JP5625684B2 - 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”. Specifically, a heat storage device using such a heat storage solution includes, for example, Patent Document 1, which is incorporated in a refrigeration cycle of an air conditioner and includes a heat storage container having a heat storage material mainly composed of water. A configuration of a heat storage device that is open to the atmosphere is disclosed. 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 904 and a plurality of heat-absorbing heat exchangers 905 are provided in the internal space of the heat-storage tank 901 and at 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.

  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. .

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

However, the oil film 907 used in the conventional heat storage device 910 focuses on preventing or suppressing the evaporation of the heat storage material 903, and is used for the oxidative deterioration and the penetration of oxygen in the air into the heat storage material 903 through this. The main focus was not placed. Therefore, when used for a long period of time, the oil film 907 of the conventional material is oxidized and deteriorated to generate an organic acid, and the generated organic acid enters the heat storage material 903 to lower its PH. Oxygen entered the heat storage material 903. When the pH of the heat storage material 903 decreases or oxygen enters, the heat storage material 903 becomes an environment in which corrosion is likely to be induced.

  To solve this problem, the heat-dissipating heat exchanger 904 and the heat-absorbing heat exchanger 905 are made of stainless steel, for example, using SUS316, which is extremely excellent in corrosion resistance. The surface is electropolished to further improve the corrosion resistance, to increase the surface area to reduce the heat receiving load, or to increase the plate thickness to improve the corrosion resistance. For this reason, the subject that the heat storage apparatus becomes expensive and heavy was newly generated. On the other hand, if the period of use is short and there is little corrosion, copper can be used, but in that case, the heat receiving load is reduced by increasing the surface area or the corrosion resistance is secured by increasing the plate thickness. The problem that the heat storage device becomes heavy has newly occurred. Furthermore, since corrosion of these heat exchangers occurs at a high temperature such as 100 ° C., there is a problem that the heat storage device cannot be raised to such a high temperature and used.

  In order to solve the above-mentioned problems, the present invention uses an oil film containing a hydrocarbon having a carbon number in a specific range, so that only a small amount of organic acid is generated and oxygen in the air hardly enters the heat storage solution. An object of the present invention is to provide a small, lightweight and high-quality heat storage device that suppresses corrosion of a heat exchanger, and a comfortable and energy-saving air conditioner using the same.

In order to solve the above problems, a heat storage device according to the present invention includes a heat storage solution layer composed of at least a heat storage solution made of water, a heat exchanger immersed in the heat storage solution layer, and an upper portion of the heat storage solution layer. The disposed evaporation preventing layer is provided with a heat storage container disposed in the internal space. The evaporation preventing layer is composed of a solvent composition comprising at least one water-insoluble solvent, the solvent composition having a pour point of less than room temperature, and the water-insoluble solvent is an α-olefin having 8 to 10 carbon atoms. It was decided that the polymer contained at least one of saturated alkanes having a carbon number in the range of 24 to 44, which was generated by performing a hydrogenation treatment after the polymerization reaction .

The evaporation prevention layer is composed of a solvent composition comprising at least one water-insoluble solvent. The solvent composition has a pour point of less than room temperature, and the water-insoluble solvent polymerizes α-olefins having 8 to 10 carbon atoms. A hydrocarbon containing at least one of saturated alkanes having a carbon number in the range of 24 to 44 produced by hydrogenation after the reaction is used. The evaporation preventing layer having such physical properties generates only a small amount of organic acid, and oxygen in the air hardly enters the heat storage solution, so that the heat exchanger can reliably reduce corrosion. Further, since this evaporation prevention layer has a pour point below room temperature, it is possible to ensure prevention or suppression of evaporation of the heat storage solution layer, and as a result, the heat storage solution layer is replenished because evaporation is suppressed. It is not necessary and can maintain good heat storage characteristics for a long time.

  In the evaporation prevention layer of the heat storage device, the pour point of the solvent composition is preferably lower than the freezing point of the heat storage solution. Even if the temperature of the heat storage device is decreased until the heat storage solution is solidified, the solvent composition can maintain fluidity, so that the evaporation preventing function can be effectively realized even in a low temperature state. Further, 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, and the pressure relaxation function can be further ensured.

  In the heat storage solution layer of the heat storage device, the specific configuration of the heat storage solution is not particularly limited, but an example in which the heat storage solution is not only water but also an aqueous solution containing a dihydric alcohol can be cited as a result. Freezing can be avoided even if the solution is below the freezing point. Moreover, when the heat storage solution is mixed with an antioxidant solution that prevents the oxidation of the dihydric alcohol, the amount of organic acid produced is reduced, and the corrosion resistance of the heat exchanger can be further ensured. Furthermore, when the heat storage solution is an aqueous solution having a pH of 6 to 11, the amount of organic acid produced is reduced, and the corrosion resistance of the heat exchanger can be further ensured.

  The heat storage device may further include a heat source that heats the heat storage solution layer and a heat storage heat exchanger that recovers heat stored in the heat storage solution layer. The heat source is preferably provided outside the heat storage solution layer, and the heat storage heat exchanger is preferably provided at a position immersed in the heat storage solution layer inside the heat storage container. According to this configuration, by providing the heating source, more suitable heat storage is possible, and by providing the heat storage heat exchanger, the stored heat can be suitably recovered, and as the heating 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 said thermal storage apparatus, it is preferable that the thermal storage container is provided so that a heating source may be enclosed. 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.

