JP5136121B2 - Inclusion hydrate having latent heat storage performance, method and apparatus for manufacturing the same, latent heat storage medium, method for increasing latent heat storage amount of clathrate hydrate, and processing apparatus for increasing the amount - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a clathrate hydrate having a latent heat storage effect and a technology related thereto, and more specifically, a clathrate hydrate having an increased latent heat storage effect, a method for manufacturing the clathrate hydrate, and a manufacturing apparatus thereof The present invention relates to a latent heat storage medium containing such clathrate hydrate as a composition, a method for increasing the latent heat storage amount of clathrate hydrate, and a processing apparatus for increasing the amount.

The latent heat storage medium is used for efficient use of thermal energy, and there are many practical examples such as a heat storage material used for air conditioning equipment, a heat transport medium, and a cold insulation material used for maintaining the quality of fresh food products. As such a heat storage medium or a composition thereof, clathrate hydrates having a quaternary ammonium compound as a guest (or guest molecule) and a water molecule as a host (or host molecule) are known (substantially). (See Patent Document 1 and Patent Document 2 as a solid and a slurry dispersed in water, respectively).
In the following, “inclusion hydrate containing quaternary ammonium compound as guest and water molecule as host” is simply “inclusion hydrate of quaternary ammonium compound” or “quaternary ammonium compound as guest. Sometimes referred to as “clathrate hydrate”.

  In general, the larger the amount of heat stored per unit weight (heat storage density), the higher the heat storage efficiency and the heat transport efficiency of the latent heat storage medium. This does not change even when the latent heat storage medium or the composition thereof is a clathrate hydrate of a quaternary ammonium compound. From this meaning, it can be said that the clathrate hydrate having a higher heat storage density is demanded.

Japanese Patent Publication No.57-35224 Japanese Patent No. 3309760

  In order to increase the heat storage density, it is possible to increase the heat storage density by increasing the solid phase ratio of the hydrate particles produced by increasing the concentration of the aqueous solution of the quaternary ammonium compound. However, if the concentration or density of the quaternary ammonium compound is increased in order to increase the heat storage density, there arises a problem that the material cost of the latent heat storage medium increases. In particular, when a slurry in which clathrate hydrate of a quaternary ammonium compound is dispersed in water is used as a latent heat storage medium or a composition thereof, the weight ratio or solid phase ratio of hydrate particles in water is set. The heat storage density can be increased by increasing the ratio, but if this ratio is excessively increased, the viscosity of the slurry increases and the fluidity decreases, resulting in a problem in the transportability.

  In order to solve the above problems, the present invention is a clathrate hydrate having a quaternary ammonium compound as a guest and having improved latent heat storage performance, a production method and a production apparatus for such clathrate hydrate, It is an object of the present invention to provide a latent heat storage medium containing such clathrate hydrate as a composition, a method for increasing the amount of latent heat storage of clathrate hydrate, and a treatment apparatus for increasing the amount.

  As a result of intensive studies to solve the above problems, the inventors have (1) generating a gas from a gas generating agent added to an aqueous solution of a quaternary ammonium compound, or generating a gas and mixing the gas into the aqueous solution. When the clathrate hydrate using the quaternary ammonium compound produced by cooling later as a guest is collected and the amount of stored heat is measured, (1a) the amount of stored heat increases compared to the case where no gas is generated, and (1b) (2) When the clathrate hydrate produced by the above operation (1) is melted, the same kind of gas is released, (3) The above ( Even if the clathrate hydrate produced by the operation of 1) is melted and the clathrate hydrate is produced by repeating the operation of the above (1), each of (1a), (1b) and (2) New knowledge that the phenomenon can be confirmed It was.

  About these phenomena, clathrate hydrates are produced by generating a gas from a gas generating agent added to an aqueous solution of a quaternary ammonium compound, or by generating a gas and cooling it after mixing the gas with an aqueous solution. (A) an clathrate hydrate formed by inclusion of the gas into the clathrate hydrate containing the quaternary ammonium compound as a guest, and (a) the gas as a guest molecule together with the quaternary ammonium compound. Clathrate hydrate formed by clathrate, (c) at least one of a mixture of clathrate hydrate with quaternary ammonium compound as guest and clathrate hydrate with gas as guest Can be explained without contradiction.

  The present invention has been made based on the above findings, and specifically has the following configuration.

  The clathrate hydrate according to the first aspect of the present invention is a clathrate hydrate having a latent heat storage performance using a quaternary ammonium compound produced by cooling an aqueous solution containing a quaternary ammonium compound as a guest. Further, the latent heat storage performance is enhanced by further enclosing a gas generated from an aqueous solution containing a quaternary ammonium compound as a guest.

  The clathrate hydrate according to the second aspect of the present invention is a clathrate hydrate having latent heat storage performance, and is generated while generating or generating gas from an aqueous solution containing a quaternary ammonium compound and a gas generating agent. After mixing the mixed gas into the aqueous solution, the quaternary ammonium compound produced by cooling the aqueous solution and the gas are used as guests.

  The clathrate hydrate according to the third aspect of the present invention is a clathrate hydrate having a quaternary ammonium compound as a guest and having latent heat storage performance, and carbon dioxide generated from an aqueous solution containing the quaternary ammonium compound. The latent heat storage performance is improved by further inclusion as a guest.

