storage container 23. For example, as long as the compressor 26 has a wide flat side surface, the thermal storage solution layer 11 may be configured only to contact the flat surfaces. Moreover, in this Embodiment, although the thermal storage container 23 has enclosed the circumference | surroundings of the compressor 26, you may surround the bottom face or upper surface of the compressor 26, for example. The same applies if the heating source is other than the compressor 26.

(Embodiment 4)
The first to third embodiments exemplify the configuration of the heat storage device, but in the present embodiment, an example of an air conditioner that is a typical application example of the heat storage device having the above configuration. This will be specifically described with reference to FIG.

[Configuration of air conditioner]
As shown in FIG. 5, the air conditioner 30 according to the present embodiment includes an indoor unit 31 and an outdoor unit 32 that are connected to each other by a refrigerant pipe. The outdoor unit 32 is the same as that of the third embodiment. This heat storage device 20C is provided. The indoor unit 31, the outdoor unit 32, and the external pipe 310 are connected to the indoor unit internal pipe 311 and the first pipe 301 and the second pipe 302 that are the outdoor unit internal pipes through the pipe joint 40.

  Inside the indoor unit 31, an indoor unit internal pipe 311 and an indoor heat exchanger 33 are provided. Inside the outdoor unit 32, the heat storage device 20C, the compressor 26, the outdoor unit internal pipe, and the outdoor heat exchanger 34 are provided. Various valve members and the like are provided. And since the indoor unit 31 and the outdoor unit 32 are mutually connected by the external piping 310 as above-mentioned, the refrigerating cycle of the air conditioning apparatus 30 is comprised by the said structure. In the following description, in the refrigerant pipe (indoor unit internal pipe 311, external pipe 310, and outdoor unit internal pipe), the upstream side or the downstream side in the direction in which the refrigerant flows is simply referred to as the upstream side or the downstream side.

  The configuration of the indoor unit 31 will be specifically described. The indoor unit internal pipe 311 connected to the external pipe 310 is connected to the indoor heat exchanger 33. In addition to the indoor heat exchanger 33, an air blower fan (not shown), upper and lower blades (not shown), left and right blades (not shown), and the like are provided inside the indoor unit 31.

  The indoor heat exchanger 33 exchanges heat between the indoor air sucked into the indoor unit 31 by the blower fan and the refrigerant flowing inside the indoor heat exchanger 33, and was heated by heat exchange during heating. While air is blown into the room (block arrow in the figure), air cooled by heat exchange is blown into the room during cooling. The upper and lower blades change the direction of air blown from the indoor unit 31 up and down as necessary, and the left and right blades change the direction of air blown from the indoor unit 31 to right and left as needed. In FIG. 5, for the convenience of explanation, the detailed configuration of the indoor unit 31 (the blower fan, the upper and lower blades, the left and right blades, etc.) is omitted.

  The configuration of the outdoor unit 32 will be specifically described. In addition to the compressor 26, the heat storage device 20C, and the outdoor heat exchanger 34, the outdoor unit 32 includes a strainer 35, an expansion valve 42, a four-way valve 41, a first An electromagnetic valve 43, a second electromagnetic valve 44, an accumulator 36, and the like are provided. Of the first pipe 301 and the second pipe 302 connected to the external pipe 310, the first pipe 301 is connected to a discharge port (not shown) of the compressor 26. Therefore, the compressor 26 is connected to the indoor heat exchanger 33 in the indoor unit 31.

  As described in the third embodiment, the compressor 26 is provided so as to be substantially integrated with the heat storage container 23 of the heat storage device 20C, and the periphery of the compressor 26 includes the heat conductive member 25. The heat storage solution layer 11 is located through. A sub-evaporation preventing layer 14 and an evaporation preventing layer 13 are formed in this order on the upper surface of the heat storage solution layer 11. In FIG. 4, for convenience of explanation, the description of the lid 232 and the air layer 12 constituting the heat storage container 23 is omitted. Inside the heat storage container 23, a heat storage heat exchanger 24 is provided so as to be immersed in the heat storage solution layer 11, and an inlet (not shown) is connected to the sixth pipe 306. The sixth solenoid valve 44 is provided in the sixth pipe 306.

