JP2008215654A - Clathrate compound forming method, heat energy storage and takeout method, heat storage device and its operation method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a clathrate compound forming method for efficiently forming a clathrate compound, a heat energy storage and takeout method, heat storage device and its operation method. <P>SOLUTION: The heat storage device comprises: a heat exchanger 2 arranged in a solution L containing a host molecule of the clathrate compound as a solvent, and a guest molecule as a solute; and a heat storage tank 1 holding the heat exchanger 2. The device performs heat storing operation of storing heat energy in the heat storage tank 1 by forming the clathrate compound L1 on a heat transfer surface of the heat exchanger 2, and a heat radiating operation of taking out the heat energy to the outside of the heat storage tank 1 by melting the clathrate compound formed on the heat transfer surface of the heat exchanger from the heat transfer surface side. The heat storage device is provided with agitating devices 3, 4 agitating the solution in a time zone of a predetermined time before the termination of the heat storage operation. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  In the present invention, a solution containing a host molecule of an inclusion compound as a solvent and a guest molecule as a solute (hereinafter referred to as “raw material solution”) is heat exchanged with a heat medium via a heat exchanger disposed in the raw material solution. Thus, the present invention relates to a technique for generating an inclusion compound on the heat transfer surface of the heat exchanger and a technique for applying this to the heat utilization field.

  The material of the material that accumulates heat (hereinafter sometimes referred to as “latent heat storage material”) is subjected to heat exchange with the heat medium via the heat exchanger, and latent heat is transferred to the heat transfer surface of the heat exchanger. A heat storage technique is known in which heat energy is stored by generating a stored material and the heat energy is extracted by melting the latent heat storage material. Typical examples include inner-melting ice storage technology (Patent Document 1) and outer-melting ice storage technology (Patent Document 2) using ice produced by freezing water as a latent heat storage material, propylene glycol, cryogen and additives. This is a heat storage technique (Patent Document 3) using sherbet-like ice formed by freezing added water as a latent heat storage material.

On the other hand, clathrate hydrate (Patent Document 4) and other clathrate compounds (Patent Document 5) are also known as latent heat accumulating substances, and are solutions containing a host molecule of a clathrate compound as a solvent and a guest molecule as a solute ( The raw material solution) is heat exchanged with the heat medium via the heat exchanger, and the clathrate compound is generated on the heat transfer surface of the heat exchanger to accumulate heat energy and melt the clathrate compound. Application to a heat storage technique for extracting the thermal energy has also been studied (Patent Document 6).
JP-A-6-11158 Japanese Utility Model Publication No. 62-117435 JP-A-63-70095 Japanese Patent Publication No.57-35224 JP 2005-41908 A JP 2000-111123 A

  However, the heat conductivity of the clathrate compound is lower than that of ice or the like. Therefore, at the time of heat storage, let's exchange heat with the heat medium through the heat exchanger, and attach and deposit the clathrate compound on the heat transfer surface of the heat exchanger, so that more clathrate compounds are generated. However, as the amount of clathrate compound increases and its thickness increases, the thermal resistance of the clathrate compound increases, making it difficult for the heat energy from the heat medium to be transferred to the raw material solution side, which leads to a new clathrate. It becomes impossible to produce a compound, that is, to accumulate more heat energy. Nevertheless, it is clearly uneconomical to continue supplying the heat exchanger with the heat medium cooled below the freezing point of the clathrate compound.

  One method for solving the above problem is to stir the raw material solution in the vicinity of the heat transfer surface of the heat exchanger. If the raw material solution is stirred, the raw material solution in the vicinity of the clathrate compound deposited and deposited on the heat transfer surface of the heat exchanger is stirred, and the heat transfer in the region where the effect of heat exchange by the heat exchanger is improved, The production rate of the clathrate compound can be increased, that is, a unit amount of the clathrate compound can be produced in a shorter time. However, after the clathrate compound has grown to a certain thickness, the improvement in heat transfer by stirring is not so effective that it can be said that the stirring is continued.

  The present invention has been made to solve the above-described problems, and improves the heat transfer property from the heat exchanger to the raw material solution through the inclusion compound generated on the heat transfer surface, and the inclusion compound It is an object of the present invention to provide a technology that can efficiently generate the heat and a technology that applies the technology to the heat utilization field.

  In order to solve the above-described object, a method for producing an inclusion compound according to the first aspect of the present invention includes a solution containing a host molecule of an inclusion compound as a solvent and a guest molecule as a solute. In the clathrate compound producing method, the method includes the step of producing a clathrate compound on the heat transfer surface of the heat exchanger by exchanging heat with the heat medium via the heat exchanger, and a predetermined time before the end of the heat exchange. The solution is agitated during the period of time.

  Here, the meanings of the following terms or expressions used in the present invention are as follows.

  (1) An “inclusion compound” means that when a plurality of molecules are combined under appropriate conditions to form a crystal, one molecule (host molecule) forms a cage, tunnel, layer or network structure. This means a compound having a structure in which another molecule (guest molecule) enters the gap, and includes not only the clathrate compound in a narrow sense (see Patent Document 5) excluding clathrate hydrate, but also this clathrate hydration. In other words, inclusion compounds in a broad sense, including products (see Patent Documents 4 and 6) also mean “inclusion compounds”. Needless to say, this is not the case with ice formed by water solidification.

  (2) “Heat exchanger” means a heat transfer object having a heat transfer surface that enables heat exchange with a heat source or a heat medium, and whether or not the heat transfer object is solid, Any size, material, etc. may be used. A plate type or a multi-tube type may be used. A heat pipe is also a kind of “heat exchanger”. In the specific description of the present invention, even if the specific description of the present invention is sometimes made using a heat transfer tube having a cavity through which a heat medium flows as a "heat exchanger", it is a "heat exchanger". It is not intended to limit the heat transfer tube.

  (3) The “heat transfer surface” of the heat exchanger refers to an outer surface of the heat exchanger where heat is exchanged by the heat exchanger and a region near the outer surface where the heat exchange effect is exerted.

  (4) “Lower” and “upper” refer to the direction in which gravity works and the opposite direction, respectively.

  (5) “Block” refers to an object having an outer shape as one aggregate, and there is no limitation on the shape as long as it is visually distinguishable from surrounding objects, unless otherwise specified. The internal structure, strength, hardness, viscosity, density, composition, etc. are not limited. The “clumps of clathrate compound” refers to those in which the clathrate compound is repeatedly formed to form a clump and can be recognized as a lump and the naked eye.