  The clathrate hydrate according to the fourth aspect of the present invention is a clathrate hydrate having latent heat storage performance, and generates carbon dioxide from an aqueous solution containing a quaternary ammonium compound and a carbonate or bicarbonate. The carbon dioxide generated or mixed is mixed with the aqueous solution, and then the aqueous solution is cooled, and both the quaternary ammonium compound and carbon dioxide produced are used as guests.

  The latent heat storage medium according to the fifth aspect of the present invention includes the clathrate hydrate according to any one of the first to fourth aspects as a composition.

  The latent heat storage medium according to the sixth aspect of the present invention is generated by generating a gas from an aqueous solution containing a quaternary ammonium compound and a gas generating agent or by mixing the generated gas with the aqueous solution and then cooling the aqueous solution. The clathrate hydrate with improved latent heat storage performance is included as a composition.

  The latent heat storage medium according to the seventh aspect of the present invention is an aqueous solution containing a quaternary ammonium compound and carbon dioxide generated from an aqueous solution containing a carbonate or bicarbonate, or after mixing the generated carbon dioxide with the aqueous solution. The clathrate hydrate produced by cooling the water and having improved latent heat storage performance is included as a composition.

  A clathrate hydrate production method according to an eighth aspect of the present invention is a clathrate hydrate production method having latent heat storage performance, wherein gas is discharged from an aqueous solution containing a quaternary ammonium compound and a gas generating agent. It has the process of improving the latent-heat storage performance by cooling the aqueous solution after mixing the generated gas with the aqueous solution.

  The clathrate hydrate production method according to the ninth aspect of the present invention is a clathrate hydrate production method having latent heat storage performance, and includes a quaternary ammonium compound and a carbonate or bicarbonate. While the carbon dioxide is generated from the aqueous solution or after the generated carbon dioxide is mixed with the aqueous solution, the latent heat storage performance is improved by cooling the aqueous solution.

  The latent heat storage medium according to the tenth aspect of the present invention includes a clathrate hydrate produced by the clathrate hydrate production method according to the eighth or ninth aspect as a composition.

  The method for increasing the latent heat storage amount of clathrate hydrate according to the eleventh aspect of the present invention is a method for increasing the latent heat storage amount of clathrate hydrate using a quaternary ammonium compound as a guest. While the gas is generated from the aqueous solution containing the compound and the gas generating agent, or after the generated gas is mixed with the aqueous solution, the aqueous solution is cooled.

  The method for increasing the latent heat storage amount of clathrate hydrate according to the twelfth aspect of the present invention is a method for increasing the latent heat storage amount of clathrate hydrate using a quaternary ammonium compound as a guest. It has the process which cools aqueous solution, after mixing carbon dioxide which generate | occur | produced the carbon dioxide from the aqueous solution containing a compound and carbonate or hydrogencarbonate, or was mixed with aqueous solution.

  A clathrate hydrate production apparatus according to a thirteenth aspect of the present invention is a clathrate hydrate production apparatus having latent heat storage performance, wherein gas is generated from an aqueous solution containing a quaternary ammonium compound and a gas generating agent. A gas generator to be generated, a mixer that mixes the generated gas with the aqueous solution, and a generator that generates clathrate hydrate with improved heat storage performance by cooling the aqueous solution mixed with the gas. It is to be prepared.

  A clathrate hydrate production apparatus according to a fourteenth aspect of the present invention is a clathrate hydrate production apparatus having latent heat storage performance, wherein gas is generated from an aqueous solution containing a quaternary ammonium compound and a gas generating agent. A gas generating mixer that generates and mixes the generated gas with an aqueous solution, and a generator that cools the aqueous solution mixed with the gas to generate clathrate hydrate with improved heat storage performance. is there.

  The clathrate hydrate production apparatus according to the fifteenth aspect of the present invention is a clathrate hydrate production apparatus having latent heat storage performance, wherein gas is generated from an aqueous solution containing a quaternary ammonium compound and a gas generating agent. A generator for generating clathrate hydrate with improved heat storage performance by cooling an aqueous solution while being generated is provided.

  The clathrate hydrate production apparatus according to the sixteenth aspect of the present invention is a clathrate hydrate production apparatus having latent heat storage performance, wherein gas is generated from an aqueous solution containing a quaternary ammonium compound and a gas generating agent. A clathrate hydrate having a heat storage performance improved by generating a gas from the aqueous solution by the gas generating means in the process of cooling by the cooling means is provided with a gas generating means for generating and a cooling means for cooling the aqueous solution. Is.

  The clathrate hydrate production apparatus according to the seventeenth aspect of the present invention is the clathrate hydrate production apparatus according to any of the thirteenth to sixteenth aspects, wherein the gas generating agent is carbonate or It is a bicarbonate and the gas is carbon dioxide.

  The treatment apparatus for increasing the latent heat storage amount of clathrate hydrate according to the eighteenth aspect of the present invention is a treatment apparatus for increasing the latent heat storage amount of clathrate hydrate using a quaternary ammonium compound as a guest. A gas generating means for generating gas from an aqueous solution containing a quaternary ammonium compound and a gas generating agent, and a cooling means for cooling the aqueous solution, and generating gas from the aqueous solution by the gas generating means in the course of cooling by the cooling means It is.

