JP2014512943A - Gas hydrate continuous production method - Google Patents

Abstract

The present invention relates to a gas hydrate continually manufacturing method using latent hydrate crystals. In particular, the present invention relates to an eleventh step of injecting a latent hydrate crystal of an aqueous solution containing a surfactant into a pipe reactor, and the latent hydrate crystal of the eleventh step is injected. A twelfth step of injecting a gas into the pipe-type reactor to generate a gas hydrate, and the gas hydrate generated in the twelfth step to the pipe-type reactor inside the pipe-type reactor And a thirteenth step of maximizing the conversion rate while circulating and transporting the entire length of the gas hydrate. In the present invention, in the thirteenth step, the gas hydrate is moved into the pipe reactor by the action of a pig ball that circulates and moves in the pipe reactor in a state where a plurality of the steps are connected at regular intervals. It is characterized by circulating and transporting.
【Task】
The present invention provides a gas hydrate continuous production process using latent hydrate crystals.
[Solution]
In the present invention, an eleventh step of injecting a latent hydrate crystal of an aqueous solution containing a surfactant into a pipe reactor, and the latent hydrate crystal of the eleventh step were injected. A twelfth step of injecting a gas into the pipe reactor to generate a gas hydrate; and the gas hydrate generated in the twelfth step is added to the entire length of the pipe reactor inside the pipe reactor. And a thirteenth step of maximizing the conversion rate while circulating and circulating over the entire section.
[Selection] Figure 6

Description

  The present invention relates to a gas hydrate continually manufacturing method using latent hydrate crystals. In particular, the present invention relates to an eleventh step of injecting a latent hydrate crystal of an aqueous solution containing a surfactant into a pipe reactor, and the latent hydrate crystal of the eleventh step is injected. A twelfth step of injecting a gas into the pipe-type reactor to generate a gas hydrate, and the gas hydrate generated in the twelfth step to the pipe-type reactor inside the pipe-type reactor And a thirteenth step of maximizing the conversion rate while circulating and transporting the entire length of the gas hydrate. In the present invention, in the thirteenth step, the gas hydrate is moved into the pipe reactor by the action of a pig ball that circulates and moves in the pipe reactor in a state where a plurality of the steps are connected at regular intervals. It is characterized by circulating and transporting.

  Natural gas is a fuel having cleanliness, safety, convenience, and the like, and has attracted attention as an alternative energy for solid fuels such as oil and coal. This natural gas is used in various fields such as home, commerce, transportation, industry, etc. as an energy source that supplies about 1/4 of the world's energy consumption, along with solid fuels such as oil and coal. It forms the basis of the energy industry.

  When such natural gas is collected from a gas field and transported as it is, the volume is very large and there is a possibility of explosion, so in order to solve such a problem, cool the natural gas to the liquefaction temperature. A method in which liquefied natural gas (LNG) is generated and stored in a dedicated tank installed in a transport ship or the like has been mainly used. Liquefied natural gas usually contains 600 times the volume of natural gas per unit volume.

  However, in the case of methane gas, which is the main component of liquefied natural gas, an extremely low temperature of about −162 ° C. is required for liquefaction, so that not only liquefied natural gas production facilities but also natural and marine gas transportation devices There is also a problem that a very large amount of money is required in the production of the.

  Another method of storing and transporting natural gas is to use compressed gas, but this method is also technically difficult to manufacture a large container due to high storage pressure, which is costly and is highly safe for high pressure explosions. There is a problem that it accompanies this problem.

  In contrast, natural gas hydrate is formed at a relatively moderate pressure and temperature while providing 170 times the volume of gas per unit volume, and once formed, storage of the hydrate is − It is made at 20 ° C. and 1 atm. Such temperature and pressure conditions are milder than the temperature and pressure conditions of liquefied natural gas and compressed gas.

  In addition, natural gas hydrate has an advantage that it is safe because it has a low possibility of explosion even if it is exposed to normal temperature and normal pressure, so that sufficient time can be secured to cope with water leakage and damage to the system. That is, natural gas hydrate is safer and more economical to store and transport than LNG and CNG (Compressed Natural Gas).