  (6) “Slurry” refers to a substance in which solid particles are dispersed or suspended in a liquid or in that state. In order to make solid particles that tend to settle into a suspended state, a surfactant may be added or mechanically stirred. In particular, the term “slurry” for an inclusion compound or a mass thereof includes a solution containing a host molecule of the inclusion compound as a solvent and a guest molecule as a solute, regardless of whether a surfactant is added or mechanically stirred. The clathrate is dispersed or suspended, or a substance in that state, but is not required until the dispersion or suspension is homogeneous. For example, when a part of the clathrate of the clathrate compound (particularly the part in contact with the solution) is dispersed or suspended in the solution but the rest remains agglomerate in the solution, the dispersion Or what is suspended is a "slurry", and it can be said that it exists in the state coexisting in the said lump of inclusion compound and the said solution.

  (7) “Stirring” means stirring an object (in the present invention, mainly a raw material solution, an inclusion compound, an inclusion compound slurry, etc.). Circulation of an object (refer to Patent Document 3) and mechanical vibration also correspond to “stirring” because results equivalent to those obtained by stirring the same occur. In the present invention, the “stirring” includes not only the stirring of the object but also other operations aimed at making the concentration or temperature of the solution uniform (for example, mixing solutions having different concentrations or temperatures). And diffusing solutions of different concentrations or temperatures).

  (8) “Harmonic melting point” means that when the clathrate compound is produced from the liquid phase of the raw material solution, the concentration of the guest molecule in the raw material solution is equal to the concentration of the guest molecule in the clathrate compound. The temperature when the composition of the liquid phase does not change before and after the generation. In the phase diagram in which the vertical axis represents the clathrate generation temperature and the horizontal axis represents the concentration of guest molecules in the raw material solution, the maximum point is the “harmonic melting point”. The concentration of guest molecules in the raw material solution that gives a harmonic melting point is called “harmonic melting point concentration”. When the clathrate compound is generated from a raw material solution having a concentration lower than the harmonic melting point concentration, the concentration of the guest molecule in the raw material solution decreases as the clathrate compound is generated, and the clathrate compound generation temperature with respect to the concentration decreases.

  In the first embodiment of the present invention, the “time period of a predetermined time before the end of heat exchange” means that the end of the predetermined time is before the end of heat exchange. In this time zone, “stirring the solution (including the inclusion compound host molecule as a solvent and the guest molecule as a solute)” means stirring the raw material solution at least once in the time zone. , Including stirring the raw material solution temporarily, continuously, continuously, intermittently or intermittently.

  Thus, since the raw material solution is agitated for a predetermined time period effective for improving heat transfer, the raw material solution in the vicinity of the clathrate compound adhering to the heat transfer surface of the heat exchanger is sufficiently stirred, The heat transfer in the region where the heat exchange effect by the heat exchanger is extended is improved, and the production rate of the clathrate compound is increased, that is, the unit amount of the clathrate compound is produced in a shorter time.

  The method for accumulating and extracting thermal energy according to the second aspect of the present invention is a method for accumulating and extracting thermal energy by generation and melting of an inclusion compound, wherein the host molecule of the inclusion compound is used as a solvent and the guest molecule The solution containing the solute as a solute is subjected to heat exchange with a heat medium via a heat exchanger disposed in the solution, thereby generating an inclusion compound on the heat transfer surface of the heat exchanger and accumulating heat energy. A first step and a second step of melting the clathrate compound formed on the heat transfer surface of the heat exchanger from the side of the heat transfer surface and taking out the heat energy. The solution is stirred in a predetermined time period before the end.

  In the second embodiment, the heat exchange for the generation of the clathrate compound in the first mode is the first step, and in addition to the first step, the step of melting the clathrate compound and extracting the thermal energy is the first step. The two steps are provided. Therefore, in this second embodiment, since “heat exchange” in the first embodiment is simply expressed as “first step”, “predetermined time period” and “stirring the solution” It is synonymous with each corresponding phrase in the form.

  The method for accumulating and extracting thermal energy according to the third aspect of the present invention repeats the first step and the second step in the method according to the second aspect, and from the end of the second step, The solution is agitated in a time zone until the start of the first step. That is, the stirring of the solution is performed during a predetermined time period in the first step and also after the second step and before the first step.

  A heat storage device according to a fourth embodiment of the present invention includes a heat exchanger disposed in a solution containing a host molecule of a clathrate compound as a solvent and a guest molecule as a solute, and a heat storage tank containing the heat exchanger. A heat storage operation for storing heat energy in the heat storage tank by generating a clathrate compound on the heat transfer surface of the heat exchanger, and a clathrate compound generated on the heat transfer surface of the heat exchanger. In a heat storage device that performs a heat radiating operation of extracting the thermal energy out of the heat storage tank by melting from the heat transfer surface side, a stirring device that stirs the solution in a predetermined time period before the end of the heat storage operation. It is characterized by providing. In the fourth embodiment, since “heat exchange” in the first embodiment is simply expressed as “heat storage operation”, the “predetermined time period” and “solution agitation” are respectively in the first embodiment. Is synonymous with the corresponding phrase.

  The operating method of the heat storage device according to the fifth embodiment of the present invention includes a heat exchanger disposed in a solution containing a host molecule of a clathrate compound as a solvent and a guest molecule as a solute, and the heat exchanger. In a method of operating a heat storage device comprising a heat storage tank and a stirring device for stirring the solution, a heat storage step of storing thermal energy in the heat storage tank by generating an inclusion compound on a heat transfer surface of the heat exchanger And a heat dissipation step of releasing the thermal energy to the outside of the heat storage tank by melting the clathrate compound generated on the heat transfer surface of the heat exchanger from the heat transfer surface side, and the heat storage step And a step of driving the stirring device in a predetermined time period before the end of the step. In the fifth embodiment, since “heat exchange” in the first embodiment is simply expressed as “heat storage step”, “time zone for a predetermined time” and “solution agitation” are respectively in the first embodiment. Is synonymous with the corresponding phrase.

  The operation method of the heat storage device according to the sixth embodiment of the present invention repeats the heat storage step and the heat dissipation step in the operation method according to the fifth embodiment, and from the end of the heat dissipation step to the start of the next heat storage operation. The stirrer is driven even in a time zone.

  According to the present invention, when the clathrate compound is generated on the heat transfer surface of the heat exchanger by exchanging heat between the raw material solution and the heat medium via the heat exchanger, the predetermined time before the end of the heat exchange. In this time zone, the raw material solution is stirred, so that effective heat transfer from the heat transfer surface of the heat exchanger to the raw material solution and from the clathrate hydrate generated on the heat transfer surface of the heat exchanger to the raw material solution is achieved. It becomes possible, and the inclusion compound can be rapidly generated and grown on the heat transfer surface of the heat exchanger. As a result, heat can be stored efficiently, and the load on the device that cools the heat medium required for heat storage can be reduced. At the same time, the raw material solution is not stirred after a predetermined time. It is possible to perform stirring in an effective range, which contributes to energy saving.