  INDUSTRIAL APPLICABILITY The present invention can provide a small, lightweight, high-quality heat storage device that is not replenished with a heat storage solution, and a comfortable and energy-saving air conditioner using the same.

Typical sectional drawing which shows an example of a structure of the thermal storage apparatus which concerns on Embodiment 1 of this invention. Effect characteristic diagram of heat storage device according to Embodiment 1 of the present invention (composition analysis result of evaporation prevention layer) Effect characteristic diagram of heat storage device according to Embodiment 1 of the present invention (characteristic diagram of water quality PH and copper ion concentration) (A) Cross-sectional view showing an example of the configuration of the heat storage device according to Embodiment 2 of the present invention, (b) Vertical cross-sectional view of the heat storage device shown in (a) The block diagram which shows an example of a structure of the air conditioning apparatus which concerns on Embodiment 3 of this invention. (A) Sectional drawing which shows an example of a structure of the conventional heat storage apparatus, Block diagram which shows an example of a structure of an air conditioning apparatus provided with the heat storage apparatus shown to (b) (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 in FIG. 1, a heat storage device 20A according to the present embodiment includes a heat storage solution layer 11 composed of at least a heat storage solution made of water, and a heat storage heat exchanger 22 immersed in the heat storage solution layer 11. The evaporation preventing layer 13 disposed on the top of the heat storage solution layer 11 is disposed in the internal space. And this evaporation prevention layer 13 is comprised with the solvent composition which consists of an at least 1 sort (s) of water-insoluble solvent, this solvent composition has the pour point below normal temperature, and this water-insoluble solvent has 24 carbon atoms. It is supposed that at least one of the hydrocarbons in the range of -44 is included.

  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 layer 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 only need to be made of a material and a shape that can stably hold the heat storage solution layer 11 in the internal space. Generally, the material is stainless steel (SUS), PPS resin, or the like. The fiber reinforced plastic (FRP) is generally 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.

  Next, the configuration of each layer formed in the heat storage container 21 will be specifically described with reference to FIG. As described above, inside the heat storage container 21, there are the heat storage solution layer 11 storing the heat storage solution and the evaporation preventing layer 13 formed on top of the heat storage solution layer. The air layer 12 may be formed by outside air flowing in from the outside. Therefore, in the case of such a use, 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, the evaporation prevention layer 13, and the air layer 12 are not particularly limited, depending on various conditions such as the shape of the heat storage container 21, the volume of the internal space, and the volume increment of the heat storage solution due to thermal expansion. An appropriate thickness 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 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 a means for adjusting the internal pressure against the pressure rise or the like, for example, a member made of a rubber material having a lid pinhole fitted in a position in contact with the internal air in the lid portion 212 can be used.

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. The position where the heat storage heat exchanger 22 is provided is
Inside the heat storage container 21, the heat storage solution layer 11 is immersed.

  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 and material of the heat storage heat exchanger 22 are 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. In addition, the structure used as this heat storage and heat recovery can also be reversed.

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.
[Composition of evaporation prevention layer]
In the present embodiment, particularly preferred evaporation prevention layer 13 has a melting point of the solvent composition below room temperature, and the water-insoluble solvent contains at least one of hydrocarbons having a carbon number in the range of 24 to 44. The composition which has been taken out can be mentioned. The hydrocarbons constituting the water-insoluble solvent are chain or alicyclic saturated alkanes (or chain or alicyclic hydrocarbons that are close to saturated alkanes, and these are referred to as saturated alkanes. It is called). Specific examples include polyalphaolefin wax, paraffin wax, mineral oil and the like containing a component having a carbon number within the above range. When the evaporation prevention layer 13 of this composition was used, the advantage which can reduce the corrosion of the heat storage heat exchanger 22, and the advantage which prevented or suppresses evaporation of the heat storage solution which comprises the heat storage solution layer 11 further were acquired.

  FIG. 2 shows a composition analysis result of a water-insoluble solvent using a GC-MS analyzer with respect to the examined evaporation prevention layer 13, and includes at least one of hydrocarbons having a carbon number in the range of 24 to 44. It turns out that it is the composition which was supposed to be.

The carbon structure of this water-insoluble solvent 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 polymerization reaction and then hydrotreated, the carbon number is within the range of 24 to 44. Saturated alkanes containing at least one of the hydrocarbons in (1) are produced. In addition, since these saturated alkanes are saturated alkanes having many branches by devising the polymerization reaction, they are liquid at room temperature. The synthetic oil, semi-synthetic oil, and mineral oil used in the present embodiment are mixed with a water-insoluble solvent obtained by using this production method at 85 to 100% by weight (% by weight).

