JP2009056344A - Manufacturing method and device of clathrate hydrate slurry, supercooling release method and device, device equipped with pooling tub, and method of increasing abundance ratio of clathrate hydrate and device for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide techniques which enable the elimination or suppression of problems resulting from manufacturing techniques of a clathrate hydrate slurry putting a liquid phase fluid bed type heat exchanger into practice, and a supercooling of a raw material solution or raw material slurry, and can manufacture the clathrate hydrate slurry stably for a long period. <P>SOLUTION: The invention is the manufacturing method of the clathrate hydrate slurry in which the clathrate hydrate is dispersed or suspended in an aqueous solution of the guest compound. The method comprises the heat exchanging process in which the heat exchange of the aqueous solution or the clathrate hydrate slurry with a cooling medium is carried out through a heat transfer surface arranged in an area of the fluid bed in which the aqueous solution or the clathrate hydrate slurry circulates. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a clathrate hydrate slurry manufacturing technique using a liquid phase fluidized bed, and more specifically, a clathrate hydrate slurry manufacturing technique using a heat exchanger to which a liquid phase fluidized bed is applied, a liquid phase fluidization. In a supercooling release technology of a raw material solution applying a bed, a clathrate hydrate slurry manufacturing apparatus applying a liquid phase fluidized bed or an apparatus comprising a storage tank containing a supercooling release device, and a clathrate hydrate slurry The present invention relates to a technique for increasing the abundance ratio of clathrate hydrate.

In the present invention, the meaning or interpretation of the following terms is as follows. The meaning or interpretation of this term does not preclude the technical scope of the present invention from reaching an equivalent scope.
(1) “Liquid phase fluidized bed” means that a specific region in a container is filled with particles, and the particles are fluidized by flowing the liquid in the region or flowable within a limited range. Refers to the device. The size of the particles to be filled may be, for example, about 1 to several millimeters in diameter or about several millimeters to several tens of millimeters, and is appropriately selected from the viewpoint of use, purpose, and response. In the present invention, the “liquid phase fluidized bed” may be referred to as “liquid phase fluidized bed” or simply “fluidized bed” or “fluidized bed” in context or for convenience.
(2) Other molecules or compounds called guest substances in tunnels, layers, networks, cages, or other structures (inclusion lattices) formed by molecules or compounds called hosts or host substances (ie, host molecules) A substance that is formed by entering (or taking in) a guest molecule is called an inclusion compound. Examples of guest molecules include quaternary ammonium salts typified by alkyl ammonium salts, alkyl phosphonium salts, and alkyl sulfonium salts. Examples of host molecules include water, cyclodextrin, and non-water such as the substance disclosed in Patent Document 9. An inclusion compound in which the host molecule is water is “inclusion hydrate”. The “clathrate hydrate” in the present invention includes quasi clathrate hydrate. The “clathrate hydrate” may be simply referred to as “hydrate” in context or for convenience.
(3) The “clathrate hydrate slurry” refers to a clathrate hydrate that is dispersed or suspended in an aqueous solution or aqueous solvent of the guest compound or guest molecule to form a slurry. Even if there is a small amount of clathrate hydrate (in other words, even if the abundance ratio of clathrate hydrate is low), if it is dispersed or suspended in the aqueous solution or water solvent, Corresponding to “product slurry”. The “clathrate hydrate slurry” may be simply referred to as “hydrate slurry” or “slurry” in context or for convenience.
(4) “Raw material solution” refers to an aqueous solution of a clathrate hydrate guest compound that is a raw material for clathrate hydrate slurry.
(5) “Raw material slurry” refers to an initial clathrate hydrate slurry that is a raw material for clathrate hydrate slurry having a higher abundance ratio of clathrate hydrate.

Since clathrate hydrate has a latent heat storage property, it can be used as a heat storage material (Patent Document 1). Among such clathrate hydrates, if the slurry itself is dispersed or suspended in an aqueous solution or aqueous solvent of a clathrate hydrate guest compound and maintains a latent heat storage property, the slurry itself Can be used as a heat storage material (Patent Document 2).
In order to produce the clathrate hydrate, the aqueous solution of the guest compound may be cooled below the production temperature of the clathrate hydrate through, for example, heat exchange with a refrigerant. If the clathrate hydrate produced by this cooling is dispersed or suspended in the aqueous solution or water solvent, clathrate hydrate slurry is obtained. Even when the aqueous solution is cooled to below the production temperature of clathrate hydrate, clathrate hydrate does not form immediately due to the supercooling phenomenon that the clathrate hydrate is not produced and remains liquid. However, if the supercooling is released and clathrate hydrate is formed, and the clathrate hydrate produced is dispersed or suspended in the aqueous solution or water solvent, it becomes clathrate hydrate slurry. . In any case, an aqueous solution of a clathrate hydrate guest compound, which is a raw material of the clathrate hydrate slurry, corresponds to the raw material solution.

If the guest compound remains as a solute in the liquid phase part of the clathrate hydrate slurry, the clathrate hydrate abundance ratio can be reduced by cooling the clathrate hydrate slurry to a lower temperature. Becomes a higher clathrate hydrate slurry. There may be a case where the liquid phase part locally causes a supercooling phenomenon, but if the supercooling is released, the clathrate hydrate abundance ratio is increased to a clathrate hydrate slurry. Become. In any case, the clathrate hydrate is a slurry obtained by dispersing or suspending the clathrate hydrate in the aqueous solution or water solvent, and the clathrate hydrate abundance ratio of the clathrate hydrate is higher. The raw material corresponds to the raw material slurry.

By cooling the raw material solution or raw material slurry to below the production temperature of clathrate hydrate, and when the supercooling phenomenon occurs in the raw material solution during the cooling, the supercooling is released, Product slurry can be produced. Actually, in order to produce the clathrate hydrate slurry, at least a raw material solution or raw material slurry, a refrigerant for cooling the raw material solution or a raw material slurry, and a heat exchanger that enables heat exchange therebetween are required. As an example of the heat exchanger, a known heat exchanger such as a plate type or a shell and tube type can be employed (see Patent Documents 3 and 4). Moreover, in order to cancel the supercooling that has occurred in the raw material solution, a supercooling canceling means is also required (see Patent Document 5).

On the other hand, the liquid phase fluidized bed has a high thermal conductivity on the heat transfer surface, and it is known that the heat transfer surface is highly resistant to dirt removal and maintenance, and is easy to maintain. Is expected (Non-patent Document 1). As an application example using a heat exchanger using a liquid phase fluidized bed (hereinafter referred to as “liquid phase fluidized bed type heat exchanger”), an example of producing a solid crystalline gas hydrate (Patent Document 6), An example in which the target component contained in the treated water is deposited on the surface of the seed crystal by crystallization and removed and recovered (Patent Document 7), in order to separate the ice adhering to the heat exchange surface of the ice making machine, An example (Patent Document 8) is known in which a softening agent is added to weaken the binding force and then the ice is removed by rubbing or colliding with a hard particle fluidized bed.
Japanese Patent Publication No.57-35224 Japanese Patent No. 3641362 JP 2002-263470 A JP 2004-85008 A Japanese Patent Laid-Open No. 2004-3718 Special Table 2002-540223 JP 2006-122896 A JP-A-3-13750 JP 2005-36197 A Hashizume Kenichi "Liquid Fluidized Bed" Chapter 1, Chapter 8, Chapter 10-12 (Published: IPC, Published Year: 2000)

However, as far as the inventors know, when producing clathrate hydrate slurry by heat exchange between a raw material solution or raw material slurry and a refrigerant, a liquid phase fluidized bed heat exchanger is used as a heat exchanger. In addition, there is no example in which a fluidized bed is applied as a means for eliminating a supercooled state generated in a raw material solution, and there is no example in which a fluidized bed is applied as a means for increasing the abundance ratio of clathrate hydrate in a slurry. .
In addition, in order to produce a clathrate hydrate slurry by heat exchange between a raw material solution or raw material slurry and a refrigerant, it is necessary to provide a heat exchanger or a supercooling release means, or such a hydrate slurry When it is necessary to provide a heat storage device that temporarily accommodates a large amount of clathrate hydrate slurry that is attached to the production device, for example, from the viewpoint of design or maintenance management or from the economical viewpoint, Basically, a simpler or more compact configuration is required, but the conventional idea of providing a heat exchanger and a supercooling release means separately (and additionally providing a heat storage device in addition to them) It is not easy to meet such a request.

  The present invention has been made in view of the above circumstances and problems, and it is possible to apply a solution of a raw material solution by applying a clathrate hydrate slurry manufacturing technique using a liquid phase fluidized bed heat exchanger and a liquid phase fluidized bed. Providing technology to eliminate or suppress the cooling phenomenon and technology to increase the existing ratio of clathrate hydrate in the slurry, and to provide technology that enables stable production of clathrate hydrate slurry over a long period of time The purpose is to do.

  In order to achieve the above object, a method for producing an clathrate hydrate slurry according to the first aspect of the present invention comprises the clathrate hydrate being dispersed or suspended in an aqueous solution or aqueous solvent of the guest compound. A clathrate hydrate slurry comprising the aqueous solution (ie, raw material solution) or the aqueous solvent, or the slurry (ie, raw material slurry) and the heat exchange between the aqueous solution, the aqueous solvent, It has a heat exchange process performed via the heat-transfer surface which contacts at least one part of the fluidized bed which the said slurry distribute | circulates.

  It is sufficient if the heat transfer surface or at least a part thereof is in contact with the fluidized bed or at least a part thereof. Therefore, the heat transfer surface may be disposed in the fluidized bed or may be disposed so as to constitute a wall surface surrounding the fluidized bed. This is not limited to the first embodiment, but can be similarly applied to other embodiments of the present invention having a heat exchanger as a constituent element.

  The clathrate hydrate slurry production apparatus according to the second aspect of the present invention is an clathrate hydrate slurry production apparatus in which clathrate hydrate is dispersed or suspended in an aqueous solution of the guest compound. A fluidized bed in which the aqueous solution (that is, the raw material solution) or the aqueous solvent or the slurry (that is, the raw material slurry) flows; and a heat exchanger that performs heat exchange between the aqueous solution or the aqueous solvent or the slurry and the refrigerant. And at least a part of the heat transfer surface of the heat exchanger is disposed so as to be in contact with at least a part of the fluidized bed.

