JP2008106123A - Clatherating hydrate having latent heat accumulation performance, its manufacturing method, its manufacturing apparatus, latent heat accumulation medium, increase method for latent heat accumulation amount of clatherating hydrate and treatment apparatus for increasing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a clatherating hydrate with a large heat accumulation density capable of retaining sufficient flowability even when it is used as a heat transportation medium in the clatherating hydrate having a latent heat accumulation performance making a quaternary ammonium compound as a guest, to provide a manufacturing method for the clatherating hydrate, and to provide a manufacturing apparatus for the clatherating hydrate. <P>SOLUTION: The manufacturing apparatus for the clatherating hydrate is provided with a gas feeding means for feeding a gas to an aqueous solution containing the quaternary ammonium compound, and a cooling means for cooling the aqueous solution. In the apparatus, by feeding the gas to the aqueous solution by the gas feeding means in the cooling process by the cooling means, the clatherating hydrate with the enhanced heat accumulation performance is manufactured making both the quaternary ammonium compound and the gas as the guests. <P>COPYRIGHT: (C)2008,JPO&INPIT

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 enhanced latent heat storage effect, a method for manufacturing such a clathrate hydrate, and a manufacturing apparatus. 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 “inclusion 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-mentioned problems, the inventors have (1) inclusion with the quaternary ammonium compound produced by cooling while blowing a gas into an aqueous solution of the quaternary ammonium compound as a guest. When the amount of stored heat is measured by collecting a hydrate, (1a) the amount of stored heat increases compared to when no gas is blown in, and (1b) not only the amount of stored heat increases but also the melting point changes, (2) When the clathrate hydrate produced by the operation of (1) is melted, the same kind of gas as that blown during the production is released. (3) The clathrate hydrate produced by the operation of (1) is melted. Then, even if the operation of (1) is repeated to produce clathrate hydrate, each phenomenon of (1a), (1b) and (2) can be confirmed. Furthermore, (4) above ((1a ), (1b) and (2) The degree of which depends on the type of gas, to obtain a new finding that.

  Regarding these phenomena, the clathrate hydrate produced by cooling with or after blowing an appropriate gas into an aqueous solution of a quaternary ammonium compound is (a) clathrate water containing a quaternary ammonium compound as a guest. A clathrate hydrate formed by incorporating a suitable gas into the interior, and (a) a clathrate hydrate formed by clathrating the suitable gas as a guest molecule together with the quaternary ammonium compound (C) It can be explained consistently by considering that it is at least one of a mixture of clathrate hydrate containing a quaternary ammonium compound as a guest and clathrate hydrate containing a suitable gas as a guest. it can.

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

  The clathrate hydrate according to the first embodiment of the present invention is a clathrate hydrate having a quaternary ammonium compound as a guest and having latent heat storage performance, and further clathrates a gas supplied from the outside as a guest. Thus, the latent heat storage performance is enhanced.

  The clathrate hydrate according to the second embodiment of the present invention is a clathrate hydrate having latent heat storage performance, and is supplied from the outside or while supplying a gas to an aqueous solution containing a quaternary ammonium compound. After mixing the gas, both the quaternary ammonium compound produced by cooling the gas and the gas are used as guests.

The latent heat storage medium according to the third aspect of the present invention includes the clathrate hydrate according to the first or second aspect as a composition.
The latent heat storage medium according to the fourth aspect of the present invention is a latent heat generated by cooling an aqueous solution containing a quaternary ammonium compound while supplying the gas from outside or mixing the gas supplied from outside. The clathrate hydrate having heat storage performance is included as a composition.

The clathrate hydrate production method according to the fifth aspect of the present invention is a clathrate hydrate production method having latent heat storage performance, which supplies gas from the outside to an aqueous solution containing a quaternary ammonium compound. Then, after mixing the gas supplied from the outside, the step of improving the latent heat storage performance by cooling the aqueous solution.
The clathrate hydrate production method according to the sixth aspect of the present invention is the clathrate hydrate production method according to the fifth aspect, wherein the gas supplied from the outside is for deoxidation of the aqueous solution. It is a gas.

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

  The method for increasing the latent heat storage amount of clathrate hydrate according to the eighth embodiment 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 supplying the gas from the outside to the aqueous solution containing the ammonium compound or mixing the gas supplied from the outside, it has a step of cooling it.

  The method for increasing the amount of latent heat storage of clathrate hydrate according to the ninth aspect of the present invention is a method for increasing the amount of latent heat storage of clathrate hydrate according to the eighth embodiment, wherein the gas supplied from the outside Is a gas for deoxidation of the aqueous solution.