  The processing apparatus for increasing the latent heat storage amount of clathrate hydrate according to the nineteenth aspect of the present invention is the processing apparatus according to the eighteenth aspect, wherein the gas generating agent is carbonate or bicarbonate. The gas is carbon dioxide.

In addition, based on matter (1) thru | or (7) hung up below, this invention shall be understood and interpreted and the technical scope shall be demarcated.
(1) Typical examples of the quaternary ammonium compounds in the present invention are alkyl ammonium salts such as tetra-n-butyl ammonium salt, tetra-isopentyl ammonium salt, and tri-n-butyl / n-pentyl ammonium salt.

(2) The latent heat storage medium in the present invention may be the clathrate hydrate itself in the present invention, and the clathrate hydrate is an essential composition, and is configured by adding or adding another composition. It may be one that is dispersed, encapsulated or suspended in another substance. The properties of the latent heat storage medium can be solid, liquid, gel, slurry, microcapsule (filled in a microcapsule), etc. There are no particular restrictions. For example, the clathrate hydrate in the present invention is a composition even if it is initially a solid or a latent heat storage medium that is processed into a liquid or gel by adding a surfactant or a gelling agent. As long as it is included, it is included in the latent heat storage medium in the present invention. In the latent heat storage medium in the present invention, there is no limitation on the mode of use, and the latent heat storage medium that is used for heat utilization at a fixed position is also used for heat utilization at the destination because it involves movement by driving force or natural convection. The latent heat storage medium is not excluded from the present invention from the viewpoint of use.

(3) The present invention is based on the conventional method for producing clathrate hydrates in which an aqueous solution containing a quaternary ammonium compound (hereinafter simply referred to as an aqueous solution) is cooled. It is a technical idea based on a new generation method that takes into account the technical matter of cooling the aqueous solution while generating gas from the aqueous solution or mixing the generated gas into the aqueous solution, There is a technical feature in that gas is generated from an aqueous solution and contained in the aqueous solution.

(4) In the present invention, the gas generating agent may be carbonate or hydrogen carbonate, and the gas to be generated may be carbon dioxide. In order to generate carbon dioxide from the carbonate or bicarbonate contained in the aqueous solution in this case, it is preferable to generate the carbon dioxide by lowering the pH of the aqueous solution. The pH may be lowered by addition of an acid or an electrochemical method using an electrode reaction.
Here, examples of the carbonate or bicarbonate include sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
In the present invention, the gas generating agent may be hydrogen peroxide and the gas to be generated may be oxygen. In this case, a reaction for generating oxygen by decomposing hydrogen peroxide with a catalyst is performed. Further, the gas generating agent may be sulfite, and the gas to be generated may be sulfur dioxide. In this case, a reaction for decomposing sulfite with an acid to generate sulfur dioxide is performed.

(5) However, in the present invention, the gas to be generated from the gas generating agent contained in the aqueous solution does not include hydrogen or helium. The clathrate hydrate produced by cooling a small molecule gas such as hydrogen or helium generated from an aqueous solution containing a quaternary ammonium compound, or after being generated and mixed, increases the latent heat storage amount. Did not happen.
On the other hand, in the present invention, the gas to be generated from the gas generating agent contained in the aqueous solution is taken into the inclusion compound containing a quaternary ammonium compound as a guest, or is included in the inclusion with water molecules together with the quaternary ammonium compound. What can be a component of the wet hydrate, specifically air, nitrogen, oxygen, carbon dioxide, argon, krypton, xenon, hydrogen sulfide, sulfur dioxide, methane, ethane, propylene, trimethylene oxide, propane, butane, Gases of molecules larger than hydrogen and helium, such as various chlorofluorocarbons, are included.
Therefore, although the technical feature of the present invention is that the gas is generated from the gas generating agent contained in the aqueous solution, the gas is a gas of a molecule larger than hydrogen or helium, and a quaternary ammonium compound is used. It can be arranged that it can be incorporated into a guest inclusion compound or can be included in a water molecule together with a quaternary ammonium compound to become a component of an inclusion hydrate.

(6) In this invention, there is no restriction | limiting in particular about the pressure at the time of producing | generating or manufacturing a clathrate hydrate with higher latent heat storage performance or a latent heat storage effect, The target clathrate hydrate can be produced | generated or manufactured. Insofar as this may be done under pressure, normal pressure or even under reduced pressure.
Focusing on the dissolution rate of gas in aqueous solution and the maximum dissolution concentration, in order to more efficiently produce or produce clathrate hydrate with a large amount of latent heat storage, pressure under pressure is lower than normal pressure. Is more preferred under reduced pressure. On the other hand, when attention is paid to the cost of equipment and operation, normal pressure is more preferable.

(7) In the manufacturing apparatus according to the thirteenth to seventeenth aspects of the present invention, a means for increasing the latent heat storage amount in a part of the heat utilization system using the latent heat storage medium containing clathrate hydrate. Incorporated as a so-called clathrate hydrate treatment device.

