JP2011064419A - Method and device of manufacturing latent heat storage slurry - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technology for stably or continuously manufacturing a latent heat storage slurry for a longer time by stabilizing an operation of a heat exchanger producing a latent heat storage substance or exchanging heat between a cold medium and a material solution. <P>SOLUTION: This method of manufacturing the latent heat storage slurry is provided to produce the latent heat storage slurry capable of producing the latent heat storage substance, and producing the latent heat storage substance in the solution by cooling the solution capable of generating supercooling in production by heat exchange with the cold medium in the heat exchanger, and includes a process for circulating a part of the solution with the latent heat storage substance included therein, from an outlet side to an inlet side of the heat exchanger, and a process for circulating a part of the cold medium from the outlet side to the inlet side of the heat exchanger. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is a product in which a latent heat storage material can be produced and dispersed or suspended in a solution that may cause supercooling during the production (hereinafter sometimes referred to as “raw material solution”). That is, the present invention relates to a technology for manufacturing a latent heat storage slurry.

The raw material solution is a solution capable of generating a latent heat storage material. Therefore, if a latent heat storage material can be further generated regardless of whether the latent heat storage material is already dispersed or suspended, it corresponds to a raw material solution.
Raw material solution is one capable of causing supercooling in the generation of latent heat storage material. Therefore, if it can cause supercooling regardless of whether the latent heat storage material is already dispersed or suspended, it corresponds to the raw material solution. For example, even if it seems that supercooling has been released over the entire surface due to the dispersion or suspension of the latent heat storage material, it can be said that the solution is not locally released from supercooling. Since the solution can cause supercooling, the solution corresponds to a raw material solution.

  The latent heat storage substance in the present invention is a substance that easily adheres to the surrounding environment (for example, the inner wall of a pipe or the heat exchange surface of a heat exchanger). Typical examples of the substance are inorganic hydrate salts and clathrate compounds. . The clathrate compound includes clathrate hydrate, and the clathrate hydrate includes quasi clathrate hydrate. If the latent heat storage material is clathrate hydrate, the aqueous solution of the guest molecule can generate clathrate hydrate, which is a latent heat storage material, and can cause supercooling during the generation. It corresponds to.

  When manufacturing a latent heat storage material slurry in which the latent heat storage material is dispersed or suspended in the raw material solution, if the latent heat storage material has the property of easily adhering to the surrounding environment, it adheres to the inner wall of the pipe. This increases the pressure loss, impedes smooth flow and further clogs or adheres to the heat exchange surface of the heat exchanger to reduce the heat exchange efficiency and stabilizes the latent heat storage slurry for a long time. It becomes difficult to manufacture continuously or continuously. In addition, if at least a part of the raw material solution is in a supercooled state, the latent heat storage material is not generated or sufficiently generated until the supercooled state is released, or at the same time the supercooled state is released. As a result of producing a large amount of latent heat storage material at a time, the amount of adhesion to the surrounding environment increases rapidly, so that it becomes difficult to stably or continuously manufacture the latent heat storage slurry for a long time.

  As a means for solving such a problem, a raw material solution in which a solid latent heat storage material is present is circulated from the outlet side to the inlet side of the heat exchanger and the heat exchanger. Techniques for cooling are known. According to this technology, since the solid-state latent heat storage material functions as a generation nucleus of the next (other) latent heat storage material, it is possible to prevent overcooling that may occur in the raw material solution (see Patent Document 1). ).

  Further, after the raw material solution is brought into a supercooled state by the first heat exchanger, the supercooled state is released downstream of the first heat exchanger, and a small amount of latent heat storage material is generated in the raw material solution. Subsequently, a technique is known in which a large amount of latent heat storage material is generated in the raw material solution by subsequently cooling with a second heat exchanger (Patent Document 2).

In the technique of Patent Document 2 (see FIG. 10), for example, in order to release at least a part of the supercooling of the raw material solution between the outlet of the first heat exchanger and the inlet of the second heat exchanger. , By refluxing the raw material solution (or latent heat storage slurry) from the outlet side to the inlet side of the second heat exchanger, the latent heat storage material dispersed or suspended therein is transferred to the next (other) latent heat. A method of supplying as a generation nucleus of a heat storage material is disclosed. Moreover, in the technique of patent document 3 (refer FIG. 2), the method of installing the buffer tank and ensuring the time required for supercooling cancellation | release is disclosed.
Moreover, in order to realize continuous production of the latent heat storage slurry for a long time, the plurality of second heat exchangers are sequentially switched, that is, the latent heat storage material adheres because it contributed to the manufacture of the latent heat storage slurry. Switch to the other second heat exchanger from which the latent heat storage material is not attached or removed, and the other second heat exchanger causes the latent heat storage performance The slurry is manufactured and the latent heat storage material adhering to the heat transfer surface of the second heat exchanger and the surrounding environment is removed. There is also a case where a method of repeatedly switching such a plurality of second heat exchangers is employed (see Patent Document 4).

  On the other hand, it is known that the amount of the latent heat storage material attached to the heat transfer surface of the heat exchanger decreases as the temperature difference between the raw material solution that exchanges heat through the heat transfer surface and the cooling medium decreases. (See Patent Document 5, paragraph 0039). When the temperature difference between the raw material solution and the cooling medium is reduced, the amount of exchange heat is reduced, the amount of latent heat storage material is reduced, and the production of latent heat storage slurry may be hindered. If it does not occur, reducing the temperature difference between the raw material solution and the cooling medium can be an option for suppressing the adhesion of the latent heat storage material to the heat transfer surface of the heat exchanger.

JP2007-107773 Patent 2002-263470 JP 2009-51906 Patent No. 3972734 JP 2009-68826

  The prior art described in Patent Document 2 described above is a production that is useful for releasing the supercooling through the reflux of the raw material solution (or latent heat storage slurry) in a system in which heat exchange between the raw material solution and the cooling medium is performed if necessary. By supplying nuclei, it is possible to appropriately control or adjust the supercooling or subcooling release of the raw material solution, suppress the adhesion of the latent heat storage material to the surrounding environment, and thus stabilize the latent heat storage slurry for a long time or It can be said that it contributes to continuous production.

  However, even if the generated nuclei are supplied by refluxing the raw material solution (or latent heat storage slurry), the problem of adhesion of the latent heat storage material to the surrounding environment due to the supercooling or release of the supercooling of the raw material solution is completely solved It can not be. For example, when the temperature of the cooling medium flowing through the heat exchanger fluctuates while supplying the production nuclei by refluxing the raw material solution, the degree of heat exchange between the cooling medium and the raw material solution or the degree of cooling of the raw material solution by the cooling medium is also increased. Since it fluctuates, the generation amount of the latent heat storage material generated from the raw solution whose supercooling has been released and the adhesion amount of the latent heat storage material to the surrounding environment also vary. If the latent heat storage slurry is manufactured for a long time under such unstable conditions, the amount of the latent heat storage material adhering to the surrounding environment gradually or cumulatively increases, or suddenly exceeds expectations. Therefore, troubles and malfunctions that occur during the production of the latent heat storage slurry become apparent with the passage of time.

  One solution to this problem is to increase the switching frequency in the conventional method (Patent Document 4) in which switching of a plurality of second heat exchangers is repeated, that is, the latent heat storage material is attached. Increasing the frequency of removing the deposits from the second heat exchanger. However, switching the second heat exchanger to remove deposits is not an inherently desirable approach from the standpoint of efficient production of latent heat storage slurries and increases the frequency of such switching. Is not inherently preferred. Switching of the plurality of second heat exchangers is as small as possible. In other words, when cooling the raw material solution while switching the plurality of second heat exchangers, one second heat exchanger is used. Since it is preferable to make the cooling time of the raw material solution as long as possible, there is a contradiction.

  Moreover, in the prior art described in patent document 5, in order to suppress adhesion of the latent heat storage material to the heat transfer surface to the heat exchanger, the raw material solution that performs heat exchange via the heat transfer surface and the cold heat When reducing the temperature difference with the medium, if either the temperature of the raw material solution or the temperature of the cooling medium is likely to fluctuate or is unstable, it becomes difficult to appropriately control or adjust the difference between the two temperatures. Therefore, it becomes impossible to effectively suppress adhesion of the latent heat storage material to the heat transfer surface. When the raw material solution is refluxed from the outlet side to the inlet side of the heat exchanger, the temperature of the raw material solution flowing through the heat exchanger can be hardly changed or stabilized. However, in order to suppress adhesion of the latent heat storage material to the heat transfer surface to the heat exchanger, it is not sufficient by itself, and it is necessary to make the temperature of the cooling medium difficult or stable.

Therefore, in order to produce a latent heat storage slurry in a stable or continuous manner for a longer time, the conventional method is insufficient, and further contrivance is necessary.
The present invention has been made in view of the above points, and by further stabilizing the operation of the heat exchanger in which the latent heat storage material is generated or the heat exchange between the cooling medium and the raw material solution is performed, the present invention is made longer. It is an object of the present invention to provide a technique capable of producing a latent heat storage slurry stably or continuously over time.

  In order to achieve the above object, the method for producing a latent heat storage slurry according to the first embodiment of the present invention is capable of generating a latent heat storage material and a solution capable of causing supercooling during the generation of the latent heat storage material. The method of manufacturing a latent heat storage slurry that generates the latent heat storage material in the solution by cooling by heat exchange with a cooling medium in the method, wherein the solution is transferred from the outlet side to the inlet side of the heat exchanger. And a step of refluxing a part of the cooling medium together with the latent heat storage material contained therein, and a step of refluxing a part of the cooling medium from the outlet side to the inlet side of the heat exchanger. .

  The apparatus for producing a latent heat storage slurry according to the second aspect of the present invention is capable of generating a latent heat storage material and cooling at least a part of the solution that may cause supercooling during the generation by heat exchange with a cooling medium. A heat exchanger to be recirculated, a first recirculation pipe for recirculating a part of the solution together with the latent heat storage material contained therein from the outlet side to the inlet side of the heat exchanger, and the outlet side of the heat exchanger And a second recirculation pipe for recirculating a part of the cooling medium from the first to the inlet side.

  In the method for producing a latent heat storage slurry according to the third aspect of the present invention, after the latent heat storage material can be generated and at least a part of the solution that may cause supercooling in the generation is in a supercooled state, An apparatus for producing a latent heat storage slurry that generates the latent heat storage material in the solution by releasing the supercooling state and subsequently cooling by heat exchange with a cooling medium in a heat exchanger, wherein the heat exchange And a step of refluxing a part of the cooling medium from the outlet side to the inlet side of the vessel.

  An apparatus for producing a latent heat storage slurry according to a fourth aspect of the present invention is capable of generating a latent heat storage material and, after making at least a part of a solution capable of causing supercooling during the production, An apparatus for producing a latent heat storage slurry that generates the latent heat storage material in the solution by releasing the supercooling state and subsequently cooling by heat exchange with a cooling medium in a heat exchanger, wherein the heat exchange A recirculation pipe for recirculating a part of the cooling medium from the outlet side to the inlet side of the vessel is provided.

  The apparatus for producing a latent heat storage slurry according to the fifth aspect of the present invention includes a first heat exchanger that can generate a latent heat storage material and cool a solution that can cause supercooling during the generation, and a first heat exchanger. A second heat exchanger that cools the solution cooled by the heat exchanger by heat exchange with a cooling medium, and a second heat exchanger that circulates a part of the solution from the outlet side to the inlet side of the second heat exchanger. And a second recirculation pipe for recirculating a part of the cooling medium from the outlet side to the inlet side of the second heat exchanger.

(1) About the effect which 1st and 2nd form of this invention show | plays In 1st and 2nd form of this invention, the production | generation nucleus useful for a supercooling release is supplied by recirculation | reflux of a part of raw material solution. At the same time, a part of the cooling medium is refluxed from the outlet side to the inlet side of the heat exchanger. When a part of the cooling medium is recirculated from the outlet side to the inlet side of the heat exchanger, the flow rate of the cooling medium flowing into the heat exchanger is increased, the temperature fluctuation of the cooling medium is reduced, and the cooling medium, the raw material solution, Fluctuations are less likely to occur in the degree of heat exchange or the degree of cooling of the raw material solution by the cooling medium. Therefore, the heat exchange between the cooling medium and the raw material solution (in other words, the operation of the heat exchanger) is stabilized, and the generation of the latent heat storage material in the raw material solution is stabilized. As a result, the amount of adhesion of the latent heat storage material to the surrounding environment does not increase more rapidly than expected, making it easier to predict the progress of adhesion and appropriately controlling the subcooling or overcooling of the raw material solution. Or it becomes easy to adjust. Even if it is inevitable that the amount of adhesion of the latent heat storage material gradually or cumulatively increases, troubles and malfunctions that occur during the production of the latent heat storage slurry will become obvious unless a longer time elapses. It becomes difficult.
In addition, when the temperature of the raw material solution is less likely to fluctuate due to reflux, and at the same time the temperature is less likely to fluctuate due to partial reflux of the cooling medium, the temperature difference between the raw material solution and the cooling medium is Since it is difficult to fluctuate and stabilizes, it becomes easy to appropriately control or adjust the supercooling or supercooling release of the raw material solution, and consequently the effect of adhesion of the latent heat storage material to the heat transfer surface of the heat exchanger Suppression is possible.
Therefore, according to each of the first and second embodiments of the present invention, the latent heat storage slurry can be manufactured stably or continuously over a longer time.