  The clathrate hydrate production apparatus according to the tenth aspect of the present invention is a clathrate hydrate production apparatus having latent heat storage performance, and supplies and mixes gas into an aqueous solution containing a quaternary ammonium compound. And a generator that cools the aqueous solution mixed with the gas to produce the clathrate hydrate with improved heat storage performance.

  The clathrate hydrate production apparatus according to the eleventh aspect of the present invention is the clathrate hydrate production apparatus according to the tenth aspect, and the residue that did not contribute to the generation of clathrate hydrate And a separator for separating the gas.

  The clathrate hydrate production apparatus according to the twelfth aspect of the present invention is a clathrate hydrate production apparatus having latent heat storage performance, and supplies gas to an aqueous solution containing a quaternary ammonium compound. And a clathrate hydrate having improved heat storage performance by supplying the gas to the aqueous solution by the gas supply means in the course of cooling by the cooling means. To manufacture.

  The processing apparatus which increases the latent heat storage amount of the clathrate hydrate which concerns on the 13th form of this invention is a processing apparatus which increases the latent heat storage amount of the clathrate hydrate which uses a quaternary ammonium compound as a guest, A mixer for supplying and mixing a gas to an aqueous solution containing a quaternary ammonium compound; and a generator for generating the clathrate hydrate by cooling the aqueous solution mixed with the gas. .

  The processing apparatus which increases the latent heat storage amount of the clathrate hydrate which concerns on the 14th form of this invention is a processing apparatus which increases the latent heat storage amount of the clathrate hydrate which uses a quaternary ammonium compound as a guest, A gas supply means for supplying a gas to the aqueous solution containing a quaternary ammonium compound; and a cooling means for cooling the aqueous solution, wherein the gas is supplied to the aqueous solution by the gas supply means in the course of cooling by the cooling means. Is.

In addition, based on matter (1) thru | or (6) hung up below, this invention shall be understood and interpreted and the technical scope shall be demarcated.
(1) Typical examples of the quaternary ammonium compound in the present invention include tetra n-butyl ammonium salt, tetraiso amyl ammonium salt, tri-n-butyl pentyl ammonium salt and the like.

(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) In the present invention, the supply of gas to an aqueous solution containing a quaternary ammonium compound (hereinafter simply referred to as an aqueous solution) is relative, and of course, when the gas is released toward the aqueous solution, the aqueous solution is directed toward the gas. This is also the case when releasing. A typical example of the former is bubbling of gas from outside the region to the region where the aqueous solution exists. In that case, the smaller the bubble particle size, the better. A typical example of the latter is spraying of an aqueous solution from outside the region to the region where the gas exists. In any case, it is preferable to supply the gas to the aqueous solution by a technique for further increasing the contact area between the gas and the aqueous solution.

(4) The present invention is a new production in which the technical matter of supplying gas to the aqueous solution from the outside is added to the conventional production method of clathrate hydrate in which an aqueous solution containing a quaternary ammonium compound is cooled. This is a technical idea based on the technique, and therefore there is a technical feature in supplying gas from the outside.
However, in the present invention, the gas to be supplied from outside does not include hydrogen or helium. In clathrate hydrates produced by cooling a small molecule gas such as hydrogen or helium supplied to an aqueous solution containing a quaternary ammonium compound from outside or from outside and mixing, the latent heat storage amount There was no increase (this may be related to the fact that no gas clathrate hydrate is produced from the small molecule gas, but this is not known at this time).
On the other hand, in the present invention, the gas to be supplied from the outside is incorporated in an inclusion compound containing a quaternary ammonium compound as a guest, or is included in water molecules together with the quaternary ammonium compound to form an inclusion hydrate. What can be an element, specifically air, nitrogen, oxygen, carbon dioxide, argon, krypton, xenon, hydrogen sulfide, methane, ethane, propylene, trimethylene oxide, propane, butane, various chlorofluorocarbons, and larger than hydrogen and helium Molecular gases are included (these are molecules of a size that has the effect of increasing the size of some or all of the inclusion lattice of the inclusion hydrate or the effect of increasing the hydration number of the inclusion hydrate. It is estimated that this is a gas, but it is not certain at this time).
Therefore, although the technical feature of the present invention is that the gas is supplied from the outside, the gas is a gas of a molecule larger than hydrogen or helium, and the inclusion compound having a quaternary ammonium compound as a guest. Or can be organized as a constituent element of clathrate hydrate by inclusion in water molecules together with quaternary ammonium compounds.