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 has 45 or more carbon atoms, it is difficult to handle because it tends to become solid at room temperature. In this way, 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 liquid at room temperature, and is easy to handle. A composition was obtained. In addition to this, this water-insoluble solvent has an advantage that it is difficult to produce an organic acid and is highly airtight, so that evaporation of the heat storage solution is prevented or suppressed, and oxygen in the air is difficult to enter the heat storage solution. .
[Verification of corrosion reduction effect of evaporation prevention layer]
The effect verification method and the result will be specifically described based on examples. The heat storage device 20A used for the effect verification will be specifically described based on examples. As the heat storage container 21, PPS resin (polyphenylene sulfide resin) was molded to obtain a box portion 211 and a lid portion 212. Next, a heat storage solution 22 prepared by immersing a heat storage heat exchanger 22 made of a copper serpentine tube in the internal space of the box portion 211 and mixing an extremely small amount of alkali in advance with deionized water to an initial pH of 7.0. The heat storage solution layer 11 is injected, and the evaporation prevention layer 13 is laminated thereon, and finally the lid portion 212 is laminated on the box portion 21 to complete the heat storage device 20A.

  Various evaluations in Examples and Comparative Examples were performed as follows. In the effect confirmation experiment, various evaporation prevention layers 13 were laminated on the heat storage solution having an initial pH of 7.0, and the characteristics before and after the test under predetermined conditions (2 weeks at 20 ° C. and 2 weeks at 100 ° C.) were evaluated. The evaluated characteristics are the evaporation prevention effect of the heat storage solution, and the PH of the heat storage solution before (initial) and after the test, and “excellent” “good” “insufficient” “extremely inferior” according to the measured property value. The ranking is divided into four stages, and each of them is represented by the symbols “◎”, “◯”, “Δ”, and “×”.

The evaporation prevention effect of the heat storage solution is a value obtained by dividing the weight reduction amount of the heat storage solution layer 11 and the evaporation prevention layer 13 under a predetermined condition by a value obtained by dividing the unit area of the evaporation prevention layer 13 by the product of the test period. As this value is larger, the weight of the heat storage solution layer 11 and the evaporation prevention layer 13 is greatly reduced, which means that there is no evaporation prevention effect of the heat storage solution. Conversely, the smaller the value, the less the weight of the heat storage solution layer 11 and the evaporation prevention layer 13 is reduced, which means that the heat storage solution has an excellent evaporation prevention effect. Weight loss of 20 ℃ is, if the 3mg or less ^/ cm 2 · day "◎", if 3~6mg ^/ cm 2 · day "○", if 6~10mg ^/ cm 2 · day "△ "10" or more / cm ² · day was evaluated as "x". Further, if the weight loss at 100 ° C. is 0.1 g or less / cm ² · day, “◎”, if it is 0.1 to 0.2 g / cm ² · day, “◯”, 0.2 to 0 if .3g ^/ cm 2 · day "△", was evaluated as "×" if the 0.3g or more ^/ cm 2 · day.

The solution PH is obtained by measuring the liquid pH of the heat storage solution before (initial) and after the test. The effect of suppressing acidity is an item for evaluating how much organic acid is generated from the evaporation preventing layer 13 and causing a decrease in PH. The greater the amount of organic acid generated, the lower the pH after the test and the acidity. Utilizing the tendency to shift to the side. In this experiment, since the PH before the test (initial) is the same value as 7.0, the PH after the test is evaluated. If the PH is 6.5 to 7.0, “◎” and the PH is 6 0.0 to 6.5, “◯”, PH is 5.5 to 6.0, “Δ”, PH is 5.5.
If it was less than "x", it evaluated as "x".

  Comprehensive evaluation evaluated each evaluation item of the evaporation prevention effect of a thermal storage solution, and the suppression effect of an organic acid comprehensively. Each evaluation item is ◎, and if there is no ◯, △ or ×, the comprehensive judgment was evaluated as “◎”. In addition, each evaluation item was ○ or ◎, and if there was no Δ or ×, the comprehensive judgment was evaluated as “◯”. 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 has x, the overall judgment was evaluated as “x” even if there were other ◎, ○, and Δ.

The evaporation prevention layer 13 used for the examination is as follows.
(Example A of the present invention)
The evaporation prevention layer 13 is implemented using a composition in which the melting point of the solvent composition is less than room temperature and the water-insoluble solvent contains at least one of hydrocarbons having a carbon number in the range of 24 to 44. It is an example. This evaporation prevention layer 13 is a composition having a pour point of −31 ° C. and a decomposition start temperature of 260 ° C., and FIG. 2 shows the analysis result of the GC-MS analyzer regarding the water-insoluble solvent of this composition. A heat storage solution using deionized water having an initial pH of 7.0 is injected into the heat storage container, and the evaporation prevention layer 13 is laminated on the top thereof, and a summary of the results of evaluating the characteristics after testing under predetermined conditions is summarized. Table 1 shows.
(Conventional example A)
Each of the above evaluations was performed in the same manner as in Example A except that a C ₁₅ H ₃₂ saturated hydrocarbon was used as the evaporation preventing layer 13. The results are shown in Table 1. This evaporation prevention layer 13 is a composition having a melting point of 10 ° C. and a boiling point of 270 ° C.
(Conventional example B)
Each evaluation was performed in the same manner as in Example A except that silicone oil was used as the evaporation preventing layer 13. The results are shown in Table 1. This evaporation prevention layer 13 is a composition having a pour point of −40 ° C. and a decomposition start temperature of 250 ° C.
(Conventional example C)
Each of the above evaluations was performed in the same manner as in Example A except that an oil (fatty acid ester) was used as the evaporation preventing layer 13. The results are shown in Table 1. This evaporation prevention layer 13 is a composition having a pour point of −20 ° C. and a decomposition start temperature of 200 ° C.
(Comparative Example I)
Each evaluation was performed in the same manner as in Example A except that a C ₂₃ H ₄₈ saturated hydrocarbon was used as the evaporation preventing layer 13. The results are shown in Table 1. This evaporation prevention layer 13 is a composition having a melting point of 46 ° C. and a boiling point of 200 ° C.
(Comparative Example II)
As the evaporation-preventing layer 13, except for using C ₁₀₀₀ ethylene resins were each evaluated in the same manner as in Example A. The results are shown in Table 1. This evaporation prevention layer 13 is a polymer resin having a melting point of 80 ° C. and a decomposition start temperature of 160 ° C., and hydrocarbons having C45 carbon number cannot be obtained by the current technology. Used for.
(Evaluation results of the present invention)
In Table 1, various evaporation prevention layers 13 were laminated on a heat storage solution using deionized water having an initial pH of 7.0, and tested under predetermined conditions (2 weeks at 20 ° C. and 2 weeks at 100 ° C.). A summary of the results.