  According to the present invention, since the latent heat storage performance of the clathrate hydrate is enhanced, the amount of the quaternary ammonium compound as the guest compound of the clathrate hydrate required for storing the necessary amount of latent heat can be reduced. In addition, the material cost can be reduced, the container required to contain the clathrate hydrate can be made smaller, and the equipment including the container can be made smaller. Reduces the amount of clathrate hydrate required to transport the same latent heat storage, especially when using clathrate hydrate (for example, in a fluid and low viscosity slurry) Therefore, not only the material cost can be reduced, but also the transportation piping can be downsized and transportation power can be reduced.

  Furthermore, according to the present invention, a gas generating agent is previously contained in an aqueous solution containing a quaternary ammonium compound, and while the gas is generated from the aqueous solution or the generated gas is mixed with the aqueous solution, the aqueous solution is cooled. Since clathrate hydrate using both quaternary ammonium compound and gas as guest is generated, clathrate hydrate using both quaternary ammonium compound and gas as guest can be easily manufactured. The entire device can be made compact.

When the present invention is viewed from a multifaceted perspective, the functions and effects provided by the respective embodiments are as follows.
According to the first and second embodiments of the present invention, clathrate hydration having a higher latent heat storage performance than that which does not take in a gas generated from an aqueous solution containing a quaternary ammonium compound or does not contain the gas. Things can be realized.
According to the third and fourth aspects of the present invention, the clathrate has higher latent heat storage performance than the carbon dioxide generated from the aqueous solution containing the quaternary ammonium compound or not containing the carbon dioxide. Hydrates can be realized.

  According to any of the fifth to seventh aspects of the present invention, a latent heat storage medium including a clathrate hydrate having higher latent heat storage performance or higher latent heat storage amount as a composition can be realized.

According to the eighth aspect of the present invention, an clathrate hydrate having a higher latent heat storage performance than that which does not take in a gas generated from an aqueous solution containing a quaternary ammonium compound or does not clathrate the gas is produced. can do.
According to the ninth aspect of the present invention, the clathrate hydrate has higher latent heat storage performance than that which does not take in carbon dioxide generated from an aqueous solution containing a quaternary ammonium compound or does not clathrate the carbon dioxide. Can be manufactured.

  According to the 10th form of this invention, the latent heat storage medium which contains the clathrate hydrate which has higher latent heat storage performance or higher latent heat storage amount as a composition is realizable.

  According to the eleventh and twelfth aspects of the present invention, increasing the latent heat storage amount of clathrate hydrate containing the quaternary ammonium compound produced as a guest by cooling an aqueous solution containing the quaternary ammonium compound. Can do.

  According to the thirteenth aspect of the present invention, the process of generating a gas from an aqueous solution containing a quaternary ammonium compound, mixing the generated gas with the aqueous solution, and then cooling the aqueous solution in the form of an apparatus is realized. Thus, a clathrate hydrate production apparatus with improved heat storage performance can be realized.

  According to the fourteenth aspect of the present invention, a process of generating a gas from an aqueous solution containing a quaternary ammonium compound and mixing the generated gas with the aqueous solution and then cooling the aqueous solution is embodied in the form of an apparatus. Thus, a clathrate hydrate production apparatus with improved heat storage performance can be realized.

  According to the fifteenth aspect of the present invention, the process of cooling the aqueous solution while generating gas from the aqueous solution containing the quaternary ammonium compound can be embodied in the form of an apparatus, and the heat storage performance can be further improved. An apparatus for producing clathrate hydrate can be realized.

  According to the sixteenth aspect of the present invention, the process of cooling the aqueous solution while generating gas from the aqueous solution containing the quaternary ammonium compound can be embodied in the form of an apparatus, and the heat storage performance can be further improved. An apparatus for producing clathrate hydrate can be realized.

  According to the seventeenth aspect of the present invention, the process of cooling the aqueous solution while generating carbon dioxide from the aqueous solution containing the quaternary ammonium compound can be embodied in the form of an apparatus, and the heat storage performance is further improved. An apparatus for producing clathrate hydrate can be realized.

  According to the eighteenth aspect of the present invention, the process of cooling the aqueous solution while generating gas from the aqueous solution containing the quaternary ammonium compound can be embodied in the form of an apparatus. A processing device that increases the latent heat storage amount can be realized.

  According to the nineteenth aspect of the present invention, the process of cooling the aqueous solution while generating carbon dioxide from the aqueous solution containing the quaternary ammonium compound can be embodied in the form of an apparatus, and clathrate hydrate It is possible to realize a processing device that increases the amount of latent heat storage.

In addition, when the clathrate hydrate melts, the gas taken into the clathrate hydrate is released, but it can be reused for the production of clathrate hydrate or used for other purposes. .
In addition, when a clathrate hydrate is produced by generating a gas from a gas generating agent added to an aqueous solution and incorporating the gas, the clathrate hydrate is incorporated into the clathrate hydrate when it melts. The released gas is released, and this gas can be used in preparing the gas generating agent.
In addition, when a clathrate hydrate is produced by decomposing a carbonate or bicarbonate added to an aqueous solution to generate carbon dioxide and incorporating this, the clathrate hydrate is dissolved when the clathrate hydrate is melted. The carbon dioxide taken in by the hydrate is released, and this carbon dioxide can be used for the reaction for regenerating the carbonate or bicarbonate.