(5) 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, normal pressure is more preferable when paying attention to the cost of equipment and operation.

  (6) In the manufacturing apparatus according to the eighth to tenth 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.

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 1st and 2nd form of this invention, the clathrate hydrate which has the latent heat storage performance higher than what does not take in the gas supplied from the outside or does not clathrate the said gas is implement | achieved. Can do.
According to the 3rd and 4th 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 5th form of this invention, the clathrate hydrate which has the latent heat storage performance higher than the thing which does not take in the gas supplied from the outside or does not clathrate the said gas can be manufactured.

According to the sixth aspect of the present invention, a deoxygenation treatment is performed by supplying a deoxidation gas (for example, nitrogen gas) to an aqueous solution containing a quaternary ammonium compound, or higher from the applied aqueous solution. An clathrate hydrate having latent heat storage performance or latent heat storage effect can be produced.
This is particularly beneficial when the clathrate hydrate particles are dispersed in an aqueous solution to form a slurry and the slurry is used as a latent heat storage medium. That is, when the slurry is in contact with an inner surface material such as a container or pipe, and when it is necessary to reduce or reduce the amount of dissolved oxygen in the slurry to prevent or suppress corrosion or deterioration of the inner surface material, If deoxidation gas is supplied to the aqueous solution corresponding to the stock solution and subjected to deoxidation treatment, the amount of corrosion inhibitor input can be reduced or the addition of corrosion inhibitor can be made unnecessary, and the latent heat storage amount of the slurry can be increased. Can play the effect of two birds with one stone.

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

  According to the 8th form of this invention, the latent heat storage amount of the clathrate hydrate which uses the said quaternary ammonium compound produced | generated by cooling the aqueous solution containing a quaternary ammonium compound as a guest can be increased.

  According to the ninth aspect of the present invention, the latent heat storage amount of the clathrate hydrate using the quaternary ammonium compound produced by cooling the aqueous solution containing the quaternary ammonium compound as the guest is deoxygenated with respect to the aqueous solution. It can be increased along with the processing. This is particularly beneficial when clathrate hydrate particles are dispersed in an aqueous solution to form a slurry, and this slurry is used as a latent heat storage medium for the same reason as in the sixth embodiment of the present invention. is there.

  According to the tenth aspect of the present invention, the step of cooling the aqueous solution after mixing the gas supplied from the outside with the aqueous solution containing the quaternary ammonium compound can be embodied in the form of an apparatus, and more heat storage An apparatus for producing clathrate hydrate with improved performance can be realized.

  According to the 11th form of this invention, the manufacturing apparatus of the clathrate hydrate which can isolate | separate the residual gas which did not contribute to the production | generation of the clathrate hydrate with which heat storage performance was improved more is implement | achieved. be able to. The separated residual gas can be reused for the production of clathrate hydrate or for other purposes.

  According to the twelfth aspect of the present invention, the process of cooling the aqueous solution while supplying gas from the outside to 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 thirteenth aspect of the present invention, the process of mixing the gas supplied from the outside with the aqueous solution containing the quaternary ammonium compound and then cooling the aqueous solution can be embodied in the form of an apparatus. A processing apparatus that increases the latent heat storage amount of the hydrate can be realized.

  According to the fourteenth aspect of the present invention, the process of cooling the aqueous solution while supplying gas from the outside to 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. .

Experimental results for confirming the effects of the present invention will be described, and then specific embodiments will be described.
The experiment uses tetra-n-butylammonium bromide (TBAB) as the quaternary ammonium compound, and in the formation process of the hydrate slurry, there are two cases, when no gas is blown and when gas is blown. The heat storage amount and melting point of the prepared hydrate slurries were compared.

The contents of the experiment are as follows.
Under normal pressure, put TBAB aqueous solution (14.4wt%) into a glass beaker, blow the gas (air, nitrogen, carbon dioxide) into the glass beaker through a bubbler, immerse the glass beaker in 0 ℃ cooling liquid and cool the gas A TBAB hydrate containing was produced to produce a hydrate slurry. During the cooling, stirring inside the beaker was continued.
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. Further, the “melting point” at which the solid hydrate in the hydrate slurry was completely dissolved was measured.
The measurement results are shown in Table 1 below. Note that Table 1 shows the heat increase ratio calculated by setting the case where no gas is blown to 1 as the increase ratio of the heat storage amount by blowing the gas.