Natural gas hydrate is a lower the temperature and the gas and water at high pressure is physically bound not chemically bond, for example, compounds produced in the form such as dry ice (dry ice), the 1 m ³ The calorific value of gas hydrate is the same as that of natural gas of about 180 m ³ . Naturally, it is buried as a crystal in which water and gas are combined on the seabed or frozen earth where the temperature is low and the pressure is high, and this is converted into water and gas under dissociation conditions. It is easily disassembled.

  Natural gas hydrates are classified according to molecular structure into type I, type II, type H, etc., and are similar in shape to ice but have a structure different from ice. Ice has a two-dimensional planar structure at low temperatures close to 0 ° C., but water molecules form a three-dimensional cavity structure when given natural gas hydrate at the appropriate pressure (see figure). 1).

The size of the single cavity is about 1 nanometer, assuming a spherical body, and the unit cell size is about 2 nanometer, so that natural gas can enter the inside of this cavity. . That is, water molecules connected by hydrogen bonds become 'host', and gas molecules become 'guest'. The general formula of gas hydrate is Gas (H ₂ O) _n . Here, n has a value of about 5 to 8 depending on the size of the gas molecule as a hydration number. A van der Waals force acts between nonpolar gas molecules and water molecules.

  A general method for producing natural gas hydrate is that a high-pressure cooled natural gas supplied through a gas nozzle installed at the upper end of the reactor is installed at the lower nozzle or the lower end of the reactor. The bubbling method that produces natural gas hydrate in contact with water sprayed through a perforated plate is mostly, and the overall reaction is exothermic, so the heat generated during the reaction is removed For this purpose, a cooling system is provided in the reactor, or a system for lowering the temperature of the reactor from the outside is provided.

  However, such a method may cause the generated natural gas hydrate to cause plugging in the raw water or natural gas injection nozzle, and when using an injection plate, the diameter of the generated raw water particles. Therefore, it is difficult to separate the generated natural gas hydrate from the unreacted water and the amount of unreacted water is high due to the low conversion rate. In addition, a lot of energy is required for the reuse process.

  In addition, existing natural gas hydrate production methods have problems in industrialization due to a long hydrate induction time and a low hydrate crystal growth rate. Here, the hydrate induction period can be defined as the period during which a solid gas hydrate crystal particle is maintained in a metastable liquid state before it is formed, and methane hydrate. The induction time is usually several days.

  That is, for mass production, the problem of shortening the induction time of long hydrates and the problem of low hydrate crystal growth rate should be solved. In order to shorten the hydrate induction time, the reaction area that can be reacted by satisfying the temperature and pressure conditions must be large. Conventionally, methods such as nozzle spraying, fine bubbles, and agitation have been used to widen the reaction area, but the conversion rate is constrained and a lot of cost is required to manufacture the apparatus.

  In order to produce hydrates, temperature and pressure conditions are important, and most of the process for producing hydrates is a cooling system for removing the heat of reaction generated during the production. system). Currently, a method of supplying cooled water to the inside and removing reaction heat through an external heat exchanger is used. However, this method is difficult to manufacture because the heat exchange must be performed through the high-pressure reactor in order to remove the heat of reaction generated when the hydrate is generated inside. When the amount of hydrate to be increased is large, mass production becomes difficult because uniform heat exchange inside the reactor is impossible.

  Also, since hydrates are generated from the cooling surface of the heat exchanger, adsorption of the surface of the heat exchanger and the hydrate (formation of ice in the refrigeration and freezer compartment) after the formation of the hydrate Lowering the thermal conductivity makes it more difficult to exchange heat in the reactor and makes it difficult to separate, thereby hindering hydrate transport.

On the other hand, conventionally, in order to continuously produce a gas hydrate, the hydrate produced in the reactor is discharged in a slurry form and then the dehydration process is performed in the reactor. By removing moisture that has not yet reacted, the gas filling rate inside the hydrate is increased. At this time, the hydrate slurry is pressurized using mechanical force or centrifugal force for dehydration. In this case, since an ice film is formed on the filtration net or filter for filtering the hydrate slurry and the dewatering ability is lowered, it is necessary to additionally install a device for periodically washing the filtration net or filter. However, according to such conventional methods, the life of the filter screen or filter, the durability of the device for cleaning the filter screen or filter, and the structural problems of the device in which the dehydration process is to be performed inside the reactor are performed. The production of equipment is difficult, and the increase in the size of equipment causes problems that make mass production difficult for commercialization.
Therefore, it overcomes the problems with the conventional method for producing gas hydrate as described above, has no induction period of gas hydrate, facilitates gas diffusion, and increases the production rate of gas hydrate crystals. Represents a high conversion rate of gas hydrate, can reduce the production cost by minimizing the steps required to remove reaction heat, and excluding the method of dehydration after the slurry formation of existing gas hydrate, ie this dehydration Development of a new process for a gas hydrate continuous production apparatus that continuously produces gas hydrate without a process is urgently required in the utilization of natural gas energy.