(2) Effects of the third and fourth embodiments of the present invention After the raw material solution is brought into a supercooled state, at least a part of the supercooled state is released, and subsequently the heat with the cooling medium in the heat exchanger When the latent heat storage material is generated in the raw material solution by cooling by exchange, if the temperature of the cooling medium fluctuates, the degree of heat exchange between the cooling medium and the raw material solution or the degree of cooling of the raw material solution by the cooling medium As the fluctuation occurs, the amount of latent heat storage material generated from the raw solution whose supercooling has been released and the amount of latent heat storage material attached to the surrounding environment also vary. Troubles and defects that occur during the manufacture of the

  On the other hand, in each of the third and fourth embodiments of the present invention, a part of the cooling medium is circulated from the outlet side to the inlet side of the heat exchanger to reduce the temperature fluctuation of the cooling medium. Variations are less likely to occur in the degree of heat exchange between the medium and the raw material solution or the degree of cooling of the raw material solution by the cooling medium. As a result, as in (1) above, the heat exchange between the cooling medium and the raw material solution is stabilized, and the generation of the latent heat storage material from the raw material solution is stabilized. Therefore, according to each of the third and fourth aspects of the present invention, after the raw material solution is brought into a supercooled state, the supercooled state is released and subsequently cooled by heat exchange with the cooling medium in the heat exchanger. Thus, even when the latent heat storage material is generated in the raw material solution, the latent heat storage slurry can be produced stably or continuously over a longer time.

  In addition, when a part of the raw material solution is refluxed from the outlet side of the heat exchanger to the inlet side, the temperature of the raw material solution is difficult or stable, and the temperature also fluctuates due to a part of the cooling medium. The difference between the temperature of the raw material solution and the cooling medium is less likely to fluctuate and is stable, and can be easily controlled or adjusted properly, and thus the heat transfer surface of the heat exchanger. It is possible to effectively suppress the adhesion of the latent heat storage material to the surface. Therefore, in this case, the latent heat storage slurry can be manufactured more effectively, stably or continuously over a longer time.

(3) Effect of the fifth embodiment of the present invention The latent heat storage material is obtained by cooling the raw material solution in the first heat exchanger and subsequently cooling it by heat exchange with the cooling medium in the second heat exchanger. When at least a part of the raw material solution is brought into a supercooled state by cooling in the first heat exchanger. Therefore, when a part of the raw material solution is refluxed from the outlet side of the second heat exchanger to the inlet side through the first reflux pipe, the latent heat storage material contained in the refluxed raw material solution acts as a production nucleus. And since the supercooling which arose in the raw material solution cooled in the 1st heat exchanger is cancelled | released, more latent-heat thermal storage substances can be produced | generated by the cooling in a 2nd heat exchanger succeeding. However, in this case, if the temperature of the cold medium in the second heat exchanger fluctuates, the degree of heat exchange between the cold medium and the raw material solution or the degree of cooling of the raw material solution by the cold medium will fluctuate. The amount of latent heat storage material generated from the released raw material solution and the amount of adhesion of the latent heat storage material to the surrounding environment also fluctuate, which may cause problems in the production of latent heat storage slurry over time. Defects become obvious.

On the other hand, in the fifth embodiment of the present invention, since a part of the cooling medium is recirculated from the outlet side to the inlet side of the second heat exchanger to reduce the temperature fluctuation of the cooling medium, the cooling medium The degree of heat exchange with the raw material solution or the degree of cooling of the raw material solution by the cooling medium is less likely to vary. As a result, the operation of the second heat exchanger in which the latent heat storage material is generated or the heat exchange between the cooling medium and the raw material solution is further stabilized.
In addition, when the temperature of the raw material solution is less likely to fluctuate and stabilize due to the reflux of a part of the cooling medium, and when the temperature is less likely to fluctuate due to the reflux of a part of the cooling medium, the difference between the temperature of the raw material solution and the cooling medium is reduced. Since it becomes difficult to fluctuate and stabilize, it becomes easy to appropriately control or adjust, and consequently, it is possible to effectively suppress adhesion of the latent heat storage material to the heat transfer surface of the heat exchanger.
Therefore, according to the fifth aspect of the present invention, the supercooling state is canceled while at least part of the raw material solution between the first heat exchanger and the second heat exchanger is released. Even when the latent heat storage material is generated by exchanging the released raw material solution with the cooling medium in the second heat exchanger, the latent heat storage slurry is produced stably or continuously over a longer period of time. can do.

  (4) In addition, as a method of reducing the temperature fluctuation of the cooling medium flowing through the heat exchanger, for example, a method of temporarily storing the cooling medium in a tank before sending it to the heat exchanger to obtain a uniform temperature. Is also possible. However, the installation of the tank requires a suitable site and space. Further, it has been found that it is not always effective as a method to be adopted when manufacturing a latent heat storage slurry (this point will be described later). In consideration of such a problem, the present invention employs a technique of refluxing a part of the cooling medium.

  (5) If a part of the cooling medium is refluxed from the outlet side to the inlet side of the heat exchanger, the temperature of the cooling medium that exchanges heat with the raw material solution in the heat exchanger becomes higher, and the heat There is a risk that the exchange efficiency is lowered, and the amount of latent heat storage material is reduced. However, if the reflux ratio of the cooling medium from the outlet side to the inlet side of the heat exchanger is appropriately adjusted, the amount of the generated latent heat storage material attached to the heat transfer surface of the heat exchanger decreases, The heat exchange efficiency increases. Therefore, a decrease in the heat exchange efficiency between the cooling medium and the raw material solution in the heat exchanger can be avoided, and the heat exchange efficiency can even be increased.

It is explanatory drawing of the conventional latent-heat thermal storage slurry manufacturing apparatus (a). It is explanatory drawing of the conventional latent-heat thermal storage slurry manufacturing apparatus (b). It is explanatory drawing of the conventional latent-heat thermal storage slurry manufacturing apparatus (c). It is explanatory drawing of the conventional latent-heat thermal storage slurry manufacturing apparatus (d). It is explanatory drawing of the latent-heat thermal storage slurry manufacturing apparatus (A) which concerns on this invention. It is explanatory drawing of the latent-heat thermal storage slurry manufacturing apparatus (B) which concerns on this invention. It is explanatory drawing of the latent-heat thermal storage slurry manufacturing apparatus (C) which concerns on this invention. It is explanatory drawing of the latent-heat thermal storage slurry manufacturing apparatus (D) which concerns on this invention. It is explanatory drawing of the structure except a part of cooling-heat-medium circulation path | route among the latent-heat thermal storage slurry manufacturing apparatuses (E) which concern on this invention. It is explanatory drawing of the latent-heat thermal storage slurry manufacturing apparatus (E) which concerns on this invention. It is explanatory drawing of the structure except a part of cooling-medium circulation path | route among the latent-heat thermal storage slurry manufacturing apparatuses (F) based on this invention. It is explanatory drawing of the latent-heat thermal storage slurry manufacturing apparatus (F) which concerns on this invention. It is explanatory drawing of a latent-heat thermal storage slurry manufacturing apparatus (d) provided with a tank. It is an experimental result for the pressure loss increase by the side of the slurry in the 2nd heat exchanger which compared an example and a comparative example. It is an experimental result for the pressure loss increase by the side of the slurry in the 2nd heat exchanger which compared an example and a comparative example. It is a comparison result of the pressure loss increase on the slurry side in the second heat exchanger. It is an experimental result for the pressure loss increase by the side of the slurry in the 2nd heat exchanger which compared an example and a comparative example.

  Hereinafter, the present invention will be described in detail by embodiments or examples. At that time, the description will be made with reference to the charts as necessary, but the same parts or corresponding or common parts in each chart will be denoted by the same reference numerals, and a part of the description will be omitted. Needless to say, the present invention is not limited to the embodiments and examples described in the drawings.

  The manufacturing method of the latent heat storage slurry which is performed in the latent heat storage slurry manufacturing apparatus according to the present invention is that according to the present invention. Therefore, the latent heat storage slurry manufacturing method executed in the embodiment or example of the latent heat storage slurry manufacturing apparatus according to the present invention described below is the latent heat storage slurry manufacturing method of the present invention. This corresponds to the embodiment or the example.

Hereinafter, an aqueous solution of a clathrate hydrate guest substance (guest molecule) is used as a raw material solution, and the clathrate hydrate is dispersed or suspended in the raw material solution (hereinafter abbreviated as “latent heat storage material slurry”). the there) to be described as an example of a latent heat storage slurry in the present invention. For valves, sensors, joints, pumps, and the like that may be installed in the piping, they should be depicted and described in the drawings as long as it is necessary to explain the prior art and the present invention.
In this specification, a place where a path is connected or connected is called a node (individually or collectively).

  From the viewpoint of clarifying the features of the present invention, in the following description, first, the form of a conventional latent heat storage material slurry manufacturing apparatus will be described based on FIGS. 1 to 4, and the present invention corresponding to each form. An embodiment of the latent heat storage material slurry manufacturing apparatus will be described with reference to FIGS.

<Description of conventional latent heat storage material slurry manufacturing technology>
1 to 4 are explanatory views of conventional latent heat storage slurry production apparatuses (a) to (d), respectively.

<Conventional Latent Heat Storage Slurry Manufacturing Device (a)>
FIG. 1 is a diagram showing a latent heat storage slurry production apparatus (a) that performs heat exchange between a raw material solution and a cooling medium using a single heat exchanger. In FIG. 1, C1 is a cooling medium circulation path for circulating the cooling medium. The cooling medium circulation path C <b> 1 is an annular piping path formed by connecting the refrigerator 1, the cooling medium circulation pump 2, and the heat exchanger 3. The refrigerator 1 includes a cooling tower, a pump, a heat exchanger, and the like, and generates a cooling medium for cooling the raw material solution and the latent heat storage slurry. C2 circulates the latent heat storage slurry having a relatively low ratio of the raw material solution or latent heat storage material contained in the heat storage tank 4 toward the heat exchanger 3, and the latent heat storage slurry is transferred to the heat storage tank 4. This is a manufacturing-side slurry circulation path for distribution toward the outside. The production-side slurry circulation path C2 is an annular piping path formed by connecting the heat exchanger 3, the heat storage tank 4, and the production-side circulation pump 5. C3 is a slurry recirculation path for recirculating a part of the raw material solution together with the latent heat storage material contained therein from the outlet side of the heat exchanger 3 to the inlet side. The slurry recirculation path C3 includes a recirculation pipe (first recirculation pipe) that connects the outlet-side node N1 and the inlet-side node N2 of the heat exchanger 3 and a part of the production-side slurry circulation path C2. It is an annular piping path that is provided and connects the heat exchanger 3 and the slurry reflux pump 6.

  In the latent heat storage slurry production apparatus (a) shown in FIG. 1, the cooling medium is cooled in the refrigerator 1 so as to follow the cooling medium circulation path C <b> 1, and then heat is exchanged from the refrigerator 1 by the cooling medium circulation pump 2. The raw material solution is cooled by heat exchange in the heat exchanger 3 and then returned to the refrigerator 1.

  The raw material solution stored in the heat storage tank 4 is sent to the heat exchanger 3 by the production-side circulation pump 5 so as to follow the production-side slurry circulation path C2, where it is cooled by heat exchange with the cold medium. At least a part of the raw material solution is in a supercooled state, and is stored again in the heat storage tank 4. The supercooled state of the raw material solution stored again in the heat storage tank 4 is gradually released in the heat storage tank 4 at the storage destination. Thereby, the abundance ratio of the latent heat storage material increases in the heat storage tank 4, and the raw material solution becomes a latent heat storage slurry. Then, the latent heat storage slurry that has been accommodated in the heat storage tank 4 is sent as a raw material solution by the manufacturing side circulation pump 5 again or cyclically so as to follow the manufacturing side slurry circulation path C2, and returned to the heat storage tank 4. . Thus, the ratio of the latent heat storage material in the latent heat storage slurry contained in the heat storage tank 4 is gradually increased to a level suitable for heat utilization.

