KR20100012491A - Method for the fast formation of gas hydrate - Google Patents

Abstract

PURPOSE: A method for quickly manufacturing gas hydrate is provided to manufacture the gas hydrate with high crystal production speed in a reactor with a single external cooler, and to make feed hydrate with reduced energy consumption. CONSTITUTION: A fed-batch type gas hydrate manufacturing method includes the following steps: injecting a deionized water aqueous solution containing potential feed hydrate to a reactor; injecting gas to the reactor in which the deionized water aqueous solution is put; and injecting a surfactant solution on the reactor. A manufacturing method of the gas hydrate further includes a step for cooling the reactor.

Description

Rapid gas hydrate manufacturing method {Method for the fast formation of gas hydrate}

The present invention relates to a rapid gas hydrate manufacturing method. More specifically, the present invention relates to a process comprising i) a first step of injecting an aqueous fresh solution containing a potential feed hydrate into a reactor, and ii) a potential seed hydrate of said first step. A second step of pressurizing a gas into the reactor into which the pure aqueous solution is injected, and iii) a third step of injecting a surfactant solution into the reactor into which the gas of the second step is injected; (Fed-batch type) gas hydrate manufacturing method and a batch type gas hydrate manufacturing method in which the order of the first step and the third step is changed.

Natural gas is a fuel with cleanliness, stability, and convenience, and has been spotlighted as an alternative energy for solid fuels such as petroleum and coal. As an energy source that supplies a quarter, it forms the basis of the global energy industry along with solid fuels such as petroleum and coal.

When the natural gas is collected from the gas field and transported as it is, the volume is too large and there is a possibility of explosion, so to solve the problem, the natural gas is cooled to the liquefaction temperature to produce a liquefied natural gas (Liquefied Natural Gas) A method of storing and transporting in a dedicated tank installed on the back has been mainly used. Liquefied natural gas usually contains 600 times the volume of natural gas per unit volume.

However, methane gas, which is a major component of liquefied natural gas (LNG), requires very low temperatures of about -162 ° C for liquefaction. There is a problem.

Compressed gas is used as another natural gas storage and transportation method, but it is also difficult to manufacture a large container due to high storage pressure, which is technically difficult and expensive, and has a problem of safety due to high pressure explosion. .

In contrast, natural gas hydrates are produced at relatively moderate pressure and temperature (40 bar at 3 ° C) while providing 170 times the volume of gas per unit volume. Is done. These temperature and pressure conditions are much milder than those of liquefied natural gas and compressed gas.

In addition, natural gas hydrate is advantageous because it is unlikely to explode even when exposed to room temperature and atmospheric pressure, thereby ensuring sufficient time to replace the leakage and breakage of the system. That is, natural gas hydrates are safer and economical to store and transport than LNG (liquefied natural gas) or CNG (compressed natural gas).

Natural gas hydrate is a compound produced by the physical combination of gas and water at low temperature and high pressure, rather than chemical bonding, like dry ice. The calorific value of 1 ㎥ of gas hydrate is about 180㎥ It is similar to the calorific value of gas. Naturally, water and gas are buried in low temperature and high pressure undersea or frozen earth, which are easily decomposed into water and gas under dissociation conditions.

Natural gas hydrates are classified into type I, type II, type Η, etc. according to their molecular structure. Ice has a two-dimensional planar structure at low temperatures near 0 ° C, whereas water molecules form a three-dimensional cavity structure when natural gas hydrate is given the appropriate pressure (20-40 bar).

The size of a single pupil is about 1 nanometer and the unit cell size is about 2 nanometers, and natural gas enters the inside of the pupil. In other words, water molecules connected by hydrogen bonds become 'hosts' and gas molecules become 'guests'. The general formula of the gas hydrate is Gas (H ₂ O) _n where n is a hydration number, which has a value of about 5 to 8 depending on the size of the gas molecules. Van der Waals forces act between the nonpolar gas molecules and the water molecules.