  Therefore, in order to solve the above-mentioned problems of the prior art, the object of the present invention is to facilitate gas diffusion during the production reaction, maximize the contact area between water and gas, and increase the gas collection speed and overall Not only shortens the hydrate formation time, but also shows high conversion and relatively low gas hydrate formation pressure, due to phase change compared to immediate gas hydrate formation in aqueous solution Since no latent heat is required, the overall reaction heat generation is reduced, the process for removing the reaction heat in the reactor is shortened, the overall reaction efficiency is increased, and the reaction heat is required to be removed. While the cooling process is shortened and has the effect of reducing production costs, it is not a method of dehydrating after the conventional gas hydrate slurry generation, but a gas hydrate that continuously produces gas hydrate without a dehydration process It is to provide a continuous production method.

  In order to achieve the above object, according to one aspect of the present invention, an eleventh step of injecting a latent hydrate crystal of an aqueous solution containing a surfactant into a pipe reactor; A twelfth step of injecting a gas into the pipe reactor into which the latent hydrate crystals of the eleventh step have been injected to generate a gas hydrate; and the gas water generated in the twelfth step. And a thirteenth step of maximizing the conversion rate while circulating the Japanese product in the pipe reactor over the entire length of the pipe reactor.

  According to another aspect of the present invention, the gas hydrate is circulated and transferred inside the pipe reactor by the action of a pig ball that circulates and moves inside the pipe reactor in a state where a plurality of pipes are connected at regular intervals. A process for continuously producing gas hydrate is provided.

  Moreover, according to the other aspect of this invention, the gas hydrate continuous manufacturing method in which a latent hydrate crystal | crystallization has a porous structure is provided.

  Furthermore, according to another aspect of the present invention, after the latent hydrate crystal having a porous structure is impregnated with an aqueous solution in i) ice particle form, or ii) slurry form, or iii) porous substance. There is provided a method for continuously producing gas hydrate by cooling, or iv) cooling an aqueous solution containing a surfactant in a superabsorbent resin (resin).

  In addition, according to another aspect of the present invention, the gas hydrate continuous further comprising the step of cooling the pipe reactor before injecting the latent hydrate crystal containing the surfactant into the pipe reactor. A manufacturing method is provided.

  According to another aspect of the present invention, the gas hydrate continuous production method further includes the step of maintaining the pressure in the pipe reactor at a constant level through an additional gas supply after injecting the gas into the pipe reactor. Is provided.

  According to the present invention, the following advantageous effects occur.

  The present invention already has a porous form of structure, such as ice particles or powdered ice particles that do not require a separate hydrate induction time to convert to gas hydrate crystals. By using such latent hydrate crystals, there is an effect of increasing the reaction gas diffusion rate, maximizing the contact area between water and gas, shortening the reaction time, and maximizing the reaction efficiency.

In addition, since the present invention forms a gas hydrate from a latent hydrate crystal, a latent heat due to a phase change is not required for the immediate formation of a gas hydrate in an aqueous solution, and the total reaction calorific value. Has the effect of reducing production costs and reducing the number of steps for removing reaction heat.
Furthermore, the present invention continuously produces the gas hydrate without such a dehydration step except for the method of dehydration after the slurry formation of the conventional gas hydrate. Therefore, there is no problem that the equipment is enlarged and mass production for commercialization becomes difficult from the beginning because the dehydration process should be performed inside the reactor.