  Example A of the present invention is a composition in which the melting point of the solvent composition is less than room temperature, and the water-insoluble solvent contains at least one of hydrocarbons having a carbon number in the range of 24 to 44. Since it uses as the evaporation prevention layer 13, it is excellent in both the evaporation prevention effect of a thermal storage solution, and the suppression effect of an organic acid.

  On the other hand, both of the conventional examples A to C were insufficient in the effect of preventing evaporation of the heat storage solution and the effect of suppressing the organic acid. In particular, when the conventional example A was tested under predetermined conditions (2 weeks at 20 ° C. and then 2 weeks at 100 ° C.), the heat storage solution layer and the evaporation preventing layer were all volatilized. Further, Comparative Examples I and II were also insufficient in both the effect of preventing evaporation of the heat storage solution and the effect of suppressing organic acid.

  The reason why the water-insoluble solvent used as the evaporation preventing layer 13 in Example A of the present invention can further reduce the corrosion of the heat storage heat exchanger 22 will be described. As will be described later, the copper used in the heat storage heat exchanger 22 corrodes and elutes more copper ions as the pH of the aqueous solution is more acidic. Therefore, the water-insoluble solvent used in the evaporation preventing layer 13 is desired to be a material that hardly generates an organic acid. Many organic acids are produced from α-olefins and little from saturated alkanes. In that respect, the water-insoluble solvent of this composition used in the evaporation preventing layer 13 is a saturated alkane (or a hydrocarbon close to the saturated alkane), so that only a small amount of organic acid is generated, and the heat storage solution It is difficult to shift the pH of the acid to the acidic side.

  Also, the copper used in the heat storage heat exchanger 22 corrodes and elutes more copper ions as the oxygen in the air enters the heat storage solution and the dissolved oxygen increases. Therefore, the water-insoluble solvent used in the evaporation preventing layer 13 is desired to be a material that does not allow oxygen in the air to enter the heat storage solution. Is difficult to penetrate. In that respect, the water-insoluble solvent used in the evaporation preventing layer 13 is liquid at room temperature, so that an airtight seal is sufficient, and oxygen in the air hardly enters the heat storage solution. From this point of view, the water-insoluble solvent has an advantage that the corrosion of the heat storage heat exchanger 22 can be further reduced.

  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 solvent composition is not particularly limited, in the present embodiment, as described above, at least one water-insoluble solvent is in the range of 85 to 100% by weight (% by weight) and added. A configuration in which the mixture containing the agent is the balance (within a maximum of 15% by weight) can be preferably exemplified. Of course, it goes without saying that the composition can be appropriately designed according to various conditions such as the performance required for the evaporation preventing layer 13 and the usage environment of the heat storage device 20A.

Although the temperature conditions of a solvent composition are not specifically limited, Since it is preferable that it is a liquid within the range of normal temperature (5-35 degreeC), a pour point is preferable in it being less than normal temperature. Further, as will be described later, the pour point of the solvent composition is preferably lower than the freezing point of the heat storage solution. Even if the temperature of the heat storage device 20A is decreased until the heat storage solution is solidified, the solvent composition can maintain fluidity, so that the evaporation preventing function can be effectively realized even in a low temperature state. Further, 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, and the pressure relaxation function can be further ensured. In particular, if the solvent composition contains a hydrocarbon having a carbon number in the range of 24 to 44, there is an advantage that the flowability of the evaporation preventing layer 13 at a low temperature can be better maintained.

  Thus, the evaporation prevention layer 13 is formed in the heat storage container 21, whereby the evaporation prevention function of the heat storage solution layer 11 can be improved. Therefore, the heat storage solution can be stably held in the heat storage container 21, and the heat storage device 20A excellent in handleability can be obtained. In addition to this, the evaporation preventing layer 13 suppresses evaporation of the heat storage solution layer 11 and therefore does not need to be replenished, and good heat storage characteristics can be maintained for a long time. In addition, the water-insoluble solvent of this composition produces only a small amount of organic acid, and oxygen in the air hardly enters the heat storage solution. Thereby, corrosion reduction of the heat storage heat exchanger 22 can be ensured over a long period of time.