  At this time, at least a part of the raw solution or a part of the latent heat storage slurry sent as a raw material solution in the supercooled state is drawn from the node N1 by the slurry reflux pump 6 along the slurry reflux path C3. It is sent to the heat exchanger 3 via N2 and returned to the node N1. When a part of the raw material solution in which at least a part is in a supercooled state moves along the slurry reflux path C3, a part or all of the supercooled state is released in the course of the movement. Many production nuclei are supplied to the raw material solution flowing in at the inlet side of the exchanger 3. By supplying the generated nuclei, the supercooling generated in the raw material solution due to the cooling in the heat exchanger 3 is released, and thus the adhesion of the latent heat storage material to the surrounding environment is suppressed.

In addition, C4 distribute | circulates the latent heat thermal storage slurry accommodated in the thermal storage tank 4 to the heat exchanger 7 by the side of a heat load, and is equivalent to the latent heat (or latent heat which the latent heat storage material has stored through the heat exchange in the heat exchanger 7). A heat utilization side slurry circulation path for allowing the raw material solution produced by the release of thermal energy (both sensible heat and sensible heat) to flow again to the heat storage tank 4, and the heat storage tank 4, the heat utilization side circulation pump 8 and the heat load It is an annular piping path formed by connecting the side heat exchanger 7.
The heat utilization-side slurry circulation path C4 is for enabling utilization of the latent heat storage slurry produced by the latent heat storage slurry manufacturing apparatus, and strictly constitutes a part of the latent heat storage slurry manufacturing apparatus. Not a thing. However, since the raw material solution that is used for heat in the heat exchanger 7 and is sent to the heat storage tank 4 is again or cyclically used for the production of the latent heat storage slurry, it is closely related to the production of the latent heat storage slurry. It can be said that there is a relationship. In this sense, the heat utilization side slurry circulation path C4 is drawn in FIG. 1 for the convenience of understanding the operation and role of the latent heat storage slurry production apparatus (the use side slurry circulation path C4 is intentionally drawn) The same applies to the latent heat storage slurry production apparatus shown in the other figures).
The heat exchanger 7 on the heat load side is a heat exchanger on the heat utilization side (for example, a heat exchanger for an indoor air conditioner that exchanges heat between the latent heat storage slurry and room air). Alternatively, it may be a heat exchanger (intermediate heat exchanger) for performing heat exchange between a heat medium that supplies heat energy to the heat exchanger on the heat utilization side and the latent heat storage slurry. “Thermal load side” merely means the direction (the right side of the drawing with respect to the heat exchanger 3). This point also applies to the latent heat storage slurry manufacturing apparatus shown in other drawings.

The latent heat storage slurry production apparatus shown in FIG. 1 includes a heat storage tank 4 between the production-side slurry circulation path C2 and the heat-use side slurry circulation path C4. The raw material solution cooled in the heat exchanger 3 is directly sent to the heat exchanger 7 on the heat load side together with the latent heat storage material generated by the cooling, and the latent heat is exchanged through the heat exchange in the heat exchanger 7. A raw material solution generated by releasing thermal energy equivalent to latent heat (or both latent heat and sensible heat) stored in the heat storage material may be recirculated or circulated through the heat exchanger 3. In this case, the two annular piping paths of the production-side slurry circulation path C2 and the heat utilization-side slurry circulation path C4 cannot exist separately, and at least the heat exchanger 3, the node N1, the heat exchanger 7 on the heat load side. Thus, there is only one annular piping path formed by connecting the production-side slurry circulation pump 5 and the node N2.
In principle, the heat storage tank 4 is not necessarily provided, and the raw material solution cooled in the heat exchanger 3 is directly sent to the heat exchanger 7 on the heat load side together with the latent heat storage material generated by the cooling. The same applies to the latent heat storage slurry production apparatus shown in the other figures.

<Conventional Latent Heat Storage Slurry Manufacturing Device (b)>
FIG. 2 is a diagram showing a latent heat storage slurry manufacturing apparatus (b) that performs heat exchange between a raw material solution and a cooling medium using two heat exchangers arranged in series. In FIG. 2, the cooling medium circulation path C1 is an annular piping path for circulating the cooling medium in the order of the second heat exchanger 32 and the first heat exchanger 31, and includes the refrigerator 1, the cooling medium circulation pump. 2, the 2nd heat exchanger 32 and the 1st heat exchanger 31 are connected. The production-side slurry circulation path C <b> 2 transfers the raw material solution (or the latent heat storage slurry having a relatively low presence ratio of the latent heat storage material) from the heat storage tank 4 to the first heat exchanger 31 and the second heat exchanger 32. It is a cyclic | annular piping path | route for distribute | circulating in order and distribute | circulating a latent-heat thermal storage slurry toward the thermal storage tank 4, 1st heat exchanger 31, 2nd heat exchanger 32, thermal storage tank 4, and manufacturing side circulation pump 5 is connected. The slurry recirculation path C3 is an annular piping path for recirculating a part of the raw material solution (or latent heat storage slurry) together with the latent heat storage material contained therein from the outlet side of the second heat exchanger 32 to the inlet side. Between the node N1 on the outlet side of the second heat exchanger 32 and the node N2 on the outlet side of the first heat exchanger 31 and on the inlet side of the second heat exchanger 32 And a part of the manufacturing side slurry circulation path C2.
The heat utilization side slurry circulation path C4 is basically the same as that shown in FIG.

  In the latent heat storage material slurry manufacturing apparatus (b) shown in FIG. 2, the cooling medium is cooled in the refrigerator 1 so as to follow the cooling medium circulation path C <b> 1, and then cooled from the refrigerator 1 by the cooling medium circulation pump 2. 2 toward the second heat exchanger 32 and further sent from the second heat exchanger 32 toward the first heat exchanger 31, and heat with the raw material solution (or latent heat storage slurry) in each heat exchanger. After the replacement, it is returned to the refrigerator 1.

  The raw material solution accommodated in the heat storage tank 4 is sent to the first heat exchanger 31 and the second heat exchanger 32 by the production-side circulation pump 5 so as to follow the production-side slurry circulation path C2, and the first In the heat exchanger 31, the heat energy corresponding to sensible heat is removed, and the raw material solution is supercooled to a certain extent. More specifically, since the raw material solution containing the latent heat storage material is supplied to the node N2 along the slurry reflux path C3, the latent heat storage material contained in the raw material solution that merges with the node N2 has another latent heat. It becomes a production nucleus of the heat storage material, and at least a part of the supercooling of the raw material solution is released. By releasing the supercooling, a small amount of latent heat storage material is generated in the raw material solution. Subsequently, the raw material solution from which at least a part of the supercooling has been released is cooled in the second heat exchanger 32 to remove the heat energy corresponding to the latent heat, thereby generating more latent heat storage material, and the latent heat storage as a whole. It becomes a latent heat storage slurry with a higher content of the active substance and is sent to the heat storage tank 4. The latent heat storage slurry that has been accommodated in the heat storage tank 4 is sent as a raw material solution by the manufacturing side circulation pump 5 again or cyclically so as to follow the manufacturing side slurry circulation path C2, and returned to the heat storage tank 4. Thus, the ratio of the latent heat storage material in the latent heat storage slurry contained in the heat storage tank 4 is gradually increased to a level suitable for heat utilization.

  At this time, a part of the raw material solution that has become the latent heat storage slurry is withdrawn by the slurry reflux pump 6 from the node N1 along the slurry reflux path C3, and is transferred to the second heat exchanger 32 via the node N2. Sent out and returned to node N1. Then, since the generated nuclei are supplied to the inlet side of the second heat exchanger 32, the supercooling generated in the raw material solution due to the cooling in the second heat exchanger 32 is released, and as a result, the latent heat to the surrounding environment is released. Adhesion of heat storage material is suppressed.

<Conventional latent heat storage slurry production device (c)>
FIG. 3 is a diagram showing a latent heat storage slurry manufacturing apparatus (c) that performs heat exchange between the raw material solution and the cold medium using two heat exchangers, and distributes the cold medium in parallel and the raw material solution in series. The configuration of the latent heat storage material slurry production apparatus (c) shown in FIG. 3 is basically the same as that of the latent heat storage material slurry production apparatus (b) shown in FIG. 2 except for the cooling medium circulation path C1. The cooling medium circulation path C1 of the latent heat storage slurry manufacturing apparatus (b) shown in FIG. 2 sends the cooling medium in series to two heat exchangers, whereas the latent heat storage material slurry manufacturing apparatus shown in FIG. The cooling medium circulation path C1 in (c) feeds the cooling medium in parallel to the two heat exchangers.
In FIG. 3, the cooling medium circulation path C1 feeds the cooling medium that has passed through the refrigerator 1 from the cooling medium circulation pump 2, branches the cooling medium at a node N3, and a part of the cooling medium and the remaining part are subjected to the first heat exchange. After joining the pipe path which flows in parallel toward the heat exchanger 31 and the second heat exchanger 32 and the cooling medium passing through the first heat exchanger 31 and the second heat exchanger 32 respectively at the node N4 And a piping path that circulates toward the refrigerator 1.

  In the latent heat storage slurry production apparatus (c) shown in FIG. 3, after the cooling medium is cooled in the refrigerator 1 so as to follow the cooling medium circulation path C <b> 1, the cooling medium circulation pump 2 removes the second cooling medium from the refrigerator 1. The heat exchanger 32 and the first heat exchanger 31 are sent in parallel, and the raw material solution is cooled by heat exchange with the cooling medium in each heat exchanger, and then returned to the refrigerator 1.

  The raw material solution is circulated in the order of the first heat exchanger 31 and the second heat exchanger 32 by the production-side circulation pump 5 so as to follow the production-side slurry circulation path C <b> 2, and is manifested in the first heat exchanger 31. Heat energy equivalent to heat is removed, and it is supercooled to some extent. The supercooling of the raw material solution is canceled due to the supply of the raw material solution containing the latent heat storage material to the node N2 along the slurry reflux path C3. Subsequently, at least a part of the raw material solution whose supercooling has been released is cooled in the second heat exchanger 32 to generate more latent heat storage material, and as a whole, the proportion of the latent heat storage material increases. The resulting latent heat storage slurry is sent to the heat storage tank 4. The latent heat storage slurry that has been accommodated in the heat storage tank 4 is sent as a raw material solution by the manufacturing side circulation pump 5 again or cyclically so as to follow the manufacturing side slurry circulation path C2, and returned to the heat storage tank 4. Thus, the ratio of the latent heat storage material in the latent heat storage slurry contained in the heat storage tank 4 is gradually increased to a level suitable for heat utilization.

  At this time, a part of the raw material solution that has become the latent heat storage slurry is withdrawn by the slurry reflux pump 6 from the node N1 along the slurry reflux path C3, and is transferred to the second heat exchanger 32 via the node N2. Sent out and returned to node N1. Then, since the generated nuclei are supplied to the inlet side of the second heat exchanger 32, the supercooling generated in the raw material solution due to the cooling in the second heat exchanger 32 is released, and as a result, the latent heat to the surrounding environment is released. Adhesion of heat storage material is suppressed.

<Conventional latent heat storage slurry production apparatus (d)>
FIG. 4 is a diagram (d) illustrating the latent heat storage slurry production apparatus in which two second heat exchangers 32 are arranged in parallel in the latent heat storage material slurry production apparatus (b) shown in FIG. 2. The latent heat storage slurry production apparatus (d) shown in FIG. 4 is patent document 4 (Patent No. 3972734) except that the latent heat storage material and the latent heat storage slurry are clathrate hydrate and hydrate slurry, respectively. is the same as the latent heat storage material slurry manufacturing apparatus described in).
In FIG. 4, there are a plurality of second heat exchangers 32, and the flow of the raw material solution and the cooling medium from one second heat exchanger to any one of the remaining second heat exchangers can be freely switched. It is configured to be. Thereby, the second heat exchanger 32 connected in series to the first heat exchanger 31 on the upstream side of the flow of the raw material solution is selectively switched from a plurality of units. Below, the case where the 2nd heat exchanger 32 is two is demonstrated for convenience.