It is a figure explaining the structure of gas hydrate. It is a conceptual diagram showing the concept of the gas hydrate continuous manufacturing apparatus using the potential hydrate crystal of this invention. It is a figure which shows the reaction heat of the pipe type reactor using the conventional gas hydrate continuous manufacturing method. It is a schematic diagram showing the reaction heat of the pipe-type reactor using the working example of the gas hydrate continuous production apparatus of the present invention. It is a schematic diagram of the gas hydrate continuous manufacturing apparatus using the working example of the gas hydrate continuous manufacturing apparatus of the present invention. It is a figure which shows a pipe type reactor separately in detail among FIG. It is a figure which shows the state and the effect which were installed so that the pig ball adjacent to each other may become a mutually different angle in this invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

  The gas hydrate continuous production method of the present invention includes an eleventh step of injecting a latent hydrate crystal of an aqueous solution containing a surfactant into a pipe reactor, and the potential of the eleventh step. A twelfth step of injecting gas into a pipe reactor into which hydrate crystals have been injected to generate a gas hydrate; and the gas hydrate generated in the twelfth step is converted into a pipe reactor. And a thirteenth step for maximizing the conversion rate while being circulated and transferred over the entire length of the pipe reactor.

Next, the present invention will be described in detail for each step with reference to FIG. 5 and FIG.
<11th Step: Injection of Potential Hydrate Crystal in Aqueous Solution Containing Surfactant>
The pipe-type ice making machine 15 injects a potential hydrate crystal of an aqueous solution containing a surfactant into the pipe-type reactor 9 (see FIG. 6).

  Here, the pipe-type reactor 9 means that the reactor is formed in a long pipe shape as shown in FIG. Explained).

  Gas hydrate refers to a compound that exists as a solid state crystal such as dry ice due to a physical bond similar to a structural bond where a low molecular weight gas and water are not chemically bonded at low temperature and high pressure. (See Figure 1).

  In addition, since the latent hydrate crystal already has a porous structure, it does not require a separate hydrate induction time to be converted into the gas hydrate crystal. Refers to the body (precursor).

  In a latent hydrate crystal having a porous structure, the aqueous solution containing the surfactant is preliminarily cooled and pulverized through a preliminary process. Or 2) A slurry form which is a suspension state of insoluble solid particles can be used.

  Also, instead of immediately cooling and pulverizing the aqueous solution, 3) the porous material is impregnated with the aqueous solution and then cooled, or 4) the superabsorbent resin (resin) absorbs the aqueous solution and then cooled. It is also possible to omit the pulverization step and immediately inject the cooled aqueous solution into the pipe reactor 9.

  At this time, the porous material or the superabsorbent resin artificially separates the aqueous solution particles to maximize the contact area between the aqueous solution and the gas. At this time, as the porous material, all commercially available materials can be used, but preferably activated carbon, silica gel, zeolite, or the like can be used. As the superabsorbent resin, all commercially-used general resins are used. Preferably, polyacrylate, polyacrylamide, polyacrylic acid, polymethacrylic acid are used. (polymethacrylic acid), polyethylene oxide, polyvinyl alcohol and the like can be used.

<Twelfth Step: Formation of Gas Hydrate in Pipe Reactor>
When the reaction gas is injected into the pipe reactor 9 into which the above-described latent hydrate crystal is injected, the latent hydrate crystal reacts with the injected gas to immediately generate a gas hydrate. (Figure 2).

  At this time, due to the structural features of the latent hydrate crystal made of porous form, gas diffusion in the potential hydrate crystal is easy, and the contact area between water and gas is maximized, and the gas is collected quickly. Not only can the rate and overall hydrate formation time be shortened, but a high conversion and a relatively low gas hydrate formation pressure can be exhibited.

  In addition, the above-described production does not require latent heat due to phase change compared to immediately forming a gas hydrate with an aqueous solution, and the total reaction heat generation is reduced. This is because the reaction in the pipe reactor 9 is reduced. By shortening the apparatus and process for removing heat, the overall cost reduction effect is achieved.

  3 and 4 show that when forming a hydrate from an aqueous solution and when forming a hydrate with a latent hydrate crystal in an ice particle state, which is an embodiment of the present invention, each should be removed externally. It is a figure which shows the emitted-heat amount. As can be seen from FIGS. 3 and 4, the calorific value is 542.4 KJ / kg when producing 1 kg of methane hydrate from an aqueous solution, but it is exothermic when producing 1 kg of methane hydrate from ice particles. The amount is 106.6 KJ / kg obtained by subtracting the endothermic amount 435.8 KJ / kg during the phase change of 1 kg of ice particles from 542.4 KJ / kg.