The evaporation prevention layer 13 is a layer that prevents or suppresses evaporation of the heat storage solution constituting the heat storage solution layer 11 (implements an evaporation prevention function), and is a variety of oils that are liquid at room temperature (at least one water-insoluble property). An organic solvent composed of a solvent composition comprising a solvent) can be used. Further, the evaporation prevention layer 13 is preferably an example in which 85 to 100% by weight (% by weight) is a solvent composition composed of a water-insoluble solvent, and the balance is composed of a mixture of additives such as antioxidants. Can be used. Although not shown in FIG. 1, the evaporation preventing layer 13 may be a plurality of layers. When two or more evaporation prevention layers 13 are formed, each evaporation prevention layer 13 is composed of a solvent composition having a different composition, and may be formed independently without being mixed with each other. The layers 13 may be mixed with each other. The water-insoluble solvent used in this solvent composition is a nonpolar solvent having substantially no polarity, low polarity that is low in polarity so that it becomes a single layer released from the aqueous layer without being substantially mixed with water at room temperature. What is necessary is just to show a liquid at least within the range of normal temperature, such as a solvent.
[Relationship between water quality PH and dissolved copper ion concentration]
In order to clarify the corrosion reduction effect of the evaporation preventing layer 13, the copper tube was immersed in an aqueous solution having different pH (oxygen dissolved in water) and tested at 100 ° C. for 2 weeks, and then the eluted copper ion concentration was measured. FIG. 3 is a characteristic diagram in which the correlation between PH and elution copper ion concentration is graphed. It can be seen that the elution copper ion concentration is sharply increased when the pH is 6 to 11 (preferably, PH is 7 to 10.5) is small, and the pH is 6 acidic or lower and the alkaline pH is 11 or higher. The reason for this will be explained. Copper is corroded and eluted as copper ions by the battery action with oxygen dissolved in water (referred to as dissolved oxygen), but the pH is in the range of 6 to 11 (preferably the pH is 7 to 10. In the neutral to weakly alkaline region such as 5), since the passive state of copper oxide is formed by dissolved oxygen, corrosion resistance is improved and copper ions are only slightly eluted. However, in the acidic region of PH6 or less, the passivation of copper oxide dissolves and becomes a large amount of Cu ²⁺ copper ions, and in the alkaline region of PH11 or more, the passivation of copper oxide dissolves and CuO ₂ ^{2. -} and HCuO ₂ ^- believed many eluting becomes copper ions.

  As shown in FIG. 3, the copper used in the heat storage heat exchanger 22 corrodes and elutes more copper ions in an aqueous solution in which oxygen is dissolved in water as the pH of the aqueous solution is more acidic. . Therefore, the water-insoluble solvent used in the evaporation preventing layer 13 is desired to be a material in which an organic acid is difficult to generate and oxygen is difficult to enter. In general terms, organic acids are produced in large amounts from α-olefins, and have a property of being produced only slightly from saturated alkanes or hydrocarbons that are close to saturated alkanes. In addition, oxygen has a property that saturated alkanes or hydrocarbons close to saturated alkanes are not easily infiltrated.

The evaporation preventing layer 13 using the “water-insoluble solvent composition containing at least one of hydrocarbons having a carbon number in the range of 24 to 44”, which is Example A of the present invention, is a saturated alkane. Or it is a hydrocarbon close to saturated alkanes. Therefore, only a small amount of organic acid is generated, and as a result, the pH of the heat storage solution is difficult to shift to the acidic side, and oxygen in the air hardly enters the heat storage solution. Because of this effect, corrosion of the heat storage heat exchanger 22 is greatly reduced. On the other hand, the conventional evaporation prevention layer made of hydrocarbons containing a large amount of α-olefin produces a large amount of organic acid. Infiltrate. Due to this effect, the heat storage heat exchanger 22 was severely corroded.
[A device for maintaining the pH of the heat storage solution at 6 to 11]
From FIG. 3, when the water quality is in the region of PH of 6 to 11 (preferably in the region of PH of 7 to 10.5), copper ions are only slightly eluted. It can be seen that it is desirable to use the water quality of the area. The evaporation prevention layer 13 using a composition containing at least one of hydrocarbons having a carbon number in the range of 24 to 44 as a water-insoluble solvent generates little organic acid. The impact on water quality PH is small. Therefore, the heat storage solution layer 11 can sufficiently secure the corrosion resistance of the heat storage heat exchanger 22 if the initial PH has a water quality in the 6-11 region. However, the heat storage solution layer 11 may be forced to use city water with a pH of 6 to 5 very rarely. For example, the heat storage solution layer 11 containing a dihydric alcohol as an antifreezing agent (antifreeze) generates a large amount of organic acid when used for a long period of time, and PH shifts to the acidic side.

  Therefore, in order to obtain the heat storage solution layer 11 in the PH 6-11 region from which copper ions are only slightly eluted, a slightly soluble base mainly composed of at least one of magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium silicate, and metal magnesium. The sexual substance is assumed to be immersed in the heat storage solution layer 11. These magnesium-based slightly soluble basic substances have the property that their pH only rises to about 10.5 when immersed in an aqueous solution, and capture the acid with an organic acid that induces a PH decrease to prevent the PH decrease. There is a nature to do. Therefore, the heat storage solution in which these slightly soluble basic substances are immersed does not increase its pH by 11 or more, and the amount of the slightly soluble basic substances necessary for neutralization by predicting the amount of organic acid to be generated in advance. The pH does not become less than 6.