  As shown in Table 1, it was confirmed that about 20% of the heat could be increased by blowing air or nitrogen, and about 40% of the heat could be increased by blowing carbon dioxide.

Next, the amount of heat storage and the melting point of the hydrate slurry produced were measured by changing the concentration of the TBAB aqueous solution in the same manner as the above experimental procedure.
The measurement results when the concentration of the TBAB aqueous solution is 8 wt% are shown in Table 2 below. The amount of heat storage was measured in a temperature range of 5 ° C to 8 ° C.

  As shown in Table 2, it was confirmed that about 10% of the heat could be increased by blowing air, and about 30% of the heat could be increased by blowing carbon dioxide.

  Next, the measurement results when the concentration of the TBAB aqueous solution is 25 wt% are shown in Table 3 below. The amount of heat storage was measured in a temperature range of 9 ° C to 12 ° C.

  As shown in Table 3, it was confirmed that about 10% of the heat could be increased by blowing air, and about 60% of the heat could be increased by blowing carbon dioxide.

Moreover, when the fluidity | liquidity of the hydrate slurry manufactured by blowing in gas was compared with the thing in the case of not blowing in gas, it turned out that there is no difference. It was confirmed that there was no change in the fluidity of the hydrate slurry as a heat transporting medium even when gas was blown in.
Furthermore, regarding the agglomeration property of the hydrate particles, it was also confirmed that the agglomeration property of the hydrate produced by blowing gas was slightly smaller than that obtained when no gas was blown.
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 the blown gas.

  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 tetra n butyl ammonium salt, tetra isoamyl ammonium salt, tri n butyl pentyl ammonium salt and the like.

Using tri-n-butyl-pentylammonium bromide (TBPAB) as the tri-n-butyl-pentylammonium salt, the increase in the amount of heat storage due to blowing gas was measured. Instead of TBAB aqueous solution, TBPAB aqueous solution was used, and the heat storage amount and melting point of the hydrate slurry produced were measured in the same manner as the above experimental procedure. The measurement results when the concentration of the TBPAB aqueous solution is 17 wt% are shown in Table 4 below.
The amount of heat storage was measured in a temperature range of 5 ° C to 8 ° C.

  As shown in Table 4, it was confirmed that the heat could be increased by about 10% as compared with the case where the air was not blown.

As shown in the above experimental example, hydrated quaternary ammonium compounds by cooling with a gas blown into a tetra-n-butylammonium bromide (TBAB) aqueous solution or tri-n-butyl-pentylammonium bromide (TBPAB) aqueous solution. It was confirmed that by generating the slurry, heat can be increased as compared with the case where no gas was blown, and this proved useful.
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. A mixer 5 that receives and supplies gas to the aqueous solution and mixes, and an aqueous solution containing the quaternary ammonium compound and gas mixed in the mixer 5 is cooled to contain the gas and the quaternary ammonium compound as a guest. A generator 9 for generating an clathrate hydrate; and a separator 11 that receives the clathrate hydrate and the unreacted gas from the generator 9 and separates the unreacted gas. Yes.
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 the pump 3 and supplied to the mixer 5.

<Mixer>
The mixer 5 supplies and mixes gas to the aqueous solution containing the quaternary ammonium compound. After the gas is mixed with the aqueous solution containing the quaternary ammonium compound by the mixer 5, the mixed fluid is sent to the generator 9 by the pump 7.
One aspect of the mixer 5 is that the mixer 5 comprises a tank filled with an aqueous solution and the gas is dispersed in the aqueous solution as fine bubbles. In this case, it is preferable that the bubble diameter is small so that the gas-liquid contact area can be increased.
As another aspect of the mixer 5, an aqueous solution may be sprayed by a spray nozzle in a gas-filled container and brought into contact with the gas to dissolve the gas in the aqueous solution.
The aqueous solution and the gas may be mixed by omitting the mixer 5 and supplying the gas to the aqueous solution in the generator 9.

<Generator>
The generator 9 has a cooling function, and cools the aqueous solution containing the quaternary ammonium compound and gas mixed in the mixer 5 to generate clathrate hydrate containing the gas and the quaternary ammonium compound as a guest. The generator 9 is preferably provided with a stirring mechanism.
The clathrate hydrate is produced and stirred in the generator 9 to produce a hydrate slurry in which the clathrate hydrate particles are dispersed in the aqueous solution.
In the generator 9, unreacted gas is present together with the above clathrate hydrate.