  The clathrate hydrate slurry manufacturing apparatus according to the third aspect of the present invention includes a clathrate hydrate slurry in which clathrate hydrate is dispersed or suspended in an aqueous solution or aqueous solvent of the guest compound. A first compartment in which a refrigerant flows, a second compartment in which the aqueous solution, the aqueous solvent, or the slurry flows, and a first compartment and a second compartment. A heat transfer surface for partitioning, and the second compartment is arranged such that at least a part of the heat transfer surface is in contact with at least a part of the fluidized bed.

  In addition, a pair of compartments composed of the first compartment and the second compartment may be continuously arranged in parallel, may be arranged in series, or arranged in a mode in which series and parallel are mixed. May be. In addition, a second compartment in the pair of compartments is further provided adjacent to the second compartment (that is, the compartment in which the aqueous solution, the aqueous solvent, or the slurry flows), and the second compartment is provided. May be cooled from both sides.

  The clathrate hydrate slurry production apparatus according to the fourth aspect of the present invention is the production apparatus according to the second or third aspect, wherein the fluidized bed is composed of a plurality of particles. It is what.

The clathrate hydrate slurry production apparatus according to the fifth aspect of the present invention is the production apparatus according to the second or third aspect, wherein the fluidized bed is composed of a plurality of particles and is supplied to the fluidized bed. And a dispersion mechanism for dispersing the flow of the aqueous solution, the aqueous solvent, or the slurry.
The dispersion mechanism may be provided with a fixed bed constituted by particles having a larger particle diameter than the particles constituting the fluidized bed, or may be constituted by providing a number of holes in the header.

  The clathrate hydrate slurry producing apparatus according to the sixth aspect of the present invention is the clathrate hydrate slurry producing apparatus according to the fourth or fifth aspect, wherein at least some of the plurality of particles include the clathrate hydrate. Is at least temporarily attached.

  The clathrate hydrate slurry production apparatus according to the seventh aspect of the present invention is the production apparatus according to any one of the fourth to sixth aspects, wherein at least some of the plurality of particles rub against each other. It is characterized by a collision.

  A supercooling release method according to an eighth aspect of the present invention is a method for releasing supercooling of an aqueous solution of a clathrate hydrate guest compound, wherein the aqueous solution in a supercooled state is at least part of a fluidized bed. It has the process of distribute | circulating to.

  A supercooling release device according to a ninth aspect of the present invention is a device for releasing supercooling of an aqueous solution of a clathrate hydrate guest compound, comprising a fluidized bed, wherein the aqueous solution in a supercooled state is The fluidized bed is configured to circulate at least part of the fluidized bed.

  A supercooling release device according to a tenth aspect of the present invention is the supercooling release device according to the ninth aspect, wherein the fluidized bed is composed of a plurality of particles.

  The supercooling release device according to an eleventh aspect of the present invention is the supercooling release device according to the tenth aspect, wherein the clathrate hydrate adheres at least temporarily to at least some of the plurality of particles. It is characterized by that.

  A supercooling release device according to a twelfth aspect of the present invention is the supercooling release device according to the tenth or eleventh aspect, wherein at least some of the plurality of particles rub or collide with each other. To do.

  The method for increasing the abundance ratio of clathrate hydrate according to the thirteenth aspect of the present invention is the clathrate hydrate in a slurry in which the clathrate hydrate is dispersed or suspended in an aqueous solution of the guest compound. A method of increasing the abundance ratio of the product, comprising the step of circulating the slurry through at least a part of the fluidized bed in which the clathrate hydrate is present after the cooling or in the course of the cooling. It is a feature.

  An apparatus for increasing the abundance ratio of clathrate hydrate according to the fourteenth aspect of the present invention is the clathrate hydrate in a slurry obtained by dispersing or suspending clathrate hydrate in an aqueous solution of the guest compound. An apparatus for increasing an abundance ratio of a substance, comprising a fluidized bed composed of a plurality of particles, and configured to circulate at least a part of the fluidized bed after the aqueous solution is cooled or in the process of being cooled. It is characterized by being.

  An apparatus including a storage tank according to a fifteenth aspect of the present invention is an apparatus including a storage tank that contains an aqueous solution of clathrate hydrate guest compound or an clathrate hydrate slurry, Any of the apparatus for producing clathrate hydrate slurry, the supercooling release apparatus according to any of the ninth to twelfth aspects, and the apparatus for increasing the abundance ratio of clathrate hydrate according to the fourteenth aspect It is characterized by providing. In this case, the clathrate hydrate slurry manufacturing apparatus according to the second aspect of the apparatus including the storage tank may include any of the characteristics of the fourth to seventh aspects. In addition, the storage tank may be a heat storage tank that contains the clathrate hydrate slurry, and in that case, the apparatus including the storage tank may be a heat storage apparatus.

  In any form of the present invention, the clathrate hydrate slurry produced from the raw material solution or the raw material slurry may be refluxed as the raw material slurry and again subjected to heat exchange with the refrigerant.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing technique of the clathrate hydrate slurry using a liquid phase fluidized bed is realizable. When the clathrate hydrate slurry is produced, heat exchange is performed between the raw material solution or the raw material slurry and the refrigerant using a liquid phase fluidized bed heat exchanger. The clathrate hydrate having a lower thermal conductivity than the raw material solution or the raw material slurry is less likely to adhere to the heat transfer surface of the exchanger, and is less likely to be contaminated. Therefore, the heat transfer efficiency of the heat transfer surface of the heat exchanger can be maintained at a high level and maintenance management is facilitated, so that the clathrate hydrate slurry can be stably produced over a long period of time.

  Moreover, according to this invention, the supercooling cancellation | release technique which uses a liquid phase fluidized bed is realizable. Since the raw material solution in the supercooled state is circulated through the liquid phase fluidized bed, the supercooling of the raw material solution can be released. The reason is as follows: (a) Inclusion hydrates are more likely to be generated by the contact, rubbing, collision, etc. of a plurality of particles constituting the fluidized bed. It is easy to produce clathrate hydrate. (C) A new clathrate hydrate produced for the reason of (a) or (b) functions as a nucleus for formation of another clathrate hydrate. It is considered that clathrate hydrate is easily formed, or the clathrate hydrate is less likely to be delayed due to any combination of the above (a) to (c) (hereinafter referred to as this). The reason is called “reason 1”).

  Furthermore, according to the present invention, the abundance ratio of clathrate hydrate in the clathrate hydrate slurry can be effectively increased. When the raw material solution in the supercooled state is passed through the liquid phase fluidized bed, the supercooling is released, so that the inclusion ratio of clathrate hydrate can be increased. In addition, even if the raw material slurry is passed through the liquid phase fluidized bed, the inclusion ratio of clathrate hydrate can be increased. The reason for this is that the raw slurry already contains clathrate hydrate which can be a nucleus for the formation of new clathrate hydrate, so that more clathrate hydrate is more likely to be produced. Even when the raw slurry that already contains the formation nuclei passes through the fluidized bed, more clathrate hydrates are produced due to at least one of the above (a) to (c). This is considered to be easier (hereinafter, this reason is referred to as “reason 2”).

  The supercooling release effect as described above and the effect of increasing the inclusion ratio of clathrate hydrate in the clathrate hydrate slurry do not decrease even when the clathrate hydrate is repeatedly generated and melted. The reason is that even if the clathrate hydrate adheres to the surface of the particles through contact, rubbing, collision, etc. of the particles constituting the fluidized bed, the surface of the particles is restored to the original state. This is presumably because the adhesion between the particles is prevented at the same time, and the fluid state is maintained for a long time. Maintaining these effects for a long time is very beneficial in the technology of stably producing clathrate hydrate slurry over a long period of time.

The effect which each form of this invention has is as follows.
According to the first aspect of the present invention, first, a method for producing a clathrate hydrate slurry using a liquid phase fluidized bed heat exchanger can be realized. In addition, due to the flow of particles that make up the fluidized bed, clathrate hydrate with lower thermal conductivity than the raw material solution or raw material slurry does not adhere to the heat transfer surface of the heat exchanger, and dirt also adheres. The heat transfer efficiency of the heat transfer surface can be maintained at a high level, and maintenance management is facilitated.
Further, the supercooling of the raw material solution is easily released, and the abundance ratio of the clathrate hydrate in the clathrate hydrate slurry is easily increased. The reason can be explained by reason 1 when the raw material solution is circulated through the fluidized bed, and can be explained by reason 2 when the raw material slurry is circulated through the fluidized bed. If the raw material slurry is not homogeneous and there is a portion where supercooling can occur, and this raw material slurry flows through the fluidized bed, it can be explained by reason 1. The reason 2 can be explained when the raw material solution in which the clathrate hydrate has already been generated as a result of the release of the supercooling (which is in a state that can be said to be a raw material slurry) is circulated through the fluidized bed.
Therefore, according to this 1st form, the method which can manufacture the clathrate hydrate slurry stably over a long time is realizable.

According to the second aspect of the present invention, first, a clathrate hydrate slurry production apparatus to which a liquid phase fluidized bed heat exchanger is applied or an apparatus in which the production method according to the first aspect is implemented is realized. be able to.
In this production apparatus, clathrate hydrate having lower thermal conductivity than the raw material solution or raw material slurry does not adhere to the heat transfer surface of the heat exchanger due to the flow of particles constituting the fluidized bed. Also, dirt becomes difficult to adhere, the heat transfer efficiency of the heat transfer surface can be maintained high, and maintenance management becomes easy.
Further, the supercooling of the raw material solution is easily released, and the abundance ratio of the clathrate hydrate in the clathrate hydrate slurry is easily increased. The reason can be explained by reason 1 when the raw material solution flows through the fluidized bed, and can be explained by reason 2 when the raw material slurry flows through the fluidized bed. If the raw material slurry is not homogeneous and there is a portion where supercooling can occur, and this raw material slurry flows through the fluidized bed, it can be explained by reason 1. This can be explained by reason 2 when the raw material solution in which the clathrate hydrate has already been generated as a result of the release of the supercooling (which is in a state of being a raw material slurry) flows through the fluidized bed.
Therefore, according to this 2nd form, the apparatus which can manufacture the clathrate hydrate slurry stably over a long time is realizable.