That is, since the aqueous solution containing the surfactant is in the form of ice particles and already has the latent heat removed, the amount of heat to be removed in the pipe reactor 9 during the reaction is reduced, whereby the pipe type The capacity and cooling time of the overall cooler 21 for removing the reaction heat in the reactor 9 are reduced.
The latent hydrate crystals described above include a surfactant, and any commonly used surfactant can be used as the surfactant, but preferably sodium dodecyl sulfate (Sodium Dodecyl Sulfate: SDS), dioctyl sodium sulfosuccinate (DSS), sodium tetradecyl sulfate, sodium hexadecyl sulfate, sodium dodecylbenzene sulfonate, xylene sulfonate ( Xylenesulfonate), sodium oleate (Sodiumoleate), 4-n-decylbenzenesulfonate (sodium laurate), 4-dodecylbenzenesulfonic acid (4-dodecylbenzenesulfonate), dodecylamine Dodecylamine hydrochloride, dodecyltrimethyl Ammonium chloride (dodecyltrimethylammonium chloride), 4-n-octylbenzene sulfonate, Ethoxylated sulfonate, Decylbenzenesulfonate, potassium oleate (Potassium oleate) ), N-decylbenzene sulfonate, alkyltrimethylammonium bromide (C10-C16 chain), dodecylamine, tetradecyltrimethylammonium chloride (Tetradecyltrimethylammonium chloride), dodecylpolysaccharide Glucoside (dodecyl polysaccharide glycoside), cyclodextrin (Cyclodextrins), glycolipids (glycolipids), lipoprotein-lipopeptides (lipoprotein-ipopeptides), phospholipids (phospholipids), para-toluenesulfonic acid (para-tolulu) Preferably, it is selected from ene sulfonic acid, trisiloxane, triton X-100 and mixtures thereof.

  As for the amount of the above-described surfactant, a small amount of about 0.5% or less of the total volume of the aqueous solution is sufficient, and the concentration of the surfactant is desirably in the range of 50 ppm to 1000 ppm.

  On the other hand, it is preferable to cool the pipe reactor 9 in advance before injecting the latent hydrate crystals containing the surfactant into the pipe reactor 9. At this time, the cooling temperature of the pipe reactor 9 is desirably in the range of −10 ° C. to 10 ° C.

  Moreover, after injecting gas into the pipe reactor 9, it is desirable to maintain the pressure in the pipe reactor 9 constant through additional gas supply. At this time, the pressure in the pipe reactor 9 is preferably in the range of 10 bar to 100 bar.

  The gas injected into the pipe reactor 9 can be methane, ethane, propane, carbon dioxide, butane, or a mixture thereof.

<Thirteenth step: Circulating and transferring gas hydrate in a pipe reactor>
However, even though the hydrate produced in the pipe reactor 9 through the twelfth step has a high conversion rate, it is not 100% conversion rate, and depending on the situation, the conversion rate reaches the required level. There may be no cases.

In this state, in order to continuously produce a gas hydrate, unreacted water must be removed through a process of performing a dehydration process after discharging the produced hydrate in a slurry form. At this time, when the hydrate slurry is pressurized using mechanical force or centrifugal force for dehydration, an ice film is formed on a filter network or a filter for filtering the hydrate slurry, and the dehydration ability is reduced. Therefore, it becomes necessary to additionally install a filter or a device for periodically cleaning the filter. However, according to such a method, due to the problem of the service life of the filter screen or filter and the durability of the device for cleaning the filter screen or filter and the problem of the device structure in which the dehydration process should be performed inside the reactor, The problem is that it is difficult to manufacture and mass production for commercialization becomes difficult due to the increase in equipment size.

  In order to solve such a problem, the present invention does not form the reactor in a normal cylinder shape, but forms it in a long pipe shape as shown in FIG. 6 (the present invention reflects this feature). For this reason, the reactor is specially referred to as a 'pipe reactor').

  As described above, the reason why the present invention adopts the pipe reactor 9 instead of the normal cylinder reactor is that the gas hydrate produced first in the pipe reactor 9 is not immediately discharged to the outside. This is because the conversion rate is maximized through the process of being circulated and transported over the entire length of the pipe reactor 9 while remaining inside the pipe reactor 9.