  C6 is a hot water circulation path for supplying hot water to any of the second heat exchangers that are disconnected from the first heat exchanger 31. The hot water circulation path C6 is an annular piping path formed by connecting the hot water tank 10, the hot water circulation pump 11, and any one of the second heat exchangers 32. T1 to T4 are temperature sensors for measuring the temperature of the raw material solution and the cooling medium. FIG. 4 shows only one second heat exchanger 321 arranged, but the other second heat exchangers are also arranged in the same manner, but the illustration is omitted. ing.

First, the production principle of the latent heat storage slurry production apparatus (d) shown in FIG. 4 is the same as that of each latent heat storage slurry production apparatus (b) shown in FIG. That is, the latent heat storage slurry production apparatus (d) includes a first heat exchanger 31 and one second heat exchanger (temporarily set as 321) connected in series in order along the flow of the raw material solution, A slurry recirculation path C3 including a recirculation pipe (first recirculation pipe) that connects the outlet-side node N1 and the inlet-side node N2 of the second heat exchanger 321 is provided.
Thereby, the raw material solution accommodated in the heat storage tank 4 is sent to the first heat exchanger 31 by the production-side circulation pump 5, where the heat energy corresponding to sensible heat is removed and supercooled to some extent. In addition, since the raw material solution containing the latent heat storage material is supplied to the node N2, more specifically, the latent heat storage material contained in the raw material solution that merges with the node N2 generates another latent heat storage material. It becomes a nucleus and at least a part of the supercooling of the raw material solution is released. By releasing the supercooling, a small amount of latent heat storage material is generated in the raw material solution. Subsequently, at least a part of the raw material solution whose supercooling is released is cooled in the second heat exchanger 321 to generate more latent heat storage material, and as a whole, the proportion of the latent heat storage material increases. The resulting latent heat storage slurry is sent to the heat storage tank 4. The latent heat storage slurry that has been accommodated in the heat storage tank 4 is sent to the first heat exchanger 31 by the production side circulation pump 5 again or as a raw material solution, and undergoes the same steps as described above. It is returned to the heat storage tank 4. Thus, the ratio of the latent heat storage material in the latent heat storage slurry contained in the heat storage tank 4 is gradually increased to a level suitable for heat utilization.

  At this time, a part of the raw material solution that has become the latent heat storage slurry is withdrawn by the slurry reflux pump 6 from the node N1 along the slurry reflux path C3, and is transferred to the second heat exchanger 321 via the node N2. Sent out and returned to node N1. Then, since the generated nuclei are supplied to the inlet side of the second heat exchanger 321, the supercooling generated in the raw material solution due to the cooling in the second heat exchanger 321 is released, and consequently the latent heat to the surrounding environment Adhesion of heat storage material is suppressed.

  Next, in correspondence with the two second heat exchangers 32, the cooling medium circulation path C1, the refrigerator 1, the cooling medium circulation pump 2, the second heat exchanger 321, and the first heat The one in which the exchanger 31 is annularly connected (cooling medium circulation path C11), and the refrigerator 1, the cooling medium circulation pump 2, the second heat exchanger 322, and the first heat exchanger 31 are annularly connected. As for two things (cooling medium circulation path C12) and the production-side slurry circulation path C2, the heat storage tank 4, the production-side circulation pump 5, the first heat exchanger 31, and the second heat exchanger 321 are connected in a ring shape. The product (manufacturing-side slurry circulation path C21), the heat storage tank 4, the production-side circulation pump 5, the first heat exchanger 31, and the second heat exchanger 322 are connected in an annular shape (manufacturing-side slurry circulation) For the two routes C22) and the slurry reflux route C3, the slurry reflux In which the pump 6 and the second heat exchanger 321 are annularly connected (slurry reflux path C31), and in which the slurry reflux pump 6 and the second heat exchanger 322 are annularly connected (slurry reflux path C32) As for the hot water circulation path C6, the hot water tank 10, the hot water circulation pump 11, and the second heat exchanger 321 connected in a ring shape (the warm water circulation path C61), the hot water tank 10 and the hot water circulation pump 11 are used. And the second heat exchanger 322 connected in an annular shape (warm water circulation path C62) are respectively set, so that the second heat exchanger for cooling the raw material solution is selectively switched. Corresponding or related cooling medium circulation paths C11 and C12, production-side slurry circulation paths C21 and C22, production-side slurry circulation paths C31 and C32, and hot water circulation paths C61 and C62 Respectively selectively switched.

That is, first, when the raw material solution is cooled by the second heat exchanger 321, the cooling medium moves along the cooling medium circulation path C <b> 11 between the second heat exchanger 321 and the first heat exchanger. 31 and the raw material solution (or latent heat storage slurry) is supplied to the first heat exchanger 31 and the second heat exchanger 321 along the production-side slurry circulation path C21, and along the slurry reflux path C31. A part of the raw material solution (or latent heat storage slurry) is recirculated from the node N1 to the node N2 together with the latent heat storage material contained therein. At this time, the hot water is supplied along the hot water circulation path C62 to the other second heat exchanger 322 that has not cooled the raw material solution, and the heat transfer surface of the other second heat exchanger 322 or its latent heat storage material adhering to the vicinity of the surrounding environment is melted removed.
Thereafter, the raw material solution is cooled when the amount of the latent heat storage material adhering to the heat transfer surface of the second heat exchanger 321 or its surrounding environment exceeds an allowable level or when a certain time has passed. The second heat exchanger 32 is switched to the second heat exchanger 322. At the same time, the cooling medium circulation path C11 is switched to C12, the production-side slurry circulation path C21 to C22, the slurry recirculation path C31 to C32, and the hot water circulation path C62 to C61. Thereafter, the cooling medium circulation paths C11 and C12, the production-side slurry circulation paths C21 and C22, the production-side slurry reflux path C31, which correspond to or relate to the selective switching of the second heat exchangers 321 and 322 for cooling the raw material solution, C32 and hot water circulation path C61, C62 are each selectively switching is repeated.

  The above switching is realized in the form of switching between the operation mode 1 and the operation mode 2 by opening and closing the valves Vs1, Vs2, Vc1 to Vc4, and Vw1 to Vw4. Table 1 summarizes the correspondence between the selected path and the opening / closing of the valve in each operation mode. The meanings of symbols and notations in Table 1 are as follows.

Operation mode 1: An operation mode for cooling the raw material solution in the heat exchanger 321 and removing deposits in the heat exchanger 322.
Operation mode 2: An operation mode for cooling the raw material solution in the heat exchanger 322 and removing deposits in the heat exchanger 321.
Vs1, Vs2: Valves disposed in the manufacturing-side slurry circulation path (arranged from the top in the figure in the order of the numbers attached to the symbols)
Vc1 to Vc4: Valves arranged in the cooling medium circulation path (arranged from the top in the figure in the order of the numbers attached to the symbols)
Vw1 to Vw4: Valves arranged in the hot water circulation path (arranged from the top in the figure in the order of the numbers attached to the symbols)
Open: Valve open Close: Valve closed

In the latent heat storage slurry production apparatus (d) shown in FIG. 4, the latent heat storage material exceeding the allowable level is present on the heat transfer surface of one second heat exchanger 321 (or 322) that has cooled the raw material solution. When adhering or when a certain period of time has elapsed, the cooling of the raw material solution is switched to the other second heat exchanger 322 (or 321) to which the latent heat storage material is not adhering or removed. Then, the raw material solution is continuously cooled by the other second heat exchanger 322 (or 321), and the heat energy of the hot water supplied instead of the cooling medium through the hot water circulation path C6 is used for the one of the first heat exchangers 322 (or 321). The latent heat storage material adhering to the heat transfer surface of the second heat exchanger 321 (or 322) and the surrounding environment nearby is melted and removed. Therefore, the latent heat storage slurry can be manufactured stably or continuously for a long time as compared with the latent heat storage slurry manufacturing apparatuses (a) to (c) shown in FIGS.
However, when a latent heat storage material exceeding the permissible level adheres to the heat transfer surface of one of the second heat exchangers 321 (or 322) that has cooled the raw material solution or its surrounding environment, or a certain time has elapsed. If the frequency of the operation of switching the cooling of the raw material solution to the other second heat exchanger 322 (or 321) to which the latent heat storage material is not attached or removed is increased, the attached latent heat storage material Since the supply frequency and supply amount of hot water necessary for melting and removing water increases, there remains a problem that the utilization efficiency of the heat energy required for producing the latent heat storage slurry is unnecessarily lowered.

  The latent heat storage slurry production apparatus (d) shown in FIG. 4 is from the viewpoint that the second heat exchanger 32 and the first heat exchanger 31 are connected in series along the flow of the cooling medium. Then, although it is the same as the latent heat storage slurry manufacturing apparatus (b) shown in FIG. 2, the 2nd heat exchanger 32 and the 1st heat exchanger 31 are connected in parallel along the flow of the cooling medium. This is different from the latent heat storage slurry production apparatus (c) shown in FIG. However, the description regarding switching the plurality of second heat exchangers of the latent heat storage slurry production apparatus (d) shown in FIG. It is possible to freely switch the cooling of the raw material solution from one second heat exchanger to any one of the remaining second heat exchangers, and in order to melt and remove the attached latent heat storage material, a hot water circulation path C6 is provided. Second heat exchangers 321 and 322 and first heat exchanger 31 along the flow of the cooling medium in FIG. This also applies to the latent heat storage slurry manufacturing apparatus (d2) (not shown) configured by connecting the two in parallel (that is, as in the cooling medium circulation path C1 in FIG. 3).

<Regarding the latent heat storage slurry production technology according to the present invention>
5 to 8 are explanatory diagrams of the latent heat storage slurry production apparatuses (A) to (D) according to the present invention, respectively. The latent heat storage slurry production apparatuses (A) to (D) according to the present invention correspond to the conventional latent heat storage material slurry production apparatuses (a) to (d), respectively. are those composed by applying the present invention to the apparatus (a) to (d).
In the latent heat storage slurry production apparatuses (A) to (D) according to the present invention, the same parts as the corresponding conventional latent heat storage material slurry production apparatuses (a) to (d), or the same or corresponding parts are the same. Reference numerals are assigned and a part of the description is omitted.

5 to 8, C5 is a cooling medium reflux path for returning a part of the cooling medium from the outlet side to the inlet side of the heat exchanger 3. The cooling medium reflux path C5 is configured such that the inlet side node Na and the outlet side of the heat exchanger 3 (32 in FIGS. 6 and 7, 321, or 322 in FIG. 8) in which the raw material solution is cooled by heat exchange with the cooling medium. A recirculation pipe (second recirculation pipe) connecting between the nodes Nb and a part of the cooling medium circulation path C1 are provided, and the heat exchanger 3 (32 in FIGS. 6 and 7, 321 in FIG. 8, or 322) and an annular pipe path formed by connecting the cold heat medium reflux pump 9.
The node Na is on the cooling medium circulation path C1 on the inlet side of the heat exchanger 3 (32 in FIGS. 6 and 7, 321 or 322 in FIG. 8) and downstream of the refrigerator 1 and the cooling medium circulation pump 2. The node Nb is located on the cooling medium circulation path C1 on the outlet side of the heat exchanger 3 (32 in FIGS. 6 and 7, 321 or 322 in FIG. 8) and upstream of the refrigerator 1. Is a specific position.

In the case of the latent heat storage slurry production apparatus (D) shown in FIG. 8, the cooling medium circulation path C1 is switched between C11 and C12. Accordingly, the cooling medium recirculation path C5 corresponds to the first heat transfer path C5. The cooling medium return path C51 including a part of the exchanger 321, the reflux pipe (second reflux pipe) connecting the nodes Na and Nb and the cooling medium circulation path C11, and the second heat exchanger 322 , Switching between the reflux pipe (second reflux pipe) connecting between the nodes Na and Nb and the cooling medium circulation path C52 including a part of the cooling medium circulation path C12.
Table 2 summarizes the correspondence between the selection path switched between the operation mode 1 and the operation mode 2 and the opening / closing of the valve. The meanings of symbols and notations in Table 2 are the same as those in Table 1.