  Of the magnesium-based slightly soluble basic substances, magnesium oxide, magnesium hydroxide, and metal magnesium are excellent in terms of long life. In particular, magnesium oxide is granular because of firing, so that it can be handled. There is an advantage that it can be used safely because it does not generate gas such as hydrogen. Therefore, the material mainly composed of magnesium oxide was examined in detail.

  Magnesium oxide has excellent neutralizing properties as a slightly soluble basic substance, but when immersed in water for a long period of time, it absorbs dissolved carbon dioxide to produce basic magnesium carbonate, reducing the neutralization ability and reducing the lifetime. There is a problem that becomes a little shorter. In order to prevent this, an attempt was made to mix a small amount of a minor component of the metal oxide with magnesium oxide. The magnesium oxide concentration was 70% or more, preferably 85% or more, and the balance was various metal oxides ( For example, when using silicic acid, aluminum oxide, iron oxide, calcium oxide, boric acid), a long life was obtained. The reason for this is that when magnesium oxide is mixed with these metal oxides, the melting point decreases and it can be fired at a low temperature, so that crystals develop and become stable oxides, and the absorbability of dissolved carbon dioxide is greatly increased. This is considered to be because it is difficult to produce basic magnesium carbonate. At the same time, the composition mainly composed of magnesium oxide complexed with various metal oxides is easy to handle because it is granular, and it has the advantage of dissolving it well and effectively capturing the generated organic acid. The liquid pH was adjusted from neutral to weak alkali. Among these, the specific composition with which good results were obtained is described below.

  The composition (1) is a composition in which silicic acid (SiO2) is mixed in an amount of 3 to 0.05%, preferably 1 to 0.1%, and the balance is magnesium oxide. The composition (2) is a composition in which aluminum oxide (AL2O3) is mixed in an amount of 2 to 0.01%, preferably 1 to 0.03%, and the balance is magnesium oxide. The composition (3) is a composition in which 3 to 0.05% of silicic acid (SiO2) and 2 to 0.01% of aluminum oxide are mixed and the balance is magnesium oxide. The composition (4) is a composition in which iron oxide (Fe2O3) is mixed in an amount of 7 to 0.01%, preferably 1 to 0.02%, and the balance is magnesium oxide. Composition (5) is a mixture of 3 to 0.05% silicic acid (SiO2), 2 to 0.01% of aluminum oxide and 7 to 0.01% of iron oxide (Fe2O3), with the balance being magnesium oxide. It is a composition. The composition (6) is a composition in which 15 to 0.1%, preferably 3 to 0.1% of calcium oxide (CaO) is mixed and the balance is magnesium oxide. Composition (7) consists of 3 to 0.05% silicic acid (SiO2), 2 to 0.01% aluminum oxide, 7 to 0.01% iron oxide (Fe2O3) and 15 to 0 calcium oxide (CaO). This is a composition in which 1% is mixed and the balance is magnesium oxide. In addition, a composition in which boron oxide (B2O3) is mixed in an amount of 3 to 0.01%, preferably 1 to 0.02%, and the balance is magnesium oxide, or the above composition (1) to boron oxide is added. It is good also as a composition which further mixed the metal oxide of (7), and made the remainder magnesium oxide.

  Magnesium oxide is generally produced by firing raw materials such as magnesium hydroxide or magnesium carbonate. Then, about the calcination temperature of a raw material, when it examined about the composition (1)-(7) which has the above-mentioned magnesium oxide as a main component, when it baked at 1500-2300 degreeC, the absorptivity of a carbon dioxide will fall significantly. It has been found that basic magnesium carbonate is difficult to produce and is granular and thus easy to handle and has an advantage of appropriately dissolving and capturing the generated organic acid to adjust the liquid pH from neutral to weak alkali. Of these, those fired at 1600 to 2100 ° C. were extremely good. This is because magnesium oxide is a material having a melting point of 2800 ° C., but these metal oxides are materials having a melting point of about 1700 to 2600 ° C. Therefore, magnesium oxide mixed with these metal oxides has a lower melting point. Can be fired at 1500 to 2300 ° C. As a result, it is considered that magnesium oxide baked at such a low temperature develops crystals and becomes a stable oxide. Conversely, magnesium oxide calcined at a temperature exceeding 2300 ° C. becomes a peroxidized state and becomes an oxide having a slightly different crystal from the original, becomes difficult to dissolve, traps the generated organic acid, and neutralizes the liquid PH. There has been a problem that the property of adjusting from weakness to weak alkali deteriorates. In addition, magnesium oxide baked at less than 1500 ° C. has a problem of inconvenience in handling because it absorbs dissolved carbon dioxide, easily forms basic magnesium carbonate, and does not easily become granular.

  When the particle size of magnesium oxide was examined, the above-mentioned compositions (1) to (7) were fired at 1500 to 2300 ° C. and then crushed to a particle size of 1 to 15 mm, preferably 2 to 12 mm. It has been found that it has the advantage of capturing the organic acid dissolved therein and adjusting the liquid pH from neutral to weak alkali. The reason for this is that when the particle size exceeds 15 mm, it becomes difficult to dissolve, and there is a problem that the property of capturing the generated organic acid and adjusting the liquid pH from neutral to weak alkali decreases, and the particle size is less than 1 mm. This is because there is a problem in handling because it becomes powdery.