The apparatus according to the third aspect of the present invention corresponds to a more limited configuration of the apparatus according to the second aspect. In the apparatus according to the third aspect, a fluidized bed that contacts the heat transfer surface is disposed in the second compartment in which the raw material solution or the raw material slurry flows, and when the raw material solution or the raw material slurry flows through the fluidized bed, It is cooled via the heat transfer surface by the refrigerant flowing through the one compartment. Therefore, according to the third embodiment, clathrate hydrate having a lower thermal conductivity than the raw material solution or the raw slurry is formed on the heat transfer surface of the heat exchanger due to the action of the flow of the particles constituting the fluidized bed. It does not adhere, dirt is less likely to adhere, the heat transfer efficiency of the heat transfer surface can be maintained high, and maintenance management is facilitated. The supercooling of the raw material solution is easily released, and the abundance ratio of the clathrate hydrate in the clathrate hydrate slurry is easily increased. The reason can be explained in the same manner as in the second embodiment.
Therefore, according to this 3rd form, the apparatus which can manufacture the clathrate hydrate slurry stably over a long time is realizable.

Moreover, in the apparatus which concerns on a 3rd form, it is heat between the fluid which distribute | circulates to each compartment by using the partition wall which partitions off a pair of adjacent compartments (a 1st compartment and a 2nd compartment) as a heat-transfer surface. A structure similar to that of a so-called plate heat exchanger that performs the exchange is adopted, and by connecting the pair of compartments side by side, the compartment through which the refrigerant circulates and the raw material solution or the raw material slurry are circulated. The separate compartments are alternately adjacent to each other. Therefore, according to the third embodiment, it is possible to ensure a larger heat transfer area and therefore higher heat exchange performance than when other types of heat exchangers are employed.
In addition, although the plate interval of a general plate heat exchanger is quite narrow, the width of the second compartment through which the raw material solution or the raw slurry flows is wide enough to form a fluidized bed. It is. On the other hand, the width of the first compartment through which the refrigerant flows may be narrow like a general plate heat exchanger.

  In the apparatus according to each of the second and third embodiments, the clathrate hydrate is dispersed in the region where the raw material solution or the raw material slurry flows (in the third embodiment, the region mainly constituted by the second compartment). It is normal and preferable that three regions, ie, a suspension region A, a fluidized bed region B, and a fixed bed region C are configured. By configuring the region in this way, in the case of the raw material solution, the flow is dispersed in the fixed bed region C, is supercooled by the heat transfer surface in the fluidized bed region B, and the supercooling is released (this Since the clathrate hydrate is formed at the stage, the raw material solution is considered to be a raw material slurry), and the supercooled released raw material solution is further cooled by the heat transfer surface in the dispersion / suspension region A Therefore, when passing through the region A, the abundance ratio of the clathrate hydrate in the raw material solution or the solid phase ratio of the clathrate hydrate slurry is increased. In the case of a raw slurry, the flow is dispersed in the fixed bed region C, cooled by the heat transfer surface in the fluidized bed region B, and more clathrate hydrate is produced, and the dispersion / suspension region A In addition, when it passes through the region A, the abundance ratio of clathrate hydrate in the raw slurry or the solid phase ratio of the clathrate hydrate slurry is increased. Thus, the amount of clathrate hydrate produced increases, and the solid phase ratio, and hence the heat storage amount or heat storage density, increases.

  According to the fourth aspect of the present invention, since the fluidized bed is composed of a plurality of particles, it is possible to realize a fluidized bed with a lot of contact, rubbing, collision, etc. between particles that trigger the release of supercooling. Therefore, an efficient clathrate hydrate slurry production apparatus can be realized.

  According to the fifth aspect of the present invention, the fluidized bed is composed of a plurality of particles, and the flow of the aqueous solution (ie, raw material solution) or clathrate hydrate slurry (ie, raw material slurry) supplied to the fluidized bed is dispersed. Since the dispersion mechanism is provided, it is possible to suppress or prevent sedimentation of particles constituting the fluidized bed and an increase in pressure loss during the course of the raw material solution or the raw material slurry. In addition, the fluidity of a plurality of particles constituting the fluidized bed, for example, the ease of particle movement, the ease of contact between particles, scratching, collision, etc. that triggers the release of supercooling, It becomes easy to maintain substantially uniform over the entire cross section perpendicular to the flow direction of the slurry.

  According to the sixth aspect of the present invention, since the clathrate hydrate adheres to at least a part of the plurality of particles constituting the fluidized bed, the clathrate hydrate is another clathrate hydrate. The clathrate hydrate slurry can be efficiently produced. Such temporary adhesion is, for example, mixing particles that have been processed so that the clathrate hydrate is easily or easily attached to the surface as a part of the plurality of particles. Can be realized.

  According to the seventh aspect of the present invention, since at least some of the plurality of particles rub or collide with each other, it is easy for clathrate hydrates to be generated triggered by such mechanical impact. A hydrate slurry can be produced efficiently.

  According to the 8th form of this invention, the supercooling cancellation | release method which applied the liquid phase fluidized bed is realizable. As the reason why the supercooling release occurs, the above reason 1 can be considered. In addition, the object which distribute | circulates a fluid bed and cancel | releases supercooling is not restricted to the raw material solution in a supercooled state. When the clathrate hydrate dispersed or suspended in the raw slurry is not homogeneous, and there is a part where the supercooling can occur (part corresponding to the raw material solution), By circulating the raw material slurry through the fluidized bed, the supercooling generated in the part can be released.

  According to each of the ninth to twelfth aspects of the present invention, it is possible to realize a supercooling release apparatus using a liquid phase fluidized bed or an apparatus in which the supercooling release method according to the eighth aspect is implemented.

  In particular, according to the tenth embodiment, since the fluidized bed is composed of a plurality of particles, it is possible to realize a fluidized bed in which there are many contacts, scratches, collisions, etc. between particles that trigger the release of supercooling. Therefore, an efficient supercooling release device can be realized.

  According to the eleventh aspect of the present invention, since the clathrate hydrate adheres to at least a part of the plurality of particles constituting the fluidized bed, the clathrate hydrate is another clathrate hydrate. It can function as a production nucleus of the product, and the clathrate hydrate can be easily generated, and an efficient supercooling release device can be realized. Such temporary adhesion is the same as in the case of the sixth embodiment. For example, the clathrate hydrate tends to adhere to the surface or easily adhere to the surface as a part of the plurality of particles. It can be realized by mixing particles that have been processed into a mixture.

  According to the twelfth aspect of the present invention, since at least some of the plurality of particles rub against each other or collide with each other, it is easy to generate clathrate hydrate triggered by such mechanical impact, and the supercooling Contribute to the release. Therefore, an efficient supercooling release device can be realized.

  According to the thirteenth aspect of the present invention, since the raw slurry is circulated through at least a part of the fluidized bed after cooling or in the course of cooling, more clathrate hydrate is contained in the raw slurry. Can be generated, and such generation can be facilitated. The reason can be explained by reason 2 described above. Therefore, a method for increasing the abundance ratio of clathrate hydrate in the clathrate hydrate slurry can be realized.

  According to the fourteenth aspect of the present invention, an apparatus for increasing the abundance ratio of clathrate hydrate in a clathrate hydrate slurry by applying a liquid phase fluidized bed or a method according to the thirteenth aspect is implemented. An apparatus can be realized.

  According to the fifteenth aspect of the present invention, the clathrate hydrate slurry producing apparatus according to the second aspect is provided in any one of the ninth to twelfth aspects, in the storage tank containing the raw material solution or the raw material slurry. Since either the supercooling release device according to the form or the device for increasing the abundance ratio of the clathrate hydrate according to the fourteenth form is arranged, the effects corresponding to each of these devices are achieved, The space and floor area originally required for laying each device can be reduced, and therefore the overall device scale can be relatively reduced. For example, when the storage tank is a heat storage tank that contains the clathrate hydrate slurry, and the apparatus including the storage tank is a heat storage apparatus, the clathrate hydrate slurry manufacturing apparatus according to the second embodiment Can be comprised in a heat storage tank, and the heat storage apparatus which has the function to manufacture a clathrate hydrate slurry can be comprised. Such a heat storage device can be made smaller as a whole as a whole when considered as equipment required for the production and accumulation of clathrate hydrate slurry. Moreover, when the said storage tank is a heat storage tank which accommodates clathrate hydrate slurry, and the apparatus provided with the said storage tank is a heat storage apparatus, the subcooling cancellation | release apparatus which concerns on any of the 9th thru | or 12th form By disposing in the heat storage tank, a heat storage device having a function of releasing the supercooling of the raw material solution or the raw material slurry can be configured. Further, when the storage tank is a heat storage tank that contains the clathrate hydrate slurry, and the apparatus including the storage tank is a heat storage apparatus, the presence ratio of the clathrate hydrate according to the fourteenth aspect is increased. By disposing the device to be placed in the heat storage tank, a heat storage device having a function of increasing the abundance ratio of clathrate hydrate in the clathrate hydrate slurry can be configured.

  In any form of the present invention, if the clathrate hydrate slurry produced from the raw material solution or the raw slurry is refluxed as the raw slurry and subjected to heat exchange with the refrigerant again, the clathrate hydrate The abundance ratio (solid phase ratio) of the clathrate hydrate constituting the slurry can be increased every time of reflux.

Hereinafter, the present invention will be described in detail by embodiments.
The technical scope of the present invention is not limited by these embodiments, and can be implemented in various forms without changing the gist of the invention. Further, the technical scope of the present invention extends to an equivalent range.

[Embodiment 1]
<Manufacturing device for clathrate hydrate slurry>
FIG. 1 is an explanatory view of an embodiment of a clathrate hydrate slurry manufacturing apparatus according to the present invention.
In this embodiment, the clathrate hydrate slurry production apparatus 1 includes a vertical cylindrical production tank 5 that cools the raw material solution to produce the clathrate hydrate slurry 3. A discharge pipe 7 for discharging the generated clathrate hydrate slurry 3 is connected to the upper end of the generation tank 5, and a supply pipe 9 for supplying a raw material solution is connected to the lower surface of the generation tank 5. A slurry storage tank 11 for storing the generated clathrate hydrate slurry is provided at the downstream end of the discharge pipe 7. A raw material solution storage tank 13 is provided at the upstream end of the supply pipe 9. The supply pipe 9 is provided with a pump 15 for sending the raw material solution to the production tank 5, a valve 17 for adjusting the flow rate, and a flow rate measuring device 19 for measuring the flow rate of the raw material solution.