  When the clathrate is generated and melted by heat exchange between the raw material solution and the heat medium via a heat exchanger (especially when these are repeated at least once), a temperature gradient is generated in the raw material solution. Tend. Further, there is a tendency that a concentration gradient is generated due to the concentration of guest molecules in the raw material solution, and this concentration gradient is usually noticeable with an increase in the number of clathrate formation and melting. However, according to the present invention, since the raw material solution is stirred in a predetermined time period during heat storage, the temperature gradient of the raw material solution and the concentration gradient of the guest molecule can be eliminated, and the raw material solution can be more homogenized. There is also an effect that the variation in physical properties of the clathrate compound produced from the above can be made smaller than before.

  According to the present invention, the effects as described above can be obtained. The effects of the embodiments of the present invention are individually described as follows.

  (I) According to the first aspect of the present invention, when the clathrate compound is generated on the heat transfer surface of the heat exchanger by exchanging heat between the raw material solution and the heat medium via the heat exchanger, Since the raw material solution is agitated in a predetermined time period before the end of heat exchange, effective heat transfer from the heat exchanger to the raw material solution is possible, and the inclusion compound is placed on the heat transfer surface of the heat exchanger. It is possible to realize a generation method that can be quickly generated and grown. According to this generation method, it is possible to reduce the load on the apparatus for cooling the heat medium necessary for heat storage, and as a result of not stirring after the predetermined time, inefficient energy is not consumed, so an effective range. Can be agitated and contributes to energy saving.

  (Ii) According to the second aspect of the present invention, in the time zone of a predetermined time before the end of the step of heat-exchanging the raw material solution and the heat medium via the heat exchanger and generating the clathrate compound, Since the solution is agitated, effective heat transfer from the heat exchanger to the raw material solution is possible, and the accumulation of heat energy that can quickly generate and grow inclusion compounds on the heat transfer surface of the heat exchanger It is possible to realize a method of taking out. In addition, it is possible to reduce the load on the apparatus for cooling the heat medium necessary for storing heat, and since stirring is not performed after the predetermined time, inefficient energy is not consumed. Can contribute to energy conservation.

  When the clathrate compound is melted by heat exchange with a heat medium through a heat exchanger arranged in the raw material solution and the heat energy is taken out, the temperature of the raw material solution is set to a temperature higher than the freezing point of the clathrate compound. Become. As a result, a temperature gradient is naturally generated in which the upper part of the raw material solution is relatively hot and the lower part is relatively cold. Further, when the accumulation and extraction of thermal energy are repeated, the guest molecules stay in the place where the clathrate compound is melted, so that the guest molecules are concentrated and a concentration gradient tends to occur. Furthermore, even when the thermal energy is extracted, the clathrate compound tends to remain unmelted. For example, when the specific gravity of the clathrate compound is larger than that of the raw material solution, the temperature of the raw material solution in the upper part of the container in which the raw material solution is stored is higher than the “clotting of clathrate compound” point, but in the lower part The raw material solution may be at a temperature below the freezing point of the clathrate compound, and the clathrate compound can remain unmelted in the lower part. This is also substantially the same state as the concentration gradient is generated simultaneously with the temperature gradient.

  On the other hand, according to the second embodiment of the present invention, since the raw material solution is stirred in a predetermined time period when the clathrate compound is generated, the relatively high temperature raw material solution and the relatively low temperature raw material solution By mixing a raw material solution having a relatively high concentration of guest molecules and a raw material solution having a relatively low concentration of guest molecules, or by mixing with a raw material solution at or above the freezing point of the inclusion compound. By melting the compound, the temperature gradient of the raw material solution and the concentration gradient of the guest molecule can be eliminated, the raw material solution can be made more homogeneous, and the variation in physical properties of the clathrate compound produced from such raw material solution has been Can also be reduced.

  (Iii) However, in the second embodiment of the present invention, since the raw material solution is stirred when the clathrate compound is starting to be generated, there is a case where the temperature gradient and the concentration gradient are not completely eliminated. On the other hand, according to the third embodiment of the present invention, the raw material solution can be stirred before the thermal energy is accumulated again after the thermal energy is taken out, so that the temperature gradient and the concentration gradient can be thoroughly eliminated. It is more effective than the case of the second embodiment, can store homogeneous heat energy, and can efficiently store and extract heat energy without waste.

  (Iv) According to the fourth aspect of the present invention, in the time zone of the predetermined time before the end of the heat storage operation for exchanging the raw material solution and the heat medium via the heat exchanger and generating the clathrate compound, Since the raw material solution is stirred by the stirrer, heat can be effectively transferred from the heat exchanger to the raw material solution, and the inclusion compound can be quickly generated and grown on the heat transfer surface of the heat exchanger. A heat storage device can be realized. In such a heat storage device, the inefficient energy is not consumed as a result of not stirring after the predetermined time, so that the load on the device for cooling the heat medium required during the heat storage operation is reduced, and stirring is performed in an effective range. Done and energy is saved. In addition, the electric power required for stirring can be covered by cheap night electric power. In addition, in a heat storage device, it is common to repeat the operation of storing and releasing heat energy, and if the raw material solution is stirred during a predetermined time period from the start of the heat storage operation, the concentration of the guest molecule is repeated. The gradient is eliminated, the raw material solution is more homogenized, and the variation in the physical properties of the clathrate compound produced from the raw material solution becomes smaller than before. As a result, the performance of the heat storage device is stabilized.

  Further, when the heat radiation operation is performed, the temperature of the raw material solution becomes higher than the freezing point of the clathrate compound. As a result, a temperature gradient is generated in the heat storage tank in which the upper part of the raw material solution is relatively high temperature and the lower part is relatively low temperature. Further, when the heat storage operation and the heat release operation are repeated, the guest molecules stay in a place where the clathrate compound is melted, so that the guest molecules are concentrated and a concentration gradient tends to occur. Furthermore, even when the thermal energy is extracted, the clathrate compound may remain unmelted. For example, when the specific gravity of the clathrate compound is larger than that of the raw material solution, the temperature of the raw material solution in the upper part of the container in which the raw material solution is stored is higher than the freezing point of the clathrate compound, but the raw material in the lower part When the solution reaches a temperature below the freezing point of the clathrate compound, the clathrate compound remains unmelted in the lower part. In particular, the heat storage device according to the fourth embodiment of the present invention includes a heat storage operation for storing thermal energy in the heat storage tank by generating an inclusion compound on the heat transfer surface of the heat exchanger, and heat transfer of the heat exchanger. The clathrate compound generated on the surface is melted from the side of the heat transfer surface to perform a heat radiating operation to extract heat energy out of the heat storage tank, that is, an internal fusion type heat storage device. In the internal fusion type heat storage device, if the specific gravity of the clathrate compound and the raw material solution is different, the unmelted clathrate compound floats or settles depending on the difference in specific gravity during the heat radiation operation, and is unevenly distributed in the heat storage tank Tend to. The presence of such an unmelted clathrate compound causes a concentration gradient and a temperature gradient of the raw material solution, and may cause a decrease in performance of the heat storage device.