  Hereinafter, the operation of the pipe reactor 9 will be described in more detail with reference to FIGS. 5 and 6.

  According to the embodiment of the present invention, the aqueous solution containing the surfactant is cooled and pulverized by the pipe type ice making machine 15 to form ice particles, and then injected into the pipe type reactor 9. When this reaction solution is supplied from the gas cylinder 1 through the nozzle 4 through the mass flow meter 3 that can measure gas injection due to the formation of gas hydrate through the pipe, the reaction gas is supplied to the pipe-type ice maker 15 in the pipe-type reactor 9. Gas hydrate is immediately formed at the outlet part (a).

  At this time, the pressure is set through the gas regulator 2 so as to maintain a constant pressure in the pipe reactor 9, and the cooling water lines 13 and 14 are connected to the pipe reaction by the cooler 21 to which the temperature controller is attached. The temperature of the pipe reactor 9 is lowered by being connected to the reactor 9.

  On the other hand, the gas hydrate produced at the outlet part (a) of the pipe-type ice making machine 15 in the pipe-type reactor 9 is not immediately discharged to the outside, but stays inside the pipe-type reactor 9 while remaining in the pipe-type reactor 9. The conversion rate is maximized by being circulated and transferred over the entire length of 9 sections.

  As described above, since the pressure and temperature are appropriately maintained over the entire length of the pipe reactor 9 by the gas regulator 2 and the cooling water lines 13 and 14, the outlet portion of the pipe ice maker 15 is provided. The gas hydrate produced in (a) does not initially have a conversion rate of 100%, or even if the conversion rate does not reach the required level depending on the situation, the total length of the pipe reactor 9 is In the process of being circulated and transferred over the section, the conversion rate is maximized when reaching the end (b) of the pipe reactor 9 while being continuously exposed to appropriate pressure and temperature conditions. Then, the gas hydrate that reaches the end (b) of the pipe-type reactor 9 and is discharged to the outside becomes ready for use without having to perform a separate dehydration step.

  In the embodiment of FIG. 6, the pipe reactor 9 is composed of two long bodies, that is, A and B, in order to increase the effect by making the overall length section of the pipe reactor 9 longer. The gas hydrate is generated at the outlet portion (a) of the pipe ice making device 15 in the pipe reactor 9 and then circulated and transferred over the entire length of the pipe reactor 9. After reaching the terminal end (b), it is discharged and collected in the primary storage tank 18 and thereafter stored in the secondary storage tank 20 through a pelletizer 19 equipped with a pressure reducing device. In such a process, the process of dehydrating the gas hydrate need not exist.

  On the other hand, the present invention uses a pig ball 16 instead of the existing screw method as a means for circulating and transferring gas hydrate over the entire length of the pipe reactor 9, thereby increasing the size of the apparatus by adopting the screw method. To prevent manufacturing costs.

That is, the present invention is characterized in that the gas hydrate is circulated and transferred inside the pipe reactor 9 by the action of the pig ball 16 that circulates and moves inside the pipe reactor 9 in a state where a plurality of pipes are connected at regular intervals. And
In the embodiment of FIG. 6, a plurality of pig balls 16 are connected to each other at regular intervals by a chain 22 inside the pipe reactor 9. In this case, it is preferable that the diameter of the pig ball 16 is close to the inner diameter of the pipe reactor 9. In this way, the pig ball 16 can effectively scrape the gas hydrate produced and attached to the inner wall of the pipe reactor 9 while moving inside the pipe reactor 9. It is.

  In the embodiment of FIG. 6, the pig ball 16 circulates and moves in the direction from a to b together with the chain 22 as the pig ball rotating wheel 17 rotates. In this process, the pig ball 16 scrapes out the gas hydrate produced and attached to the inner wall of the pipe reactor 9 and then continuously extrudes it in the direction of travel. It is transferred in the direction from a to b by the action of the pig ball 16.