The generation tank 5 is formed of a transparent vinyl chloride pipe having an inner diameter of 80 mm and a height of about 1 m. Although the production tank 5 is thus formed of a vertical cylindrical shape, it does not necessarily have to be a vertical shape or a cylindrical shape.
The generation tank 5 is preferably formed of a material that is at least partially transparent. By forming at least a part of the generation tank 5 with a transparent body, it is possible to confirm whether or not the liquid in the generation tank 5 is clouded, whereby the clathrate hydrate is dispersed in the aqueous solution of the guest compound. Or it can confirm that it is suspended (it is the clathrate hydrate slurry in this invention).
In the lowermost part (water box portion) of the generation tank 5, the raw material solution supplied to the generation tank 5 is uniformly dispersed (the distribution in the cross section of the generation tank 5 is made uniform) and supplied to the fluidized bed 25 described later. A dispersion mechanism 21 having a function to perform is provided. The dispersion mechanism 21 is made of an alumina ball having a diameter of about 20 mm, for example.

Above the dispersing mechanism 21 is provided an anchoring means 23 for preventing sedimentation of alumina particles constituting the fluidized bed 25 described later. The anchoring means 23 is typically a wire mesh or a perforated plate, and may be an opening that does not allow alumina particles to settle.
Above the mooring means 23, a fluidized bed 25 in which fluidized particles are stacked is formed. Typical fluid particles (fluid medium) forming the fluidized bed 25 are ceramic particles such as alumina, silica and zirconia, and metal particles such as stainless steel and titanium. The optimum material, particle size, and the like are selected according to the type of raw material solution, the flow rate of the raw material solution to be set, the residence time of the clathrate hydrate slurry to be generated, and the like.

The fluidized bed 25 is formed, for example, by filling the production tank 5 with 1 liter of alumina particles having a diameter of about 1 mm.
A heat exchanger 27 is installed in the fluidized bed 25. The heat exchanger 27 has a heat transfer tube in a coil shape, and causes the outer surface of the heat transfer tube to function as a heat transfer surface (heat exchange surface) by circulating a refrigerant therein. The heat exchanger 27 is accompanied by a cooling temperature setting device (not shown) that sets the cooling temperature of the raw material solution by adjusting the flow rate of the refrigerant.
The refrigerant temperature is set to 0 ° C., for example.
The material of the heat transfer tube is typically stainless steel, titanium or the like, but is preferably selected from materials having at least excellent thermal conductivity and wear resistance.

A space for dispersing or suspending clathrate hydrate is provided above the fluidized bed 25. An overflow outlet 29 for discharging the generated clathrate hydrate slurry 3 is provided at the upper end of the generation tank 5, and the aforementioned discharge pipe 7 is connected to the overflow outlet 29. .
The upper end surface of the generation tank 5 may be opened or covered.

As shown in FIG. 1, the production tank 5 configured as described above is composed of three regions: a clathrate hydrate dispersion / suspension region A, a fluidized bed region B, and a fixed bed region C. become.
The clathrate hydrate dispersion / suspension region A is disposed in the production tank 5 on the downstream side of the fluidized bed region B, and is a region for dispersing or suspending the clathrate hydrate.
The fluidized bed region B is a region in which the fluidized bed 25 is disposed in the production tank 5 and is disposed on the downstream side of the fixed bed region C.
The fixed bed region C is a region where the dispersion mechanism 21 is disposed in the generation tank 5. The mooring means 23 and the fixed floor region C may be defined.

Each region A, B, C is provided with at least one temperature measuring device 31 for measuring the temperature of each region A, B, C. By measuring the temperature in each of the areas A, B, and C by the temperature measuring device 31, the operating state of the manufacturing apparatus 1 can be monitored.
The manufacturing apparatus 1 is provided with a temperature adjusting means (not shown) so that the raw material solution can be supplied through the supply pipe 9 at a predetermined temperature (for example, 8 ° C.).

  In this embodiment, the raw material solution storage tank 13 and the slurry storage tank 11 are provided separately. However, the raw material solution or the raw material slurry may be supplied to the manufacturing apparatus 1 by using these as one tank. . That is, the raw material solution storage tank 13 and the slurry storage tank 11 are made into one tank, the clathrate hydrate slurry produced | generated within the manufacturing apparatus 1 is stored in the said one tank, and the package stored in the said one tank is stored. The wet hydrate slurry may be refluxed as a raw material slurry to the production apparatus 1 and used again for heat exchange with the refrigerant. Thereby, the abundance ratio (solid phase ratio) of the clathrate hydrate constituting the clathrate hydrate slurry can be increased every time of reflux.

<Driving method>
Next, an operation method of the clathrate hydrate slurry production apparatus will be described.
(1) A raw material solution having a predetermined concentration is stored in the raw material solution storage tank 13 in advance.
(2) The pump 15 is started and the flow rate is measured by the flow rate measuring device 19. Based on this measured value, the flow rate of the raw material solution is a predetermined flow rate, for example, 13.5 L / min (in the height direction of the generation tank 5). The raw material solution is supplied to the production tank 5 by controlling the valve 17 so as to be equivalent to a flow rate of 4.5 cm per second.
(3) After confirming that the alumina particles are visually observed from the outside, that is, that the fluidized bed is formed, the refrigerant starts to flow through the heat exchanger 27, and the refrigerant temperature is set by the cooling temperature setting device. Is set to 0 ° C., and a 0 ° C. refrigerant is circulated through the heat exchanger 27.
(4) In the fluidized bed region B, the raw material solution is cooled by the heat exchanger 27 to produce an clathrate hydrate to produce a clathrate hydrate slurry, and then the clathrate hydrate slurry 3 produced Is recovered in the slurry storage tank 11.
In addition, the clathrate hydrate slurry may be produced by storing the raw material slurry in the raw material solution storage tank 13 instead of the raw material solution and supplying it to the generation tank 5.

<Effect confirmation>
Next, effects produced by the implementation of the above operation method will be described in comparison with a comparative example.
(I) Comparative Example 1
The above operation method was carried out with the alumina particles having a diameter of about 1 mm and the alumina particles having a diameter of about 20 mm removed from the production apparatus 1 from the fluidized bed region B and the fixed bed region C, respectively.
While an 11 wt% aqueous solution of tetra n-butylammonium bromide (TBAB) at 8 ° C. (measured value of the temperature measuring device 31c) was flowed from the bottom of the production tank 5 at a flow rate of 13.5 L / min, The aqueous solution was cooled by flowing a coolant set at ° C. At the time when the measured value of the temperature measuring device 31b in the region where the heat exchanger 27 is provided is lowered to 3 ° C., the liquid flowing through the discharge pipe 7 is not cloudy and the formation of clathrate hydrate slurry is not confirmed. It was. Moreover, the measured value of the temperature measuring device 31a was also about 3.5 degreeC.

(Ii) Comparative Example 2
The above operation method was carried out in the state where the fixed bed region C of the production apparatus 1 was filled with alumina particles having a diameter of about 20 mm and the other conditions were the same as those in Comparative Example 1. However, the liquid flowing through the discharge pipe 7 was not clouded, and the formation of clathrate hydrate slurry was not confirmed. Moreover, the measured value of the temperature measuring device 31a was also about 3.5 degreeC.

(Iii) In the cases of (i) and (ii) above, the liquid stored in the slurry storage tank 11 became cloudy with the passage of time, and production of clathrate hydrate slurry was confirmed. Moreover, when the raw material solution in which the production | generation of the clathrate hydrate slurry accommodated in the slurry storage tank 11 was not confirmed was supplied again to the manufacturing apparatus 1, the liquid which flows through the discharge pipe 7 will become cloudy, and clathrate Formation of a hydrate slurry was confirmed. These phenomena are presumed to be caused by the fact that the raw material solution was supercooled by the heat exchanger 27 and the supercooling was canceled due to the passage of time or mechanical shock (such as passing through the pump 15 during reflux).
In any case, in Comparative Example 1 and Comparative Example 2, the generation of clathrate hydrate slurry was not confirmed at the time of discharge from the generation tank 5.

(Iv) Example 1
On the other hand, the fluidized bed region B and the fixed bed region C of the production apparatus 1 were filled with alumina particles having a diameter of about 1 mm and alumina particles having a diameter of about 20 mm, respectively, and other conditions were compared with those in Comparative Example 1 ((i The above operation method was carried out in the same manner as)).
First, when an 11 wt% TBAB solution at 8 ° C. (measured value of the temperature measuring device 31c) was flowed from the bottom at a flow rate of 13.5 L / min, the height of the packed bed of alumina particles in the fluidized bed region B was about 1.5. It was confirmed by visual observation that a fluidized bed of alumina particles was formed by expanding to about twice.
Subsequently, when the TBAB aqueous solution was cooled by flowing a refrigerant set at 0 ° C. through the heat exchanger 27, the measured value of the temperature measuring device 31b provided in the fluidized bed region B dropped to 4 ° C., and then 5 The temperature rose to 0 ° C., and the liquid flowing through the discharge pipe 7 became cloudy, confirming the formation of clathrate hydrate slurry. This phenomenon is caused by the fact that the raw material solution flows through the liquid phase fluidized bed in the fluidized bed region B, so that the supercooling of the raw material solution is released, and further, the clathrate hydrate generated by the release of the supercooling is at least In the dispersion / suspension area A, it is dispersed or suspended in the raw material solution to form an clathrate hydrate slurry.

In addition, when the clathrate hydrate slurry stored in the slurry storage tank 11 is refluxed and supplied again to the production apparatus 1 as a raw slurry, the inclusion ratio of the clathrate hydrate in the raw slurry (solid phase ratio) ) Is not too high, the fluidized state of the alumina particles in the fluidized bed region B is maintained, and it is confirmed that the white turbidity of the raw slurry passing through the fluidized bed region B is increased, and the solid phase ratio is increased. Was confirmed.
As described above, it is possible to produce clathrate hydrate slurry by promoting heat exchange and cooling of the raw material solution in the fluidized bed region using the production apparatus 1, and to promote the supercooling release of the raw material solution or the raw material slurry. And the presence ratio of clathrate hydrate in the clathrate hydrate slurry was found to increase.

[Embodiment 2]
<Manufacturing device for clathrate hydrate slurry (plate heat exchanger)>
FIG. 2 is an explanatory view of another embodiment of the clathrate hydrate slurry manufacturing apparatus according to the present invention.
In this embodiment, the clathrate hydrate slurry manufacturing apparatus 101 includes a heat exchanger that employs a structure similar to a so-called plate heat exchanger.