  Of the first pipe 301 and the second pipe 302 connected to the external pipe 310, the second pipe 302 is branched into a third pipe 303 and a sixth pipe 306 that are outdoor unit internal pipes. The second pipe 302 includes the strainer 35, and as described above, one is connected to the external pipe 310 and the other is connected to the third pipe 303 through the expansion valve 42. The sixth pipe 306 is branched from the second pipe 302 on the upstream side of the strainer 35.

  The third pipe 303 connects the expansion valve 42 and the outdoor heat exchanger 34, and the outdoor heat exchanger 34 is connected to the suction port (not shown) of the compressor 26 via the fourth pipe 304. Further, an accumulator 36 for separating the liquid-phase refrigerant and the gas-phase refrigerant is provided on the fourth pipe 304 on the compressor 26 side. The discharge port of the compressor 26 is connected to the first pipe 301, and the fifth pipe 305 branches from between the discharge port of the compressor 26 and the four-way valve 41 in the first pipe 301. ing. A first electromagnetic valve 43 is provided in the fifth pipe 305. The first pipe 301 is connected between the expansion valve 42 of the third pipe 303 and the outdoor heat exchanger 34 via the fifth pipe 305.

  The sixth pipe 306 branched from the second pipe 302 is connected to the inlet part (not shown) of the heat storage heat exchanger 24 as described above, but the outlet part ( (Not shown) is connected to the fourth pipe 304 via the seventh pipe 307. The seventh pipe 307 branches from the fourth pipe 304 at a position upstream from the accumulator 36.

  Further, an intermediate portion between the first pipe 301 and the fourth pipe 304 is connected by a four-way valve 41. Specifically, in the first pipe 301, the four-way valve 41 is provided on the upstream side from the position where the fifth pipe 305 branches, and in the fourth pipe 304, on the upstream side from the position where the seventh pipe 307 branches. A four-way valve 41 is provided at a position downstream from the position connected to the outdoor heat exchanger 34.

  Here, among the outdoor unit internal pipes, the fourth pipe 304 constitutes a heat pump circulation path, and the fifth pipe 305 and the sixth pipe 306 constitute a refrigerant bypass path. That is, the air conditioning apparatus 30 according to the present embodiment has a heat pump type configuration. With this configuration, the heating operation can be performed non-stop in parallel with the defrosting operation, as will be described later. This point will be described later.

  Each device or member (refrigerant pipe, pipe joint 40, indoor heat exchanger 33, blower fan, upper and lower blades, left and right blades, outdoor heat exchanger 34, strainer 35, expansion valve 42, excluding the compressor 26 and the heat storage device 20C. The specific configuration of the four-way valve 41, the first electromagnetic valve 43, the second electromagnetic valve 44, the accumulator 36, etc.) is not particularly limited, and a known configuration can be suitably used. Further, the number of devices and members including the compressor 26 and the heat storage device 20C, the arrangement, and the like are not limited to the configuration illustrated in FIG. 5, and may be other arrangements capable of realizing a heat pump configuration.

  The compressor 26, the blower fan, the upper and lower blades, the left and right blades, the four-way valve 41, the expansion valve 42, the first electromagnetic valve 43, the second electromagnetic valve 44, and the like are electrically connected to a control device (not shown, for example, a microcomputer). Connected to each other and controlled by the control device.

[Operation of air conditioner]
Next, the operation of the air-conditioning apparatus 30 having the above-described configuration will be specifically described with reference to FIG. 5 by taking normal heating operation and defrosting / heating operation as examples.