In the latent heat storage slurry production apparatuses (A) to (D) shown in FIGS. 5 to 8, the raw material solution is cooled in the heat exchanger 3 (32 in FIGS. 6 and 7, 321 or 322 in FIG. 8). Since a part of the cooling medium is recirculated from the outlet side to the inlet side of the heat exchanger along the cooling medium reflux path C5, the temperature variation of the cooling medium flowing into the heat exchanger is reduced, and the cooling medium and Variations are less likely to occur in the degree of heat exchange with the raw material solution or the degree of cooling of the raw material solution by the cooling medium. Therefore, the heat exchange between the cooling medium and the raw material solution (in other words, the operation of the heat exchanger) is stabilized, and the generation of the latent heat storage material in the raw material solution is stabilized. As a result, the amount of adhesion of the latent heat storage material to the surrounding environment does not increase more rapidly than expected, making it easier to predict the progress of adhesion and appropriately controlling the subcooling or overcooling of the raw material solution. Or it becomes easy to adjust. Even if it is inevitable that the amount of adhesion of the latent heat storage material gradually or cumulatively increases, troubles and malfunctions that occur during the production of the latent heat storage slurry will become obvious unless a longer time elapses. It becomes difficult.
Therefore, the latent heat storage slurry production apparatuses (A) to (D) can be operated stably or continuously for a longer time.

Further, in the latent heat storage slurry manufacturing apparatuses (A) to (D) shown in each of FIGS. 5 to 8, the temperature of the raw material solution is not easily changed or stabilized as a part of the raw material solution is refluxed. When the part of the cooling medium is refluxed, the temperature is hardly changed or stabilized, so that the difference between the temperature of the raw material solution and the cooling medium is difficult to be changed and stabilized, and thereby the supercooling of the raw material solution is performed. Or it becomes easy to appropriately control or adjust the supercooling release, and by extension, it is possible to effectively suppress the adhesion of the latent heat storage material to the heat transfer surface of the heat exchanger.
Accordingly, the latent heat storage slurry production apparatuses (A) to (D) are more preferable apparatuses that can be operated stably or continuously for a longer time.

  In particular, in the case of the latent heat storage slurry production apparatus (D) shown in FIG. 8, it is necessary to frequently switch the plurality of second heat exchangers 321 and 322 in order to remove the attached latent heat storage material. In other words, since the cooling time of the raw material solution per second heat exchanger can be set longer, the production of the latent heat storage slurry becomes more efficient.

  In the latent heat storage slurry production apparatus (C) shown in FIG. 7, the cooling medium recirculation path C5 has a node Na (node Na) on the inlet side of the heat exchanger 32 where the raw material solution is cooled by heat exchange with the cooling medium. Is on the downstream side of the refrigerator 1 and is a specific position upstream of the node N3, which is a branch point between the first heat exchanger 31 and the second heat exchanger 32), and between the node Nb on the outlet side Is provided with a recirculation pipe (second recirculation pipe) for connecting the heat exchanger 32 to the inlet side of the heat exchanger 32 where the raw material solution is cooled by heat exchange with the cooling medium (node Na *). (* Is a specific position downstream from the node N3 and upstream from the heat exchanger 32) and a reflux pipe (second reflux pipe) for connecting the outlet side Nb. The cooling medium reflux path C5 * may be used. However, when both are compared, the former (in the case of a reflux pipe connecting Na and Nb) reduces the temperature fluctuation of the cooling medium flowing through the first heat exchanger 31, and the whole As the production of the latent heat storage slurry is more stable.

  This means that the former (in the case of the circulation pipe connecting Na and Nb) also reduces the temperature fluctuation of the cooling medium flowing through the first heat exchanger 31, and the latent heat storage slurry as a whole is reduced. It is preferable that the production becomes more stable. Preferably, the latent heat storage slurry production apparatus (d1) having the cooling medium circulation path C1, that is, a plurality of second heat exchangers 32 in FIG. By freely switching the cooling of the raw material solution from the heat exchanger to any of the remaining second heat exchangers, and by adding a hot water circulation path C6 to melt and remove the attached latent heat storage material A latent heat storage slurry production apparatus (D1) (not shown) or a latent heat storage slurry production apparatus (d2) having a cooling medium circulation path C1, that is, a second along the flow of the cooling medium in FIG. Heat exchanger 3 1, 322 and the first heat exchanger 31 are connected in parallel (that is, connected as in the cooling medium circulation path C1 in FIG. 3), a latent heat storage slurry manufacturing apparatus (D2) (not shown). Is also true.

  Next, the latent heat storage material slurry manufacturing apparatus (E) of this invention is demonstrated based on FIG. From the viewpoint of clarifying the features of the invention, FIG. 9 shows a configuration in which a part of the cooling medium circulation path, which is the feature point, is excluded from the configuration of the latent heat storage material slurry manufacturing apparatus (E) of the present invention. This will be described first.

<Description of a portion of the latent heat storage material slurry manufacturing apparatus (E) excluding a part of the cooling medium circulation path>
9 except for a part of the cooling medium circulation path in the latent heat storage slurry production apparatus (E), the conventional latent heat storage slurry production apparatus (a) shown in FIG. A plurality of heat exchangers 3A, 3B... (In FIG. 9, for convenience of explanation, two heat exchangers 3A, 3B... Are connected in parallel to the respective flows of the latent heat storage slurry) and the cooling medium. The heat exchangers 3A and 3B are replaced with (represented only to depict).

In FIG. 9, the cooling medium circulation path C1 branches the cooling medium sent from the cooling medium circulation pump 2 and passed through the refrigerator 1 at the node N3, and then a part and the rest of the cooling medium are respectively transferred to the heat exchanger 3A. And the piping path that circulates in parallel toward the heat exchanger 3B and the cooling medium that has passed through the heat exchanger 3A and the heat exchanger 3B are merged at the node N4 and then circulated toward the cooling medium circulation pump 2. It consists of a piping route.
The production-side slurry circulation path C2 allows the raw material solution (or latent heat storage slurry having a relatively low presence ratio of latent heat storage materials) taken out from the heat storage tank 4 and sent out from the slurry circulation pump 5 to pass through the node N2. After branching at the rear node N5, a pipe path through which a part and the remainder of the raw material solution flow in parallel toward the heat exchanger 3A and the heat exchanger 3B, respectively, and the heat exchanger 3A and the heat exchanger 3B are provided. After the raw material solutions that have passed through each other are merged at the node N6, the raw material solution is passed through the node N1 and then sent to the heat storage tank 4.
The slurry recirculation path C3 is an annular piping path for recirculating a part of the raw material solution (or latent heat storage slurry) together with the latent heat storage material contained therein from the exit side to the entrance side of both heat exchangers 3A and 3B. The circulation pipe (first circulation pipe) for connecting between the outlet node N1 and the inlet node N2 of both heat exchangers 3A and 3B and a part of the production-side slurry circulation path C2 It is prepared.
The heat utilization side slurry circulation path C4 is basically the same as that shown in FIG.

In the latent heat storage material slurry manufacturing apparatus shown in FIG. 9, the cooling medium is sent to the refrigerator 1 by the cooling medium circulation pump 2 along the cooling medium circulation path C <b> 1 and cooled in the refrigerator 1. After being sent to the node N3 via Na, it is branched at the node N3 and subsequently sent to the heat exchanger 3A and the heat exchanger 3B connected in parallel, and the raw materials are supplied to the heat exchangers 3A and 3B. After heat exchange with the solution, it is returned to the refrigerator 1 via a node N4 that is a junction and a node Nb that will be described later.
Na is a node on the cooling medium circulation path C1 on the inlet side of both heat exchangers 3A and 3B and downstream of the refrigerator 1, and Nb is on the outlet side of both heat exchangers 3A and 3B. This is a node on the cooling medium circulation path C1 on the upstream side of the cooling medium circulation pump 2.

  The raw material solution stored in the heat storage tank 4 is sent to the heat exchangers 3A and 3B through the node N5 which is a branch point by the manufacturing side circulation pump 5 along the manufacturing side slurry circulation path C2, respectively. The heat exchangers 3A and 3B are cooled by heat exchange with the cooling medium, so that at least a part of the raw material solution is in a supercooled state and is stored in the heat storage tank 4 again. The supercooled state of the raw material solution stored again in the heat storage tank 4 is gradually released in the heat storage tank 4 at the storage destination. Thereby, the abundance ratio of the latent heat storage material increases in the heat storage tank 4, and the raw material solution becomes a latent heat storage slurry. Then, the latent heat storage slurry that has been accommodated in the heat storage tank 4 is sent as a raw material solution again or cyclically along the production side slurry circulation path C2 as a raw material solution, and returned to the heat storage tank 4. Thus, the ratio of the latent heat storage material in the latent heat storage slurry contained in the heat storage tank 4 is gradually increased to a level suitable for heat utilization.

  At this time, at least a part of the raw solution or a part of the latent heat storage slurry sent as a raw material solution in the supercooled state is drawn from the node N1 by the slurry reflux pump 6 along the slurry reflux path C3. It is sent to both heat exchangers 3A and 3B via N2, and returned to the node N1. When a part of the raw material solution in which at least a part is in a supercooled state moves along the slurry reflux path C3, part or all of the supercooled state is released in the course of the movement. More production nuclei are supplied to the inlet side of the heat exchangers 3A and 3B. By supplying the generated nuclei, the supercooling generated in the raw material solution due to the cooling in each of the heat exchangers 3A and 3B is released, and thereby the adhesion of the latent heat storage material to the surrounding environment is suppressed.

<Latent heat storage slurry production apparatus (E) according to the present invention>
FIG. 10 is an explanatory view of the latent heat storage material slurry manufacturing apparatus (E) of the present invention. The latent heat storage material slurry manufacturing apparatus (E) is obtained by adding a cooling medium reflux path C5 to the latent heat storage slurry manufacturing apparatus shown in FIG. 9, and the configuration other than the cooling medium reflux path C5 has already been based on FIG. Explains.

In FIG. 10, C5 is a cooling medium reflux path for returning a part of the cooling medium from the outlet side to the inlet side of the heat exchangers 3A and 3B. The cooling medium recirculation path C5 is a recirculation pipe (second pipe) connecting between the node Na on the inlet side and the node Nb on the outlet side of the heat exchangers 3A and 3B in which the raw material solution is cooled by heat exchange with the cooling medium. A recirculation pipe) and a part of the cooling medium circulation path C1, and is an annular piping path formed by connecting the heat exchangers 3A and 3B and the cooling medium recirculation pump 9.
Na is a specific position on the cooling medium circulation path C1 on the inlet side of both heat exchangers 3A and 3B and on the downstream side of the refrigerator 1, and Nb is on the outlet side of both heat exchangers 3A and 3B. The specific position on the cooling medium circulation path C1 on the upstream side of the cooling medium circulation pump 2.

In the latent heat storage slurry production apparatus (E) shown in FIG. 10, a part of the cooling medium that cools the raw material solution in the heat exchangers 3A and 3B passes from the outlet side of the heat exchanger along the cooling medium reflux path C5. Since the refrigerant is recirculated to the inlet side, the temperature variation of the cooling medium flowing into the heat exchanger is reduced, and the degree of heat exchange between the cooling medium and the raw material solution or the cooling of the raw material solution by the cooling medium is less likely to occur. Become. Therefore, the heat exchange between the cooling medium and the raw material solution (in other words, the operation of the heat exchanger) is stabilized, and the generation of the latent heat storage material in the raw material solution is stabilized. As a result, the amount of adhesion of the latent heat storage material to the surrounding environment does not increase more rapidly than expected, making it easier to predict the progress of adhesion and appropriately controlling the subcooling or overcooling of the raw material solution. Or it becomes easy to adjust. Even if it is inevitable that the amount of adhesion of the latent heat storage material gradually or cumulatively increases, troubles and malfunctions that occur during the production of the latent heat storage slurry will become obvious unless a longer time elapses. It becomes difficult.
Therefore, the latent heat storage slurry production apparatus (E) becomes an apparatus that can be operated stably or continuously for a longer time.

In addition, in the latent heat storage slurry production apparatus (E) shown in FIG. 10, when a part of the raw material solution is refluxed, the temperature is hardly changed or stabilized, and at the same time, a part of the cooling medium is refluxed. Therefore, the temperature hardly changes or stabilizes, so that the difference between the temperature of the raw material solution and the cooling medium becomes difficult to change and is stabilized, thereby appropriately controlling or adjusting the supercooling or overcooling release of the raw material solution. As a result, it is possible to effectively suppress adhesion of the latent heat storage material to the heat transfer surface of the heat exchanger.
Therefore, the latent heat storage slurry production apparatus (E) becomes a more preferable apparatus that can be stably or continuously operated for a longer time.

  Next, the latent heat storage material slurry manufacturing apparatus (F) of this invention is demonstrated based on FIG. From the viewpoint of clarifying the features of the invention, FIG. 11 shows the configuration of the latent heat storage material slurry manufacturing apparatus (F) of the present invention, excluding a part of the cooling medium circulation path, which is a feature of the device. This will be described above.