The manufacturing apparatus 101 includes nine substantially rectangular parallelepiped compartments partitioned by a heat transfer surface 107. These compartments are configured such that a raw material compartment 105 through which a raw material solution or a raw material slurry flows and a refrigerant compartment 103 through which a refrigerant flows are alternately arranged. That is, the raw material compartment 105 and the refrigerant compartment 103 are alternately arranged adjacent to each other via the heat transfer surface 107, and the raw material solution or raw material slurry and the refrigerant exchange heat. A fluidized bed 125 is formed by fluidizing particles by putting fluidized particles in the material compartment 105 and circulating a material solution or material slurry.
The refrigerant compartment 103 and the raw material compartment 105 respectively correspond to the first compartment and the second compartment in the manufacturing apparatus according to the third embodiment of the present invention.

A connecting pipe 108c communicating with each raw material compartment 105 is provided at the lower part of each raw material compartment 105, and the connecting pipe 108c is connected to the raw material solution supply pipe 108 via a raw material solution supply header 105h.
At the upper part of each raw material compartment 105, a communication pipe 109 is provided that communicates between the adjacent raw material compartments 105 through the refrigerant compartment 103. By providing this communication pipe 109, the clathrate hydrate slurry 102 in the raw material compartment 105 arranged on the right side in the figure is moved sequentially to the raw material compartment 105 on the left side in the figure through the communication pipe 109, and finally the left end. It is discharged from the clathrate hydrate slurry discharge pipe 110 connected to the raw material compartment 105 arranged in the above.

  A slurry storage tank for storing the generated clathrate hydrate slurry 102 is provided at the downstream end portion of the clathrate hydrate slurry discharge pipe 110, and an upstream end portion of the raw material solution supply pipe 108 is provided at the upstream end portion. A raw material solution storage tank for storing the raw material solution or the raw material slurry is provided (none is shown). The raw material solution supply pipe 108 is provided with a pump for sending the raw material solution or the raw material slurry to the raw material compartment 105, a valve for adjusting the flow rate, and a flow rate measuring device for measuring the flow rate of the raw material solution or the raw material slurry (see FIG. Neither is shown).

Hereinafter, each configuration will be described in more detail.
<Heat transfer surface>
The material of the heat transfer surface 107 is typically stainless steel or the like, but may be selected from materials excellent in thermal conductivity and wear resistance.

<Raw material compartment>
The raw material compartment 105 is composed of three regions: a clathrate hydrate dispersion / suspension region A, a fluidized bed region B, and a fixed bed region C.
In the raw material compartment 105 composed of these three regions, first, the flow of the raw material solution or the raw material slurry is dispersed in the fixed bed region C, and in the case of the raw material solution by the heat transfer surface 107 in the fluidized bed region B. By subcooling this and releasing the supercooling by the flow of particles (see reason 1 above), in the case of a raw slurry, this is cooled and the existing clathrate hydrate is used as a production nucleus or Inclusion hydrates are generated by the flow of particles (see reason 2 above). Thus, the clathrate hydrate is dispersed or suspended in the raw material solution or raw material slurry in the dispersion / suspension region A, and further cooled by the heat transfer surface 107. As a result, the amount of clathrate hydrate produced can be increased, and the solid phase rate of the clathrate hydrate slurry can be increased (the amount of heat storage or the heat storage density is increased).

Hereinafter, each region will be described in detail.
(Fixed floor area)
The fixed bed region C is located at the lowermost part of the raw material compartment 105, and uniformly distributes the raw material solution or the raw material slurry supplied to the raw material compartment 105 (the distribution in the cross section of the raw material compartment 105 is made uniform). And a region having a function of supplying to a fluidized bed 125 described later. The fixed bed region is, for example, a dispersion mechanism 121 formed by laminating alumina balls having a diameter of about 20 mm, and a mooring means provided above the dispersion mechanism 121 to prevent sedimentation of alumina particles constituting the fluidized bed 125 described later. 123 (dispersion plate).
The fixed bed region C may be formed by depositing alumina balls in a water box that is particularly provided at the lowermost part of the raw material compartment 105. The mooring means 123 is typically a wire mesh or a perforated plate, and may be an opening that does not allow alumina particles to settle.

(Fluidized bed area)
The fluidized bed region B is a region formed by the fluidized bed 125 that is located above the mooring means 123 and filled with fluidized particles. After the raw material solution is brought into a supercooled state by the heat transfer surface 107, the supercooling is released by the flow of particles (see reason 1 above), or the clathrate hydrate already present after the raw material slurry is cooled The clathrate hydrate is produced as a production nucleus or by flow of particles (see reason 2 above).
As a typical fluid medium for forming the fluidized bed 125, ceramic particles such as alumina, silica, and zirconia, and metal particles such as stainless steel and titanium can be used. Then, the optimum material and particle size are selected according to the kind of the raw material solution or raw material slurry, the flow rate of the raw material solution or raw material slurry to be set, the residence time of the clathrate hydrate slurry to be generated, and the like. In this embodiment, alumina particles having a diameter of about 1 mm may be filled into the fluidized bed 125.

  Further, the cooling effect can be enhanced by providing protrusions or fins on the heat transfer surface 107 in the fluidized bed region B to increase the heat transfer area. A separate heat exchanger may be set in the fluidized bed region B to further enhance the cooling effect. For example, a heat transfer tube through which the refrigerant circulates may be provided so that adjacent refrigerant compartments 103 communicate with each other, and the heat transfer tubes may be arranged in the fluidized bed region B of each raw material compartment 105.

(Dispersion / suspension area)
The dispersion / suspension area A is a space that is positioned above the fluidized bed 125 and further cooled by the heat transfer surface 107 while dispersing or suspending the clathrate hydrate. As a result, the amount of clathrate hydrate produced can be increased, and the solid phase rate of the clathrate hydrate slurry can be increased (the amount of heat storage or the heat storage density is increased).
In order to further enhance the cooling effect in the dispersion / suspension area A, the heat transfer surface 107 in the dispersion / suspension area A is provided with protrusions or fins to increase the heat transfer area, or a heat exchanger is added. Just do it. Alternatively, a clathrate hydrate slurry 102 discharged from the raw material compartment 105 may be further cooled by additionally installing a heat exchanger downstream of the clathrate hydrate slurry discharge pipe 110.

<Refrigerant compartment>
A refrigerant supply pipe 111 that supplies a refrigerant to each refrigerant chamber is connected to the lower part of each refrigerant compartment 103. A cooling temperature setting device (not shown) that sets the cooling temperature of the raw material solution by adjusting the flow rate of the refrigerant and the like is provided on the upstream side of the refrigerant supply pipe 111. A refrigerant discharge pipe 112 is connected to the upper part of each refrigerant compartment 103 to discharge the heat-exchanged refrigerant.
In addition, although the space | interval of the plate of the general plate type heat exchanger, ie, the heat transfer surface 107, is quite narrow, the width | variety of the raw material compartment 105 has the width | variety of the grade which the fluidized bed 125 is formed. The width of the refrigerant compartment 103 may be narrow as is the interval between the plates of a general plate heat exchanger.

  In the clathrate hydrate slurry manufacturing apparatus 101 configured as described above, a fluidized bed 125 is formed in the raw material compartment 105 to circulate the raw material solution or the raw material slurry, and the refrigerant is passed through the heat transfer surface 107. Since it is configured to cool, clathrate hydrate having a lower thermal conductivity than the raw material solution or raw material slurry adheres to the heat transfer surface 107, and the heat transfer efficiency of the heat transfer surface 107 decreases. It can be prevented by the flow of the particles constituting the fluidized bed 125, the heat transfer efficiency of the heat transfer surface 107 of the heat exchanger can be kept high, and the clathrate hydrate slurry can be produced with high efficiency. In addition, since the performance of preventing and removing dirt on the heat transfer surface 107 is high, maintenance management becomes easy.

  In addition, since a structure similar to a plate heat exchanger in which the raw material compartment 105 and the refrigerant compartment 103 are partitioned by a plate-shaped heat transfer surface 107 is adopted, heat exchange by another method, for example, a shell and tube method is employed. The heat transfer area is larger than the heat exchanger and the heat exchange performance is improved. Further, since the plurality of refrigerant compartments 103 and the raw material compartments 105 are alternately adjacent to each other, the heat transfer area can be increased with respect to the installation area of the manufacturing apparatus, and the heat exchange performance is improved. Furthermore, since the fluidized bed 125 is circulated while the raw material solution or the raw material slurry is being cooled or cooled, the inclusion hydrate is easily generated for the reasons 1 and 2 described above, and the inclusion water is highly efficient. It becomes possible to produce a Japanese slurry.

<Driving method>
Next, an operation method of the clathrate hydrate slurry manufacturing apparatus configured as described above will be described.
(1) A raw material solution having a predetermined concentration is stored in advance in a raw material solution storage tank.
(2) The pump is started, the flow rate is measured by a flow rate measuring device, and the flow rate of the raw material solution is set to a predetermined flow rate (the flow rate at which the flowing particles filled in the raw material compartment 105 flow) based on the measured value. The raw material solution is supplied to the raw material compartment 105 by controlling the valve so that the flow rate becomes the same.
(3) After confirming that the fluidized particles are flowing, that is, that the fluidized bed 125 is formed, the refrigerant starts to flow into the refrigerant compartment 103, and the refrigerant temperature is set to a predetermined temperature by the cooling temperature setting device. The refrigerant is set to flow through the refrigerant compartment 103.
(4) After the raw material solution is supercooled through the heat transfer surface 107 in the fluidized bed region B, the supercooling is released by the flow of the fluidized particles, and clathrate hydrate is produced to produce the clathrate hydrate slurry. Thereafter, the generated clathrate hydrate slurry is collected in the slurry storage tank through the clathrate hydrate slurry discharge pipe 110.
Alternatively, the clathrate hydrate slurry may be manufactured by storing the raw material slurry in the raw material solution storage tank instead of the raw material solution and supplying the raw material slurry to the raw material compartment 105.

  In the example shown in FIG. 2, the clathrate hydrate slurry 102 generated in each raw material compartment 105 is connected to the upper end of each raw material compartment 105 by a communication pipe 109 so that the raw material disposed at the left end in the figure. The clathrate hydrate slurry discharge pipe 110 connected to the compartment 105 is configured to be discharged. However, as a configuration for discharging the clathrate hydrate slurry 102, a discharge pipe is provided in each raw material compartment 105. The clathrate hydrate slurry 102 produced in the raw material compartment 105 may be individually taken out from the discharge pipe provided in each chamber.