  First, the normal heating operation will be described. In this case, the first electromagnetic valve 43 and the second electromagnetic valve 44 are controlled to be closed, and the refrigerant discharged from the discharge port of the compressor 26 flows through the first pipe 301 and flows from the four-way valve 41 to the external pipe 310 and the indoors. It reaches the indoor heat exchanger 33 via the machine internal pipe 311. In the indoor heat exchanger 33, the refrigerant condenses by heat exchange with room air. The refrigerant flows from the indoor heat exchanger 33 through the second pipe 302 to the expansion valve 42 and is decompressed by the expansion valve 42. The decompressed refrigerant reaches the outdoor heat exchanger 34 through the third pipe 303. In the outdoor heat exchanger 34, the refrigerant evaporates due to heat exchange with outdoor air, and this refrigerant flows through the fourth pipe 304 and returns from the four-way valve 41 to the suction port of the compressor 26. The heat (waste heat) generated in the compressor 26 is accumulated in the heat storage solution layer 11 in the heat storage container 23 from the outer wall of the compressor 26 via the heat conductive member 25.

  Next, defrosting / heating operation will be described. When the frost is generated in the outdoor heat exchanger 34 during the normal heating operation and further the frost is grown, the ventilation resistance of the outdoor heat exchanger 34 is increased and the air volume is decreased, so that the inside of the outdoor heat exchanger 34 is reduced. The evaporation temperature of the liquid drops. Therefore, when a temperature sensor (not shown) for detecting the piping temperature of the outdoor heat exchanger 34 detects that the evaporation temperature has decreased as compared with the time of non-frosting, the controller performs the defrosting / heating from the normal heating operation. An instruction to drive is output.

  When the normal heating operation is shifted to the defrosting / heating operation, the first electromagnetic valve 43 and the second electromagnetic valve 44 are controlled to open, and in addition to the refrigerant flow during the normal heating operation described above, the first electromagnetic valve 43 and the second electromagnetic valve 44 are discharged from the discharge port of the compressor 26. Part of the vapor-phase refrigerant flows through the fifth pipe 305 and the first electromagnetic valve 43, joins the refrigerant flowing through the third pipe 303, heats the outdoor heat exchanger 34, and condenses into a liquid phase. Thereafter, it flows through the fourth pipe 304 and returns to the suction port of the compressor 26 via the four-way valve 41 and the accumulator 36.

  Further, a part of the liquid-phase refrigerant that is divided between the indoor heat exchanger 33 and the strainer 35 in the second pipe 302 is stored in the heat storage heat exchanger 24 via the sixth pipe 306 and the second electromagnetic valve 44. By absorbing heat from the solution layer 11, it is evaporated and vaporized. The gas phase refrigerant flows through the seventh pipe 307, joins the refrigerant flowing through the fourth pipe 304, and returns from the accumulator 36 to the suction port of the compressor 26.

  The refrigerant that returns to the accumulator 36 includes liquid phase refrigerant that returns from the outdoor heat exchanger 34, and this liquid phase refrigerant is mixed with high-temperature gas-phase refrigerant that returns from the heat storage heat exchanger 24. The evaporation of the liquid phase refrigerant is promoted, the liquid phase refrigerant is prevented from returning to the compressor 26 through the accumulator 36, and the reliability of the compressor 26 can be improved.

  The temperature of the outdoor heat exchanger 34 that has become below freezing due to the attachment of frost at the start of defrosting and heating is heated by the gas-phase refrigerant discharged from the discharge port of the compressor 26, and the frost is melted at around zero degrees. When the frost has finished melting, the temperature of the outdoor heat exchanger 34 begins to rise again. If the temperature sensor detects the temperature increase of the outdoor heat exchanger 34, the control device determines that the defrosting is completed, and the control device outputs an instruction from the defrosting / heating operation to the normal heating operation. .

  Thus, in this Embodiment, since the air conditioning apparatus 30 is a heat pump type, even if frost formation has arisen in the outdoor heat exchanger 34 at the time of heating operation or in winter, it is a refrigerant | coolant bypass path. Refrigerant can be collected and defrosted by flowing a refrigerant through certain fifth pipe 305 and sixth pipe 306. Therefore, since the heating operation can be performed in parallel with the defrosting operation, for example, even in a cold morning in winter, the heating can be performed in a short time. In addition, since waste heat from the compressor 26 can be effectively recovered, an energy saving operation is possible.