  Experimental results for confirming the effects of the present invention will be described, and then specific embodiments will be described.

  A gas generating agent for generating a gas is added to an aqueous solution of a quaternary ammonium compound in advance, and the gas and the quaternary ammonium compound are cooled while being generated or mixed with the gas generating agent while being generated and mixed. An experiment was conducted to measure the amount of heat stored in clathrate hydrate by including clathrate hydrate as a guest.

As a gas generating agent, for example, carbonate or hydrogen carbonate is added to an aqueous solution of a quaternary ammonium compound, and carbon dioxide is generated from the carbonate or hydrogen carbonate in the aqueous solution, or carbon dioxide is generated to the aqueous solution. When the clathrate hydrate using the quaternary ammonium compound produced by cooling after mixing as a guest is collected and the amount of stored heat is measured, the amount of stored heat increases and the melting point changes compared to when no gas is generated. Can be confirmed. Furthermore, when the clathrate hydrate produced is melted, a phenomenon in which carbon dioxide is released can be confirmed.
Carbon dioxide can be generated from carbonate or bicarbonate in an aqueous solution by lowering the pH of the aqueous solution. The pH can be lowered by adding an acid or by an electrochemical method using an electrode reaction. Good.
In addition, when carbon dioxide taken into the clathrate hydrate is released by melting the clathrate hydrate, the carbon dioxide released in the reaction to regenerate carbonate or bicarbonate should be used. Can do.

[Experiment]
Inclusion using a quaternary ammonium compound as a guest by adding a carbonate or hydrogen carbonate to an aqueous solution of the quaternary ammonium compound and cooling it while generating carbon dioxide from the carbonate or hydrogen carbonate in the aqueous solution. An experiment was conducted to measure the amount of heat stored in the hydrate. When tetra-n-butylammonium bromide (TBAB) is used as the quaternary ammonium compound, carbon dioxide is generated by adding carbonate or hydrogen carbonate to the aqueous solution in the formation process of the hydrate slurry, An experiment was conducted with the case where the hydrate slurry was not generated, and the heat storage amount and melting point of the produced hydrate slurry were compared.

The contents of the experiment are as follows.
A raw material aqueous solution was prepared by dissolving 15.0 wt% of TBAB and 4.0 wt% of sodium bicarbonate in water. The pH of the raw material aqueous solution after preparation was 8.3.
Under normal pressure, the raw material aqueous solution was put into a glass beaker, and the glass beaker was immersed in a cooling liquid at 0 ° C. to be cooled to produce a hydrate, thereby producing a hydrate slurry. During the cooling, stirring inside the beaker was continued. At this time, in the process of cooling, a small amount of sulfuric acid was added to lower the pH of the raw material aqueous solution to 6.8 and carbon dioxide was generated from sodium bicarbonate, and carbon dioxide was not generated without adding sulfuric acid. Two kinds of experiments were conducted.
The produced hydrate slurry was put in a heat insulating container and heated by an electric heater immersed while stirring to dissolve the hydrate slurry. The amount of heat stored in the temperature range of 7 ° C. to 10 ° C. was measured from the amount of heat applied at that time and the hydrate slurry temperature. Moreover, melting | fusing point which the solid hydrate in a hydrate slurry melt | dissolves completely was measured.

  The measurement results are shown in Table 1 below. Table 1 shows the heat increase ratio calculated by assuming that the increase ratio of the heat storage amount due to the generation of carbon dioxide does not generate carbon dioxide.

  As shown in Table 1, it was confirmed that when carbon dioxide was generated from sodium bicarbonate, the heat could be increased by about 20% compared to the case where carbon dioxide was not generated.

In addition, it was confirmed that the hydrate slurry produced while generating oxygen dioxide has sufficient fluidity as a heat transport medium as in the case where oxygen dioxide is not generated.
In addition, fine bubbles were generated while the hydrate slurry was heated and the hydrate solid melted. It was confirmed that the gas component collected from the bubbles was oxygen dioxide.

  In the above experimental example, tetra-n-butylammonium bromide (TBAB) was used as the quaternary ammonium compound, but the same effect can be obtained for quaternary ammonium compounds other than TBAB. Other examples of quaternary ammonium compounds include alkyl ammonium salts such as tetra-n-butyl ammonium salt, tetra-isopentyl ammonium salt, and tri-n-butyl / n-pentyl ammonium salt.

  The following embodiments are based on the results of such experiments.

[Embodiment]
FIG. 1 is an explanatory view of an apparatus for producing clathrate hydrate according to the present embodiment. Hereinafter, the clathrate hydrate manufacturing apparatus according to the present embodiment will be described with reference to FIG.
The clathrate hydrate manufacturing apparatus according to the present embodiment stores an aqueous solution containing a quaternary ammonium compound, and stores a clathrate hydrate that is generated. An aqueous solution preparation device 2 that receives supply of a gas generation agent from a gas generation agent preparation device 7 that will be described later and prepares an aqueous solution containing the gas generation agent, and an aqueous solution that contains the gas generation agent from the aqueous solution preparation device 2. The gas generation mixer 3 that is supplied and the pH of the aqueous solution is adjusted by the pH adjusting means 4 to generate a gas from the aqueous solution, and the gas generated in the aqueous solution is mixed, and the quaternary ammonium compound mixed in the gas generation mixer 3 And a generator 5 for cooling the aqueous solution containing the gas and generating the clathrate hydrate containing the gas and a quaternary ammonium compound as a guest, and the clathrate hydrate and the unreacted gas from the generator 5 A separator 6 for separating the gas of the unreacted receiving sheet, from the separator 6 is supplied with gas and a gas generating agent prepared device 7 for preparing a gas generating agent.
Hereinafter, each configuration will be described in detail.