[Embodiment 3]
<Supercooling release device>
FIG. 3 is an explanatory diagram of the supercooling release device 201 according to the embodiment of the present invention. The supercooling release device 201 releases the supercooling of the raw material solution or raw material slurry by circulating the raw material solution or raw material slurry that is already in the supercooled state, thereby obtaining the clathrate hydrate slurry 203.

In this embodiment, the supercooling release device 201 includes a vertical cylindrical supercooling release tank 205 that releases supercooling of the raw material solution in a supercooled state. A discharge pipe 207 for discharging the raw material solution 203 (that is, clathrate hydrate slurry 203) after the release of cooling is connected, and the lower surface of the supercooling release tank 205 is cooled by another heat exchanger (not shown). A supply pipe 209 for supplying the raw material solution in the supercooled state to the supercooling release device 201 is connected.
The supercooling release tank 205 is equivalent to the production tank 5 shown in FIG. 1 with the heat exchanger 27 removed, and the other structure is the same as that of the production tank shown in FIG. The structure will be described below.

The supercooling release tank 205 has a vertical cylindrical shape, but does not necessarily have to be vertical or cylindrical. However, it is preferable that at least a part is formed of a transparent material. By making at least a part of the supercooling release tank 205 transparent, it can be confirmed whether or not the liquid in the supercooling release tank 205 is clouded, whereby the supercooled raw material solution is released from the supercooling and the inclusion is performed. It can be confirmed that the slurry is a hydrate slurry 203).
In the lowermost part (water box portion) of the supercooling release tank 205, the raw material solution supplied to the supercooling release tank 205 is uniformly dispersed (the distribution in the cross section of the supercooling release tank 205 is made uniform), which will be described later. A dispersion mechanism 211 having a function of supplying the fluidized bed 215 is provided.

Above the dispersion mechanism 211, an anchoring means 213 for preventing sedimentation of alumina particles constituting a fluidized bed 215 described later is provided. The anchoring means 213 is typically a wire mesh or a perforated plate, and may have an opening that does not allow alumina particles to settle.
A fluidized bed 215 in which fluidized particles are stacked is formed above the mooring means 213. Typical fluid particles (fluid medium) forming the fluidized bed 215 are ceramic particles such as alumina, silica and zirconia, and metal particles such as stainless steel and titanium. The optimum material and particle size are selected according to the type of the raw material solution, the flow rate of the raw material solution to be set, the residence time of the clathrate hydrate slurry to be generated, and the like.

A space for dispersing or suspending clathrate hydrate is provided above the fluidized bed 215. The upper end of the supercooling release tank 205 is provided with an overflow discharge port 217 for discharging the clathrate hydrate slurry generated after the supercooling release, and the overflow discharge port 217 has the above-described discharge pipe. 207 is connected.
The upper end surface of the supercooling release tank 205 may be opened or covered.

As shown in FIG. 3, the supercooling release tank 205 configured as described above includes the clathrate hydrate dispersion / suspension area A, fluidized bed area B, and fixed bed area C as in FIG. It consists of three areas.
The clathrate hydrate dispersion / suspension region A is a region disposed downstream of the fluidized bed region B in the supercooling release tank 205.
The fluidized bed region B is a region where the fluidized bed 215 is disposed in the supercooling release tank 205 and is disposed on the downstream side of the fixed bed region C.
The fixed bed area C is an area where the dispersion mechanism 211 is disposed in the supercooling release tank 205. The mooring means 213 and the fixed floor region C may be defined.

Next, the operation and effect of the present embodiment configured as described above will be described.
(1) A pump (not shown) is driven, and the raw material solution in a supercooled state is supplied to the supercooling release device 201 through the supply pipe 209.
(2) The raw material solution in the supercooled state is uniformly dispersed in the fixed bed region and reaches the fluidized bed 215 arranged above the dispersion plate. When the raw material solution passes through the fluidized bed 215, a plurality of particles (fluid medium) constituting the fluidized bed 215 are fluidized.
(3) A plurality of particles constituting the fluidized bed cause contact, rubbing, collision and the like. Such contact, rubbing, collision and the like make it easy to produce clathrate hydrate, which contributes to the release of supercooling of the raw material solution.
(4) Therefore, the supercooled state of the raw material solution is canceled by passing through the fluidized bed region B. Then, in the dispersion / suspension region A, the newly generated clathrate hydrate is dispersed or suspended in the raw material solution that has passed through the fluidized bed region B, thereby forming a clathrate hydrate slurry.
(5) Thus, it becomes possible to cancel the supercooling of the raw material solution.

In this embodiment, since the fluidized bed 215 is composed of a plurality of particles, it is possible to realize the fluidized bed 215 in which the raw material solution is easily circulated and has many mechanical contacts that trigger the release of supercooling. In addition, since the clathrate hydrate produced | generated by cancellation | release of the supercooling of a raw material solution functions as a production | generation nucleus of a new clathrate hydrate, supercooling cancellation | release may be accelerated | stimulated further. Thus, according to this embodiment, an efficient supercooling release device using a liquid phase fluidized bed can be realized.
In addition, it is preferable to mix the particles which are processed so that the clathrate hydrate easily adheres to the surface or easily adheres to a part of the fluidized particles constituting the fluidized bed 215. As a result, the clathrate hydrate adhered at least temporarily to the surface of the particles can function as a generation nucleus of another clathrate hydrate, and therefore, the clathrate hydrate slurry can be produced more efficiently. Can do.

[Embodiment 4]
FIG. 4 is a diagram showing a main part of an apparatus including a storage tank according to an embodiment of the present invention, and the apparatus including the storage tank according to the present embodiment produces clathrate hydrate slurry. The clathrate hydrate slurry production apparatus 301 (hereinafter referred to as production apparatus 301) is accommodated in the storage tank 300. Hereinafter, the details of the apparatus will be described, and then the operation method of the apparatus will be described.

(Explanation of the device)
<Reservoir>
The storage tank 300 is for storing the produced clathrate hydrate slurry 302. Before the clathrate hydrate slurry is produced by the clathrate hydrate slurry production apparatus 301, the raw material solution or A raw material slurry is accommodated and used as a storage tank for a raw material solution or the like. However, if there is a separate tank for storing the raw material solution and the raw material slurry, the storage tank 300 may be initially empty.
In the storage tank 300, a partition member 340 that forms a fixed partition on the outer periphery of the manufacturing apparatus 301 is installed in a bottomless state so as to surround the manufacturing apparatus 301. By providing the partition member 340, the clathrate hydrate slurry produced by the production apparatus 301 can be smoothly discharged from the clathrate hydrate slurry discharge pipe 310 described later.
The storage tank 300 is provided with a clathrate hydrate slurry discharge pipe 310 for discharging the stored clathrate hydrate slurry 302 to the outside of the tank. One end side of the clathrate hydrate slurry discharge pipe 310 is disposed between the partition member 340 and the manufacturing apparatus 301.
In addition, if the clathrate hydrate slurry 302 accommodated in the storage tank is used as a heat storage material (including a cold transport medium), the storage tank 300 can be regarded as a heat storage tank.

<Manufacturing equipment>
The production apparatus 301 has substantially the same configuration as the clathrate hydrate slurry production apparatus 1 of the first embodiment. That is, the manufacturing apparatus 301 is configured to include a cylindrical generation tank 305 and a dispersion mechanism 321, mooring means 323, fluidized bed 325, and heat exchanger 327 inside the generation tank 305.
The generation tank 305 is installed in the storage tank 300 by being suspended from the ceiling portion of the storage tank 300. The generation tank 305 is submerged so that the part of the fluidized bed 325 where the heat exchanger 327 is disposed is below the liquid level of the raw material solution and raw material slurry 302 stored in the storage tank 300, that is, the part of the fluidized bed 325 is submerged. Are arranged to be. With such an arrangement, the cooling effect of the refrigerant flowing through the heat exchanger 327 reaches the raw material solution and the raw material slurry 302, and a new effect in the storage tank 300 outside the generation tank 305 is obtained using the cooling effect. The clathrate hydrate can be produced or the clathrate hydrate slurry thus produced can be efficiently maintained.
Note that it is more preferable that the submerged portion of the outer shell of the generation tank 305 is made of a material having high thermal conductivity because the above-described cooling effect is easily achieved.

  One end of a raw material solution supply pipe 308 that supplies a raw material solution or raw material slurry is connected to the bottom of the generation tank 305, and the other end side of the raw material solution supply pipe 308 passes through the storage tank 300 and It extends to the outside.

A ceiling portion 307 is provided at the top of the generation tank 305, and the generated clathrate hydrate slurry is discharged from the generation tank 305 to the storage tank 300 side on the ceiling 307 and the upper side surface of the generation tank 305. An overflow outlet 317 is provided.
The clathrate hydrate slurry 302 discharged from the overflow outlet 317 is once stored in the storage tank 300 and discharged through the clathrate hydrate slurry discharge pipe 310 provided in the storage tank 300.

The overflow outlet 317 provided on the upper side surface of the generation tank 305 is provided so as to be substantially at the same position as the liquid level of the clathrate hydrate slurry (or raw material solution) 302 stored in the storage tank 300. Yes.
However, the installation position of the overflow discharge port 317 is not limited to this, and the installation position, size, shape, etc. of the clathrate hydrate slurry formed by passing through the fluidized bed 325 is discharged out of the manufacturing apparatus. Appropriately devised so that it can be easily done.

The configurations of the dispersion mechanism 321, the mooring means 323, the fluidized bed 325, and the heat exchanger 327 installed in the generation tank 305 are the same as those in the first embodiment. Therefore, as in the first embodiment, the clad hydrate dispersion / suspension region A, fluidized bed region B, and fixed bed region C are formed in the generation tank 305. (See FIG. 1).
The heat exchanger 327 is connected to a refrigerant supply pipe 311 that supplies refrigerant to the heat exchanger 327 from outside the manufacturing apparatus 301 and a refrigerant discharge pipe 312 that discharges the heat-exchanged refrigerant to the outside of the manufacturing apparatus 301. ing.

