JP4857929B2 - Gas clathrate manufacturing method and apparatus - Google Patents

Description

  In the present invention, for example, a raw material gas such as natural gas and a raw material liquid (fresh water, seawater, antifreeze, liquid host material, host material solution, etc.) are reacted to form a gas clathrate (gas hydrate when the host material is water). In the present specification, the gas clathrate refers to a gas clathrate manufacturing method and apparatus for manufacturing a gas clathrate.

A gas clathrate is an ice-like substance that contains gas molecules such as natural gas and carbon dioxide in a high concentration inside a cage structure formed by water molecules. Gas clathrate, mainly gas hydrate, can contain a large amount of gas per unit volume, and can be stored and transported at a relatively high temperature under atmospheric pressure compared to liquefied natural gas. Application to storage is attracting attention.
For this reason, hitherto, studies have been focused on the use of naturally occurring gas clathrate, but in recent years, attempts have been made to produce it industrially by paying attention to this property.

As an industrial manufacturing method of gas clathrate, the raw material gas is made into fine bubbles, mixed with raw material water in the middle of the line, and the mixing / dissolving process in which the raw material gas is dissolved in the raw material water, and the mixed / dissolved reaction There has been proposed a gas hydrate manufacturing method including a process of generating gas hydrate by cooling while flowing in a pipeline (see Patent Document 1).
This gas hydrate manufacturing method can efficiently perform gas diffusion / dissolution in raw water and removal of generated reaction heat, and can make the apparatus simple and compact.
JP 2002-356665 A

In the production process of the gas clathrate, an important factor governing the production rate of the gas clathrate is the diffusion dissolution rate of the gas into the raw water.
In this regard, in the method proposed in Patent Document 1, the contact area between the source gas and the source water is increased by making the source gas into fine bubbles in order to increase the diffusion and dissolution rate of the gas into the source water. Yes.

However, when a gas clathrate is generated by the fine bubble flow method, a gas clathrate is generated at the interface between the raw material gas and the raw material liquid, that is, the outer peripheral surface of the fine bubbles, and this covers the entire outer peripheral surface to generate a shell clathrate. It is thought that it is done. When the shell clathrate is generated, the raw material gas inside the shell is prevented from contacting the surrounding raw material liquid, and the gas clathrate generation reaction may not proceed further.
In addition to the case where the shell clathrate is regularly generated as described above, it is conceivable that the gas clathrate aggregates and the raw material gas is confined in the gap between the aggregated clathrates. In the same manner as above, the contact between the raw material gas confined inside and the raw material liquid is hindered, and the production reaction may not proceed any further.
For this reason, the gap between the raw material gas and the gas clathrate aggregate (referred to as “gas clathrate aggregate” in this specification as a concept including both the shell clathrate and the gas clathrate aggregate) in the shell clathrate Since the raw material gas confined in is left unreacted, there is a problem that the ratio of the raw material gas supplied as fine bubbles to the clathrate (conversion rate) cannot be sufficiently increased.

  The present invention has been made to solve such problems, and an object of the present invention is to provide a gas clathrate production method and apparatus capable of sufficiently increasing the rate at which the raw material gas is converted into the clathrate.

The aforementioned problem is that the gas clathrate aggregate formed by the gas clathrate once generated is crushed, the internal raw material gas is released into the raw material liquid, and the released gas is flowed through the reaction pipe again to generate the clathrate. This can be solved by further progressing the reaction.
This invention is made | formed based on this knowledge, and has the following structures specifically.

(1) A gas clathrate production method according to the present invention is a method for producing a gas clathrate by reacting a raw material liquid and a raw material gas. A gas clathrate production step for producing a gas clathrate by cooling the mixed / dissolved material while flowing into the reaction pipe, and a gas clathrate aggregate (raw gas ) formed by the produced gas clathrate Gas clathrate is generated on the outer peripheral surface of the fine bubbles of the gas, and the gas clathrate that covers the entire outer peripheral surface and the gas clathrate are aggregated together, and the raw material gas is confined in the gap between the aggregated clathrate and characterized in that the concept) containing both rate aggregates with a gas clathrate aggregate crushing step for crushing in the course of the reaction pipe Is shall.