  Further, as described in the third embodiment, the heat storage device 20C effectively prevents excessive evaporation of the heat storage solution because the evaporation prevention layer 13 and the sub-evaporation prevention layer 14 are formed in the heat storage container 23. In addition to being able to achieve (realization of the evaporation prevention function), it is possible to suppress the heat storage solution from leaking out of the heat storage container 21 or being exposed to the air layer 12 (realization of the leakage prevention function), and further, the pressure of the heat storage solution layer 11 Even if the temperature rises greatly, a part of the vapor or free gas escapes from the liquid evaporation preventing layer 13 to the air layer 12, so that the pressure does not rise excessively and can sufficiently cope with the pressure rise of the heat storage solution. (Pressure relaxation function can be realized).

  In addition, in this Embodiment, although the air conditioning apparatus 30 becomes a heat pump type structure, it is not limited to this, and it cannot be overemphasized that structures other than a heat pump type may be sufficient. Further, in place of the heat storage device 20C, the heat storage device 20A or 20B described in the first or second embodiment may be provided, or a heat storage device having another configuration within the scope of the present invention may be provided. Furthermore, in this Embodiment, although the compressor 26 is used as a heat source, you may use other apparatuses, such as an electric heater, as a heat source.

  Furthermore, in this Embodiment, although the air conditioning apparatus was illustrated as an example which applies heat storage apparatus 20A-20C which concerns on this invention, of course, this invention is not limited to this, A heat storage apparatus is provided other than an air conditioning apparatus. It can be suitably used for various devices. Specifically, a refrigerator, a water heater, a heat pump type washing machine can be mentioned, for example.

  The present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to this. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention. Various evaluations and evaluations in the following examples and comparative examples were performed as follows.

(Details of evaluation items)
[Evaporation rate]
This evaluation item is for evaluating the evaporation prevention function, and was evaluated by characteristics at 100 ° C. Specifically, a 31% aqueous solution of ethylene glycol was filled as a heat storage solution in a heat storage container, an evaporation preventing layer was laminated 20 mm on the top, and left in a 100 ° C. drier for 5 days to measure weight loss.

Weight loss with (X mg), and dividing by the cross-sectional area of the evaporation preventing layer (Scm ²⁾ and the test period (Y date), the evaporation rate [X / (S * Y) mg / (cm 2 · day)] Calculated. It means that the smaller the calculated value, the more excellent the evaporation preventing effect. Note that the evaporation rate was evaluated only by the evaporation prevention layer without filling the heat storage solution, and the value of the evaporation rate was calculated in consideration of the weight reduction rate of the material itself constituting the evaporation prevention layer.

  When the calculated value was 1 or less, it was evaluated as “、”, when it was 2-4, “◯”, when it was 5-6, “Δ”, when it exceeded 7, it was evaluated as “x”.

[Convenience of transportation]
This evaluation item is for evaluating the leakage prevention function. After the evaluation of the evaporation rate, it is already normal temperature at this point, but the heat storage container is inclined 45 degrees to store the heat storage solution (ethylene glycol 31% aqueous solution). It was evaluated whether or not the ink protruded from the evaporation prevention layer. “◎” if it does not protrude at all, “○” if the amount of the solution that protrudes is very small, such as 雫, “△” if the solution is slowly but gradually protrudes, If it protruded, it was evaluated as “×”.

[Pressure resistance]
This evaluation item is for evaluating the pressure relaxation function, and after the completion of the evaluation of the evaporation rate, how much the evaporation preventing layer has moved from the initial stage was evaluated.