(Description of driving method)
The storage tank 300 initially stores a raw material solution and a raw material slurry 302. If there is a separate tank for storing the raw material solution and the raw material slurry, the tank 300 may be initially empty.
The raw material solution or raw material slurry 302 stored in the storage tank 300 is discharged from the clathrate hydrate slurry discharge pipe 310 to the outside of the storage tank 300 by a pump not shown, and the discharged raw material solution or raw material slurry is used as the raw material. The solution is supplied to the manufacturing apparatus 301 through the solution supply pipe 308.
When a tank for storing the raw material solution and the raw material slurry is provided separately, the raw material solution or the raw material slurry is supplied from the other tank to the manufacturing apparatus 301 through the raw material solution supply pipe 308.

  The raw material solution or raw material slurry supplied to the manufacturing apparatus 301 passes through the dispersion mechanism 321 and the mooring means 323 and is cooled by the refrigerant through the heat exchanger 327 in the process of passing through the fluidized bed 325. At the time of cooling, the supercooled raw material solution is released from supercooling in the process of passing through the fluidized bed 325, and the resulting clathrate hydrate is dispersed or suspended in the raw material solution and clathrate hydrated. It becomes a product slurry.

In the process of passing through the fluidized bed 325, clathrate hydrate does not adhere to the heat transfer surface of the heat exchanger 327 due to the flow of particles constituting the fluidized bed, and dirt does not easily adhere. The heat transfer efficiency of the heat transfer surface can be maintained at a high level, and maintenance management is facilitated.
Further, the supercooling of the raw material solution is easily released, and the abundance ratio of the clathrate hydrate in the clathrate hydrate slurry is easily increased.
Furthermore, if the clathrate hydrate adheres to the surface of the fluidized particles constituting the fluidized bed when the raw material solution or the raw slurry is cooled, it becomes a production nucleus, and a new clathrate hydrate is produced. Is promoted.
Accordingly, whether the raw material solution or the raw material slurry passes through the fluidized bed, the clathrate hydrate slurry having an increased abundance ratio of the clathrate hydrate is obtained as compared to before passing. The clathrate hydrate slurry moves into the storage tank 300 outside the generation tank 305 through the overflow discharge port 17 and is stored in the storage tank 300. At this time, since the clathrate hydrate slurry 302 that has moved into the storage tank 300 is collected in a certain compartment by the compartment member 340, the clathrate hydrate slurry discharge pipe 310 is smoothly discharged.

  The clathrate hydrate slurry 302 accommodated in the storage tank 300 is sent to the outside of the storage tank 300 through the clathrate hydrate slurry discharge pipe 310 and used for a desired purpose such as cooling of the air conditioning system. After part or all of the clathrate hydrate is melted and returned to the aqueous solution as a result of being used for a desired purpose, it may be returned to the storage tank 300 as a raw material solution or a raw material slurry. The raw material solution at this time may or may not be in a supercooled state.

  When it is necessary to accumulate the clathrate hydrate slurry in the storage tank 300, the clathrate hydrate slurry may not be taken out from the clathrate hydrate slurry discharge pipe 310 to the outside of the tank. In addition, when it is necessary to increase the amount of clathrate hydrate present in the storage tank 300 (hence, the solid phase ratio of the clathrate hydrate slurry), the clathrate hydrate accommodated in the storage tank 300 is used. The slurry is sent out of the storage tank 300 through the clathrate hydrate slurry discharge pipe 310, returned again into the storage tank 300 as a raw slurry, and thereafter the clathrate hydrate slurry is repeatedly circulated until the desired abundance is reached. That's fine.

If it is an apparatus provided with the storage tank in this Embodiment, since the manufacturing apparatus 301 of the clathrate hydrate slurry which concerns on this invention is arrange | positioned in the storage tank 300 which accommodates a raw material solution or a raw material slurry, the said manufacture In addition to the operational effects corresponding to the apparatus 301, it is possible to reduce the space and floor area originally required for the laying of the manufacturing apparatus 301. Therefore, the overall apparatus scale can be relatively reduced.
For example, when the storage tank 300 is a heat storage tank that contains the clathrate hydrate slurry, and the device including the storage tank 300 is a heat storage apparatus, clathrate hydration for producing the clathrate hydrate slurry The product slurry manufacturing apparatus 301 is disposed in the heat storage tank, and a heat storage apparatus having a function of manufacturing the clathrate hydrate slurry is configured. Thereby, the installation required for the production and accumulation of clathrate hydrate slurry can be made smaller as a whole.
In the present embodiment, the manufacturing apparatus 301 is submerged in the raw material solution, raw material slurry, or clathrate hydrate slurry in the storage tank 300. This configuration also leads to the manifestation of the effect of making the equipment required for the production and accumulation of clathrate hydrate slurry smaller as a whole.

  In the present embodiment, the generation tank 305 is installed by being suspended from the ceiling portion of the storage tank 300. However, the installation method of the generation tank 305 is not limited to this method. For example, the generation tank 305 may be installed directly on the bottom of the storage tank 300 or with an appropriate support mechanism (including a base) interposed.

Moreover, in said embodiment, as a countermeasure when the hydrate slurry which overflowed in the storage tank 300 dissipates in the storage tank 300, and it becomes difficult to take out from the clathrate hydrate slurry discharge pipe 310 outside a storage tank. In the example, the partition member 340 is provided so as to surround the manufacturing apparatus 301.
However, the partition member 340 is not necessarily provided so as to surround the manufacturing apparatus 301, and the clathrate hydrate slurry that has come out from the overflow discharge port 317 is easily collected in the clathrate hydrate slurry discharge pipe 310. The installation position, dimensions, shape, etc. may be determined as described above. Thereby, dissipation of the clathrate hydrate slurry can be moderately suppressed, and the clathrate hydrate slurry discharge pipe 310 can be easily taken out of the tank.
Therefore, the clathrate hydrate slurry can be produced more efficiently.

[Embodiment 5]
FIG. 5 is a diagram showing a main part of an apparatus including a storage tank according to an embodiment of the present invention. The apparatus including the storage tank according to the present embodiment is a raw material solution or a raw material in a supercooled state. A supercooling release device 401 that releases supercooling of the slurry is accommodated in the storage tank 400. The supercooling release device 401 releases the supercooling of the raw material solution or raw material slurry in the supercooled state, and clathrate hydrate slurry is generated. Hereinafter, the details of the apparatus will be described, and then the operation method of the apparatus will be described.

(Explanation of the device)
<Reservoir>
Although the storage tank 400 is for storing the produced clathrate hydrate slurry 402, the supercooling release device 401 releases the supercooling of the raw material solution or the raw material slurry to generate the clathrate hydrate slurry. Before starting, a raw material solution and a raw material slurry are accommodated and used as a storage tank for the raw material solution and the like. However, if there is a separate tank for storing the raw material solution and the raw material slurry, the storage tank 400 may be initially empty.
In the storage tank 400, a partition member 440 that forms a fixed partition on the outer periphery of the supercooling release device 401 is installed in a bottomless state so as to surround the supercooling release device 401. By providing the partition member 440, the clathrate hydrate slurry generated after the supercooling is released by the supercooling release device 401 can be smoothly discharged from the clathrate hydrate slurry discharge pipe 410 described later.
The storage tank 400 is provided with a clathrate hydrate slurry discharge pipe 410 for discharging the stored clathrate hydrate slurry 402 to the outside of the tank. One end side of the clathrate hydrate slurry discharge pipe 410 is disposed between the partition member 440 and the supercooling release device 401.
In addition, if the clathrate hydrate slurry 402 accommodated in the storage tank 400 is used as a heat storage material (including a cold transport medium), the storage tank 400 can be regarded as a heat storage tank.

<Supercooling release device>
The supercooling release device 401 has substantially the same configuration as the supercooling release device 201 of the third embodiment. That is, the supercooling release device 401 includes a cylindrical supercooling release tank 405 and a dispersion mechanism 421, mooring means 423, and fluidized bed 425 inside the supercooling release tank 405.
The supercooling release tank 405 is installed in the storage tank 400 by being suspended from the ceiling portion of the storage tank 400.

  One end of a raw material solution supply pipe 408 for supplying a raw material solution or raw material slurry is connected to the bottom of the supercooling release tank 405, and the other end side of the raw material solution supply pipe 408 passes through the storage tank 400 and is stored in the storage tank. It extends to the outside of 400.

A ceiling portion 407 is provided on the upper portion of the supercooling release tank 405, and the clathrate hydrate slurry generated on the ceiling portion 407 and the upper side surface of the supercooling release tank 405 is transferred from the supercooling release tank 405 to the storage tank 400. An overflow outlet 417 for discharging to the side is provided.
The clathrate hydrate slurry discharged from the overflow outlet 417 is once stored in the storage tank 400 and discharged through the clathrate hydrate slurry discharge pipe 410 provided in the storage tank 400.

The overflow outlet 417 provided on the upper side surface of the supercooling release tank 405 is provided so as to be substantially at the same level as the liquid level of the clathrate hydrate slurry (or raw material solution) 402 accommodated in the storage tank 400. It has been.
However, the installation position of the overflow discharge port 417 is not limited to this, and the installation position, size, shape, etc. of the clathrate hydrate slurry formed by passing through the fluidized bed 425 is discharged out of the manufacturing apparatus. Appropriately devised so that it can be easily done.

  The configurations of the dispersion mechanism 421, the mooring means 423, and the fluidized bed 425 installed in the supercooling release tank 405 are the same as those in the third embodiment. Therefore, as in the third embodiment, the supercooling release tank 405 is formed with three regions, a clathrate hydrate dispersion / suspension region A, a fluidized bed region B, and a fixed bed region C. (See FIG. 3).

(Description of driving method)
Initially, the storage tank 400 stores a raw material solution and a raw material slurry 402. If there is a separate tank for storing the raw material solution or the raw material slurry, the tank 400 may be initially empty.
The raw material solution or raw material slurry stored in the storage tank 400 is discharged from the clathrate hydrate slurry discharge pipe 410 to the outside of the storage tank 400 by a pump not shown, and the discharged raw material solution or raw material slurry is not shown. It cools by making it heat-exchange with a refrigerant | coolant via a heat exchanger, and makes it a supercooled state. Thereafter, the supercooled raw material solution or raw material slurry is supplied to the supercooling release device 401 through the raw material solution supply pipe 408. When a tank for storing the raw material solution and the raw material slurry is provided separately, the supercooling release device 401 is provided through the raw material solution supply pipe 408 after the raw material solution or the raw material slurry is brought into a supercooled state from the other tank. To supply.