<Separator>
The separator 11 receives the clathrate hydrate and the unreacted gas from the generator 9 and separates the unreacted gas.
The type of the separator 11 is arbitrary, and for example, a cyclone separator or the like can be used. However, in order to minimize slurry droplet mixing 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 11 is returned to the gas tank 13 and sent again to the mixer 5 by the pump 15 to be mixed with the aqueous solution. However, when the gas is inexpensive and does not affect the environment, for example, air, the gas may be diffused without being circulated.

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 the pump 3 and supplied to the mixer 5. In the mixer 5, gas is supplied from the gas tank 13 to the supplied aqueous solution to mix the aqueous solution and the gas, and the gas is dissolved in the aqueous solution. The aqueous solution containing the quaternary ammonium compound and gas mixed in the mixer 5 is supplied to the generator 9 by the pump 7. In the generator 9, the supplied aqueous solution is cooled to generate a clathrate hydrate containing a gas and a quaternary ammonium compound as a guest, and the clathrate hydrate particles are obtained by stirring in the generator 9. A hydrate slurry is produced in which is dispersed in an aqueous solution. The hydrate slurry and unreacted gas generated in the generator 9 are supplied to the separator 11, 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 11 is returned to the gas tank 13 and supplied to the mixer 5 again for use.

  The clathrate hydrate containing the gas stored in the heat storage tank 1 and the quaternary ammonium compound as a guest has an increased amount of heat storage compared to the case where no gas is contained, as shown in the above experimental results. Yes. Thus, according to the present embodiment, a hydrate slurry having a large heat storage amount can be generated with a simple device.

  In addition, by cooling in advance the gas to be dispersed and mixed in the aqueous solution in the mixer 5, it is possible to help cool the aqueous solution in the generator 9 and efficiently generate hydrate.

  In the above example, the gas and the aqueous solution are mixed by the separately provided mixer 5, but the gas may be dispersed and mixed in the aqueous solution in the generator 9 without providing the mixer 5.

[Embodiment 2]
FIG. 2 is an explanatory diagram of the cooling air-conditioning equipment according to Embodiment 2 of the present invention.
The cooling air-conditioning equipment of the present embodiment includes the clathrate hydrate production apparatus of the first embodiment, and uses clathrate hydrate slurry generated by the production apparatus as a heat transport medium. 2, the same parts as those in FIG. 1 are denoted by the same reference numerals.

  In addition to the configuration of the clathrate hydrate manufacturing apparatus according to the first embodiment, the air conditioning system according to the present embodiment receives the clathrate hydrate slurry stored in the heat storage tank 1 and cools the room. And a second separator 19 that separates gas and liquid in the hydrate slurry that has been cold-utilized by the cold-heat utilization device 17.

In the cooling air-conditioning equipment configured as described above, for example, the aqueous solution in the heat storage tank 1 is extracted and supplied to the mixer 5 at night, and a hydrate slurry is generated by the generator 9 so that the cooling operation can be performed during the daytime. A hydrate slurry is stored in the heat storage tank 1 as a heat transport medium to be used.
During the daytime cooling operation, the hydrate slurry in the heat storage tank 1 is flowed by the pump 21 to the indoor air conditioner as a heat transport medium. 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 19.
The mixed fluid returned to the second separator 19 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 mixer 5. Further, the gas separated by the second separator 19 is stored in the gas tank 13 and then sent to the mixer 5 and mixed with 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. Further, since the gas supplied from the gas tank 13 can be circulated and used, the cost can be reduced when the gas is expensive. Further, even if the gas affects the environment, it does not affect the environment because it is not released to the outside.

Note that when the gas supplied from the gas tank 13 is an inexpensive gas that does not affect the environment, such as air, the gas may be diffused without being circulated.
Further, the hydrate slurry generated by the generator 9 without providing the heat storage tank 1 may be supplied to the cold energy utilization device 17. In this case, it is preferable to increase the capacity of the mixer 5.

  Further, in the above embodiment, the aqueous solution and the gas are mixed in the mixer 5 and cooled by the generator 9. However, by using a liquid refrigerant instead of the gas supplied to the mixer 5, the liquid refrigerant May be mixed with an aqueous solution to cool the aqueous solution with the heat of evaporation of the liquid refrigerant and to generate a hydrate containing vaporized gas.