<Description of a portion of the latent heat storage material slurry manufacturing apparatus (F) excluding a part of the cooling medium circulation path>
A portion of the latent heat storage slurry production apparatus (F) shown in FIG. 11 excluding a part of the cooling medium circulation path is a raw material solution (or in the conventional latent heat storage slurry production apparatus (b) shown in FIG. A plurality of heat exchangers 32A, 32B in which the second heat exchanger 32 is connected in parallel to each flow of the latent heat storage slurry and the cooling medium (in FIG. 11, for convenience of explanation) , The two heat exchangers 32A and 32B are illustrated in FIG.

In FIG. 11, the cooling medium circulation path C <b> 1 is an annular piping path for circulating the cooling medium, and the cooling medium circulation pump 2, the refrigerator 1, the second heat exchanger 32, and the first heat exchanger 31. Are connected.
The production-side slurry circulation path C <b> 2 passes the raw material solution (or the latent heat storage slurry having a relatively low ratio of the latent heat storage material) from the heat storage tank 4 to the first heat exchanger 31 and the second heat exchanger 32. It is a cyclic | annular piping path | route for distribute | circulating in order and distribute | circulating a latent-heat thermal storage slurry toward the thermal storage tank 4, 1st heat exchanger 31, 2nd heat exchanger 32, thermal storage tank 4, and manufacturing side circulation pump 5 is connected. The second heat exchanger 32 includes a plurality of heat exchangers 32A and 32B connected in parallel to the flow of the cooling medium and the flow of the raw material solution.

  The slurry recirculation path C3 is an annular shape for recirculating a part of the raw material solution (or latent heat storage slurry) together with the latent heat storage material contained therein from the exit side to the entrance side of the second heat exchangers 32A and 32B. It is a piping path and is located on the outlet side of the second heat exchangers 32A and 32B, on the outlet side of the first heat exchanger 31 and on the inlet side of the second heat exchangers 32A and 32B. A circulating pipe (first circulating pipe) for connecting to a certain node N2 and a part of the manufacturing-side slurry circulation path C2 are provided. Since the heat utilization side slurry circulation path C4 is basically the same as that shown in FIG. 1, the description thereof is omitted.

In the latent heat storage material slurry manufacturing apparatus shown in FIG. 11, the cooling medium is sent out by the cooling medium circulation pump 2 along the cooling medium circulation path C <b> 1 and cooled in the refrigerator 1, and then passes through the node Na. Sent to the node N3, branched to the second heat exchangers 32A and 32B at the node N3, and heat exchange with the raw material solution was performed in the second heat exchangers 32A and 32B. After that, it further merges at the node N4, is sent toward the first heat exchanger 31 via the node Nb, and after the heat exchange with the raw material solution is performed in the first heat exchanger 31, the cooling medium Returned to the circulation pump 2.
The node Na is a node on the cooling medium circulation path C1 on the inlet side of the second heat exchangers 32A and 32B and on the downstream side of the refrigerator 1, and the node Nb is the second heat exchanger 32A, This is a node on the cooling medium circulation path C1 on the outlet side of 32B and on the upstream side of the first heat exchanger 31.

  The raw material solution accommodated in the heat storage tank 4 is sent to the first heat exchanger 31 by the production-side circulation pump 5 along the production-side slurry circulation path C2, and is then a branch point via the node N2. It is sent toward the second heat exchangers 32A and 32B at the node N5. In the first heat exchanger 31, the raw material solution is supercooled to a certain degree by removing heat energy corresponding to sensible heat by heat exchange with the cooling medium. More specifically, since the raw material solution containing the latent heat storage material is supplied to the node N2 along the slurry reflux path C3, the latent heat storage material contained in the raw material solution that merges with the node N2 has another latent heat. It becomes a production nucleus of the heat storage material, and at least a part of the supercooling of the raw material solution is released. By releasing the supercooling, a small amount of latent heat storage material is generated in the raw material solution. Subsequently, the raw material solution from which at least a part of the supercooling has been released is cooled in each of the second heat exchangers 32A and 32B to generate more latent heat storage material, and the overall ratio of the latent heat storage material is present. Becomes a more latent heat storage slurry and is sent to the heat storage tank 4 via a node N6 which is a junction. The latent heat storage slurry that has been accommodated in the heat storage tank 4 is sent as a raw material solution again or cyclically along the production side slurry circulation path C2 as a raw material solution, and returned to the heat storage tank 4. Thus, the ratio of the latent heat storage material in the latent heat storage slurry contained in the heat storage tank 4 is gradually increased to a level suitable for heat utilization.

  At this time, a part of the raw material solution that becomes the latent heat storage slurry is withdrawn from the node N1 by the slurry reflux pump 6 along the slurry reflux path C3, and passes through the node N2 to each second heat exchanger 32A. , 32B and returned to node N1. Then, since the generated nuclei are supplied to the inlet side of each of the second heat exchangers 32A and 32B, the supercooling generated in the raw material solution by the cooling in each of the second heat exchangers 32A and 32B is released. , Adhesion of the latent heat storage material to the surrounding environment is suppressed.

<Latent heat storage slurry manufacturing apparatus (F) according to the present invention>
FIG. 12 is an explanatory view of the latent heat storage material slurry manufacturing apparatus (F) of the present invention. The latent heat storage material slurry manufacturing apparatus (F) is obtained by adding a cooling medium reflux path C5 to the latent heat storage slurry manufacturing apparatus shown in FIG. 11, and the configuration other than the cooling medium circulation path C5 has already been based on FIG. Explains.

In FIG. 12, C5 is a cooling medium reflux path for returning a part of the cooling medium from the outlet side to the inlet side of the heat exchangers 32A and 32B. The cooling medium recirculation path C5 is a recirculation pipe (second pipe) connecting between the node Na on the inlet side and the node Nb on the outlet side of the heat exchangers 32A and 32B in which the raw material solution is cooled by heat exchange with the cooling medium. A pipe for recirculation) and a part of the cooling medium circulation path C 1, and is an annular pipe path formed by connecting the heat exchangers 32 A and 32 B and the cooling medium reflux pump 9.
The node Na is a specific position on the cooling medium circulation path C1 on the inlet side of the second heat exchangers 32A and 32B and downstream of the refrigerator 1, and the node Nb is the second heat exchanger 32A. , 32B and at a specific position on the cooling medium circulation path C1 on the upstream side of the first heat exchanger 31.

In the latent heat storage slurry production apparatus (F) shown in FIG. 12, a part of the cooling medium that cools the raw material solution in the heat exchangers 32A and 32B passes from the outlet side of the heat exchanger along the cooling medium reflux path C5. Since the refrigerant is recirculated to the inlet side, the temperature variation of the cooling medium flowing into the heat exchanger is reduced, and the degree of heat exchange between the cooling medium and the raw material solution or the cooling of the raw material solution by the cooling medium is less likely to occur. Become. Therefore, the heat exchange between the cooling medium and the raw material solution (in other words, the operation of the heat exchanger) is stabilized, and the generation of the latent heat storage material in the raw material solution is stabilized. As a result, the amount of adhesion of the latent heat storage material to the surrounding environment does not increase more rapidly than expected, making it easier to predict the progress of adhesion and appropriately controlling the subcooling or overcooling of the raw material solution. Or it becomes easy to adjust. Even if it is inevitable that the amount of adhesion of the latent heat storage material gradually or cumulatively increases, troubles and malfunctions that occur during the production of the latent heat storage slurry will become obvious unless a longer time elapses. It becomes difficult.
Therefore, the latent heat storage slurry production apparatus (F) is an apparatus that can be operated stably or continuously for a longer time.

In addition, in the latent heat storage slurry production apparatus (F) shown in FIG. 12, when a part of the raw material solution is refluxed, the temperature becomes difficult or stable, and at the same time, a part of the cooling medium is refluxed. Therefore, the temperature hardly changes or stabilizes, so that the difference between the temperature of the raw material solution and the cooling medium becomes difficult to change and is stabilized, thereby appropriately controlling or adjusting the supercooling or overcooling release of the raw material solution. As a result, it is possible to effectively suppress adhesion of the latent heat storage material to the heat transfer surface of the heat exchanger.
Therefore, the latent heat storage slurry production apparatus (F) becomes a more preferable apparatus that can be stably or continuously operated for a longer time.

  The first heat exchanger described in FIGS. 6 to 8 and 12 is depicted as an apparatus in which heat exchange is performed between a cold medium and a raw material solution that flow with each other. Here, the role of the first heat exchanger is to cool the raw material aqueous solution, remove the thermal energy corresponding to sensible heat from the raw material solution, and bring at least a part thereof into a supercooled state. Therefore, the first heat exchanger can be replaced by a known cooling means as long as it plays its role.

<Verification of the effect of the present invention>
In the following verification experiment, the cold medium is cold water, and the latent heat storage slurry is an clathrate hydrate slurry in which clathrate hydrate is dispersed or suspended in water or a raw material solution. Moreover, the clathrate hydrate slurry in which the existing ratio of clathrate hydrate delivered from the heat storage tank as a raw material solution is small and the clathrate hydrate slurry produced may be simply referred to as slurry.

[Verification Experiment 1]
<Relationship between fluctuation range of temperature difference between cooling medium and raw material solution and stable operation of slurry production apparatus>
Using the slurry manufacturing apparatus (d) shown in FIG. 4, an experiment was conducted to verify the relationship between the fluctuation range of the temperature difference between the cooling medium and the raw material solution and the stable operation of the slurry manufacturing apparatus. The average value of the temperature difference between the slurry inlet and the cold water inlet of the heat exchanger 321 is the same, but the case where the variation range of the temperature difference is different was verified for the stable operation of the slurry manufacturing apparatus.
The first heat exchanger 31 includes a plate heat exchanger (height 1.1 m, width 0.4 m, depth 0.2 m, amount of water retained on one side 0.01 m ³ , counter flow system), and the second heat exchanger 321. In 322, a slurry production experiment was carried out using a plate heat exchanger (height 1.6 m, width 0.6 m, depth 0.1 m, retained water amount 0.01 m ³ on one side, counter flow system). As a raw material solution, a 16 wt% aqueous solution of tetra n-butylammonium bromide (TBAB) was used.

A thermometer T1 is provided on the cold water inlet side of the heat exchanger 321, a thermometer T2 is provided on the outlet side, the temperature of the cold water is measured, the flow rate of the circulating cold water is measured, and the temperature of the cold water on the inlet side and the outlet side is measured. Calculate the exchange heat of cold water based on the difference and the flow rate of cold water. A thermometer T3 is installed on the inlet side of the slurry of the heat exchanger 321 and a thermometer T4 is installed on the outlet side to measure the temperature of the slurry, and further the flow rate of the circulating slurry is measured. The heat transmission rate was calculated from the amount of heat exchanged for cold water, the inlet temperature of the cold water, the outlet temperature, the inlet temperature of the slurry, and the outlet temperature. Moreover, the pressure loss was installed in the inlet side and outlet side of the slurry of the heat exchanger 321, and the pressure loss on the slurry side of the heat exchanger was measured. The flow rate of the liquid flowing through the heat exchanger 31 and the heat exchanger 321 was kept constant, and the flow rate inside the heat exchanger was kept constant.
By heat exchange between the cold water and the raw material solution in the first heat exchanger 31, heat energy equivalent to sensible heat is taken from the raw material solution and at the same time a (some) supercooled state is created. Subsequently, at the node N2, a part of the slurry exiting the second heat exchanger 321 is refluxed, and the slurry is mixed with the raw solution in the supercooled state to release the supercooling. Then, heat energy corresponding to latent heat is taken away by heat exchange between the cold water and the raw material solution that has been subcooled in the second heat exchanger 321 to produce a large amount of clathrate hydrate to produce a latent heat storage slurry. .

Table 3 shows the cold water inlet temperature of the heat exchanger 321 as experimental conditions, the fluctuation range of the cold water inlet temperature, the slurry inlet temperature (as a raw material solution), the temperature difference between the slurry inlet temperature and the cold water inlet temperature, and the average temperature. The fluctuation range of the difference and the temperature difference is shown. The inlet temperature of the slurry is a stable temperature by refluxing the slurry.
The average temperature difference which is the average value of the temperature difference between the slurry inlet and the cold water inlet of the heat exchanger 321 is the same 2.4 ° C., but the fluctuation range of the temperature difference is as large as 0.7 ° C., and 0.3 ° C. In the small case, the stability of the operation of the slurry manufacturing equipment was verified.