<Heat storage tank>
The heat storage tank 1 stores an aqueous clathrate hydrate generated while storing an aqueous solution containing a quaternary ammonium compound. The aqueous solution containing the quaternary ammonium compound stored in the heat storage tank 1 is pumped out by a pump (not shown) and supplied to the aqueous solution preparation device 2.

<Aqueous solution preparation device>
The aqueous solution preparation device 2 adds the gas generating agent supplied from the gas generating agent preparation device 7 to the aqueous solution containing the quaternary ammonium compound to prepare an aqueous solution containing the gas generating agent and the quaternary ammonium compound.

<Gas generation mixer>
The gas generating mixer 3 lowers the pH of the aqueous solution containing the gas generating agent and the quaternary ammonium compound by the pH adjusting means 4, generates gas from the gas generating agent, and further mixes the gas generated in the aqueous solution. The pH adjusting means 4 may be one that adds an acid, or one that is based on an electrochemical method using an electrode reaction.
Note that the gas generating mixer 3 may be omitted, and a gas may be generated from the gas generating agent in the generator 5 to mix the aqueous solution and the gas. Moreover, you may make it provide a gas generator and a mixer separately instead of the gas generation mixer 3. FIG.

<Generator>
The generator 5 has a cooling function, and cools the aqueous solution containing the quaternary ammonium compound and gas mixed in the gas generating mixer 3 to generate clathrate hydrate containing the gas and the quaternary ammonium compound as a guest. To do. The generator 5 is preferably provided with a stirring mechanism.
The clathrate hydrate is generated, and stirring is performed in the generator 5 to generate a hydrate slurry in which the clathrate hydrate particles are dispersed in the aqueous solution.
In the generator 5, unreacted gas is present together with the above clathrate hydrate.

<Separator>
The separator 6 receives the clathrate hydrate and the unreacted gas from the generator 5 and separates the unreacted gas.
The type of the separator 6 is arbitrary, and a cyclone separator, for example, can be used. However, in order to minimize the mixing of slurry droplets into the separated gas, for example, a collision separation type mist separator is also used. It is desirable to use it.
The gas separated by the separator 6 is sent to the gas generating agent preparation device 7 and used for the reaction for generating the gas generating agent.

A method for producing clathrate hydrate using the clathrate hydrate production apparatus configured as described above will be described below.
The heat storage tank 1 is filled with an aqueous solution containing a quaternary ammonium compound, and this aqueous solution is pumped out by a pump (not shown) and supplied to the aqueous solution preparation device 2. In the aqueous solution preparation device 2, the gas generating agent supplied from the gas generating agent preparation device 7 is added to the supplied aqueous solution to prepare an aqueous solution. In the gas generating mixer 3, the pH of the aqueous solution containing the supplied quaternary ammonium compound and the gas generating agent is lowered by the pH adjusting means 4, gas is generated from the gas generating agent, and the gas generated in the aqueous solution is further mixed. The gas is dissolved in the aqueous solution. The aqueous solution containing the quaternary ammonium compound and gas mixed in the gas generating mixer 3 is supplied to the generator 5 by a pump (not shown). In the generator 5, the supplied aqueous solution is cooled to generate clathrate hydrate containing a gas and a quaternary ammonium compound as a guest, and stirring is performed in the generator 5, whereby clathrate hydrate particles are produced. A hydrate slurry is produced in which is dispersed in an aqueous solution. The hydrate slurry and unreacted gas generated in the generator 5 are supplied to the separator 6, and the hydrate slurry and unreacted gas are separated. The separated hydrate slurry is stored in the heat storage tank 1. On the other hand, the gas separated by the separator 6 is sent to the gas generating agent preparation device 7 and used for the reaction for generating the gas generating agent.

  The clathrate hydrate containing the gas stored in the heat storage tank 1 and the quaternary ammonium compound as a guest stores heat as compared with the case where the gas generated from the aqueous solution is not included, as shown in the above experimental results. The amount is increasing. Thus, according to the present embodiment, a hydrate slurry having a large heat storage amount can be generated with a simple device.

  In the above example, the gas is generated by the separately provided gas generating mixer 3 and the aqueous solution is mixed with the gas. However, without providing the gas generating mixer 3, the gas is generated from the gas generating agent in the generator 5. The clathrate hydrate containing a gas and a quaternary ammonium compound as a guest may be produced by cooling the aqueous solution while being generated and mixed with the aqueous solution.