  At this time, it is desirable that adjacent pig balls 16 among the plurality of connected pig balls 16 are installed at different angles. As shown in FIG. 7, this causes a loss in the continuous production amount of gas hydrate by allowing the succeeding pig ball 16 to scrape off the gas hydrate that the preceding pig ball 16 has not yet scraped. In addition, it is possible to prevent the gas hydrate from being continuously deposited on the inner wall of the pipe reactor 9.

<When not using latent hydrate crystals>
On the other hand, the technical idea of the present invention can have high utility even when the latent hydrate crystal as described above is not used.

The reason for this is that the conversion rate of the hydrate produced in the reactor is very low when the latent hydrate crystals are not used, so in order to continuously produce the gas hydrate in this state This is because the necessity of performing the dehydration process must be further increased. In this case, the introduction of the pipe reactor and the concept of circulating gas hydrate through the pipe reactor, which are the technical idea of the present invention, enables continuous production of gas hydrate without a dehydration step. .
Accordingly, the present invention provides a twenty-first step for producing a gas hydrate in a pipe reactor, and the gas hydrate produced in the twenty-first step is converted into a pipe reactor inside the pipe reactor. And a gas hydrate continuous production method having a twenty-second step of maximizing the conversion rate while circulating and transporting the entire length section. At this time, the specific contents of the 21st step and the 22nd step are the same as described above, and therefore, the redundant description thereof will be omitted below.

  Although the present invention has been described in connection with specific embodiments, the present invention has been described in detail without departing from the scope and spirit of the invention as defined by the appended claims and their equivalents. It will be apparent to those skilled in the art that various changes in the details can be made. Accordingly, the embodiments and the accompanying drawings started from the present invention are not intended to limit the technical idea of the present invention, but to explain them. The scope of thought is not limited. The protection scope of the present invention should be construed by the following claims, and all technical ideas within the equivalent scope should be construed as being included in the scope of the right of the present invention.

According to the present invention, since gas hydrate is formed from potential hydrate crystals, reaction time can be reduced, reaction efficiency can be maximized, production costs can be reduced, and reaction heat can be removed. Therefore, the present invention is a technology that can realize its practical and economical value in the field of resource securing and energy production.

1: Gas tank 2: Gas regulator 3: Mass flow meter (MFC)
4: Dual nozzle 5: Aqueous solution tank 6: Pump 7: First thermocouple
8: Second thermocouple 9: Pipe reactor 10: Drain valve 11: Pressure gauge 12: Gas discharge line 13: Coolant in
14: Coolant out
15: Pipe type ice making machine 16: Pig ball 17: Pig ball rotating wheel 18: Primary storage tank 19: Pelletizer 20: Secondary storage tank 21: Cooler 22: Chain

It is a figure explaining the structure of gas hydrate. It is a conceptual diagram showing the concept of the gas hydrate continuous manufacturing method using the potential hydrate crystal of this invention. It is a figure which shows the reaction heat of the pipe type reactor using the conventional gas hydrate continuous manufacturing method. It is a schematic diagram showing the heat of reaction of the pipe type reactor using the working example of the gas hydrate continuous manufacturing method of the present invention. It is a schematic diagram of the gas hydrate continuous manufacturing apparatus using the working Example of the gas hydrate continuous manufacturing method of this invention. It is a figure which shows a pipe type reactor separately in detail among FIG. It is a figure which shows the state and the effect which were installed so that the pig ball adjacent to each other may become a mutually different angle in this invention.

Claims (24)