  If there is no movement at all, “◎” is around 1 mm (equivalent to 5% of the evaporation prevention layer height of 20 mm), and “◯” is about 4 ± 1 mm (with respect to the evaporation prevention layer height of 20 mm). If it is a movement of 1.5 to 2.5%), it was evaluated as “Δ”, and if it was a movement of 6 mm or more (corresponding to 3% or more with respect to the height of the evaporation preventing layer 20 mm), it was evaluated as “X”.

[Machinability]
Although this evaluation item is not related to the evaluation of the evaporation prevention function, the leakage prevention function, and the pressure relaxation function, the evaluation was performed because the cost increase of the heat storage device can be suppressed if the evaporation prevention layer can be easily formed. Specifically, the workability was evaluated as to whether an evaporation prevention layer can be formed by a simple method and quality control.

  If the raw material is stored in a container and the evaporation prevention layer without liquid leakage can be easily formed by heating for the experiment, “◎”, the main raw material is stored in the container and the end face is made of an auxiliary adhesive. Evaporation with less liquid leakage is possible by simply covering and “○” if an evaporation prevention layer with little liquid leakage can be formed, storing the main raw material in a container and covering the end surface with an auxiliary member in a complicated manner. If the prevention layer could be formed, “Δ” was evaluated. If the raw material used as the evaporation prevention layer was stored in a container and an evaporation prevention layer without liquid leakage could not be formed even using a complicated method, the evaluation was “X”.

[Production amount of organic acid]
Although this evaluation item is not related to the evaluation of the evaporation prevention function, the leakage prevention function, and the pressure relaxation function, if no organic acid is generated from the evaporation prevention layer, the deterioration of the quality of the heat storage solution can be suppressed, Since it was not necessary to replenish or replace the heat storage solution excessively, it was possible to suppress an increase in the cost of the heat storage device. Specifically, for the amount of organic acid produced, a test method in which this method was partially improved was adopted based on the test method defined in ASTM-D2619.

  First, 150 g of a material used as an evaporation preventing layer was mixed with 50 g of deionized water and 3.3 g of copper powder, put into an Erlenmeyer flask, a water-cooled tube was attached to the upper part, and a reflux test was performed at a water temperature of 95 ° C. for 48 hours. . Immediately after the test, the copper powder and the supernatant oil were separated, only water was taken out, and the concentrations of eluted formic acid and acetic acid were analyzed. If the total concentration of formic acid and acetic acid is less than 10 ppm, it is judged as an extremely small amount, and if it is in the range of less than 10-40 ppm, it is judged as a minute amount, and “◯”, within the range of less than 40-100 ppm. If it was, it was judged to be a medium amount, “Δ”, and if it was 100 ppm or more, it was judged to be a large amount and evaluated as “×”.

[Comprehensive judgment]
Comprehensive evaluation evaluated each evaluation item of the said evaporation rate, conveyance convenience, pressure resistance, workability, and the amount of organic acid production comprehensively.

  Each evaluation item was “◎” or “○”, and if there was no Δ or “x”, the comprehensive judgment was evaluated as “◎”. In addition, each evaluation item was “good”, and if there were no “good”, “△”, and “x”, the comprehensive judgment was evaluated as “good”. Further, if there is Δ in any one of the evaluation items, the overall judgment was evaluated as “Δ” even if there were ◎ and ○. In addition, if even one of the evaluation items had x, the comprehensive judgment was evaluated as “x” even if there were other ◎, ○ or Δ.

(Production of crystalline poly α-olefin)
Two types of crystalline poly-α-olefin A and crystals are polymerized by using any of the α-olefin monomers having 16 to 44 carbon atoms using the production method disclosed in Patent Document 4. Poly α-olefin B was produced. In the following examples, any one of these crystalline poly-α-olefins was used as an evaporation preventing layer.

Example 1
A heat storage solution layer is formed with a 31% aqueous solution of ethylene glycol, which is a heat storage solution, in the heat storage container, and crystalline poly α-olefin A (melting point 60 ° C., ΔH = 120 J / g, density is formed on the heat storage solution layer. 0.90 g / cm ³ ) was laminated to form an evaporation preventing layer, and each of the above evaluations was performed. The results are shown in Table 1.