(2) In addition, in the method for producing a gas clathrate by reacting a raw material liquid and a raw material gas, a mixing / dissolving step in which the raw material gas is mixed into a raw material liquid into fine bubbles and mixed / dissolved, and mixed / dissolved A gas clathrate production process in which a gas clathrate is generated by cooling while flowing through a reaction pipe, and a gas clathrate aggregate formed by the produced gas clathrate ( a gas class on the outer peripheral surface of fine bubbles of the raw material gas) The concept includes both a shell clathrate that forms a rate and covers the entire outer surface and a gas clathrate aggregate in which the gas clathrate aggregates and the raw material gas is confined in the gap between the aggregated clathrates) Gas clathrate aggregate extraction and crushing process for extracting and crushing the crushed gas clathrate aggregate and the released gas Gas clathrate and gas injection process is injected into 応管 path, it is characterized in that it comprises a.

(3) Further, in the above (1) or (2), the gas released from the crushed gas clathrate aggregate is made into fine bubbles.

(4) In addition, in the method of producing a gas clathrate by reacting a raw material liquid and a raw material gas, a mixing / dissolving step in which the raw material gas is made into fine bubbles and mixed / dissolved in the raw material liquid, and mixed / dissolved A gas clathrate generating step of generating a gas clathrate by cooling while flowing in the reaction pipe, and a gas clathrate aggregate formed by the generated gas clathrate (the gas class at the outer peripheral surface of the fine bubbles of the raw material gas) The concept includes both a shell clathrate that forms a rate and covers the entire outer surface and a gas clathrate aggregate in which the gas clathrate aggregates and the raw material gas is confined in the gap between the aggregated clathrates) And a gas clathrate injection step for injecting into a raw material liquid to be used for the mixing / dissolution step. .

(5) A gas clathrate production apparatus according to the present invention is a device for producing a gas clathrate by reacting a raw material liquid and a raw material gas. A fine bubble generator that generates bubbles and dissolves in the raw water, a reaction pipe that cools the mixture of the mixed and dissolved raw material liquid and raw material gas, and a gas clathrate coagulation formed by the generated gas clathrate Aggregate (a gas clathrate is generated on the outer peripheral surface of the fine bubbles of the raw material gas, and the shell clathrate and the gas clathrate covering the entire outer peripheral surface are agglomerated with each other, and the raw material gas is formed in the gap between the aggregated clathrates. Patent that the concept) including both trapped gas clathrates aggregates with a gas clathrate aggregates crusher for crushing in the course of the reaction pipe It is an.

(6) Also, in an apparatus for producing a gas clathrate by reacting a raw material liquid and a raw material gas, the raw material liquid and the raw material gas are mixed in the middle of the line to generate fine bubbles of the raw material gas and dissolve in the raw material water. Gas bubble extractor for extracting a gas clathrate aggregate formed by the generated gas clathrate, a fine bubble generator to be generated, a reaction pipe for cooling the mixed and dissolved raw material liquid and raw material gas mixture And the extracted gas clathrate aggregate (the gas clathrate is formed on the outer peripheral surface of the fine bubbles of the raw material gas, and the shell clathrate and the gas clathrate covering the entire outer peripheral surface are aggregated to form an aggregate. gas clathrate aggregates crusher for crushing the concept) containing both gas clathrate aggregates feed gas is confined in the gap clathrate was, Gas clathrate and gas injection device for injecting granulated gas clathrate aggregates and released gas to the reaction pipe, is characterized in that it comprises a.

(7) The gas clathrate extraction device according to the above (6) includes a branch pipe provided on the upper side in the vertical direction in the flow path downstream of the reaction pipe, and a pump provided in the branch pipe. It is characterized by comprising.
In addition, the vertical direction upper side of the flow path means that the center of the branch pipe is vertically above the center of the flow path on the downstream side of the reaction pipe.

(8) The gas clathrate extraction device according to the above (6) is characterized in that the gas clathrate extraction device includes a concentrating device using a density difference.

(9) Further, in any of the above-described (5) to (8), the apparatus includes a fine bubble generating device that converts the gas released from the crushed gas clathrate aggregate into fine bubbles. It is what.

