JP4062510B2 - Gas clathrate manufacturing method and manufacturing apparatus - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a gas clathrate production apparatus for producing a gas clathrate by reacting a raw material gas such as natural gas with a raw material liquid (fresh water, seawater, antifreeze liquid, etc.).
[0002]
[Prior art]
The gas clathrate (simply referred to as “clathrate”. In addition, when the host substance is water, it is referred to as “gas hydrate”, but in the present specification, “gas clathrate” includes gas hydrate). It is an ice-like substance that contains gas molecules such as natural gas and carbon dioxide in a high concentration inside the cage structure composed of 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.
[0003]
The conventional gas hydrate production method is a method for producing hydrate by reacting water with a hydrate-forming substance in a hydrate-generating container. In the method for producing hydrate, bubbles are formed in the hydrate-forming substance in the aqueous phase in the hydrate-generating container. There is one that supplies and causes a hydration reaction by spraying water in the vapor phase in the hydrate production vessel in a sprayed state (for example, see Patent Document 1).
[0004]
In addition, there is one in which a plurality of hydrate production units are connected in series for the purpose of obtaining a mixed gas such as natural gas having the same composition as the initial mixed gas composition (see, for example, Patent Document 2).
[0005]
[Patent Document 1]
JP 2000-264851 A [Patent Document 2]
Japanese Patent Laid-Open No. 2001-10985
[Problems to be solved by the invention]
However, the above prior art has the following problems.
In the prior art described in Patent Document 1, the entire amount of the raw material gas supplied in the hydrate production container cannot be hydrated. Therefore, when a mixed gas such as natural gas (for example, a mixed gas of methane, ethane, propane, or butane) is used as a raw material gas, a gas with a low production pressure that is likely to be hydrated (butane is the most hydrated in this example). There is a problem that the gas composition of the raw material gas and the hydrate is different as a result.
[0007]
In addition, a configuration in which a plurality of hydrate production units are connected in series has a problem that the apparatus becomes complicated and the cost increases.
[0008]
The present invention has been made to solve such problems, and an object of the present invention is to obtain a gas clathrate production apparatus capable of producing a gas clathrate having the same composition as that of the raw material gas in a simple and compact manner.
[0009]
[Means for Solving the Problems]
(1) A gas clathrate production apparatus according to the present invention is an apparatus for producing a gas clathrate by reacting a raw material liquid and a raw material gas.
A gas flow rate adjusting means for adjusting the flow rate of the raw material gas to be supplied, a gas pressure adjusting means for adjusting the pressure of the raw material gas, a raw material liquid flow rate adjusting means for adjusting the flow rate of the supplied raw material liquid, and a raw material for adjusting the pressure of the raw material liquid Liquid pressure adjusting means, a line mixer for mixing the raw material liquid and the raw material gas in the middle of the line and dissolving the raw material gas in the raw material liquid, and a reaction line for cooling while flowing the mixed raw material liquid A cooling device for cooling the reaction pipe, and pressure adjusting means for adjusting the pressure of the reaction pipe,
The gas flow rate adjusting means, the gas pressure adjusting means, the raw material liquid flow rate adjusting means, the raw material liquid pressure adjusting means, and the cooling capacity of the cooling device so that the total amount of the raw material gas supplied to the line mixer can be clathrated. When setting the reaction pipe length and the reaction pipe diameter, and providing a pressure detector for detecting the pressure at the outlet of the reaction pipe, when the detected value of the pressure detector exceeds a predetermined value One or both of the gas flow rate adjusting means and the raw material liquid flow rate adjusting means are adjusted.
[0010]
(2) In an apparatus for producing a gas clathrate by reacting a raw material liquid and a raw material gas,
A gas flow rate adjusting means for adjusting the flow rate of the raw material gas to be supplied, a gas pressure adjusting means for adjusting the pressure of the raw material gas, a raw material liquid flow rate adjusting means for adjusting the flow rate of the supplied raw material liquid, and a raw material for adjusting the pressure of the raw material liquid Liquid pressure adjusting means, a line mixer for mixing the raw material liquid and the raw material gas in the middle of the line and dissolving the raw material gas in the raw material liquid, and a reaction line for cooling while flowing the mixed raw material liquid A cooling device for cooling the reaction pipe, and pressure adjusting means for adjusting the pressure of the reaction pipe,
The pressure P at the outlet of the reaction pipe is higher than the clathrate generation minimum pressure P ₀ , the temperature T in the reaction pipe is lower than the clathrate generation maximum temperature T ₀ , and the raw material supplied to the line mixer The gas flow rate adjusting means, the gas pressure adjusting means, the raw material liquid flow rate adjusting means, the raw material liquid pressure adjusting means, the cooling capacity of the cooling device, so that all the generated heat when the gas is clathrated can be completely removed, While setting the reaction pipe length and the reaction pipe diameter, a pressure detector for detecting the pressure at the outlet of the reaction pipe is provided, and when the detected value of the pressure detector exceeds a predetermined value, One or both of the gas flow rate adjusting means and the raw material liquid flow rate adjusting means are adjusted.