  On the other hand, according to the fourth embodiment of the present invention, since the raw material solution is agitated in a predetermined time period during the heat storage operation, the relatively high temperature raw material solution and the relatively low temperature raw material solution Unmelted inclusion compound melts by mixing or by mixing a raw material solution having a relatively high concentration of guest molecules with a raw material solution having a relatively low concentration, and particularly by mixing with a raw material solution above the freezing point of the inclusion compound. As a result, the temperature gradient of the raw material solution and the concentration gradient of the guest molecules are eliminated, the raw material solution becomes more homogeneous, and the variation in physical properties of the clathrate compound produced from the raw material solution becomes smaller than before. Therefore, according to the fourth aspect of the present invention, it is possible to realize a heat storage device capable of storing homogeneous heat energy and having stable performance.

  In addition, it is more thorough to eliminate the temperature gradient and concentration gradient by stirring the raw material solution with the stirrer after the heat dissipation operation and before the start of the heat storage operation, so that homogeneous heat energy is accumulated, and the heat storage operation and the heat dissipation operation are performed. This is more preferable in terms of realizing a heat storage device that is efficiently performed without waste.

  (V) According to the fifth aspect of the present invention, it is possible to realize an operation method suitable for the heat storage device according to the fourth aspect of the present invention, in particular, the inner fusion heat storage device. That is, since the raw material solution is agitated in a predetermined time period during the heat storage process in which the raw material solution and the heat medium are heat-exchanged through the heat exchanger and the clathrate compound is generated, the heat exchanger is changed to the raw material solution. Heat transfer can be performed effectively, and an inclusion compound can be rapidly generated and grown on the heat transfer surface of the heat exchanger. As a result of this operation, in the heat storage step, the inefficient energy is not consumed as a result of not stirring after the predetermined time, so that the load on the apparatus for cooling the necessary heat medium can be reduced, and the effective range The energy can be saved by stirring with. Note that the power required for stirring may be provided by inexpensive nighttime power. Further, in the operation of the heat storage device, it is normal that the heat storage process and the heat dissipation process are repeatedly executed, and at the time of the repetition, by stirring the raw material solution in the time zone from the start of the heat storage operation until a predetermined time elapses. The concentration gradient of the raw material solution and the concentration gradient of the guest molecule can be eliminated, the raw material solution can be made more homogeneous, and the variation in physical properties of the clathrate compound produced from the raw material solution can be made smaller than before. . Thereby, the performance of the heat storage device can be stabilized.

  In addition, when the heat dissipation step is executed, the temperature of the raw material solution becomes higher than the freezing point of the clathrate compound, so that a temperature gradient is generated in the heat storage tank. Further, when the heat storage step and the heat release step are repeatedly executed, the guest molecules stay in a place where the clathrate compound is melted, so that the guest molecules are concentrated and a concentration gradient tends to occur. Furthermore, even when the thermal energy is extracted, the clathrate compound may remain unmelted. In particular, during operation of an internal fusion type heat storage device such as the heat storage device according to the fourth embodiment of the present invention, if the specific gravity of the clathrate compound and the raw material solution is different, the difference in specific gravity during the heat dissipation process Accordingly, the unmelted clathrate compound floats or settles and is unevenly distributed in the heat storage tank, and the presence of the unmelted clathrate compound causes the concentration gradient and temperature gradient of the raw material solution. On the other hand, according to the fifth embodiment of the present invention, since the raw material solution is agitated in a predetermined time period during the heat storage step, the mixing of the relatively high temperature raw material solution and the relatively low temperature raw material solution is performed. Unmelted clathrate compound melts by mixing raw material solution with relatively high concentration of guest molecule and raw material solution with relatively low guest molecule, and especially by mixing with raw material solution above the freezing point of the clathrate compound The temperature gradient of the raw material solution and the concentration gradient of the guest molecule can be eliminated, the raw material solution can be made more homogeneous, and the variation in the physical properties of the clathrate compound produced from the raw material solution can be made smaller than before. . Therefore, according to the fifth embodiment of the present invention, it is possible to accumulate homogeneous heat energy and to realize the operation of the heat storage device having stable performance.

  (Vi) However, in the fifth embodiment of the present invention, since the raw material solution is stirred when the clathrate compound is starting to be produced, there is a tendency that the temperature gradient and the concentration gradient are not thoroughly eliminated. On the other hand, according to the sixth embodiment of the present invention, since the raw material solution is agitated after the heat dissipation process and before the heat storage process is started, it is possible to thoroughly eliminate the temperature gradient and the concentration gradient, so that the case of the fifth embodiment is achieved. It is effective, can store homogeneous heat energy, and can efficiently store and extract heat energy without waste.

  (Vii) Although the heat storage device according to the fifth embodiment and the heat storage device according to the sixth embodiment are internally fused, the present invention also includes other types of heat storage devices within the range. For example, the heat storage device described in Patent Document 6 stores heat energy by causing a raw material solution to exchange heat with a heat medium via a heat exchanger and generating an inclusion compound on the heat transfer surface of the heat exchanger. At the same time, the clathrate is peeled off and dispersed or suspended in a raw material solution to form a slurry, and the slurry is taken out and then melted, and then the thermal energy is taken out. For example, the clathrate generation method in the heat storage device of Patent Document 6 falls within the technical category planned by the first embodiment of the present invention.

  In addition, the stirring of the raw material solution in each embodiment of the present invention involves the formation and melting of the clathrate compound (the first and second steps in the second and third embodiments, the heat storage operation and the heat dissipation in the fourth embodiment). The operation and the fifth and sixth embodiments correspond to the heat storage step and the heat release step), respectively, and are performed at least once. Therefore, the raw material solution may be stirred once after the clathrate is formed and melted, for example, five times.

  Hereinafter, as an embodiment of the present invention, a heat storage air conditioner using the heat storage device in the first embodiment and this heat storage device in the second embodiment will be described. In these embodiments, specific examples of clathrate compounds are clathrate hydrates. However, other clathrate compounds are excluded from the present invention just because the specific examples are clathrate hydrates. is not.

  In the present invention, the concentration of the guest molecule in the raw material solution may be a concentration that gives a harmonic melting point (harmonic melting point concentration), or a concentration lower than or higher than that.