(10) Moreover, in an apparatus for producing a gas clathrate by reacting a raw material liquid and a raw material gas, the raw material liquid and the raw material gas are mixed in the middle of the line to generate fine bubbles of the raw material gas and dissolve in the raw material water. A fine bubble generator, a reaction pipe for cooling a mixture of the mixed raw material liquid and raw material gas, and a gas clathrate aggregate formed by the generated gas clathrate (periphery of fine bubbles of the raw material gas) A gas clathrate is formed on the surface, which is a shell clathrate covering the entire outer peripheral surface, and a gas clathrate aggregate in which the gas clathrate aggregates and the raw material gas is confined in the gap between the aggregated clathrate And a gas clathrate recirculation path for returning the gas to the upstream side of the fine bubble generator.

  In the present invention, the gas clathrate aggregate formed by the generated gas clathrate is crushed to release the internal raw material gas, and the released gas is allowed to flow through the reaction pipe again. The reaction can be further advanced, and the production efficiency can be increased.

[Embodiment 1]
FIG. 1 is a system diagram showing main components of an embodiment of the present invention. First, the component apparatus of this Embodiment is demonstrated based on FIG. In the following description, natural gas hydrate (natural gas is natural gas and raw material liquid is water (freshwater or seawater)), which is attracting attention as a new transport and storage medium for natural gas (hereinafter simply referred to as “hydride”). "Rate").
The hydrate production apparatus according to the present embodiment includes a gas booster 1 that boosts the pressure of a raw material gas such as natural gas, raw water pumps 3 and 5 that pressurize raw water, and a mixture of raw water and raw material gas. A line mixer 7 for dissolving the gas in the raw water, a reaction line 9 for generating hydrate by cooling while flowing the material mixed in the line mixer 7, and a chiller 11 as a cooling device for cooling the reaction line 9. I have.
In addition, a hydrate recirculation device 15 that recirculates a part of the hydrate by returning the hydrate aggregate formed by the hydrate generated in the reaction pipe to the reaction pipe 9 is provided.
Further, a post-processing device 17 that performs post-processing of the generated hydrate is provided.
Each component device is connected by a pipe indicated by a solid line with an arrow in the figure.
In FIG. 1, various control valves and the like are omitted in order to avoid complication of the drawing.

The configuration of main components among the above-described components will be described in more detail.
<Line mixer>
As shown in FIG. 2 (cited from page 7 of the “OHR Line Mixer” catalog of Nishika Sangyo Co., Ltd.), the line mixer 7 of the present embodiment has a two-stage shape with a large diameter on the inlet side and a small diameter on the outlet side. A plurality of mushrooms comprising a cylindrical body 21, having a wing body 23 called a guide vane in a large diameter portion 21a of the cylindrical body 21, and extending from the inner peripheral surface of the cylinder to the center in a small diameter portion 21b. A collision body 25 having a shape is included.
In such a line mixer 7, the raw water supplied to the line mixer 7 by the raw water pump 3 is swirled by the wing body 23 and pushed outward by a violent centrifugal force, which is a mushroom-like collision body 25. The raw material gas is engulfed therein and crushed into ultrafine bubbles, and the raw material water and the raw material gas are mixed. As a result, the contact area between the source gas and the source water is increased, and the source gas is efficiently dissolved in the source water.

  In addition, as a fine bubble generator, it replaces with the line mixer 7 and a venturi tube may be used, and the other apparatus which can make gas fine bubbles can be used.

<Reaction pipeline>
The reaction pipe 9 is composed of one or a plurality of bent pipes, and the peripheral surface of the pipe is cooled by a chiller 11. As described above, since the reaction pipe 9 is used, cooling from the surroundings can be performed efficiently, so that the configuration of the apparatus can be simplified and made compact.
Specific examples of the reaction pipe 9 include a double pipe heat exchanger in which a passage through which a refrigerant flows is formed around a pipe through which a raw material gas and a raw material liquid flow, and a shell and tube heat exchanger (multi-tubular cylindrical type). Heat exchanger).