[0011]
(3) Further, in the above (1) or (2), the line mixer generates a fine bubble of a raw material gas.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
In the following embodiments, a gas hydrate which is an aspect of a gas clathrate will be described as an example.
FIG. 6 is an explanatory view of the outline of a gas hydrate production process according to an embodiment of the present invention, and shows a case where natural gas is used as a raw material gas. First, the outline of the gas hydrate manufacturing process will be described with reference to FIG.
Natural gas is cooled to 1 to 10 ° C. and heavy components are separated as condensate (S1). On the other hand, the water is also cooled to 1 to 10 ° C. (S2), and the cooling water and natural gas react at 1 to 10 ° C. and 50 atm to generate gas hydrate (S3). The generated slurry-like gas hydrate is separated and dehydrated to form a highly concentrated slurry or solid (S4), and the water and unreacted gas separated here are returned to the reaction step (S3) again.
[0016]
The separated and dehydrated gas hydrate is frozen at a temperature of about −15 ° C. (S5). This freezing treatment is intended to stabilize the gas hydrate by freezing the water adhering to the surface of the gas hydrate that has been separated and dehydrated in S4 to form an ice shell.
After the freezing process, a depressurizing process is performed to depressurize from 50 atm to atmospheric (S6). Thereafter, the frozen gas hydrate is formed into pellets (S7), stored in a storage facility such as a silo (S8), and loaded on a loading facility such as a belt conveyor as required (S9). It is used for long-distance transportation by a transportation device such as a transportation ship (S10).
The above is the outline of the gas hydrate manufacturing process. In the present embodiment, the entire amount can be hydrated in the step (S3) of generating a slurry gas hydrate from water and natural gas in the above process. By doing so, the composition of the raw material gas composed of the composite gas and the composition of the hydrate are made the same. Hereinafter, this point will be described in detail.
[0017]
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.
The gas hydrate production apparatus of the present embodiment includes a gas booster 1 (corresponding to the gas pressure adjusting means of the present invention) that boosts the pressure of a raw material gas such as natural gas, and a raw water pump 3 that boosts the raw water. , 19 (corresponding to the raw water pressure adjusting means of the present invention), the raw water and the raw material gas are mixed to dissolve the raw material gas in the raw material water, and the mixture mixed by the line mixer 5 is cooled while flowing. A reaction line 7 for generating gas hydrate, a chiller 17 as a cooling device for cooling the reaction line 7, and a separator 9 for separating the gas hydrate generated in the reaction line 7 and raw water. Yes.
[0018]
And each component apparatus is connected by piping shown with the continuous line which attached the arrow in the figure. Further, the separator 9 is provided with a pressure detector 10, and a valve 12a (corresponding to a gas flow rate adjusting means) and a valve 12b (corresponding to a raw material water amount adjusting means) installed in a piping line by a signal of the pressure detector 10 The valve 12c (corresponding to the gas pressure adjusting means) is controlled to adjust the pressure and flow rate of the piping line.
[0019]
In the above configuration, the pressure P of the separator 9 (corresponding to the pressure at the outlet of the reaction pipe 7) is higher than the lowest hydrate generation pressure P ₀ , and the temperature T in the reaction pipe 7 is the highest hydrate generation temperature T _0. The cooling capacity of the valves 12a, 12b, 12c, the gas booster 1, the raw material water pumps 3, 19, the chiller 17, the length of the reaction pipe 7 and the diameter of the reaction pipe 7 are set so that the temperature becomes lower. ing.