An eleventh step of injecting a latent hydrate crystal of an aqueous solution containing a surfactant into the pipe reactor;
A twelfth step of injecting a gas into the pipe reactor into which the latent hydrate crystals of the eleventh step have been injected to produce a gas hydrate;
A thirteenth step for maximizing the conversion rate while circulating and transporting the gas hydrate produced in the twelfth step over the entire length of the pipe reactor inside the pipe reactor;
A process for continuously producing a gas hydrate, comprising:   The thirteenth step is characterized in that the gas hydrate is circulated and transferred inside the pipe reactor by the action of a pig ball that circulates and moves inside the pipe reactor in a state where a plurality of steps are connected at regular intervals. The method for continuously producing a gas hydrate according to claim 1.   The gas hydrate continuous production method according to claim 2, wherein the diameter of the pig ball is close to the inner diameter of the pipe reactor.   3. The gas hydrate continuous production method according to claim 2, wherein adjacent pig balls among the plurality of connected pig balls are installed at different angles.   2. The gas hydrate continuous production method according to claim 1, wherein the latent hydrate crystal has a porous structure.   6. The gas hydrate continuous production method according to claim 5, wherein the latent hydrate crystals having a porous structure are in the form of ice particles in an aqueous solution.   6. The gas hydrate continuous production method according to claim 5, wherein the latent hydrate crystals having a porous structure are in a slurry form of an aqueous solution.   The gas hydrate continuous production method according to claim 6 or 7, wherein the latent hydrate crystals are generated by cooling and grinding an aqueous solution.   The latent hydrate crystal having a porous structure is obtained by cooling a porous material impregnated with an aqueous solution after impregnating the porous material with an aqueous solution. Gas hydrate continuous production method.   The gas hydrate continuous production method according to claim 9, wherein the porous substance is selected from activated carbon, silica gel, or zeolite.   The latent hydrate crystal having the porous structure is one that absorbs an aqueous solution containing a surfactant in the superabsorbent resin and then cools the superabsorbent resin in which the aqueous solution is absorbed. The method for continuously producing a gas hydrate according to claim 5.   The gas hydrate continuous production according to claim 11, wherein the superabsorbent resin is selected from polyacrylate, polyacrylamide, polyacrylic acid, polymethacrylic acid, polyethylene oxide, or polyvinyl alcohol. Method.   The surfactant is sodium dodecyl sulfate (SDS), diisooctyl sodium sulfosuccinate (DSS), sodium tetradecyl sulfate, sodium hexadecyl sulfate, sodium dodecylbenzene sulfonate, xylene sulfonate, sodium oleate, 4-n -Decylbenzenesulfonate, sodium laurate, 4-dodecylbenzenesulfonate, dodecylamine hydrochloride, dodecyltrimethylammonium chloride, 4-n-octylbenzenesulfonate, ethoxylated sulfonate, decylbenzenesulfonate, Potassium oleate, n-decylbenzene sulfonate, alkyltrimethylammonium bromide (C10-C16 chain), dodecylamine, tetradecyltrimethylammonium chloride, dodecyl poly Gas water according to claim 1, characterized in that it is selected from saccharide glucosides, cyclodextrins, glycolipids, lipoprotein-lipopeptides, phospholipids, para-toluenesulfonic acid, trisiloxane, Triton X-100 and mixtures thereof. Japanese continuous production method.   The method for continuously producing a gas hydrate according to claim 13, wherein the volume of the surfactant is within 0.5% of the volume of the entire aqueous solution.   The gas hydrate continuous production method according to claim 13, wherein the concentration of the surfactant is in the range of 50 to 1000 ppm.   The gas water according to claim 1, further comprising the step of cooling the pipe reactor before injecting a latent hydrate crystal containing a surfactant into the pipe reactor. Japanese continuous production method.   The method for continuously producing gas hydrate according to claim 16, wherein the cooling temperature of the pipe reactor is in the range of -10 ° C to 10 ° C.   The gas hydrate according to claim 1, further comprising the step of maintaining a constant pressure in the pipe reactor through an additional gas supply after injecting gas into the pipe reactor. Continuous manufacturing method.   The gas hydrate continuous production method according to claim 18, wherein the pressure in the pipe reactor is in the range of 10 bar to 100 bar.   The gas hydrate continuous production method according to claim 1, wherein the gas injected into the pipe reactor is methane, ethane, propane, carbon dioxide, butane, or a mixture thereof. A twenty-first step of producing gas hydrate in a pipe reactor;
A 22nd step of maximizing the conversion rate while circulating and transferring the gas hydrate produced in the 21st step over the entire length of the pipe reactor inside the pipe reactor;
A method for continuously producing a gas hydrate, comprising:   The twenty-second step is characterized in that the gas hydrate is circulated and transferred inside the pipe reactor by the action of a pig ball that circulates and moves inside the pipe reactor in a state where a plurality of them are connected at regular intervals. The gas hydrate continuous production method according to claim 21.   The gas hydrate continuous production method according to claim 22, wherein the diameter of the pig ball is close to the inner diameter of the pipe reactor.   23. The gas hydrate continuous production method according to claim 22, wherein adjacent pig balls among the plurality of connected pig balls are installed at different angles.