<First embodiment>
As shown in FIG. 1, the heat storage device of the present embodiment stores a raw material solution L made of an aqueous solution containing a hydrate-generating substance in a heat storage tank 1. A heat exchanger 2 (here, a heat transfer tube) that exchanges heat with the heat medium (refrigerant) of the cycle is accommodated. The heat transfer tube as the heat exchanger 2 is formed by meandering up and down in the illustrated example in order to increase the heat transfer area when a heat medium is passed through the tube to perform the heat exchange. To make it longer. A circulation path 3 is attached to the heat storage tank 1 in order to send the raw material solution from the bottom to the top, and a pump 4 is provided in the circulation path 3. By sending the raw material solution L at the bottom of the heat storage tank 1 through the circulation path 3 to the upper part of the tank, the raw material solution is stirred in the tank.

  In this embodiment, this stirring is performed in a time zone from the start of heat exchange until a predetermined time elapses before the end.

  In the apparatus of this embodiment shown in FIG. 1, when a low-temperature heat medium is circulated through the heat transfer tube as the heat exchanger 2, the heat medium exchanges heat with the raw material solution L on the surface of the heat transfer tube. L is cooled and clathrate hydrate L1 is produced. The clathrate hydrate L1 adheres to and accumulates on the surface of the heat exchanger 2, or the clathrate hydrate L1 peels off from the surface of the heat exchanger 2 and is dispersed or suspended in the form of particles in the raw material solution. There is something that generates FIG. 1 shows a state in which a clathrate hydrate lump is adhered and formed around the heat transfer tube as the heat exchanger 2. The massive clathrate hydrate L1 produced by cooling the clathrate hydrate aqueous solution is formed in a substantially coaxial sheath shape and a substantially cylindrical shape around the heat transfer tube. As an example of the arrangement of the heat transfer tubes as the heat exchanger, the one meandering in the up-and-down direction is shown, but the present invention is not limited to this, and for example, it may be arranged so as to meander in the horizontal direction.

  With respect to the heat storage device of this embodiment shown in FIG. 1, a circulation path 3 is provided for extracting the raw material solution L from the bottom of the heat storage tank 1 by the pump 4 and returning it to the top of the heat storage tank 1 in order to examine the timing of stirring and the heat storage efficiency. FIG. 2 shows an experiment for investigating the relationship between the heat storage elapsed time and the heat storage speed in the case of stirring the raw material solution L in the heat storage tank 1 and in the case of not performing stirring without operating the pump 4. The result was obtained.

  In this experiment, an aqueous solution having a concentration (harmonic melting point concentration) less than the concentration giving the harmonic melting point of the clathrate hydrate forming substance tetra-n-butylammonium bromide (TBAB) was used as the raw material solution. However, in the present invention, the concentration of the guest molecule in the raw material solution may be a concentration that gives a harmonic melting point (harmonic melting point concentration), or a concentration lower than or higher than that.

  In FIG. 2, the horizontal axis is the ratio of the elapsed time from the start of heat exchange to the time until the end of heat storage, and is expressed as “heat storage elapsed time ratio”. The vertical axis represents the heat storage amount per unit time of the heat energy cooled and stored by heat exchange with the heat medium in the heat exchanger, and is expressed as “heat storage speed”. According to this figure, it has shown that heat storage is performed efficiently, so that the heat storage speed is large.

(Specify the specified time)
Next, FIG. 2 is examined in order to specify the predetermined time for stirring by the range of the solid phase ratio. According to FIG. 2, the temperature of the raw material solution is initially lowered after the heat exchange is started, and when the temperature of the raw material solution L near the surface of the heat exchanger 2 reaches the clathrate hydrate generation start temperature, the clathrate is included. Hydrate L1 begins to be produced, and clathrate hydrate particles are dispersed or suspended in the raw material solution to produce a hydrate slurry. As the heat exchange is continued, the clathrate hydrate particles increase, the solid phase ratio (weight ratio of clathrate hydrate L1 to the hydrate slurry) increases, and the clathrate water is further added to the surface of the heat exchanger 2. A lump of Japanese product is formed.

  At the stage where the clathrate hydrate is not formed (raw material solution stage) and at the stage where the solid phase ratio is low (corresponding to low heat storage density), the raw material solution is stirred to pass through the heat exchanger. It can be seen that the heat exchange is efficiently performed and the heat storage speed is increased.

  When the heat storage elapsed time ratio was 0.5 and the solid phase ratio was large (corresponding to a large heat storage density), there was no difference in the heat storage speed due to the presence or absence of stirring of the raw material solution.

  That is, when the heat storage elapsed time ratio is 0.5 or less, stirring of the raw material solution prevents a decrease in heat transfer due to hydrate deposition on the surface of the heat exchanger 2, and heat exchange is efficient. Indicates what is being done. However, if the solid phase ratio increases and the heat storage elapsed time ratio exceeds 0.5, the amount of hydrate in the raw material solution or hydrate slurry increases, and the amount of hydrate adhering to the heat exchange surface increases. Since the amount of hydrate having a low thermal conductivity increases and the heat conductivity decreases, the effect of increasing the heat exchange efficiency by stirring is not recognized.

  The appropriate range of the solid phase ratio that has the effect of increasing the heat exchange efficiency by stirring the raw material solution is the TBAB concentration, the type / temperature / flow rate of the heat medium circulated in the heat exchanger, the heat exchanger and the heat storage tank Depending on the structure, stirring method, stirring strength (ratio to the total amount of the raw material solution replaced per hour), heat storage speed, etc., the effect of stirring the raw material solution is generally recognized in the range where the solid phase ratio is less than 10 to 15 wt%. (See Table 1). Similar results were obtained for clathrate hydrate-generating substances other than TBAB.

  Therefore, the raw material solution or hydrate slurry in the heat storage tank is agitated in the time zone from the start of heat exchange in the heat storage operation until the solid phase ratio of the hydrate slurry generated reaches about 10 to 15 wt%. Thus, the heat transfer can be improved, the heat exchange efficiency can be increased, and the inclusion compound can be efficiently generated. After the solid phase ratio of the hydrate slurry reaches about 10 to 15 wt%, it is not necessary to perform stirring, so stirring is performed in an effective range, and energy can be saved.

  Thus, in this embodiment, the “predetermined time” during which stirring is performed is preferably set as the time until the solid phase ratio reaches about 10 to 15 wt%.

  In addition to specifying by the solid phase ratio, the cumulative value of the heat energy that is cooled and stored by heat exchange with the heat medium in the heat exchanger (accumulated heat energy), that is, the time for stirring by the accumulated heat storage amount, The “predetermined time” may be specified.

(Measurement method of solid fraction)
In the present embodiment, the “predetermined time” is specified as the time when the solid phase ratio becomes a suitable value as described above. For this specification, it is determined whether it is time to stop stirring. The solid phase ratio must be measured.