Even in the same chiller, the cooling capacity (heat removal amount per unit time) of the chiller varies depending on the temperature of the refrigerant, and the higher the refrigerant temperature, the larger the cooling capacity. Therefore, “setting of the cooling capacity” in the present invention includes setting of the temperature of the refrigerant that cools the reaction pipe line 7.
[0020]
The configuration of main components among the above-described components will be described in more detail.
As shown in FIG. 2 (cited from page 7 of “OHR Line Mixer” catalog of Nishika Sangyo Co., Ltd.), the line mixer 5 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 11 and having a wing body 13 called a guide vane in a large diameter portion 11a of the cylindrical body 11, and extending from the inner peripheral surface of the cylinder to the center in a small diameter portion 11b. A colliding body 15 is provided.
In such a line mixer 5, the raw water supplied to the line mixer 5 by the raw water pump 3 is swirled by the wing body 13 and pushed outward by a violent centrifugal force, which is a mushroom-like collision body 15. 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.
[0021]
The reaction pipe 7 is composed of one or a plurality of bent pipes, and the peripheral surface of the pipe is cooled by a chiller 17. As described above, since the reaction pipe 7 is used, cooling from the surroundings can be efficiently performed, so that the gas / raw water is supplied by a cooling coil or the like as in the conventional examples shown in Patent Documents 1 and 2. There is no need for direct cooling, and the configuration of the apparatus can be simplified and made compact.
[0022]
Specific examples of the reaction pipe 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 heat exchanger). Etc.).
[0023]
By the way, the reaction pipe line 7 as described above can be used because the raw material gas and the raw water are mixed and dissolved by the line mixer 5 in advance, and the reaction pipe line 7 can be thought of as an apparatus configuration focusing on cooling. Because it can. That is, in the examples shown in Patent Documents 1 and 2, mixing / dissolution and reaction cooling of the source gas and source water are performed in a tank-shaped pressure vessel, so a space with a certain spread is required for mixing / dissolution. However, in this embodiment, since mixing and dissolution of raw material gas and raw material water and reaction cooling were separated, cooling could not be performed only from the periphery of the reaction vessel. Thus, cooling with a simple configuration as in the above example is possible.
[0024]
The separator 9 mainly separates gas hydrate and raw water. Examples of the separator 9 include a decanter, a cyclone, a centrifuge, a belt press, a screw concentrator / dehydrator, and a rotary dryer. It is done.
The separator 9 is supplied with a pressurized source gas, and the pressure of the separator 9 is adjusted to be higher than the lowest hydrate generation pressure P ₀ by this source gas pressure. By adjusting the pressure of the separator 9 to be higher than P ₀ , the pressure in the reaction pipe line 7 on the upstream side becomes higher than P ₀ .
[0025]
Next, a manufacturing process for manufacturing a gas hydrate by the apparatus of the present embodiment configured as described above will be described.
The pressure of the source gas is increased to a predetermined pressure by the gas booster 1. The raw water 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 5 respectively. The raw material gas and the raw water supplied to the line mixer 5 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.
[0026]
A raw material gas dissolved in raw water (including undissolved fine bubbles) is sent to the reaction pipe 7, cooled by a chiller 17, and converted into fine bubbles and mixed and dissolved in the raw water. The raw material gas is entirely gas hydrated.
[0027]
In order to realize the total gas hydrate conversion, the pressure P at the outlet of the reaction pipe is higher than the lowest hydrate generation pressure P ₀ , and the temperature T in the reaction pipe is lower than the highest hydrate generation temperature T _0. The raw material liquid flow rate, the raw material liquid pressure, the raw material gas flow rate, the raw material gas pressure, the cooling capacity, so that all the heat generated when the raw material gas mixed and dissolved by the line mixer 5 is hydrated can be completely removed. It is necessary to set the reaction pipe length and the reaction pipe diameter.
That is, in order to increase the total amount of hydrate, it is necessary to set seven parameters such as the raw material liquid flow rate, the raw material liquid pressure, the raw material gas flow rate, the raw material gas pressure, the cooling capacity, the reaction pipe length, and the reaction pipe diameter. Hereinafter, the relationship between these parameters and the hydrate generation amount will be described.
[0028]
First, the relationship between the raw material water flow rate and the amount of hydrate produced when there is sufficient cooling capacity will be described.
When the amount of water is larger than the amount of water determined from the hydration number of the hydrate (below), the flow rate of the raw water is basically irrelevant to the amount of hydrate produced.