The hydrate slurry manufactured by the clathrate hydrate manufacturing apparatus configured as described above can be used as a heat transport medium used for cooling air conditioning equipment.
In the cooling air-conditioning equipment, for example, the aqueous solution in the heat storage tank 1 is extracted at night and supplied to the aqueous solution preparation device 2, hydrate slurry is generated by the generator 5 through the gas generating mixer 3, and the air conditioning is cooled in the daytime. A hydrate slurry is stored in the heat storage tank 1 as a heat transport medium used during operation.
During the daytime cooling operation, the hydrate slurry in the heat storage tank 1 is flowed to the indoor air conditioner as a heat transport medium by a pump. In an indoor air conditioner, the hydrate slurry exchanges heat with air to supply cold heat to cool the room. By this heat exchange, the hydrate of the hydrate slurry is melted to become a mixed fluid of an aqueous solution and a gas and returned to the second separator provided in the return piping system.
The mixed fluid returned to the second separator is separated into an aqueous solution and a gas, the aqueous solution is returned to the heat storage tank 1, and a part thereof is sent directly to the aqueous solution preparation device 2. Further, the gas separated by the second separator is sent to the gas generating agent preparation device 7 and used for the reaction for generating the gas generating agent.

Also, in the indoor air conditioner, the hydrate slurry is hydrated by increasing the pH of the hydrate slurry before or at the same time as the hydrate slurry exchanges heat with air to supply cold heat. When the gas melts, the gas generated from the hydrate reacts with the components in the aqueous solution to return to the gas generating agent so that the gas is not separated from the aqueous solution.
For example, a case where sodium hydrogen carbonate is used as a gas generating agent will be described. Before or simultaneously with cooling the aqueous solution to form a hydrate slurry, carbon dioxide is generated from sodium bicarbonate by lowering the pH of the aqueous solution to produce a hydrate containing carbon dioxide as a guest. At this time, sodium carbonate and water are produced and contained in the aqueous solution. The carbon dioxide generated when the hydrate melts reacts with sodium carbonate and water in the aqueous solution by raising the pH of the hydrate slurry before or simultaneously with melting the hydrate of the hydrate slurry. Thus, sodium hydrogen carbonate can be prevented from separating from the aqueous solution.

  As described above, according to the present embodiment, a hydrate slurry having a large heat storage amount can be manufactured and used with a simple configuration.

Moreover, you may make it supply the hydrate slurry produced | generated with the generator 5 to the cold-heat utilization apparatus, without providing the thermal storage tank 1. FIG. In this case, it is preferable to increase the capacity of the mixer.
In addition, the cold energy utilization device does not need to be integrated with the indoor air conditioner. For example, the cold heat utilization device may cool the water and guide the cooled water to the indoor air conditioner to use the cold energy. Absent.
Solid surfaces such as pipes and container walls are not cooled to the extent that they contribute to hydrate formation, and the effect of cooling is directly and effectively produced by hydrate formation and hydrate formation is effectively carried out. . And since the production | generation of a hydrate mainly advances in aqueous solution, it does not adhere to piping, a container wall, etc.
As the refrigerant, natural refrigerants and various chlorofluorocarbons can be used.

  In each of the above-described embodiments, the effect of increasing the amount of heat storage when the clathrate hydrate containing a gas and a quaternary ammonium compound as a guest is used as a heat storage agent has been described. The clathrate hydrate containing the compound as a guest can obtain different effects when used for other purposes.

  For example, when a latent heat storage medium containing clathrate hydrate containing a gas as a guest is used as a cold insulation material such as food, a more preferable preservation state can be maintained if a gas is selected according to the object to be kept cold. In other words, when seafood, vegetables, or florets that you want to preserve at low temperatures require oxygen, such as cold objects that are living at the cellular level, when generating clathrate hydrates that are components of cold insulation To contain oxygen as a guest. In this way, oxygen is released when the clathrate hydrate is melted, so that it is possible to keep cold while supplying oxygen to the cold object, and it is possible to realize a state more suitable for storage. .

On the contrary, in the case of suppressing oxidation by oxygen, if nitrogen or the like is used as a gas contained as a guest, it can be stored at a low temperature while suppressing oxidation. Moreover, it can respond | correspond similarly when the cold-retaining atmosphere is made into other gas atmosphere.
In addition, what is necessary is just to utilize the bag body using the raw material which does not leak aqueous solution, and has gas permeability as a cold storage container.

Moreover, the latent heat storage medium containing the clathrate hydrate containing a gas and a quaternary ammonium compound as a guest can be used as a heat / gas transport medium capable of simultaneously transporting heat and gas.
A latent heat storage medium containing a clathrate hydrate containing a gas and a quaternary ammonium compound as a guest can be used as a heat transport medium in a slurry state. In that case, it is possible to produce a hydrate slurry containing a desired gas, send it to a place where heat is needed, and use it, and use the gas generated when the clathrate hydrate is dissolved. .