<Hydrate recirculation device>
The hydrate recirculation device 15 is a device for returning the hydrate aggregates formed by the hydrate that has already been produced into the reaction pipe for recirculation. In this embodiment, the hydrate recirculation device 15 has one end connected to the extraction pipe 40 on the downstream side of the reaction pipe 9 and the other end connected to the middle of the reaction pipe 9 so as to be a part of the hydrate aggregate. Is returned to the reaction pipe 9, a pump 53 provided in the return pipe 51 for sending hydrate aggregates to the reaction pipe side, and a hydrate provided in the return pipe 51 and sent by the pump 53. A hydrate crushing / bubble refining device 55 that crushes the aggregates and makes the gas released by crushing into fine bubbles is provided as a main component.

  The connection position of the return pipe 51 with the reaction pipe line 9 is preferably a position where the degree of supercooling of the fluid in the reaction pipe line is 4 ° C. or less, more preferably 2 ° C. or less. By connecting the return pipe 51 to this position, the crushed hydrate is injected at this position. Since this position is in a supercooled state, generation of hydrate starts using the injected hydrate as a crystal nucleus. Details will be described later.

The amount of hydrate aggregate returned to the return pipe 51 side can be adjusted by the flow rate of the pump 53.
The hydrate crushing / bubble refining device 55 crushes the hydrate aggregate and gasifies the gas released by crushing.
As a specific example of such a hydrate crushing / bubble refining device 55, the same one as the above-mentioned fine bubble generator, that is, a line mixer, a venturi tube, or the like can be used. In some cases, the hydrate aggregates can be crushed and the bubbles of the released gas can be refined with a single device. The mechanism of crushing and bubble refinement in these devices is as follows.
When a line mixer is used, the hydrate is crushed by vigorous shearing, and at the same time, the released gas is made into fine bubbles by shearing.
Further, when a venturi tube is used, it is crushed by the internal pressure of the shell-like hydrate or aggregate gap in the low pressure portion, and the released gas is made into fine bubbles by the impact of the rapid pressure recovery portion in the venturi tube.

<Post-processing device>
The post-treatment device 17 collects the hydrate, unreacted gas, and unreacted water mixture from the produced hydrate, unreacted gas, and unreacted water, a separation device that separates the hydrate, unreacted gas, and unreacted water. It includes an agglomerating apparatus for agglomerating and a freezing apparatus for freezing the agglomerated hydrate at a temperature of about −15 ° C.

Next, a manufacturing process for manufacturing a hydrate using the apparatus of the present embodiment configured as described above will be described.
The pressure of the raw material gas such as natural gas is increased to a predetermined pressure sufficient for hydrate generation by the gas booster 1. The raw water (unreacted water and / or make-up water separated by the separator) is also boosted to a predetermined pressure by the raw water pump 3. These pressurized source gas and source water are cooled by a cooler (not shown) and supplied to the line mixer 7 respectively.
The raw material gas and raw material water supplied to the line mixer 7 are mixed with a violent momentum by the mechanism described above. At this time, the raw material gas becomes fine bubbles and is mixed into the raw material water, and the dissolution of the raw material gas is promoted.

A raw material gas dissolved in raw water (including undissolved fine bubbles) is sent to the reaction pipe 9, cooled by a chiller 11, and mixed and dissolved in the raw water. Is started.
At the outlet of the reaction pipe 9, a part of the fluid (hydrate, unreacted gas, unreacted water mixture) at the outlet of the reaction pipe is sent to the return pipe 51 connected to the extraction pipe 40. Hydrates in this mixture form hydrate aggregates and are in a state of trapping unreacted gas. When the mixture is supplied to the hydrate crushing / bubble refiner 55, the hydrate aggregates are crushed, the trapped gas is released, and the released gas is mixed and dissolved as fine bubbles in unreacted water. To do. Since this is returned to the middle of the reaction pipe 9 again, the released gas can be hydrated, and the conversion efficiency to hydrate is improved.