Hydrate hydration number (composition ratio of water and gas: ratio of water molecule to gas molecule in hydrate) is theoretically 5.75 for methane hydrate (water per mole of gas molecule). Molecule 5.75 mol). However, since gas molecules do not necessarily enter all the ridges formed with water molecules, the hydration number is greater than 5.75 (more than 5.75 mol of water molecules per mol of gas molecules). It is.
[0029]
When the amount of raw material water is less than the amount determined from the hydration number, the amount of hydrate produced is proportional to the raw material water flow rate. In this case, a hydrate of gas and solid remains when the generation is completed.
Strictly speaking, it is conceivable that the amount of generated water is changed due to a change in the heat transfer coefficient on the inner surface of the pipe (a change in cooling efficiency) with a change in the raw material water flow rate (= change in flow velocity in the reaction pipe).
[0030]
The relationship between the raw material gas flow rate and the hydrate production amount is the same as the relationship with the raw material water flow rate. That is, when there is sufficient cooling capacity, the gas flow rate is irrelevant to the amount of hydrate produced when there is more gas than the amount of gas determined from the hydration number of the hydrate. On the other hand, when the amount of gas is less than the amount determined from the hydration number, the amount of hydrate produced is proportional to the gas flow rate. In this case, raw water and solid hydrate remain when the generation is completed.
[0031]
In the present embodiment, a pump 19 is provided to return the unreacted raw water separated by the separator in FIG. 1 to the line mixer, and the raw water is more than the amount determined from the hydration number, and the raw gas is It is assumed that hydrate is generated by supplying a small amount.
[0032]
Next, the relationship between the raw material water and the pressure and temperature of the raw material gas and the amount of hydrate produced will be described.
Within the hydrate generation range, the higher the pressure and the lower the temperature, the easier it is to generate. Therefore, when there is sufficient cooling capacity (heat removal heat per unit time), the generation rate is higher as the pressure is higher and the temperature is lower in the generation range. When the cooling capacity is limited, the generation rate is determined by the cooling capacity.
When mixing and dissolving the raw material gas and raw material water, the pressures of both are the same except when considered from a very microscopic viewpoint.
Moreover, although the temperature of both may differ at the beginning of mixing, it becomes equal while flowing through the reaction pipe.
[0033]
Next, the relationship between the cooling capacity and the hydrate generation amount will be described.
When the raw material gas is methane, the calorific value (generated heat) associated with hydrate formation is as follows per mole of methane.
・ Approximately 14.5 kcal / mol (at 0 ℃)
・ About 17 kcal / mol (at 10 ℃)
[0034]
If the gas diffusion and dissolution in the raw material water is sufficient, the amount of hydrate produced is proportional to the amount of cooling (heat removal) heat. Therefore, if the gas diffusion and dissolution into the raw material water is sufficient, but the cooling capacity is insufficient, the temperature of the raw material water in which the raw material gas is dissolved rises along with the hydrate formation, and the hydrate corresponding to the pressure at that time Generation stops when the maximum production temperature (higher pressure is reached) is reached. If there is an unreacted source gas at that time, it remains as a dissolved gas in the source water or in the form of bubbles. In other words, the sufficient cooling capacity means that the temperature can be kept within the generation range while the entire amount of the raw material gas is hydrated.
[0035]
However, when the cooling capacity is excessive, the fluid temperature in the reaction pipe line is lowered while hydration progresses, and there is a risk of freezing. Therefore, the cooling capacity is not necessarily large.
The cooling capacity is determined by the capacity of the chiller and the reaction pipe specifications (pipe length, diameter, wall thickness, material, etc.), and the heat transfer capacity determined by the temperature difference between the refrigerant and the fluid in the reaction pipe.
[0036]
Finally, the relationship between the reaction pipe length and the reaction pipe diameter and the amount of hydrate produced will be described.
In general, the reaction pipe length and the reaction pipe diameter are set so as to make full use of the cooling capacity of the chiller, so that the reaction pipe length and the reaction pipe diameter are not related to the amount of hydrate produced alone. It is related to hydrate generation through the parameter of cooling capacity. This will be specifically described below.