A general method for producing natural gas hydrate is to generate natural gas hydrate by contacting water injected through a high pressure cooled natural gas supplied through a gas nozzle installed at the top of the reactor or a porous plate installed at the bottom of the reactor. Bubbling is the most common method, and since the entire reaction is exothermic, a cooling system is installed in the reactor or a system for lowering the temperature of the reactor from the outside to remove heat generated during the reaction.

However, this method has the disadvantage that the generated natural gas hydrate can cause plugging in the raw water or the natural gas injection nozzle, and when the spray plate is used, the mass transfer resistance is large due to the large diameter of the generated raw water particles. It is difficult to separate the generated natural gas hydrate and the unreacted water, and due to the low conversion rate, the amount of unreacted is high, which requires a lot of energy for the separation and reuse process.

In addition, the existing natural gas hydrate production method has a problem in industrialization due to long hydrate induction time and low hydrate crystal growth rate. Herein, the hydrate induction period may be defined as a period of time maintained in a meta-stable liquid state before the formation of solid gas hydrate crystal grains, and methane hydrate induction time is usually several days.

Rogers and Zhong recently reported that the induction time for ethane hydrates was reduced to about 40 minutes using surfactants of sodium dodecyl sulfate (SDS) and double-cooling systems inside and outside the reactor. (2002). The overall production rate of ethane hydrate increased approximately 700 times compared to the case without SDS.

However, nucleation (derivation of hydrate crystals) is probabilistic, and rapid derivation does not occur consistently and repeatedly even with the same experimental conditions and surfactant concentrations. Will receive.

Therefore, the development of a new process for the gas hydrate manufacturing method that can overcome the problems of the conventional gas hydrate manufacturing method and increase the gas hydrate crystal generation rate without gas hydrate induction period is urgently required in the utilization of natural gas energy It was.

The present invention utilizes a small amount of potential seed hydrate solution capable of forming seed hydrate particles to produce gas hydrates at high crystallization rate without induction period in a reactor with a single external cooling device. It aims to manufacture.

It is an object of the present invention to provide a method comprising the steps of i) injecting an aqueous fresh solution containing a potential feed hydrate into a reactor, and ii) a pure aqueous solution containing a potential seed hydrate of said first step. A second step of pressurizing a gas into the injected reactor, and iii) a third step of injecting a surfactant solution into the reactor into which the gas of the second step is injected. batch type).

It is also an object of the present invention to i) pressurize a gas into the reactor, ii) a pure aqueous solution containing potential seed hydrate in the reactor into which the gas of the first step is injected. a second step of injecting a fresh solution, and iii) a third step of injecting a surfactant solution into a reactor into which a pure aqueous solution containing the potential seed hydrate of said second step is injected. fed-batch type).

It is also an object of the present invention to i) first step of simultaneously injecting an aqueous fresh solution containing pressurize and seed hydrate into the reactor, and ii) the gas of the first step. fed-batch type comprising a second step of injecting a surfactant solution into a reactor into which a pressurize and an aqueous fresh solution containing a seed feed hydrate are simultaneously injected ) Is achieved by providing a method for producing a gas hydrate.

In addition, an object of the present invention is i) a first step of injecting a surfactant solution into the reactor, ii) a second step of pressurizing a gas into the reactor into which the surfactant solution of the first step is injected; And iii) a batch type gas hydrate comprising a third step of injecting an aqueous fresh solution containing potential seed hydrate into the reactor into which the gas of the second step is injected. By providing a method.

It is also an object of the present invention to i) a first step of injecting a surfactant solution into the reactor, ii) containing a potential seed hydrate in the reactor into which the first step of the surfactant solution is injected. A second step of injecting an aqueous fresh solution, and iii) a third step of pressurizing a reactor into which a pure aqueous solution containing the potential seed hydrate of said second step is injected. (batch type) is achieved by providing a method for producing a gas hydrate.