  By reducing the fluctuation range of the cold water inlet temperature and stabilizing the cold water inlet temperature, the fluctuation range of the temperature difference between the slurry inlet and the cold water inlet can be reduced. In the heat exchanger 321, when the cold water flow rate and the slurry flow rate are constant, the exchange heat amount is determined by the temperature difference between the slurry inlet and the cold water inlet. For this reason, when the variation in the temperature difference between the slurry inlet and the cold water inlet is large, the exchange heat amount fluctuates greatly, but when the variation in temperature difference is small, the exchange heat amount is almost constant.

  For the cases shown in Table 3, the increase in pressure loss and the heat passage rate of the slurry flow path of the heat exchanger 321 after the slurry manufacturing operation for 5 hours is performed in the case where the fluctuation of the inlet temperature of the cold water is large. 1 as shown in Table 4. In the case of small fluctuation, the increase in pressure loss was small and the heat transfer rate was large. From the results, the following could be confirmed.

If the temperature of the chilled water inlet is not stable and fluctuates greatly, and the temperature difference between the slurry inlet and the chilled water inlet is not stable, the fluctuation of the slurry temperature becomes more acute with sudden increase or decrease of the exchange heat, and the overcooling is released. Is not performed stably. If the supercooling release does not occur stably, the supercooling release occurs abruptly, and a latent heat storage material may be rapidly generated inside the heat exchanger. If the latent heat storage material is suddenly generated inside the heat exchanger, the latent heat storage material will block the slurry flow path of the heat exchanger, increasing the pressure loss in the slurry flow path of the heat exchanger and smoothing the flow of the slurry. Feeding is hindered and stable slurry production cannot be performed. Further, since the latent heat storage material adheres to the heat transfer surface of the heat exchanger, the heat passage rate indicating the heat exchange characteristics of the heat exchanger is lowered, and the amount of exchange heat is lowered, so that stable slurry production cannot be performed.
On the other hand, by reducing the fluctuation range of the cold water inlet temperature to stabilize the temperature of the cold water inlet, the fluctuation of the temperature difference between the slurry inlet and the cold water inlet is reduced and stabilized, and the exchange heat quantity becomes substantially constant. For this reason, the slurry is stably released from the supercooling, and the sudden supercooling release in the heat exchanger can be avoided. If the slurry is stably released from overcooling, the latent heat storage material will not be abruptly generated inside the heat exchanger and the slurry flow path will not block the slurry flow path, preventing an increase in pressure loss. it can be slurry can smoothly Nagareoku are stable slurry preparation. In addition, since it is possible to suppress the latent heat storage material from adhering to the heat transfer surface of the heat exchanger, it is possible to suppress a decrease in the heat passage rate and maintain a high heat passage rate. Slurry manufacturing is possible.

  If the average temperature difference between the slurry inlet and the chilled water inlet is the same, the fluctuation range of the temperature difference between the slurry inlet and the chilled water inlet should be reduced in order to produce the latent heat storage material stably or continuously over a longer period of time. It was revealed that is effective. For that purpose, it is necessary to stabilize the temperature of both the slurry inlet and the cold water inlet. In addition to the conventional technology of refluxing the slurry side to stabilize the slurry inlet temperature, the temperature of the cold water side can be stabilized by refluxing the cold water side, resulting in a stable temperature difference between the slurry and the cold water. The exchange heat amount becomes constant, the slurry can be stably released from overcooling, and the latent heat storage material can be manufactured stably or continuously over a longer period of time.

[Verification experiment 2]
<Comparison between the slurry manufacturing apparatus of the present invention and a slurry manufacturing apparatus provided with a tank>
The slurry manufacturing apparatus (D) (Example 1) provided with the cold water recirculation path shown in FIG. 8 and the tank 13 for temporarily storing the cold water as the means for reducing the fluctuation range of the cold water inlet temperature are connected to the cold water circulation pump 2 and the heat. About the slurry manufacturing apparatus (comparative example 1, shown in FIG. 13) provided between the exchangers 321, the stable operation of the slurry manufacturing apparatus was verified. The raw material solution and the heat exchanger were the same as those in the verification experiment 1. In Example 1, the ratio of the reflux of cold water was 55 vol% of the cold water sent from the outlet of the heat exchanger 321.

  Table 5 shows the cold water inlet temperature, the fluctuation range of the cold water, the temperature difference between the slurry inlet and the cold water inlet, the average temperature difference, and the fluctuation range of the temperature difference. In both Example 1 and Comparative Example 1, the fluctuation range of the chilled water temperature is reduced, and the fluctuation range of the temperature difference between the slurry inlet and the chilled water inlet can be suppressed to 0.5 ° C.

  Table 6 shows the increase in pressure loss in the slurry flow path of the heat exchanger 321 after the slurry manufacturing operation for 5 hours.

In both Example 1 and Comparative Example 1, the fluctuation range of the temperature difference between the slurry inlet and the cold water inlet was suppressed to be as small as 0.5 ° C. However, the increase in pressure loss was more when the tank 13 of Comparative Example 1 was provided. It was getting bigger. The temperature difference between the slurry inlet and the cold water inlet was 1.4 ° C. in Example 1, but was as large as 2.5 ° C. in Comparative Example 1.
From this result, when the temperature of the chilled water inlet is stabilized and the fluctuation range of the temperature difference between the slurry inlet and the chilled water inlet is made approximately the same, the temperature difference itself between the slurry inlet and the chilled water inlet is reduced as in the first embodiment. It was found that the increase in pressure loss can be suppressed. For this reason, the temperature difference between the slurry inlet and the chilled water inlet is reduced, the temperature of the chilled water inlet is stabilized, and the fluctuation range of the temperature difference is reduced, thereby producing the latent heat storage material stably or continuously over a longer period of time. can do.

In order to produce a latent heat storage material stably or continuously over a longer period of time, the temperature difference between the slurry inlet and the chilled water inlet is stabilized by reducing the temperature difference between the slurry inlet and the chilled water inlet while the temperature of the chilled water inlet is stabilized. as slurry manufacturing apparatus for reducing the width, further consider the slurry manufacturing apparatus provided with a tank 13.
In the slurry manufacturing apparatus provided with the tank 13 shown in FIG. 13 used in Comparative Example 1, the cold water inlet temperature was 5.1 to 5.2 ° C. in Comparative Example 1, but it was 6.2 ° C., which was the same as that in Example 1. As an example, it is considered to reduce the temperature difference between the slurry inlet and the cold water inlet (Comparative Examples 2 and 3).

<Comparative Examples 2 and 3>
In Comparative Example 2, the amount of cold water supplied from the refrigerator 1 is the same as that of Comparative Example 1, the temperature of the cold water at the heat exchanger inlet side is stabilized using the tank 13 for temporarily storing the cold water, and the cold water inlet temperature is set to 6 This is a slurry manufacturing apparatus in which the temperature difference between the slurry inlet and the cold water inlet is reduced to about 2 ° C. to the same extent as in the first embodiment. In Comparative Example 2, the chilled water inlet temperature is set to 6.2 ° C., the temperature difference between the slurry inlet and the chilled water inlet is reduced to 1.4 ° C., the chilled water temperature is stabilized, and the fluctuation of the temperature difference between the slurry inlet and the chilled water inlet is reduced. Thereby, adhesion of the latent heat storage material in the heat exchanger can be reduced, an increase in pressure loss can be suppressed, and the latent heat storage material can be manufactured stably or continuously over a longer period of time. However, compared with the comparative example 1, since the amount of exchange heat becomes small because the temperature difference between the slurry inlet and the cold water inlet is small, there arises a problem that the capacity of the slurry manufacturing apparatus is lowered.
Therefore, Comparative Example 3 which is a slurry manufacturing apparatus that increases the amount of cold water supplied from the refrigerator 1 in Comparative Example 2 and does not decrease the amount of exchange heat will be examined. In Comparative Example 3, the temperature difference between the slurry inlet and the chilled water inlet is reduced, the chilled water temperature is stabilized, and the fluctuation of the temperature difference between the slurry inlet and the chilled water inlet is reduced, thereby reducing the adhesion of the latent heat storage material in the heat exchanger. In addition, the increase in pressure loss can be suppressed and the exchange heat quantity can be maintained high, and the latent heat storage material can be produced stably or continuously over a longer period of time.
However, in Comparative Example 3, since the amount of cold water supplied from the refrigerator is 2.3 times, it is necessary to increase the capacity of the refrigerator by 2.3 times (the amount of cold water is set to the capacity of the refrigerator). In the case of proportionality), there is a problem that the equipment cost and the operating cost increase because the specification of the refrigerator is increased. Also, if the amount of chilled water is increased up to 2.3 times, using the same piping as in Comparative Example 1 or 2, the chilled water flow rate inside the piping increases and the pressure loss increases rapidly. Many problems arise, such as the problem that the equipment cost becomes high, the problem that the piping installation area increases, the problem that the pipe becomes large, and the weight increases when the pipe becomes large, which is not preferable in construction. Further, if the amount of cold water is increased up to 2.3 times, the tank 13 for stabilizing the temperature of the cold water needs to be increased, which causes a problem because the equipment cost increases and the installation area increases.

  Although the above problems occur in Comparative Example 3, the temperature difference between the slurry inlet and the cold water inlet is small in the slurry manufacturing apparatus for refluxing cold water according to the present invention, but the cold water is refluxed and merged with the cold water sent from the refrigerator. Therefore, since there is much quantity of the cold water which flows in into a heat exchanger, exchange heat quantity can be maintained highly. Therefore, the tank 13 is not necessary and the size of the refrigerator need not be changed, and only the cold water reflux line C5 and the cold water reflux pump 9 are provided. As for the diameter of the cold water side pipe, only the pipe connecting the node Na where the cold water reflux line C5 joins the cold water circulation path C1 to the node Nb through the heat exchanger only needs to be enlarged.

[Verification Experiment 3]
<Comparison between a slurry production apparatus that circulates cold water and a slurry production apparatus that does not circulate cold water>
A slurry production apparatus (Example 2) that recirculates cold water and a slurry production apparatus (Comparative Example 4) that does not recirculate cold water using a slurry production apparatus (D) provided with a cold water recirculation path shown in FIG. An experiment was conducted to verify the stable operation of the manufacturing equipment.
In the slurry manufacturing apparatus (D), heat energy equivalent to sensible heat is taken from the raw material solution by heat exchange between the cold water and the raw material solution in the first heat exchanger 31, and at the same time, a (some) supercooled state is created. . Subsequently, at the node N2, a part of the slurry exiting the second heat exchanger 321 is refluxed, and the slurry is mixed with the raw solution in the supercooled state to release the supercooling. Then, heat energy corresponding to latent heat is taken away by heat exchange between the cold water and the raw material solution that has been subcooled in the second heat exchanger 321 to produce a large amount of clathrate hydrate to produce a latent heat storage slurry. .
The first heat exchanger 31 includes a plate heat exchanger (height 1.1 m, width 0.4 m, depth 0.2 m, amount of retained water 0.01 m ³ on one side, counter-flow system), and the second heat exchanger 321. In 322, a slurry production experiment was performed using a plate heat exchanger (height 1.6 m, width 0.6 m, depth 0.1 m, water content 0.01 m ³ on one side, counter flow system). As a raw material solution, a 16 wt% aqueous solution of tetra n-butylammonium bromide (TBAB) was used. In Example 2, the ratio of refluxing cold water was such that 55 vol% of cold water fed from the outlet of the heat exchanger 321 was refluxed.

  The temperature of cold water and slurry was measured in the same manner as in verification experiment 1, and the temperature difference between the inlet temperature of the slurry and the inlet temperature of the cold water, the average temperature difference, and the fluctuation range of the temperature difference are shown in Table 7. In Example 2, since the cold water inlet temperature is stabilized by the cold water recirculation, the variation width of the temperature difference between the slurry inlet and the cold water inlet is 0.4 ° C., which is about half that of Comparative Example 4 in which the cold water does not recirculate. While the temperature difference at the cold water inlet is reduced, the temperature difference is not easily changed and stabilized.

It was also measured pressure loss of the slurry side of the heat exchanger in the same manner as the verification experiment 1. FIG. 14 shows the change over time of the increase in pressure loss on the slurry side of the heat exchanger 321 from the start of the slurry production operation to the point of 5 hours, and Table 7 shows the increase in pressure loss after 5 hours. In Comparative Example 4 where the cold water was not refluxed, the pressure loss increased to 40 kPa, whereas in Example 2 where the cold water was refluxed, the pressure loss increased only to 13 kPa.
By circulating the cold water, the temperature difference between the slurry inlet and the cold water inlet can be stabilized, and sudden increase and decrease in the amount of exchange heat can be avoided, the slurry can be overcooled stably, and the heat transfer surface inside the heat exchanger can be removed. The adhesion of the latent heat storage material can be suppressed, the increase in pressure loss can be suppressed to 1/3 or less, and the latent heat storage slurry can be produced stably or continuously over a long period of time.