(Example 2)
Example 1 except that crystalline poly α-olefin B (melting point: 40 ° C., ΔH = 80 J / g, density: 0.90 g / cm ³ ) was used as the evaporation preventing layer, and this was laminated on the heat storage solution layer. Each evaluation was performed in the same manner as in 1. The results are shown in Table 1.

Example 3
In the heat storage container, a heat storage solution layer is formed with a 31% aqueous solution of ethylene glycol, which is a heat storage solution, and on the heat storage solution layer, a hydrocarbon comprising a poly α-olefin having 24 to 44 carbon atoms as a sub-evaporation prevention layer System oil A (density 0.83, pour point −50 ° C.) and the crystalline poly α-olefin A used in Example 1 were mixed and laminated as an evaporation preventing layer, and each evaluation was performed. The results are shown in Table 1.

Example 4
Hydrocarbon oil B (density 0.87, pour point −25 ° C.) made of mineral oil having 24 to 46 carbon atoms was used as the sub-evaporation prevention layer, and this was used as the crystalline poly α- used in Example 1 above. Each of the above evaluations was performed in the same manner as in Example 3 except that the mixture was further laminated on the evaporation prevention layer made of olefin A, and these were laminated on the heat storage solution layer. The results are shown in Table 1.

(Example 5)
As the evaporation preventing layer, the crystalline poly α-olefin B used in Example 2 is used, and a sub-evaporation preventing layer made of hydrocarbon oil B made of mineral oil having 24 to 46 carbon atoms is mixed and laminated thereon. And each said evaluation was performed like the said Example 4 except having laminated | stacked these 1 type | formulas on the thermal storage solution layer. The results are shown in Table 1.

(Comparative Example 1)
As the evaporation preventing layer, only the hydrocarbon-based oil A used as the sub-evaporation preventing layer in Example 3 was used and this was laminated on the heat storage solution layer in the same manner as in Example 1 above. Evaluation was performed. The results are shown in Table 1.

(Comparative Example 2)
As the evaporation preventing layer, only the hydrocarbon-based oil B used as the sub-evaporation preventing layer in Example 4 was used, and this was laminated in the same manner as in Example 1 except that this was laminated on the heat storage solution layer. Evaluation was performed. The results are shown in Table 1.

(Comparative Example 3)
Each evaluation was performed in the same manner as in Example 1 except that only liquid paraffin (a colorless liquid at room temperature, non-volatile) was used as the evaporation preventing layer, and this was laminated on the heat storage solution layer. . The results are shown in Table 1.

(Comparative Example 4)
Each evaluation was performed in the same manner as in Example 1 except that only solid paraffin (colorless solid at room temperature, non-volatile) was used as the evaporation preventing layer, and this was laminated on the heat storage solution layer. . The results are shown in Table 1.

(Comparative Example 5)
Each evaluation was performed in the same manner as in Example 1 except that only silicone oil was used as the evaporation preventing layer and this was laminated on the heat storage solution layer. The results are shown in Table 1.

(Comparative Example 6)
Each of the evaluations was performed in the same manner as in Example 1 except that only the oil (liquid at room temperature) was used as the evaporation preventing layer, and this was laminated on the heat storage solution layer. The results are shown in Table 1.

(Comparative Example 7)
Each evaluation was performed in the same manner as in Example 1 except that only a 1 mm thick polyethylene resin was used as the evaporation preventing layer and this was laminated on the heat storage solution layer. The results are shown in Table 1.

  As shown in Table 1, if the evaporation prevention layer or the evaporation prevention layer and the sub-evaporation prevention layer in the present invention are formed, the evaporation rate is ◯ or higher, and other evaluation items are also ◯ or more. It can be seen that the evaporation prevention function, the leakage prevention function, and the pressure relaxation function can all be effectively realized and the cost increase of the heat storage device can be avoided. On the other hand, in the general liquid evaporation prevention layer or solid evaporation prevention layer used in the comparative example, although excellent results are obtained for specific evaluation items, items with low evaluation are also included, the evaporation prevention function, It became clear that not all the leakage prevention function and the pressure relief function could be realized.