  Specifically: An aqueous solution and condensed liquid refrigerant are supplied to the mixer 5 and mixed. The pressure of the mixed liquid is reduced to a pressure at which the liquid refrigerant evaporates at a temperature equal to or lower than the temperature at which the clathrate hydrate is generated by a pressure reducing valve provided in the middle of the pipe for sending the mixed liquid to the generator 9. As a result, the liquid refrigerant is vaporized and the aqueous solution is cooled by heat of evaporation, and a hydrate containing the gaseous refrigerant and the quaternary ammonium compound as a guest is generated.

Thus, the following effect is acquired by directly cooling aqueous solution using refrigerant | coolant gas as gas which increases heat storage amount.
When the refrigerant condensate is depressurized, its periphery is surrounded by an aqueous solution, and the direct effect of cooling (temperature decrease) due to vaporization of the refrigerant condensate accompanying the depressurization mainly affects the aqueous solution present around the condensate. . For this reason, solid surfaces such as pipes and container walls are not cooled to such an extent that they contribute to hydrate formation, and the cooling effect is effective directly and effectively for hydrate formation and hydrate formation is effective. To be done. 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 said embodiment, although the clathrate hydrate containing a gas and a quaternary ammonium compound as a guest was demonstrated for the use as a thermal storage agent, the heat storage amount increase effect was demonstrated, gas and a quaternary ammonium compound were used. The clathrate hydrate contained 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. It is explanatory drawing of the air conditioning equipment which concerns on one embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Heat storage tank 5 Mixer 9 Generator 11 Separator 17 Cold utilization apparatus 19 2nd separator

Claims (13)

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 a gas supplied from the outside as a guest. Hydrate. Both the quaternary ammonium compound and the gas produced by cooling the gas supplied from outside or mixed with the gas supplied to the aqueous solution containing the quaternary ammonium compound are used as guests. Clathrate hydrate having latent heat storage performance characterized by A latent heat storage medium comprising the clathrate hydrate according to claim 1 or 2 as a composition. A clathrate hydrate produced by cooling a gas supplied from the outside or mixed with an externally supplied aqueous solution containing a quaternary ammonium compound and then cooled to increase the latent heat storage performance as a composition. A latent heat storage medium comprising: A method for producing clathrate hydrate having latent heat storage performance,
Inclusion water comprising the step of enhancing the latent heat storage performance by cooling the aqueous solution while supplying the gas from the outside or mixing the gas supplied from the outside to the aqueous solution containing a quaternary ammonium compound Japanese manufacturing method. The said gas is the gas for deoxidation of the said aqueous solution, The manufacturing method of the clathrate hydrate of Claim 5 characterized by the above-mentioned. A latent heat storage medium comprising a clathrate hydrate produced by the production method according to claim 5 or 6 as a composition. A method for increasing the latent heat storage amount of clathrate hydrate using a quaternary ammonium compound as a guest,
The aqueous solution containing the quaternary ammonium compound has a step of cooling the gas supplied from the outside or after mixing the gas supplied from the outside and then cooling the latent heat storage amount of clathrate hydrate Increase method. The method for increasing a latent heat storage amount of clathrate hydrate according to claim 8, wherein the gas is a gas for deoxidizing the aqueous solution. An apparatus for producing clathrate hydrate having latent heat storage performance,
A mixer for supplying and mixing a gas to an aqueous solution containing a quaternary ammonium compound; a generator for cooling the aqueous solution mixed with the gas to produce an clathrate hydrate having an improved heat storage performance; An apparatus for producing clathrate hydrate, comprising: An apparatus for producing clathrate hydrate having latent heat storage performance,
A gas supply means for supplying a gas to the aqueous solution containing a quaternary ammonium compound; and a cooling means for cooling the aqueous solution. The gas supply means supplies the gas to the aqueous solution in the course of cooling by the cooling means. The clathrate hydrate manufacturing apparatus characterized in that the clathrate hydrate with improved heat storage performance is manufactured. A treatment apparatus for increasing the latent heat storage amount of clathrate hydrate containing a quaternary ammonium compound as a guest, wherein the gas is mixed with a mixer for supplying and mixing a gas to an aqueous solution containing a quaternary ammonium compound And a generator for cooling the aqueous solution to produce the clathrate hydrate. A treatment apparatus for increasing the latent heat storage amount of clathrate hydrate containing a quaternary ammonium compound as a guest, a gas supply means for supplying a gas to an aqueous solution containing the quaternary ammonium compound, and a cooling means for cooling the aqueous solution And the gas supply means supplies the gas to the aqueous solution in the course of cooling by the cooling means.

Images