As for the relationship between the reaction pipe length and the cooling capacity, when the other conditions are the same, the longer the reaction pipe length, the larger the cooling capacity. The relationship between the reaction pipe diameter and the cooling capacity is a little more complicated. If the pipe diameter is reduced, the flow velocity in the pipe increases and the heat transfer coefficient inside the pipe increases, but the surface area of the pipe decreases. There is a relationship that increases and decreases in
By the way, in general, in heat exchangers, the pipe diameter is reduced to increase the pipe inner surface heat transfer coefficient, and the surface area is reduced by increasing the pipe length or the number of pipes. And
[0037]
The relationship between the hydrate generation amount and the seven parameters is as described above. Hereinafter, the mechanism of the total amount hydrate will be described on the assumption that these parameters are appropriately set.
FIG. 3 is an explanatory diagram for explaining the mechanism of hydration of the total amount in the reaction pipe line 7. Focusing on a certain amount of raw material gas supplied to the reaction pipe line 7, this raw material gas is hydrated. The mechanism which performs is typically shown with progress of time.
In FIG. 3, the vertical axis represents raw material gas and raw water (hereinafter, “raw water” means both raw water only and raw water dissolved) ), The amount of gas hydrate, the upper side of the bold line is methane, and the lower side is propane. The horizontal axis indicates the flow of time, and the time to be noted is indicated by (1) to ○ 10 (indicated by circled numbers in the figure, the same applies hereinafter) (this (1) to ○ 10). In order to clarify the positional relationship in the system diagram 1 of FIG.
For convenience of explanation, it is assumed that the raw material gas is a mixed gas of two types of gas, methane and propane, and the ratio is 17: 6 for methane: propane (see (1)).
[0038]
In the line mixer 5, the raw material gas and the return water (the mixed gas is dissolved in the raw material water to reach an equilibrium concentration) and make-up water are mixed (see (2)). In FIG. 3, the gas is not dissolved immediately after mixing.
The raw material gas becomes fine bubbles by the line mixer 5 and dissolves in the raw material water, so that the whole raw material water reaches an equilibrium concentration (see (3)).
[0039]
When the raw water reaches the equilibrium concentration, the pressure P in the reaction line 7 is set higher than the lowest hydrate generation pressure P _{0 and} the temperature T in the reaction line 7 is set lower than the highest hydrate generation temperature T _0. Therefore, generation of gas hydrate is started. At this time, methane and propane are dissolved in the raw water, but since propane is more easily hydrated, a gas hydrate having a higher propane content than the raw material gas composition is generated (4). Reference: In the figure, the graph showing the amount of gas hydrate is one memory above the bold line and two memories below.
[0040]
Although the generation of gas hydrate involves heat generation, the temperature of the reaction line 7 is kept at a temperature lower than the maximum hydrate generation temperature T ₀ by removing the heat corresponding to the heat generation amount by cooling the chiller 17. Be drunk. In order to increase the speed of hydration, it is better to set the temperature to be somewhat lower than T ₀ and set the pressure to be higher than P ₀ to some extent. The temperature reduction range is preferably about 2 ° C. or higher. However, if the water is cooled too much, the raw water is solidified and the flow in the reaction pipe 7 is hindered. Therefore, the cooling capacity in the chiller 17 is set so that the raw water does not fall below the freezing point.
When gas hydrate is generated, the amount of raw material water also decreases. However, in order to avoid complication of the figure, the amount of raw material water is from (4) to (9) in FIG. It is described so as not to change.
[0041]
When the gas hydrate is generated, the dissolved gas concentration decreases, and the raw material gas further dissolves until the equilibrium concentration is reached, and further gas hydrate with a high propane content is generated (see (5) (6)). The gas hydrate flows through the reaction line 7 together with the raw water.
Since the total amount of propane was dissolved in the raw water in (6), only methane was dissolved in the raw water, and gas hydrates containing more methane than the raw material gas composition began to form (see (7)). ), The same reaction continues (see (8) and (9)).
At the outlet of the reaction pipe 7, the entire amount of the supplied raw material gas is hydrated (see ○ 10) and sent to the separator 9 together with the raw water.
[0042]
The gas hydrate with a high content of propane produced in the first half and the gas hydrate with a high content of methane produced in the second half are sent to the separator 9 after the start of the reaction in the reaction line 7. However, since the total amount of the raw material gas is hydrated, the entire generated hydrate has the same composition as the raw material gas.