Moreover, crushing the hydrate aggregates and returning them to the reaction line 9 has the effect of preventing the blockage of the reaction line 9 in addition to the effect of improving the hydrate conversion efficiency. This point will be described below. In order to more effectively expect the effect of preventing the reaction line 9 from being blocked, it is preferable that the degree of supercooling is returned to a position of 4 ° C. or less in the middle of the reaction line 9 as described above.
When the hydrate is returned to the reaction pipe 9, this becomes a crystal nucleus, and hydrate conversion of the raw material gas mixed and dissolved in the raw water is started.

At this time, the degree of supercooling is 4 ° C. or less, and the degree of supercooling is relatively small, so that the production reaction proceeds slowly rather than rapidly. Moreover, since the injected crystal nuclei spread over the entire cross section of the reaction pipe and hydrate formation proceeds by the crystal nuclei, not only the wall surface of the reaction pipe with the highest degree of supercooling in the cross section of the reaction pipe, but also from the wall. The production reaction proceeds even in a sufficiently central part of the reaction pipe.
As described above, since the production reaction itself is gentle, the reaction pipe line 9 is prevented from being blocked due to the rapid production of a large amount of hydrate.
In addition, since hydrate is generated in the entire region in the cross section of the reaction pipe, the wall surface where the degree of supercooling is maximum in the cross section of the reaction pipe and the wall due to the intensive formation of hydrate in the very vicinity thereof. Occlusion due to adhesion and growth is also prevented.

The hydrate and unreacted gas that have not been returned to the return pipe 51 at the outlet of the reaction pipe 9 are sent to the post-processing device 17 for post-processing. The hydrate separated by the post-processing apparatus is further subjected to processing such as dehydration, stabilization, molding, etc. in the apparatus or in another apparatus, and is transferred to the next step.
The unreacted water separated by the post-treatment device 17 is sent again to the fine bubble generator 7 by the pump 5 and becomes raw water.
In addition, the unreacted gas separated by the post-processing device 17 is supplied to the fine bubble generator 7 again after being pressurized by a booster (not shown) via a pipe (not shown).

  As described above, in the present embodiment, the hydrate aggregate is crushed to release the gas contained in the hydrate aggregate and return to the reaction pipe 9 again, so the present invention must be used. It becomes possible to hydrate the gas that has remained unreacted in the inside of the shell hydrate or in the gaps between the hydrate aggregates, and the hydrate conversion rate of the raw material gas is improved.

In addition, since the hydrate that has been crushed is returned to the reaction line 9, the hydrate formation reaction can be allowed to proceed slowly with a relatively low degree of supercooling, and at the lowest temperature in the cross section of the reaction line. The hydrate formation reaction can proceed not only at the wall surface with a high degree of cooling, or in the very vicinity thereof, but also at the center of the pipe cross section.
As a result, it is possible to prevent the reaction line 9 from being blocked, and to maximize the features of the fine bubble flow method.

  In the above embodiment, the type of raw material water is not specified, but, for example, fresh water, seawater, antifreeze, and the like are conceivable. It is also conceivable to use a raw material liquid such as a liquid host material or a host material solution instead of the raw water. It goes without saying that the name of the substance produced in this case is not gas hydrate but gas clathrate.

It should be noted that the effect of the present invention can be further enhanced if a part of the fluid is extracted from the outlet of the reaction pipe if it is extracted from a relatively upper part of the extraction pipe 40.
In other words, hydrate aggregates in which unreacted gas is confined in shell-like hydrates and gaps have a smaller apparent density than other hydrates because of gas in the interior and gaps. A large amount of unreacted gas other than the trapped gas is also present in the upper part of the pipe, so that they are again led to the hydrate crushing / bubble refiner 55 to be microbubbled, and again This is because it will flow through the reaction pipe and be hydrated.

Moreover, the same effect as extracting from the comparatively upper part of the extraction piping 40 mentioned above can be implement | achieved also by providing the concentrator (for example, the concentrator by centrifugal force) using a density difference in the extraction part.
The concentrator is not particularly limited as long as it can mainly separate unreacted water from a mixture of hydrate, unreacted gas, and unreacted water flowing out from the outlet of the reaction pipe. For example, a swirling flow type concentrating device can be used.
FIG. 3 is an explanatory diagram of a swirling flow type concentrator. Based on FIG. 3, the function of the apparatus will be outlined.
A mixture of hydrate, unreacted gas and unreacted water flows from the tangential inflow pipe 31 in the tangential direction of the inflow portion large diameter cylinder 33, and a swirl flow is formed in the inflow portion large diameter cylinder 33. Thereafter, the mixture of hydrate, unreacted gas, and unreacted water passes through the gradually reducing pipe 35 to strengthen the swirling flow, and a strong swirling flow having a large free vortex component is formed in the swirling flow pipe 37. Is done.