  Next, a method for measuring the solid phase ratio of the hydrate slurry in order to determine the stirring stop timing will be described.

  The solid phase ratio is obtained by measurement based on the difference in physical properties between the solid phase hydrate and the liquid phase raw material solution. For example, the measurement of the change of the hydrate slurry electrical resistance between the electrodes provided in the heat storage tank based on the difference in conductivity, or the measurement of the change in the liquid level in the heat storage tank based on the difference in density can be mentioned. Furthermore, the relationship between the temperature of clathrate hydrate formation and the concentration of the hydrate-generating substance in the solution and the initial hydrate-generating substance solution concentration data are stored in advance, and the stored data and the heat storage tank The solid phase ratio can also be calculated from the measured value of the hydrate slurry temperature.

  When an aqueous solution of a hydrate-forming substance that forms a hydrate is cooled, hydrate particles are formed when the temperature falls below the hydrate formation temperature, and the hydrate particles are dispersed or suspended in the aqueous solution to form a hydrate slurry. Is generated. When cooling is continued, hydrate particles increase, and the solid phase ratio (referred to the weight ratio of hydrate particles to hydrate slurry) increases. There is a certain relationship between the temperature of the hydrate slurry and the solid fraction, as determined by the initial concentration of the aqueous solution of the hydrate-forming substance that forms the hydrate.

  For example, the graph of FIG. 3 shows the relationship between the temperature of the hydrate slurry of an aqueous solution of tetra n-butylammonium bromide (TBAB) having an initial concentration of 14 wt% and the solid fraction. The solid phase ratio can be determined based on the known initial concentration of the aqueous solution of the hydrate-generating substance and the measured hydrate slurry temperature. Therefore, the solid phase ratio is obtained from the measurement value provided by the measuring instrument provided in the heat storage tank, and when the obtained solid phase ratio is within the predetermined range, the raw material solution or the hydrate slurry is stirred, and the solid phase ratio When the value exceeds a predetermined range, stirring is stopped.

(Other methods for setting the specified time)
The heat storage rate is measured as another method to specify the time that can be effective to promote the heat transfer of the solution or hydrate slurry by stirring the solution from the start of heat exchange. Can be determined. By measuring the heat storage speed and stirring the solution, it is determined whether or not the heat storage speed is higher than that when not stirring, and stirring is performed while the heat storage speed is exceeded.

  The heat storage rate is calculated from the flow rate of the heat medium, the temperature of the heat medium at the inlet / outlet of the heat storage tank, and the like. There are the following methods for estimating the heat storage rate instead of measuring the flow rate and temperature of the heat medium. The operation of the compressor during the heat storage operation is controlled according to the heat storage state, and in detail, the operation frequency is controlled. The relationship between the heat storage speed and the operating frequency of the compressor is obtained in advance, and the heat storage speed can be converted by measuring the operating frequency of the compressor.

  By measuring the operating frequency of the compressor and monitoring the operating status, the heat storage speed can be obtained and a predetermined time for stirring can be determined.

<Second embodiment>
Hereinafter, as a second embodiment of the present invention, a heat storage type air conditioning system using a heat storage device will be described with reference to FIG.

  FIG. 4 shows a regenerative air conditioning system according to this embodiment, which shows components for regenerative air conditioning and a control device therefor.

  In FIG. 4, the heat storage device has the same configuration as the device of FIG. 1, stores the raw material solution L as a heat storage material in the heat storage tank 1, and a heat exchanger (heat transfer tube) 2 is provided therethrough, A circulation path 3 is attached to the heat storage tank 1, and a pump 4 is provided in the circulation path 3. A heat medium (refrigerant) flows into and out of the heat exchanger 2.

  The heat storage tank 1 is further provided with a solid phase rate sensor 5 and a heat storage amount sensor 6.

  The solid phase rate sensor 5 measures the temperature of the heat storage material as data for calculating the solid phase rate of the heat storage material. In the example of calculating the solid phase ratio described later, the temperature of the hydrate slurry of the heat storage material is measured as a solid phase ratio sensor, but other calculation methods, for example, a method of calculating from the electrical resistance of the hydrate slurry, heat storage In the case of the method of calculating from the change in the liquid level of the material, the change in the electric resistance or the liquid level is measured. The heat storage amount sensor 6 measures the heat storage material temperature, the heat storage material liquid level, and the like as data for calculating the heat storage amount.

  The circulation path 3 and the pump 4 function as a stirrer, extract the aqueous solution L as a heat storage material from the bottom of the heat storage tank 1 and circulate it so as to return to the vicinity of the liquid surface at the top of the heat storage tank 1. When a distribution pipe is provided so as to disperse and return the aqueous solution in the vicinity of the liquid surface, the stirring effect can be enhanced.

  The heat storage material of this heat storage type air conditioning system is an aqueous solution of clathrate hydrate generating substance that generates clathrate hydrate, and the heat storage material having a freezing point of clathrate hydrate higher than 0 ° C. and lower than 20 ° C. Used. For example, there is an aqueous solution of tetra n-butylammonium bromide (TBAB).

  A pressure reducing valve 7 for reducing the pressure of the heat medium flowing into the heat exchanger 2 is provided at one end of the heat exchanger 2 of such a heat storage device, and an opening / closing valve 8 is provided outside the heat storage tank 1 at the other end. The pipes are branched from the pressure reducing valve 7 and the on-off valve 8 to the outdoor side and the indoor side, respectively, and reach the outdoor heat exchanger 10 outside and the indoor heat exchanger 20 indoors.

  The outdoor heat exchanger 10 installed outdoors is configured such that the heat medium (refrigerant) of the refrigeration cycle that constitutes the regenerative air conditioning system exchanges heat with the outside air. The compressor 11 is connected in series. Thus, the heat storage device and the outdoor heat exchanger 10 are connected by a closed pipe.

  On the other hand, an open / close valve 9 is provided in the indoor line branched from the pressure reducing valve 7, and a plurality of indoor heat exchangers 20 installed in the room are arranged in parallel to open and close the open / close valve 9 side and the open / close valve. It is connected between the valve 8 side. In the illustrated example, two indoor heat exchangers 20 are installed, and are connected to the on-off valve 9 side via pressure reducing devices 21, respectively. The decompression device 21 decompresses the heat medium flowing into the indoor heat exchanger.

  Further, the pipe line between the on-off valve 9 and the pressure reducing device 21 is connected to the pipe line between the heat exchanger 2 and the on-off valve 8 to form one flow path 30.

  As described above, these components are connected by the heat medium pipe and the on-off valves 8 and 9 for switching the flow path of the heat medium, and controlled by the control device 40 described later to form a refrigeration cycle circuit. .