In addition, in (circle) 10, the reduction | decrease of raw material water by reaction of (4)-(circle) 10 is expressed in the form put together. In ○ 10, the raw material water of equilibrium concentration remains, but this is supplied again to the line mixer 5 by the raw material water pump 19.
[0043]
On the other hand, the generated gas hydrate is taken out from the separator 9 and sent to a post-processing step (steps after S5 in FIG. 6).
In the separator 9, the water level in the separator 9 is detected by the level meter 21, and the water level in the separator 9 is controlled to be above a certain level by controlling the valve 12 d. This is because the raw water has a sealing effect so that the gas does not flow into the raw water return line. Then, the raw water unnecessary for the sealing water is boosted to a predetermined pressure by the raw water pump 19 and supplied to the line mixer 5 as described above.
[0044]
As described above, in the present embodiment, the raw material gas is continuously dissolved in the raw material water by the line mixer 5 so that the total amount of the raw material gas supplied using the pipe-shaped reaction pipe 7 is hydrated. Therefore, a gas hydrate having the same composition as that of the supplied source gas can be generated.
[0045]
Further, in the present embodiment, since the reaction between the raw water and the raw material gas is performed while moving the pipe line, all of the substances (generated gas hydrate and raw water) are once separated up to the separator 9. A mechanism for taking out only the generated gas hydrate is unnecessary, and the configuration of the apparatus can be simplified.
Further, since the entire amount is hydrated, no unreacted gas is sent to the separator 9, and piping and a compressor for returning the unreacted gas to the line mixer 5 are not necessary. In this sense, the configuration of the apparatus is simple. Can be
[0046]
In the above description, the explanation was made on the assumption that the supplied raw material gas was hydrated at the outlet of the reaction pipe 7, but the raw material gas was not hydrated at the reaction pipe 7 under various conditions. In such a case, the following may be performed.
[0047]
If the entire amount of the raw material gas is not hydrated in the reaction pipe line 7, the unreacted raw material gas is supplied to the separator 9. In that case, the pressure of the separator 9 increases. Therefore, whether or not the entire amount of the raw material gas is hydrated in the reaction pipe line 7 can be determined by detecting the pressure increase in the separator 9.
Therefore, when a pressure increase in the separator 9 is detected by the pressure detector 10 installed in the separator 9 and the pressure increase value exceeds a preset value, the source gas flows into the separator 9. It may be determined that the entire amount has not been hydrated and the supply amount may be reduced by narrowing the valve 12a.
[0048]
The excess source gas supplied to the separator 9 is hydrated in the separator 9, thereby reducing the pressure of the separator 9 to a predetermined value. Of course, when the pressure of the separator 9 cannot be lowered to a predetermined value only by hydration in the separator 9, a return pipe that leads from the separator 9 to the line mixer 5 is provided, and excess source gas is removed. Return it. This also applies to FIGS. 4 and 5 described later.
[0049]
In the above embodiment, no means for adjusting the pressure is provided between the line mixer 5 and the reaction pipe 7.
However, as shown in FIG. 4, a pressure detector 23 and a pressure adjustment valve 25 may be provided between the line mixer 5 and the reaction pipe line 7.
By adjusting the pressure adjustment valve 2, the pressure on the line mixer 5 side can be increased, and dissolution of the raw material gas into the raw water by the line mixer 5 can be further promoted.
[0050]
Further, in order to further promote the dissolution of the raw material gas in the raw material water, as shown in FIG. 5, a staying portion 29 as a flow rate adjusting means for reducing the flow rate of the fluid flowing in the line downstream of the line mixer 5 is provided. It may be provided. By providing the staying part 29, it is possible to earn time for the raw material gas that has become fine bubbles in the line mixer 5 to be dissolved in the raw material water, thereby promoting dissolution.
In addition, as a specific example of the retention part 29, the tank which has a fixed volume can be considered.
[0051]
Further, as another example of the line mixer, a so-called Venturi tube type that sucks and mixes the raw material gas by thinning the middle of the cylindrical body to generate a negative pressure may be used. Alternatively, a device that performs gas-liquid mixing using a swirling flow in a conical or truncated conical container, such as a swirling fine bubble generating device disclosed in Japanese Patent Application Laid-Open No. 2000-447 may be used. In short, the line mixer in the present specification widely includes those on the line that can continuously mix gas and liquid.
In the above embodiment, one or a plurality of bent pipes are shown as an example of the reaction pipe 7. However, a plurality of branched straight pipes may be used.