  Although the effect determination of the present invention was performed with a heat storage device using a typical crystalline poly α-olefin, the same excellent effect was obtained in the various examples described in the first to third embodiments. . Moreover, since the example of the various heat storage apparatuses described in the first to third embodiments can be applied to the air conditioner described in the fourth embodiment, the heating operation can be performed in parallel with the defrosting operation. For example, heating can be performed in a short time even on a cold morning in winter. In addition, since waste heat from the compressor 26 can be effectively recovered, an energy saving operation is possible.

  It should be noted that the present invention is not limited to the description of each of the above-described embodiments and examples, and various modifications are possible within the scope shown in the claims, and different embodiments and a plurality of modifications are possible. Embodiments obtained by appropriately combining the technical means disclosed in the above are also included in the technical scope of the present invention.

  The present invention can be used not only suitably for a heat storage device and an air conditioner, but also effectively used for a refrigerator, a water heater, a heat pump type washing machine, and the like.

DESCRIPTION OF SYMBOLS 11 Thermal storage solution layer 12 Air layer 13 Evaporation prevention layer 14 Subevaporation prevention layer 20A, 20B, 20C Thermal storage apparatus 21,23 Thermal storage container 22,24 Thermal storage heat exchanger 25 Thermal conductive member 26 Compressor (heating source, heater )
214,234 Vent

Claims (12)

A heat storage container having a vent hole communicating with the outside air is provided, and in the heat storage container, a heat storage solution layer and an evaporation prevention layer are formed in this order from the lower side, and the upper part of the evaporation prevention layer communicates with the outside air. The heat storage solution layer is composed of a heat storage solution consisting of at least water, the air layer is formed by outside air flowing in from the vent holes, and the evaporation prevention layer includes at least the following (a), ( A heat storage device comprising a crystalline higher α-olefin that satisfies the condition of b).
(A) A polymer in which the α-olefin monomer has 16 to 44 carbon atoms and uses at least one of these monomers.
(B) In a melting behavior measurement using a differential scanning calorimeter (DSC), a polymer whose melting point exceeds at least 35 ° C. and only one peak temperature is observed.   The heat storage apparatus according to claim 1, wherein the crystalline higher α-olefin has high crystallinity in a side chain portion.   In the heat storage container, at least one sub-evaporation prevention layer is further mixed with the evaporation prevention layer or formed as an independent layer below the evaporation prevention layer. The heat storage device according to claim 1, wherein the heat storage device is composed of a solvent composition comprising at least one water-insoluble solvent, and the melting point of the solvent composition is less than room temperature.   The heat storage device according to claim 3, wherein a specific gravity of the crystalline higher α-olefin is smaller than a specific gravity of the solvent composition.   The heat storage device according to claim 3 or 4, wherein a melting point of the solvent composition is lower than a freezing point of the heat storage solution.   6. The solvent composition according to claim 3, wherein the solvent composition contains at least one of hydrocarbons having a carbon number in the range of 24 to 44 as the water-insoluble solvent. The heat storage device described in 1.   The heat storage device according to any one of claims 1 to 6, wherein the heat storage solution is an aqueous solution containing a dihydric alcohol.   The heat source for heating the heat storage solution and the heat exchanger for heat storage for recovering the heat stored in the heat storage solution are further provided, according to any one of claims 1 to 7, The heat storage device described. The heat source is provided outside the heat storage solution layer, and the heat storage heat exchanger is provided at a position immersed in the heat storage solution inside the heat storage container. 8. The heat storage device according to 8.   The heat storage device according to claim 8 or 9, wherein the heat storage container is provided so as to surround the heating source.   The heat storage device according to any one of claims 8 to 10, wherein the heat storage container is in contact with the heating source via a heat conductive member.   An air conditioner comprising the heat storage device according to any one of claims 1 to 11.