Moreover, the heat passage rate of the heat exchanger was calculated in the same manner as in the verification experiment 1, and Table 7 shows the rate of decrease in the heat passage rate of the heat exchanger. The rate of decrease in the heat passage rate after 5 hours is calculated based on the heat passage rate after 1 hour from the start of slurry production. In Comparative Example 4 in which cold water is not refluxed, the rate of decrease in heat passage rate is reduced to 50%, whereas in Example 2 in which cold water is refluxed, the rate of decrease in heat passage rate is only reduced to 36%. There wasn't.
By circulating the chilled water, the temperature difference between the slurry inlet and the chilled water inlet is stabilized, and sudden increase / decrease in the amount of exchange heat can be avoided, and the slurry is stably released from overcooling to the heat transfer surface inside the heat exchanger. Adhesion of the latent heat storage material can be suppressed, and deterioration of heat transfer characteristics can be suppressed. For this reason, it is possible to reduce the rate of decrease of the heat passage rate that exhibits heat exchange characteristics with respect to the passage of time.
By circulating cold water as in Example 2, the temperature difference between the slurry inlet and the cold water inlet can be stabilized, the heat transfer rate can be maintained high, and the latent heat storage property can be stably or continuously over a long period of time. A slurry can be produced.

  By reducing the fluctuation range of the cold water inlet temperature by circulating the cold water and stabilizing the temperature of the cold water inlet, the fluctuation of the temperature difference between the slurry inlet and the cold water inlet is reduced and stabilized, and the exchange heat amount is made substantially constant. To do. For this reason, the slurry is stably released from the supercooling, and the sudden supercooling release in the heat exchanger can be avoided. If the slurry is stably released from overcooling, the latent heat storage material will not be abruptly generated inside the heat exchanger and the slurry flow path will not block the slurry flow path, preventing an increase in pressure loss. Thus, the slurry can be smoothly fed and stable slurry production can be achieved. In addition, since it is possible to reduce the adhesion of latent heat storage materials to the heat transfer surface of the heat exchanger, it is possible to suppress a decrease in the heat transfer rate and maintain a high heat transfer rate, thereby suppressing a decrease in the exchange heat amount and being stable. it is a slurry production.

[Verification Experiment 4]
<Verification of heat exchange amount>
In the slurry manufacturing apparatus for recirculating cold water according to the present invention, a portion of the cold water sent from the heat exchanger is recirculated to the inlet side of the heat exchanger, so that it flows into the heat exchanger as compared with the case where the cold water is not recirculated. The cold water inlet temperature is high, and the logarithmic average temperature difference of the heat exchanger is small. Therefore, the amount of exchange heat was verified. Using the apparatus and raw material solution used in the verification experiment 3, for the slurry manufacturing apparatus that recirculates cold water (Example 3) and the slurry manufacturing apparatus that does not recirculate cold water (Comparative Example 5), the exchange heat amount of the slurry manufacturing apparatus is Experiments to verify were performed.

As in the verification experiment 1, the pressure loss on the slurry side of the heat exchanger was measured. FIG. 15 shows the change over time of the increase in pressure loss on the slurry side of the heat exchanger 321 from the start of operation of the slurry production apparatus to 10 hours. In Comparative Example 5 where the cold water was not refluxed, the pressure loss increased to 160 kPa, whereas in Example 3 where the cold water was refluxed, the pressure loss increased only to 60 kPa.
By circulating the cold water, the temperature difference between the slurry inlet and the cold water inlet can be stabilized to avoid sudden increase and decrease in the amount of exchange heat, and the slurry can be stably released from overcooling to the heat transfer surface inside the heat exchanger. The adhesion of the latent heat storage material can be suppressed, the increase in pressure loss can be significantly suppressed, and the latent heat storage slurry can be produced stably or continuously over a long period of time.

Further, as in the verification experiment 1, the heat exchange rate and the heat passage rate of the heat exchanger are calculated and shown in Table 8. The average temperature of the cold water inlet is 5.0 ° C. in Comparative Example 5, whereas in Example 3, the average temperature becomes high in order to recirculate a part of the heat-exchanged cold water sent from the heat exchanger 321. 9 ° C. The logarithmic average temperature difference is 1.0 ° C. in Comparative Example 5, whereas it is 0.7 ° C. in Example 3 because the cold water inlet temperature is high due to cold water reflux.
On the other hand, in Example 3, since the flow rate of the cold water flowing into the heat exchanger due to the cold water reflux increases, the flow rate of the cold water inside the heat exchanger becomes 2.2 times that of the comparative example 5, and the amount of exchange heat increases. Thereby, the heat passage rate of Example 3 at the start of operation of the slurry manufacturing apparatus is 1.4 times larger than that of Comparative Example 5. The heat passage rate after 10 hours from the start of operation of the slurry manufacturing apparatus is reduced to 0.5 in Comparative Example 5 when the heat passage rate at the start of operation in Comparative Example 5 is 1. On the other hand, in Example 3, it is about 0.9 (the rate of decrease in the heat passage rate is 36%), and the decrease in the heat passage rate can be reduced.
The amount of exchange heat 10 hours after the start of operation of the slurry manufacturing apparatus is 1.3 times as large as that of Comparative Example 5 in Example 3. Although the logarithmic average temperature difference of Example 3 is smaller than that of Comparative Example 5, the flow rate of cold water increases due to the cold water recirculation, so that the amount of exchange heat increases and the decrease in the heat passage rate when the operation is continued is reduced. by being able to confirm that it is possible to maintain a high amount of heat exchange.

  In a heat storage air-conditioning system using clathrate hydrate slurry, the time for producing the slurry by the slurry production apparatus to store heat is usually about 10 hours. In the slurry manufacturing apparatus of Example 3, the fact that one second heat exchanger can be continuously operated stably for 10 hours means that from one second heat exchanger to the other second heat exchanger. There is no need to switch to, and the second heat exchanger can be made one. Further, the hot water circulation path C6 is not required, the slurry manufacturing apparatus can be made compact, the equipment cost can be reduced, and the slurry manufacturing apparatus can be installed even in a narrow space.

[Verification Experiment 5]
<Ratio of refluxing cold water>
Using the slurry manufacturing equipment that circulates cold water and the raw material solution used in verification experiment 3, an experiment (Example 4) was conducted to verify the effect on the manufacturing stability of the slurry manufacturing equipment by changing the ratio of circulating cold water did. The ratio of the flow rate of the refrigerated cold water to the flow rate of the chilled water delivered from the refrigerator is the ratio of the chilled water flow rate, and when the refrigeration rate is 50 vol%, 70 vol%, 80 vol%, 90 vol%, 10 hours from the start of the slurry manufacturing operation. the increase pressure loss of the slurry side of the heat exchanger after the measure, shown in Figure 16.

The increase in pressure loss 10 hours after the start of the slurry production operation is 150 kPa when the cold water is not refluxed, but can be significantly reduced to 60 kPa when the cold water reflux ratio is 50 vol%. When the chilled water reflux rate is greater than 50 vol%, the increase in pressure loss decreases, but when the chilled water reflux rate is greater than 70 vol%, the decrease in the increase in pressure loss decreases and is almost the same.
As the amount of chilled water recirculation increases, the amount of chilled water flowing through the heat exchanger increases, so it is necessary to increase the diameter of the inflow pipe. Therefore, it is appropriate to set the cold water reflux ratio between 50 vol% and 70 vol%. However, the appropriate range of the cold water reflux ratio may vary depending on the conditions of the slurry manufacturing apparatus.

[Verification Experiment 6]
<Slurry manufacturing equipment using large heat exchanger>
The slurry manufacturing apparatus (D) shown in FIG. 8 was configured using a heat exchanger larger than the heat exchanger of the slurry manufacturing apparatus used in the verification experiments 1 to 5, and the experiment was performed. The heat exchanger 31 is a plate heat exchanger (height 1.8m, width 0.6m, depth 0.3m, amount of water held on one side 0.06m ³ , counter flow system), and the heat exchangers 321 and 322 are plate types Using a heat exchanger (height 2m, width 0.8m, depth 0.6m, retained water volume 0.2m ³ on one side, counter flow system), a latent heat storage slurry production experiment was conducted. As the solution, an aqueous solution of tetra n-butylammonium bromide (TBAB) having a concentration of 16 wt% was used. Experiments were conducted to verify the stable operation of the slurry production apparatus for the slurry production apparatus that recirculates cold water (Example 5) and the slurry production apparatus that does not recirculate cold water (Comparative Example 6). In Example 5, 20% by volume of cold water fed from the outlet of the heat exchange 321 was refluxed.

  The temperature of cold water and slurry was measured in the same manner as in the verification experiment 1, and the temperature difference between the inlet temperature of the slurry and the inlet temperature of the cold water, the average temperature difference, and the fluctuation range of the temperature difference are shown in Table 9. In Example 5, since the cold water inlet temperature is stabilized by the cold water recirculation, the fluctuation range of the temperature difference between the slurry inlet and the cold water inlet is 0.6 ° C., which is smaller than that of Comparative Example 6 in which the cold water is not recirculated. While the temperature difference between the inlet and the cold water inlet is reduced, the temperature difference is less likely to fluctuate and can be stabilized.

It was also measured pressure loss of the slurry side of the heat exchanger in the same manner as the verification experiment 1. FIG. 17 shows changes over time in the amount of increase in pressure loss on the slurry side of the heat exchanger 321 from the start of operation to the time point when 5 hours have elapsed. In Comparative Example 6 in which the cold water was not refluxed, the pressure loss increased to 170 kPa, while in Example 5 in which the cold water was refluxed, the pressure loss increased only to 100 kPa.
Recirculating cold water stabilizes the temperature difference between the slurry inlet and the cold water inlet, avoids sudden increases and decreases in the amount of exchange heat, and enables stable release of slurry supercooling, and heat transfer inside the heat exchanger The adhesion of the latent heat storage material to the surface can be suppressed, the increase in pressure loss can be suppressed, and the latent heat storage slurry can be produced stably or continuously over a long period of time.
Even when the size of the heat exchanger was changed, it was found that the same effect as in the verification experiment 3 was obtained.

DESCRIPTION OF SYMBOLS 1 Refrigerator 2 Cooling medium circulation pump 3 Heat exchanger 31 1st heat exchanger 32 2nd heat exchanger 321, 322 2nd heat exchanger 3A, 3B Heat exchanger 32A, 32B Heat exchanger 4 Thermal storage tank 5 Production-side circulation pump 6 Slurry recirculation pump 7 Heat exchanger 8 on heat load side Heat utilization-side circulation pump 9, 9 * Cooling medium recirculation pump 10 Hot water tank 11 Hot water circulation pump 13 Tank C 1 Cold heat medium circulation path C 2 Production-side slurry circulation Path C3 Slurry return path (first return pipe)
C4 Heat utilization side slurry circulation path C5, C5 * Cooling medium reflux path (second reflux pipe)
C6 Hot water circulation path N1 to N6, Na, Na *, Nb Nodes T1 to T4 Temperature sensor

Claims (3)

A latent heat storage material capable of generating a latent heat storage material that can generate a latent heat storage material in the solution by cooling a solution that may cause supercooling during the generation by heat exchange with a cooling medium in a heat exchanger. A method for producing a porous slurry, the step of refluxing a part of the solution together with the latent heat storage material contained therein from the outlet side to the inlet side of the heat exchanger, and the inlet from the outlet side of the heat exchanger And a step of refluxing a part of the cooling medium on the side, a method for producing a latent heat storage slurry. After at least a part of the solution capable of generating a latent heat storage material that can cause supercooling at the time of generation is subcooled, the supercooled state is released, and then heat exchange with the cooling medium in the heat exchanger is performed. A method for producing a latent heat storage slurry that generates the latent heat storage material in the solution by cooling with a step, wherein a part of the cooling medium is refluxed from the outlet side to the inlet side of the heat exchanger A process for producing a latent heat storage slurry, comprising: A first heat exchanger capable of generating a latent heat storage material and capable of cooling a solution that may cause supercooling during the generation, and the solution cooled by the first heat exchanger by heat exchange with a cooling medium A second heat exchanger to be cooled, a first reflux pipe for refluxing a part of the solution from the outlet side of the second heat exchanger to the inlet side, and an inlet from the outlet side of the second heat exchanger And a second recirculation pipe for recirculating a part of the cooling medium on the side, a latent heat storage slurry manufacturing apparatus.

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