  The control device 40 for operating the heat storage device includes a storage means 41 for storing the data base, a measurement data input means 42 for inputting measurement data, and an operation for performing an operation based on outputs from these means 41 and 42. Means 43 and operation control means 44 for controlling the components based on the output from the computing means 43 are provided. The measurement data input means 42 receives measurement data from the solid phase rate sensor 5 and the heat storage amount sensor 6 provided in the heat storage tank 1. The calculation means 43 has a solid phase rate calculation means 43A and a heat storage amount calculation means 43B for calculating the solid phase rate and the heat storage amount based on the data from the storage means 41 and the measurement data input means 42, respectively. Further, the operation control means 44 includes an operation mode switching means 44A and a stirrer operation control means 44B that operate in response to a calculation result from the calculation means.

  Next, each means which comprises the above-mentioned control apparatus 40 is further explained in full detail.

A. Storage means The storage means 41 stores various databases. The stored database is a hydrate formation curve representing the relationship between the hydrate formation start temperature of the heat storage material as a characteristic of the heat storage material and the concentration of the hydrate formation material in the aqueous solution, and the temperature of the hydrate slurry. There is a curve showing the relationship between the solid phase ratio, the specific heat of the heat storage material, the amount of latent heat, the initial concentration of the heat storage material, the weight of the heat storage material, and the planned heat storage amount based on the cooling demand. The planned heat storage amount is set by predicting the heat storage demand set from a program that predicts the heat storage amount required for the next day based on information such as season and day of the week, past cold demand data stored in the storage means, etc. Set.

B. Measurement Data Input Unit The measurement data input unit 42 refers to hardware and software for inputting data output from the solid phase rate sensor 5 and the heat storage amount sensor 6 provided in the heat storage tank 1 to the calculation unit.

C. Arithmetic means The arithmetic means 43 is realized by executing a program by a CPU or the like. The calculation means 43 is based on the relationship curve between the heat storage material temperature input by the measurement data input means 42 and the initial concentration of the heat storage material stored by the storage means, the hydrate slurry temperature of the heat storage material and the solid phase ratio. Solid phase ratio calculating means 43A for calculating the phase ratio, heat storage material temperature and heat storage material liquid level input by the measurement data input means 42, hydrate generation curve of the heat storage material stored in the storage means 41, specific heat And a heat storage amount calculating means 43B for calculating the heat storage amount from the latent heat amount, the initial concentration, and the weight.

D. Operation Control Unit The operation control unit 44 is a stirrer operation control unit 44B that controls the stirrer operation based on the solid phase ratio output from the calculation unit 43, a heat storage amount output from the calculation unit 43, and a storage unit 41 in advance. Operation mode switching means 44A that performs operation control of the refrigeration cycle based on the planned heat storage amount stored in the storage unit, that is, operation mode switching such as heat storage operation, heat storage use cooling operation, and heat storage non-use cooling operation. Specifically, the operation mode switching unit 44 </ b> A performs operation control of the compressor 11 and opening / closing control of the on-off valves 8 and 9.

  Next, operation | movement of this thermal storage type | formula air conditioning system comprised as mentioned above is demonstrated. In this system, it is possible to switch to a heat storage operation, a heat storage-use supercooling cooling operation, and a general cooling operation.

(A) Heat storage operation During the heat storage operation, the on-off valve 8 is "opened" and the on-off valve 9 is "closed" after the stirring device is started. Further, a heat medium (refrigerant) is circulated through the heat exchanger 2 (heat transfer tube) in the heat storage tank 1. In the state of the on-off valve as described above, the heat medium discharged from the compressor 11 is condensed in the outdoor heat exchanger 10. The liquefied heat medium is depressurized by the pressure reducing valve 7, and the depressurized heat medium evaporates in the heat exchanger 2, cools the heat storage material, generates a hydrate, and stores heat. In the heat storage operation, the surface of the heat exchanger 2 housed in the heat storage tank 1 becomes a cooling surface, the TBAB aqueous solution as the heat storage material is cooled, clathrate hydrate is generated, and the clathrate hydrate particles are the aqueous solution. A hydrate slurry dispersed or suspended therein is produced. Further, a hydrate is formed in a lump around the heat exchanger 2.

  When the stirrer is started as described above when starting the heat storage operation, the aqueous solution L of the heat storage material is extracted from the bottom of the heat storage tank 1 and is circulated so as to return to the vicinity of the liquid surface at the top of the heat storage tank 1. Since the aqueous solution of the heat storage material is agitated by circulating the aqueous solution of the heat storage material, effective heat transfer from the heat exchanger 2 to the aqueous solution becomes possible, and the clathrate compound is quickly applied to the heat transfer surface of the heat exchanger 2. Can be generated and grown. Thereby, the load of the compressor 11 which cools a refrigerant | coolant required at the time of heat storage can be decreased more.

  Here, the timing determination of the end of the stirring operation will be described.

  Based on the relationship between the heat storage material temperature input by the measurement data input means 42 and the initial concentration of the heat storage material stored in the storage means 41, the hydrate slurry temperature of the heat storage material and the solid phase ratio, the solid phase ratio is calculated. To do. An appropriate range of a solid phase rate that can increase heat storage speed by increasing the heat storage speed by stirring is obtained in advance as a predetermined range, and when the calculated solid phase rate reaches the upper limit of the predetermined range, stirring is stopped. By doing in this way, it can stir in an effective range and can also contribute to the energy saving of the circulation pump for stirring.

(B) Supercooling cooling operation using heat storage During the supercooling cooling operation using heat storage, the on-off valves 8 and 9 are closed. The pressure reducing valve 7 is fully opened.

  In the state of the on-off valve as described above, the refrigerant discharged from the compressor 11 is condensed in the outdoor heat exchanger 10. The liquefied heat medium (refrigerant) exchanges heat with the heat storage material in the heat exchanger 2 in the heat storage tank 1 via the opened pressure reducing valve 7 and enters a supercooled state.

  The heat medium that has been in a supercooled state via the heat exchanger 2 is depressurized by the decompression device 21, evaporated by the indoor heat exchanger 20, cools the room, and returns to the compressor 11 again.

(C) General cooling operation (cooling operation without heat storage)
During general cooling operation that does not use heat storage, the on-off valve 9 is set to “open” and the on-off valve 8 is set to “closed”. In the state of the on-off valve as described above, the heat medium discharged from the compressor 11 is condensed in the outdoor heat exchanger 10. The liquefied heat medium is depressurized by the depressurization device 21 via the opened on-off valve 9. The heat medium evaporates in the indoor heat exchanger 20, cools the room, and returns to the compressor 11 again.