  The supercooled raw material solution or raw material slurry supplied to the supercooling release device 401 passes through the dispersion mechanism 421 and the mooring means 423, undergoes release of supercooling in the process of passing through the fluidized bed 425, and is generated as a result. The clathrate hydrate is dispersed or suspended in the raw material solution to produce a clathrate hydrate slurry. Further, when the clathrate hydrate is produced, if clathrate hydrate adheres to the surface of the fluidized particles constituting the fluidized bed 425, it becomes a generation nucleus, and a new clathrate hydrate is formed. Generation is promoted. Therefore, whether the raw material solution or the raw material slurry passes through the fluidized bed 425, the clathrate hydrate slurry in which the inclusion ratio of the clathrate hydrate is increased as compared with that before the passage is obtained. The clathrate hydrate slurry moves into the storage tank 400 outside the supercooling release tank 405 through the overflow discharge pipe 417 and is stored in the storage tank 400. At this time, since the clathrate hydrate slurry 402 that has moved into the storage tank 400 is collected in a certain compartment by the compartment member 440, the clathrate hydrate slurry discharge pipe 410 is smoothly discharged.

  The clathrate hydrate slurry 402 accommodated in the storage tank 400 is sent to the outside of the storage tank 400 through the clathrate hydrate slurry discharge pipe 410 and used for a desired purpose such as cooling of the air conditioning system. After some or all of the clathrate hydrate has melted and returned to the aqueous solution as a result of being used for the desired purpose, it is cooled by heat exchange with a refrigerant through a heat exchanger (not shown), and is supercooled. After being brought into a state, it is returned to the storage tank 400.

  When it is necessary to accumulate the clathrate hydrate slurry in the storage tank 400, the clathrate hydrate slurry may be removed from the clathrate hydrate slurry discharge pipe 410 outside the tank. In addition, when it is necessary to increase the amount of clathrate hydrate present in the storage tank 400 (hence, the solid phase ratio of the clathrate hydrate slurry), the clathrate hydrate accommodated in the storage tank 400 is used. The slurry is sent out of the storage tank 400 through the clathrate hydrate slurry discharge pipe 410, cooled by heat exchange with the refrigerant through a heat exchanger (not shown), and returned to the storage tank 400 again as a raw slurry, Thereafter, the circulation of the clathrate hydrate slurry may be repeated until the desired abundance is reached.

If it is an apparatus provided with the storage tank in this Embodiment, since the supercooling cancellation | release apparatus 401 which concerns on this invention is arrange | positioned in the storage tank 400 which accommodates a raw material solution or a raw material slurry, in the said supercooling cancellation | release apparatus 401 In addition to providing the corresponding operational effects, it is possible to reduce the space and floor area originally required for laying the supercooling release device 401, and thus the overall device scale can be relatively reduced.
For example, when the storage tank 400 is a heat storage tank that contains the clathrate hydrate slurry and the apparatus including the storage tank 400 is a heat storage apparatus, the supercooling of the raw material solution or the raw material slurry is released and the clathrate hydration is released. The supercooling release device 401 for generating the material slurry is arranged in the heat storage tank, and the heat storage device having a function of releasing the supercooling is configured. Thereby, the installation required for supercooling release and clathrate hydrate slurry accumulation can be made smaller as a whole.
In the present embodiment, the supercooling release device 401 is submerged in the raw material solution, raw material slurry, or clathrate hydrate slurry 402 in the storage tank 400. This configuration also leads to the manifestation of the effect of reducing the size of the equipment required for releasing the supercooling and accumulating the clathrate hydrate slurry as a whole.

  In this embodiment, an example in which the supercooling release tank 405 is installed by suspending from the ceiling portion of the storage tank 400 has been described, but the installation method of the supercooling release tank 405 is not limited to this method. For example, the supercooling release tank 405 may be installed directly on the bottom of the storage tank 400 or with an appropriate support mechanism (including a base) interposed.

Moreover, in said embodiment, as a countermeasure when the hydrate slurry which overflowed in the storage tank 400 dissipates in the storage tank 400, and it becomes difficult to take out from the clathrate hydrate slurry discharge pipe 410 outside a storage tank. The example in which the partition member 440 is provided so as to surround the supercooling release device 401 is shown.
However, the partition member 440 is not necessarily provided so as to surround the supercooling release device 401, and the clathrate hydrate slurry 402 that has come out from the overflow outlet 417 enters the clathrate hydrate slurry discharge pipe 410. What is necessary is just to determine the installation position, a dimension, a shape, etc. so that it may gather easily. Thereby, dissipation of the clathrate hydrate slurry can be moderately suppressed, and the clathrate hydrate slurry discharge pipe 410 can be easily taken out of the tank.

  In the description of each of the embodiments described above, a mode is described in which the fluid particles constituting the fluidized bed have a higher specific gravity than the raw material solution or the raw material slurry, and the raw material solution or the raw material slurry flows through the fluidized bed from below to above. However, the present invention is not limited to such a form. That is, the embodiment in which the fluidized particles constituting the fluidized bed have a specific gravity smaller than that of the raw material solution or the raw material slurry and the raw material solution or the raw material slurry flows from the upper side to the lower side of the fluidized bed is also included.

It is explanatory drawing of the manufacturing apparatus of the clathrate hydrate slurry which concerns on one Embodiment of this invention. It is explanatory drawing of the manufacturing apparatus of the clathrate hydrate slurry which concerns on other embodiment of this invention. It is explanatory drawing of the overcooling cancellation | release apparatus which concerns on one Embodiment of this invention. It is explanatory drawing of an apparatus provided with the storage tank which accommodates the clathrate hydrate slurry which concerns on one Embodiment of this invention. It is explanatory drawing of an apparatus provided with the storage tank which accommodates the clathrate hydrate slurry which concerns on other embodiment of this invention.

DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus 3,102 Clathrate hydrate slurry 5 Generation tank 7,207 Discharge pipe 9,209 Supply pipe 11 Slurry storage tank 13 Raw material solution storage tank 15 Pump 17 Valve 19 Flow rate measuring apparatus 21, 121, 211 Dispersion mechanism 23 , 123, 213 Mooring means 25, 125, 215 Fluidized bed 27 Heat exchanger 29, 217 Overflow outlet 31 Temperature measuring device 101 Manufacturing device 103 Refrigerant compartment (first compartment)
105 Raw material compartment (second compartment)
DESCRIPTION OF SYMBOLS 107 Heat-transfer surface 108 Raw material solution supply pipe 109 Communication pipe 110 Cladding hydrate slurry discharge pipe 111 Refrigerant supply pipe 112 Refrigerant discharge pipe 201 Supercooling release device 203 Raw material solution after supercooling release (clathion hydrate slurry)
205 Supercooling release tank 300 Storage tank (heat storage tank)
301 Production apparatus 302 clathrate hydrate slurry (or raw material solution or raw material slurry)
305 Generation tank 307 Ceiling part 308 Raw material solution supply pipe 310 Clathrate hydrate slurry discharge pipe 311 Refrigerant supply pipe 312 Refrigerant discharge pipe 317 Overflow outlet 321 Dispersion mechanism 323 Mooring means 325 Fluidized bed 327 Heat exchanger 340 Partition member 400 Storage Tank (heat storage tank)
401 Supercooling release device 402 clathrate hydrate slurry (or raw material solution or raw material slurry)
405 Supercooling release tank 407 Ceiling part 408 Raw material solution supply pipe 410 Inclusion hydrate slurry discharge pipe 417 Overflow discharge port 421 Dispersion mechanism 423 Mooring means 425 Fluidized bed 440 Partition member

Claims (8)

A method for producing a clathrate hydrate slurry in which clathrate hydrate is dispersed or suspended in an aqueous solution or aqueous solvent of the guest compound,
A heat exchange step of performing heat exchange between the aqueous solution or the water solvent or the slurry and the refrigerant through a heat transfer surface that contacts at least a part of the fluidized bed through which the aqueous solution or the water solvent or the slurry flows. A method for producing a clathrate hydrate slurry, wherein: An apparatus for producing a clathrate hydrate slurry in which clathrate hydrate is dispersed or suspended in an aqueous solution or aqueous solvent of the guest compound,
A fluidized bed through which the aqueous solution or the water solvent or the slurry flows, and a heat exchanger that performs heat exchange between the aqueous solution or the water solvent or the slurry and the refrigerant, and at least a heat transfer surface of the heat exchanger. An apparatus for producing a clathrate hydrate slurry, wherein a part thereof is disposed so as to be in contact with at least a part of the fluidized bed. An apparatus for producing a clathrate hydrate slurry in which clathrate hydrate is dispersed or suspended in an aqueous solution or aqueous solvent of the guest compound,
A first compartment through which a refrigerant flows, a second compartment through which the aqueous solution, the aqueous solvent, or the slurry flows, and a heat transfer surface that partitions the first compartment and the second compartment. The clathrate hydrate slurry producing apparatus, wherein the second compartment is disposed so that at least a part of the heat transfer surface is in contact with at least a part of the fluidized bed. A method for releasing supercooling of an aqueous solution of a clathrate hydrate guest compound comprising:
A method for releasing supercooling, comprising the step of circulating the aqueous solution in a supercooled state through at least a part of a fluidized bed. An apparatus for releasing supercooling of an aqueous solution of a clathrate hydrate guest compound, comprising a fluidized bed, wherein the aqueous solution in a supercooled state is circulated through at least a part of the fluidized bed. A supercooling release device characterized by that. A method for increasing the abundance ratio of the clathrate hydrate in a slurry in which the clathrate hydrate is dispersed or suspended in an aqueous solution of the guest compound,
A method comprising circulating the slurry to at least a part of a fluidized bed after cooling or in the course of cooling. An apparatus for increasing the abundance ratio of the clathrate hydrate in a slurry in which the clathrate hydrate is dispersed or suspended in an aqueous solution of the guest compound, the clathrate hydrate comprising a fluidized bed, and the aqueous solution is cooled An apparatus configured to circulate at least a part of the fluidized bed after or in the process of being cooled. 6. An apparatus for producing an clathrate hydrate slurry according to claim 2, comprising a storage tank for containing an aqueous clathrate hydrate guest compound solution or clathrate hydrate slurry. A device comprising any one of the above-described supercooling release device and a device for increasing the abundance ratio of clathrate hydrate according to claim 7.

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