  Therefore, as a material mainly composed of magnesium oxide, MgO is 98.70 to 99.10%, CaO is 0.60 to 0.90%, SiO2 is 0.15 to 0.20%, and Fe2O3 is 0.05. Using a composition (particle size: 3 to 10 mm) containing 0.10%, 0.10% AL2O3, 0.05-0.10% B2O3, and 0.02 to 0.05% B2O3 An effect confirmation experiment was conducted.

This effect confirmation experiment was carried out with a heat storage solution (1) using city water with an initial pH of 5.2 and a heat storage solution (2) using an ethylene glycol aqueous solution adjusted to PH5 by mixing formic acid and glycolic acid. . The heat storage solution (2) is based on a solution in which about 70% of deionized water is mixed with 30% of ethylene glycol, a dihydric alcohol, and a small amount of added solution. By using this basic solution for a long time, It is a heat storage solution prepared by previously mixing formic acid and glycolic acid to be adjusted to PH5.

In the test, the above-described magnesium oxide-based slightly soluble basic substance and the copper tube of the heat storage heat exchanger 22 were immersed in each of the heat storage solutions, and the characteristics tested at 100 ° C. for one month were evaluated. The heat storage solution in which the magnesium-based slightly soluble basic substance is immersed has a pH of 7 to 9 after the test and has a good PH adjustment effect, and accordingly, is a heat storage heat exchanger 22. The corrosion resistance of copper is also good. On the other hand, in the heat storage solution that does not use the slightly soluble basic substance, the PH after the test remains 5, and accordingly, the corrosion resistance of the heat storage heat exchanger 22 is extremely inferior. became.
[Composition of heat storage solution]
The heat storage solution constituting the heat storage solution layer 11 may be a heat storage medium (thermal-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. It is done. 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.

  When the heat storage solution is an aqueous solution containing a dihydric alcohol, an antioxidant solution (for example, sodium nitrite) that prevents the oxidation of the dihydric alcohol is reduced to 0.0. When a heat storage solution containing several percent is used, the amount of organic acid produced can be further reduced, and the corrosion resistance of the heat exchanger can be further ensured. Antioxidants include vitamin C (ascorbic acid), vitamin E (tocopherol), BHT (dibutylhydroxytoluene), BHA (butylhydroxyanisole), sodium erythorbate, coffee bean extract (chlorogenic acid), green tea extract Even if (catechin) or rosemary extract is used, the same effect can be obtained, and the specific type and amount thereof are not particularly limited.

  In addition, the specific type of additive added to the heat storage solution is not particularly limited. In addition to the antifreezing agent such as the dihydric alcohol, the pH adjusting agent, the supercooling inhibitor, the thickener, Various additives known in the field of the heat storage material composition such as a heat accelerator, a moisture evaporation inhibitor, a corrosion inhibitor, and a rust inhibitor (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 composition of the heat storage solution constituting the heat storage solution layer 11 used in the above-described effect confirmation experiment will be described. A heat storage solution having an ethylene glycol concentration of 30% has characteristics of a boiling point of 103 ° C. and a freezing temperature of −15 ° C. Additives added in small amounts prevent the oxidation of copper rust inhibitors (eg, benzotriazole, mercaptobenzotriazole, tolyltriazole, etc.), antifungal agents (eg, sodium benzoate, etc.), and ethylene glycol. An antioxidant solution (for example, sodium nitrite).

  These effect confirmation experiments were conducted by (3) a mixed solution of 85% ethylene glycol and 15% water (boiling point 130 ° C. and freezing temperature −43 ° C.), and (4) a mixed solution of 85% propylene glycol and 15% water (boiling point). Was conducted at 120 ° C. and a freezing temperature of −53 ° C., and (5) a mixed solution of 30% propylene glycol and 70% water (boiling point was 102 ° C. and freezing temperature was −15 ° C.). The heat storage solution in which the magnesium-based slightly soluble basic substance is immersed has a pH of 7 to 9 after the test and has a good PH adjustment effect, and accordingly, is a heat storage heat exchanger 22. The corrosion resistance of copper also improved.

  In such an effect confirmation experiment, when a heat storage solution of a mixture of a dihydric alcohol such as ethylene glycol or propylene glycol and an antioxidant solution (for example, sodium nitrite) to prevent its oxidation is used, As a result, the yield can be reduced, and as a result, even better heat exchanger (copper) corrosion resistance was obtained.

  Although this invention was concretely demonstrated based on the Example and the comparative example, this 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.

(Embodiment 2)
Although the heat storage device 20A according to the first embodiment is composed of the heat storage container 21 and the heat storage heat exchanger 22, the heat storage device 20B according to the second embodiment further includes a heating source 26, The waste heat of the heating source 26 can be stored. The configuration will be specifically described with reference to FIGS. 4 (a) and 4 (b).