When a swirl flow is formed, hydrate and unreacted gas having a specific gravity smaller than that of water are concentrated near the center, and the concentrated hydrate and unreacted gas are concentric downstream provided in the swirl flow line 37. It is extracted from the extraction tube 39. In this way, a part of what is extracted from the downstream extraction pipe 39 is returned to the return pipe 51, and the rest is sent to the post-processing device 17.
On the other hand, the unreacted water separated from the hydrate and unreacted gas is discharged from the downstream extraction pipe 41 provided on the downstream side wall of the swirling flow line 37, and is again regenerated by the fine bubble generator 7 by a pump (not shown). To be used as raw material water.

  By using a concentrating device, unreacted water can be separated from the mixture of hydrate, unreacted gas, and unreacted water and returned to the fine bubble generator 7 side. Part) and the processing capacity can be reduced, the load on the post-processing device 17 can be reduced, and the equipment can be made compact.

[Embodiment 2]
FIG. 4 is an explanatory diagram of the second embodiment of the present invention, and the same or corresponding parts as those of the first embodiment are denoted by the same reference numerals.
In the present embodiment, the return pipe 51 in the hydrate recirculation device 15 is connected to the upstream side of the line mixer 7, and the hydrate crushing / bubble refiner 55 in the first embodiment is omitted.

  In the present embodiment, the fine bubble generator 7 functions as the hydrate crushing / bubble refiner 55 in the first embodiment. Therefore, there is no need to install a separate hydrate crushing / bubble micronizer 55, so that the apparatus configuration can be simplified.

  In the above-described embodiment, the hydrate aggregates are once extracted after passing through the reaction pipe 9 and returned to the reaction pipe again. By installing a generator, the hydrate aggregates may be crushed and the bubbles may be refined in the middle of the reaction line 9. Thus, the method of installing the hydrate crushing / bubble refiner in the middle of the reaction pipe line 9 may be performed alone or in combination with the first and second embodiments.

It is explanatory drawing of the apparatus structure which concerns on one embodiment of this invention. It is explanatory drawing of the line mixer which concerns on one Embodiment of this invention. It is explanatory drawing of the concentration apparatus used for one Embodiment of this invention. It is explanatory drawing of the apparatus structure which concerns on other embodiment of this invention.

Explanation of symbols

    7 fine bubble generator, 9 reaction line, 11 chiller, 13 concentrator, 15 hydrate recirculator, 51 return pipe, 53 pump, 55 hydrate crusher / bubble refiner.

Claims (10)