It is explanatory drawing of the manufacturing apparatus of the clathrate hydrate which concerns on one embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Heat storage tank 2 Aqueous solution preparation device 3 Gas generation mixer 5 Generator 6 Separator

Claims (19)

A clathrate hydrate having a quaternary ammonium compound produced by cooling an aqueous solution containing a quaternary ammonium compound as a guest and having latent heat storage performance,
The clathrate hydrate characterized in that the latent heat storage performance is enhanced by further clathrating a gas generated from an aqueous solution containing a quaternary ammonium compound as a guest. While generating a gas from an aqueous solution containing a quaternary ammonium compound and a gas generating agent, or mixing the generated gas with the aqueous solution, the aqueous solution is cooled, and then both the quaternary ammonium compound and the gas generated are cooled. A clathrate hydrate having latent heat storage performance characterized by being a guest. A clathrate hydrate having a quaternary ammonium compound as a guest and having latent heat storage performance, wherein the latent heat storage performance is enhanced by further including carbon dioxide generated from an aqueous solution containing the quaternary ammonium compound as a guest. Clathrate hydrate characterized by that. The quaternary ammonium compound and the quaternary ammonium compound produced by cooling the aqueous solution after mixing the generated carbon dioxide with the aqueous solution while generating carbon dioxide from an aqueous solution containing a carbonate or bicarbonate. A clathrate hydrate having latent heat storage performance, wherein both the carbon dioxide and the carbon dioxide are guests. A latent heat storage medium comprising the clathrate hydrate according to any one of claims 1 to 4 as a composition. A clathrate hydrate with improved latent heat storage performance that is generated by cooling the aqueous solution after generating the gas from an aqueous solution containing a quaternary ammonium compound and a gas generating agent or by mixing the generated gas with the aqueous solution. A latent heat storage medium comprising: as a composition. While generating carbon dioxide from an aqueous solution containing a quaternary ammonium compound and a carbonate or bicarbonate, or by mixing the generated carbon dioxide with the aqueous solution, the latent heat storage performance is improved by cooling the aqueous solution. A latent heat storage medium comprising the clathrate hydrate as a composition. A method for producing clathrate hydrate having latent heat storage performance,
The method includes the step of enhancing the latent heat storage performance by generating a gas from an aqueous solution containing a quaternary ammonium compound and a gas generating agent or by mixing the generated gas with the aqueous solution and then cooling the aqueous solution. Production method of clathrate hydrate. A method for producing clathrate hydrate having latent heat storage performance,
A step of enhancing the latent heat storage performance by cooling the aqueous solution after carbon dioxide is generated from an aqueous solution containing a quaternary ammonium compound and a carbonate or bicarbonate, or mixed with the generated carbon dioxide. A method for producing clathrate hydrate, comprising: A latent heat storage medium comprising a clathrate hydrate produced by the production method according to claim 8 or 9, as a composition. A method for increasing the latent heat storage amount of clathrate hydrate using a quaternary ammonium compound as a guest,
The latent heat of clathrate hydrate comprising the step of cooling the aqueous solution while generating the gas from the aqueous solution containing the quaternary ammonium compound and the gas generating agent or mixing the generated gas with the aqueous solution. How to increase the amount of heat storage. A method for increasing the latent heat storage amount of clathrate hydrate using a quaternary ammonium compound as a guest,
A package comprising the step of cooling the aqueous solution after the carbon dioxide is generated from the aqueous solution containing the quaternary ammonium compound and carbonate or hydrogen carbonate or mixed with the generated carbon dioxide. Method of increasing the amount of latent heat storage of wetted hydrate. An apparatus for producing clathrate hydrate having latent heat storage performance,
A gas generator for generating a gas from an aqueous solution containing a quaternary ammonium compound and a gas generating agent; a mixer for mixing the generated gas with the aqueous solution; and the heat storage performance by cooling the aqueous solution mixed with the gas. A clathrate hydrate manufacturing apparatus, comprising: An apparatus for producing clathrate hydrate having latent heat storage performance,
A gas generating mixer for generating a gas from an aqueous solution containing a quaternary ammonium compound and a gas generating agent, and mixing the generated gas with the aqueous solution; and cooling the aqueous solution mixed with the gas to enhance the heat storage performance. And a generator for producing the clathrate hydrate. An apparatus for producing clathrate hydrate having latent heat storage performance,
A clathrate water comprising a generator that cools the aqueous solution while generating a gas from an aqueous solution containing a quaternary ammonium compound and a gas generating agent to produce the clathrate hydrate with enhanced heat storage performance. Japanese manufacturing equipment. An apparatus for producing clathrate hydrate having latent heat storage performance,
A gas generating means for generating a gas from an aqueous solution containing a quaternary ammonium compound and a gas generating agent; and a cooling means for cooling the aqueous solution, wherein the gas is generated from the aqueous solution by the gas generating means in the course of cooling by the cooling means. The clathrate hydrate manufacturing apparatus is characterized in that the clathrate hydrate is produced by generating the heat storage performance. The clathrate hydrate manufacturing apparatus according to any one of claims 13 to 16, wherein the gas generating agent is carbonate or hydrogen carbonate, and the gas is carbon dioxide. A treatment apparatus for increasing the latent heat storage amount of clathrate hydrate containing a quaternary ammonium compound as a guest,
A gas generating means for generating a gas from an aqueous solution containing a quaternary ammonium compound and a gas generating agent; and a cooling means for cooling the aqueous solution, wherein the gas is generated from the aqueous solution by the gas generating means in the course of cooling by the cooling means. A processing apparatus characterized by generating The processing apparatus according to claim 18, wherein the gas generating agent is carbonate or bicarbonate, and the gas is carbon dioxide.

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