[0052]
Moreover, in said embodiment, although the kind of raw material water was not specified, fresh water, seawater, an antifreeze liquid etc. can be considered, for example. 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.
[0053]
【The invention's effect】
As described above, in the present invention, since the raw material gas mixed and dissolved in the raw material liquid is hydrated using the pipe-like reaction pipe, the same composition as the supplied raw material gas is used. A gas clathrate of composition can be generated.
[Brief description of the drawings]
FIG. 1 is a system diagram showing main components of an embodiment of the present invention.
FIG. 2 is an explanatory diagram of a line mixer 5 according to an embodiment of the present invention.
FIG. 3 is an explanatory diagram for explaining the mechanism of hydration of the total amount in the reaction pipe line 7;
FIG. 4 is an explanatory diagram of another aspect of one embodiment of the present invention.
FIG. 5 is an explanatory diagram of another aspect of one embodiment of the present invention.
FIG. 6 is an explanatory diagram of a gas hydrate production process of the present invention.
[Explanation of symbols]
1 Gas booster 3, 19 Raw material water pump 5 Line mixer 7 Reaction line 9 Separator 10 Pressure detector 12a Valve (gas flow rate adjusting means)
12b Valve (Raw material amount adjustment means)
12c valve (gas pressure adjusting means)

Claims (3)

In an apparatus for producing a gas clathrate by reacting a raw material liquid and a raw material gas,
  A gas flow rate adjusting means for adjusting the flow rate of the raw material gas to be supplied, a gas pressure adjusting means for adjusting the pressure of the raw material gas, a raw material liquid flow rate adjusting means for adjusting the flow rate of the supplied raw material liquid, and a raw material for adjusting the pressure of the raw material liquid Liquid pressure adjusting means, a line mixer for mixing the raw material liquid and the raw material gas in the middle of the line and dissolving the raw material gas in the raw material liquid, and a reaction line for cooling while flowing the mixed raw material liquid A cooling device for cooling the reaction pipe, and pressure adjusting means for adjusting the pressure of the reaction pipe,
  The gas flow rate adjusting means, the gas pressure adjusting means, the raw material liquid flow rate adjusting means, the raw material liquid pressure adjusting means, and the cooling capacity of the cooling device so that the total amount of the raw material gas supplied to the line mixer can be clathrated. When setting the reaction pipe length and the reaction pipe diameter, and providing a pressure detector for detecting the pressure at the outlet of the reaction pipe, when the detected value of the pressure detector exceeds a predetermined value A gas clathrate manufacturing apparatus characterized by adjusting one or both of the gas flow rate adjusting means and the raw material liquid flow rate adjusting means. In an apparatus for producing a gas clathrate by reacting a raw material liquid and a raw material gas,
  A gas flow rate adjusting means for adjusting the flow rate of the raw material gas to be supplied, a gas pressure adjusting means for adjusting the pressure of the raw material gas, a raw material liquid flow rate adjusting means for adjusting the flow rate of the supplied raw material liquid, and a raw material for adjusting the pressure of the raw material liquid Liquid pressure adjusting means, a line mixer for mixing the raw material liquid and the raw material gas in the middle of the line and dissolving the raw material gas in the raw material liquid, and a reaction line for cooling while flowing the mixed raw material liquid A cooling device for cooling the reaction pipe, and pressure adjusting means for adjusting the pressure of the reaction pipe,
  The pressure P at the outlet of the reaction pipe is the lowest clathrate generation pressure P ₀ The temperature T in the reaction pipe is higher, and the clathrate generation maximum temperature T ₀ The gas flow rate adjusting means, the gas pressure adjusting means, and the raw material liquid flow rate adjusting means so that the heat generated when the raw material gas supplied to the line mixer is completely clathrated can be completely removed. A pressure detector for setting the raw material liquid pressure adjusting means, the cooling capacity of the cooling device, the length of the reaction pipe and the diameter of the reaction pipe, and detecting the pressure at the outlet of the reaction pipe, and the pressure detector A gas clathrate manufacturing apparatus characterized in that either or both of the gas flow rate adjusting means and the raw material liquid flow rate adjusting means are adjusted when the detected value of the gas exceeds a predetermined value. The gas clathrate manufacturing apparatus according to claim 1 or 2, wherein the line mixer generates fine bubbles of a raw material gas.

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