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

  Similarly to 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 substantially rectangular parallelepiped shape, similar to the box portion 211 in the first embodiment, but the shape of the internal space for storing the heat storage solution is different from the box portion 211, As shown in FIG. 4, it has a substantially U-shaped cross section so as to surround the side surface of the compressor 26. As shown in FIG. 1 and FIG. 4, 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 evaporation preventing layer 13 is laminated above the heat storage solution layer 11, and further, above the evaporation preventing layer 13, the air layer 12 is formed by outside air flowing in through the air holes 234 provided in the lid portion 232. Is formed.

  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, since the heat storage container 23 is in contact with the compressor 26 via the heat conductive member 25, the heat from the compressor 26 can be favorably recovered by the heat storage device 20B. 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-ternary copolymer) or silicone rubber is selected as the resin composition, Even if there are irregularities on the side surface of the compressor 26, 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 further smoother. Can be.

  Also in the present embodiment, the evaporation preventing layer 13 described in the first embodiment is 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 20B can be obtained.

  In addition, in this Embodiment, although the compressor 26 was illustrated as a heat source, it is not limited to this, It is not limited to this, It is another heat source with which the apparatus with which heat storage apparatus 20B 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 3)
The first and second embodiments exemplify the configuration of the heat storage device, but in this 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. The heat storage device 20B 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 20B, the compressor 26, various internal pipes of the outdoor unit, and outdoor heat exchange are provided. A vessel 34, 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 20B, 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 one. 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 second embodiment, the compressor 26 is provided so as to be substantially integrated with the heat storage container 23 of the heat storage device 20B, and the periphery of the compressor 26 includes the heat conductive member 25. The heat storage solution layer 11 is located through. An evaporation preventing layer 13 is formed on the upper surface of the heat storage solution layer 11. In FIG. 5, 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 is branched from between the discharge port of the compressor 26 and the four-way valve 41 in the first pipe 301. Yes. A first electromagnetic valve 43 is provided in the fifth pipe 305. The first pipe 301 is disposed on the outdoor unit 32 side at an intermediate position of the indoor heat exchanger 33 from the discharge port of the compressor 26.

  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.

  In addition, each apparatus or member except the compressor 26 and the heat storage device 20B (refrigerant piping, pipe joint 40, indoor heat exchanger 33, blower fan, upper and lower blades, left and right blades, outdoor heat exchanger 34, strainer 35, and expansion valve 42 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 20B, 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, the heating can be performed in a short time even in the cold morning of winter, for example. In addition, since waste heat from the compressor 26 can be effectively recovered, an energy saving operation is possible.

  Furthermore, as described in the second embodiment, the heat storage device 20B has the evaporation prevention layer 13 formed in the heat storage container 23, so that excessive evaporation of the heat storage solution can be effectively prevented (of the evaporation prevention function). In addition, the heat storage solution can be prevented from leaking out of the heat storage container 23 or exposed to the air layer 12 (realization of a leakage prevention function), and even if the pressure of the heat storage solution layer 11 increases greatly. Since a part of the vapor or free gas escapes from the liquid evaporation preventing layer 13 to the air layer 12, the pressure does not increase excessively and can sufficiently cope with the pressure increase of the heat storage solution (pressure relaxation function). Realization).

  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, instead of the heat storage device 20B, the heat storage device 20A described in the first 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-20B 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.

  Further, the present invention is not limited to the description of each of the above-described embodiments, and various modifications can be made within the scope of the claims, and each is disclosed in different embodiments and a plurality of modifications. Embodiments obtained by appropriately combining the technical means provided 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 20A, 20B Thermal storage device 21,23 Thermal storage container 22,24 Thermal storage heat exchanger 25 Thermal conductive member 26 Compressor (heating source, heater)
214,234 Vent

Claims (10)

A heat storage container in which a heat storage solution layer composed of at least a heat storage solution made of water, a heat exchanger immersed in the heat storage solution layer, and an evaporation prevention layer disposed on the heat storage solution layer are disposed in the internal space. The evaporation prevention layer is composed of a solvent composition composed of at least one water-insoluble solvent, the solvent composition has a pour point less than room temperature, and the water-insoluble solvent is carbon 8-10. A heat storage device comprising at least one of saturated alkanes having a carbon number in the range of 24 to 44 produced by a hydrogenation treatment after the α-olefin is polymerized .   The heat storage device according to claim 1, wherein a pour point of the solvent composition is lower than a freezing point of the heat storage solution.   The heat storage device according to claim 1, wherein the heat storage solution is an aqueous solution containing a dihydric alcohol.   The heat storage device according to claim 3, wherein the heat storage solution is an aqueous solution containing an antioxidant liquid that prevents oxidation of a dihydric alcohol.   The heat storage device according to any one of claims 1 to 4, wherein the heat storage solution is an aqueous solution of PH6-11.   The said heat exchanger is a heat exchanger for thermal storage which collect | recovers the heat stored in the said thermal storage solution layer, The heat source which heats the said thermal storage solution was further provided in any one of Claim 1 to 5 Heat storage device.   The said heat source is provided in the exterior of the said thermal storage solution layer, and the said heat storage heat exchanger is provided in the position immersed in the said thermal storage solution layer inside the said thermal storage container. The heat storage device described in 1. The heat storage device according to claim 6 or 7, wherein the heat storage container is provided so as to surround the heating source.   The heat storage device according to any one of claims 6 to 8, 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 9.