In a method for producing a gas clathrate by reacting a raw material liquid and a raw material gas, a mixing / dissolving process in which the raw material gas is made into fine bubbles and mixed / dissolved in the raw material liquid; A gas clathrate generating step for generating a gas clathrate by cooling while flowing, and a gas clathrate aggregate formed by the generated gas clathrate (a gas clathrate is generated at the outer peripheral surface of the fine bubbles of the raw material gas, This concept includes both a shell clathrate and gas clathrate covering the entire outer peripheral surface and a gas clathrate aggregate in which the raw material gas is confined in a gap between the aggregated clathrate). And a gas clathrate aggregate crushing step for crushing in the middle of the gas clathrate production method. In a method for producing a gas clathrate by reacting a raw material liquid and a raw material gas, a mixing / dissolving process in which the raw material gas is made into fine bubbles and mixed / dissolved in the raw material liquid; A gas clathrate generating step for generating a gas clathrate by cooling while flowing, and a gas clathrate aggregate formed by the generated gas clathrate (a gas clathrate is generated at the outer peripheral surface of the fine bubbles of the raw material gas, This is a concept that includes both gas clathrate aggregates in which the shell clathrate and gas clathrate covering the entire outer peripheral surface are aggregated and the raw material gas is confined in the gaps between the aggregated clathrate). Gas clathrate aggregate extraction and crushing process, and the crushed gas clathrate aggregate and released gas are poured into the reaction line. Gas clathrate production method and gas clathrates and gas injection process is, comprising the to.   The gas clathrate production method according to claim 1 or 2, wherein the gas released from the crushed gas clathrate aggregate is made into fine bubbles. In a method for producing a gas clathrate by reacting a raw material liquid and a raw material gas, a mixing / dissolving process in which the raw material gas is made into fine bubbles and mixed / dissolved in the raw material liquid; A gas clathrate production step for producing a gas clathrate by cooling while flowing, and a gas clathrate aggregate formed by the produced gas clathrate (a gas clathrate is produced at the outer peripheral surface of the fine bubbles of the raw material gas, This is a concept including both gas clathrate aggregates in which the shell clathrate and gas clathrate covering the entire outer peripheral surface are aggregated and the raw material gas is confined in the gaps between the aggregated clathrate). A gas clathrate production characterized by comprising: a gas clathrate injection step for injecting into a raw material liquid to be used for the dissolution step Law. In an apparatus for producing a gas clathrate by reacting a raw material liquid and a raw material gas, a fine bubble generator for mixing the raw material liquid and the raw material gas in the middle of the line to generate fine bubbles of the raw material gas and dissolving it in the raw material water And a reaction pipe line for cooling the mixture of the mixed raw material liquid and the raw material gas, and a gas clathrate aggregate formed by the generated gas clathrate ( a gas clathrate on the outer peripheral surface of the fine bubbles of the raw material gas) This includes a shell clathrate that covers the entire outer peripheral surface and a gas clathrate aggregate in which the gas clathrate aggregates and the raw material gas is confined in the gap between the aggregated clathrate) A gas clathrate agglomeration device for crushing in the middle of the reaction pipe. In an apparatus for producing a gas clathrate by reacting a raw material liquid and a raw material gas, a fine bubble generator for mixing the raw material liquid and the raw material gas in the middle of the line to generate fine bubbles of the raw material gas and dissolving it in the raw material water And a reaction pipe line for cooling the mixture of the mixed raw material liquid and the raw material gas, and a gas clathrate aggregate formed by the generated gas clathrate ( a gas clathrate on the outer peripheral surface of the fine bubbles of the raw material gas) This includes a shell clathrate that covers the entire outer peripheral surface and a gas clathrate aggregate in which the gas clathrate aggregates and the raw material gas is confined in the gap between the aggregated clathrate) A gas clathrate extractor for extraction, a gas clathrate aggregate crusher for crushing the extracted gas clathrate agglomerate, and a crushed gas Clathrate aggregates and gas clathrates and gas injection device to release gas injected into the reaction pipe, a gas clathrate production apparatus characterized by comprising a.   The gas clathrate extraction device comprises a branch pipe provided on the upper side in the vertical direction in the flow path downstream of the reaction pipe, and a pump provided in the branch pipe. 6. The gas clathrate production apparatus according to 6.   The gas clathrate extraction apparatus according to claim 6, wherein the gas clathrate extraction apparatus includes a concentrator using a density difference.   The gas clathrate production apparatus according to any one of claims 5 to 8, further comprising a fine bubble generating device that makes a gas released from the crushed gas clathrate aggregate into fine bubbles. In an apparatus for producing a gas clathrate by reacting a raw material liquid and a raw material gas, a fine bubble generator for mixing the raw material liquid and the raw material gas in the middle of the line to generate fine bubbles of the raw material gas and dissolving it in the raw material water And a reaction pipe line for cooling the mixed and dissolved raw material liquid and raw material gas mixture, and a gas clathrate aggregate formed by the generated gas clathrate (the gas clathrate on the outer peripheral surface of the fine bubbles of the raw material gas) This includes a shell clathrate that covers the entire outer peripheral surface and a gas clathrate aggregate in which the gas clathrate aggregates and the raw material gas is confined in the gap between the aggregated clathrate) And a gas clathrate recirculation passage returning to the upstream side of the fine bubble generator.

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