  Next, the stirring operation of the raw material solution will be further described. A stirring operation may be performed after completion of the heat storage use cooling operation. When the heat release using the heat storage cooling operation is performed to recover the cold from the stored heat storage agent, the temperature of the raw material solution becomes higher than the freezing point of the clathrate compound. In particular, a temperature gradient of a high temperature and a relatively low temperature occurs below. Further, when the heat storage step and the heat release step are repeatedly executed, the guest molecules stay in a place where the clathrate compound is melted, so that the guest molecules are concentrated and a concentration gradient may be generated. Furthermore, even if the thermal energy is taken out, the clathrate compound may remain unmelted, and no further thermal energy can be taken out. In particular, during operation of an internal fusion type heat storage device such as the heat storage device according to the present embodiment, if the specific gravity of the clathrate compound and the raw material solution is different, the difference in specific gravity is not determined during the heat dissipation process. The melted clathrate compound floats or settles and is unevenly distributed in the heat storage tank, and the presence of such unmelted clathrate compound causes the concentration gradient and temperature gradient of the raw material solution.

  In contrast, a step of stirring the heat storage material is provided after the heat storage use cooling operation is completed and before the heat storage operation is started again. When this stirring is performed, a relatively high temperature raw material solution and a relatively low temperature raw material solution can be mixed, and a raw material solution having a relatively high concentration of guest molecules and a relatively low raw material solution are mixed. Or by melting the unmelted clathrate compound by mixing with the raw material solution above the freezing point of the clathrate compound, eliminating the temperature gradient of the raw material solution and the concentration gradient of the guest molecule, making the raw material solution more homogeneous The variation in physical properties of the clathrate compound produced from the raw material solution can be reduced.

  Thus, homogeneous heat energy can be stored, and heat energy can be stored and taken out efficiently without waste.

  The present invention is not limited to the above form, and various modifications are possible. For example, the stirring device can be changed.

  FIG. 5 shows an example of a heat storage device provided with a stirring device using a circulation pump. In FIG. 1, the raw material solution is extracted from the bottom of the heat storage tank 1 and circulated so as to return to the vicinity of the raw material solution surface in the upper part of the heat storage tank, but in FIG. 5, the aqueous solution present near the liquid surface of the heat storage tank 1 during heat storage or By sending the slurry to the vicinity of the bottom of the heat storage tank 1 with the pump 4, the heat storage material is forcedly convected to improve heat transfer characteristics. The discharge pipe tip may be reduced in diameter to increase the flow velocity. In addition, the suction and discharge portions may be provided at a plurality of locations instead of one location, and the agitation effect can be enhanced by providing a distribution pipe so that suction or discharge is performed in a distributed manner. If the density of the aqueous solution or slurry existing near the liquid surface of the heat storage tank during heat storage is smaller than the density of the aqueous solution or slurry existing near the bottom, the discharge holes provided in the distribution pipe should be discharged downward or diagonally downward. Then, the stirring effect can be enhanced.

  Next, as shown in FIG. 6, a stirring device for rotating the stirring blade 4A may be provided to stir the aqueous solution or slurry to improve the heat transfer characteristics.

  Furthermore, as shown in FIG. 7, an air diffuser that discharges bubbles may be provided at the bottom of the heat storage tank, and an agitation device that supplies air by the air pump 4B and stirs the raw material solution or slurry by floating the bubbles may be provided.

It is a schematic block diagram of the thermal storage apparatus as 1st embodiment of this invention. It is a figure which shows the relationship between the heat storage elapsed time and the heat storage speed in the case where stirring is not performed in the apparatus of FIG. It is a figure which shows the relationship between hydrate slurry temperature and a solid-phase rate. It is a block diagram of the thermal storage type | formula air conditioning system as 2nd embodiment of this invention. It is a figure of the stirring apparatus as other embodiment. It is the figure of the stirring apparatus as other embodiment. It is the figure of the stirring apparatus as other embodiment.

Explanation of symbols

1 Heat storage tank 2 Heat exchanger (heat transfer tube)
3 Stirring device (circulation path)
4 Stirrer (pump)
L (raw material) solution L1 inclusion compound

Claims (6)

A solution containing a host molecule of the clathrate compound as a solvent and a guest molecule as a solute is subjected to heat exchange with a heat medium via a heat exchanger disposed in the solution, thereby enclosing the heat transfer surface of the heat exchanger. In a method for producing an inclusion compound, which comprises a step of producing an inclusion compound,
The method for producing an clathrate compound, wherein the solution is stirred in a predetermined time period before the end of heat exchange. In a method of accumulating and extracting thermal energy by generating and melting an inclusion compound, a solution containing a host molecule of the inclusion compound as a solvent and a guest molecule as a solute is passed through a heat exchanger disposed in the solution. A first step of generating a clathrate compound on the heat transfer surface of the heat exchanger by heat exchange with the heat medium to accumulate heat energy, and a clathrate generated on the heat transfer surface of the heat exchanger A second step of melting the compound from the side of the heat transfer surface and taking out the heat energy;
A method for accumulating and taking out thermal energy, characterized in that the solution is stirred for a predetermined time period before the end of the first step.   The thermal energy according to claim 2, wherein the solution is stirred in a time zone from the end of the second step to the start of the first step while repeating the first step and the second step. To store and retrieve data. A heat exchanger disposed in a solution containing a host molecule of a clathrate compound as a solvent and a guest molecule as a solute; and a heat storage tank for housing the heat exchanger, wherein the clathrate is included in the heat transfer surface of the heat exchanger A heat storage operation for storing thermal energy in the heat storage tank by generating a compound, and the heat generated by melting a clathrate compound generated on the heat transfer surface of the heat exchanger from the heat transfer surface side. In a heat storage device that performs a heat dissipation operation to extract energy out of the heat storage tank,
A heat storage device comprising a stirring device for stirring the solution in a predetermined time period before the end of the heat storage operation. A heat storage device comprising: a heat exchanger disposed in a solution containing a host molecule of a clathrate compound as a solvent and a guest molecule as a solute; a heat storage tank containing the heat exchanger; and a stirrer for stirring the solution In driving method,
A heat storage process for storing thermal energy in the heat storage tank by generating a clathrate compound on the heat transfer surface of the heat exchanger, and a clathrate compound generated on the heat transfer surface of the heat exchanger. Having a heat dissipation step of releasing the thermal energy out of the heat storage tank by melting from the hot surface side;
A method for operating a heat storage device, comprising: a step of driving the stirring device in a predetermined time period before the end of the heat storage step.   The said agitation apparatus is driven also in the time slot | zone from the completion | finish of one of the thermal radiation processes to the start of the next thermal storage operation | movement while repeating the said thermal storage process and the said thermal radiation process. Operation method of the heat storage device.

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