It is also an object of the present invention to provide a process comprising i) a first step of injecting a surfactant solution into a reactor, and ii) a pressurize and a potential seed hydrate in the reactor into which the first step of the surfactant solution is injected. It is achieved by providing a batch type gas hydrate manufacturing method comprising a second step of simultaneously injecting an aqueous fresh solution containing a potential feed hydrate.

In addition, an object of the present invention is i) a first step of injecting gas into the reactor (ii) a second step of injecting a surfactant solution into the reactor into which the gas of the first step is pressurized And iii) a third step of injecting an aqueous fresh solution containing a potential seed hydrate into the reactor into which the surfactant solution of the second step is injected. (batch type) is achieved by providing a method for producing a gas hydrate.

The present invention is a novel method for rapidly forming gas hydrates from a pure aqueous solution without using the memory effect of water or gas hydrate particles already formed, and using a small amount of potential seed hydrate aqueous solution under relatively mild conditions of pressure and temperature in the reactor. It creates hydrates and simultaneously forms natural gas hydrates on them, allowing for rapid reactions.

Seed hydrate formation in the reactor takes place at atmospheric pressure or at relatively low pressures below 10 bar at temperatures above the freezing point of water. The seed hydrate can form gas hydrates immediately without a hydrate induction time with an aqueous solution containing a small amount of surfactant, and the hydrate quickly forms a porous structure along the reactor wall. This rapid hydrate manufacturing method can be applied to both batch type and fed-batch type processes.

The method for producing a fed-batch type gas hydrate of the present invention comprises the following steps: i) a first step of injecting an aqueous fresh solution containing a potential feed hydrate into the reactor, ii) the first A second step of pressurizing the reactor into which the pure aqueous solution containing the potential seed hydrate of the step is injected, and iii) injecting a surfactant solution into the reactor into which the gas of the second step is injected; The third step is made.

In addition, the fed-batch type gas hydrate manufacturing method of the present invention comprises: i) a first step of pressurizing a gas into the reactor, ii) a potential seed hydrate into the reactor into which the gas of the first step is injected ( a second step of injecting an aqueous fresh solution containing a potential feed hydrate, and iii) adding a surfactant solution to a reactor into which a pure aqueous solution containing a potential seed hydrate of said second step is injected. The third step is to inject.

In addition, the method for producing a fed-batch type gas hydrate of the present invention includes: i) a first injecting an aqueous fresh solution containing pressurize and seed hydrate into a reactor at the same time; Step ii) injecting a surfactant solution into the reactor into which the first step of pressurize and aqueous fresh solution containing a potential feed hydrate are simultaneously injected; Consists of steps.

Here, a potential feed hydrate is a compound that can be a seed that forms a hydrate, and a salt that forms sI, sII, sH hydrate formers or semi-clathrate compounds is seed hydrate. This can be

sI, sII and sH hydrates are classified according to the molecular structure of hydrates, especially type H, which was artificially produced only in laboratories, but has recently been found in the seabed of 200-500 m depth on the west coast of Canada (see Figure 1).

A semi-clathrate compound refers to a compound containing a structure in which one molecule creates a three-dimensional network structure and another molecule enters a gap when two molecules are determined together under suitable conditions.

The seed hydrate solution is tetrahydrofuran (THF), 1,3-dioxolane (1,3-dioxolane), tetrahydropyran, cyclopentane, acetone, difluoro Difluoromethane (HFC-32), isobutane, isobutylene, n-butane, propane, LPG (C3 + C4), methyl Methylcyclohexane, methylcyclopentane, neohexane, methyl tert-butyl ether, adamantine, tetra n-butyl ammonium bromide nbutylammonium bromide), tetra-n-butylammonium fluoride and tetra-nbutylammonium chloride.

On the other hand, as another potential seed hydrate, sodium dodecyl sulfate (SDS), diisoctyl sodium sulfosuccinate (DSS), sodium tetradecyl sulfate, sodium hexadecyl sulfate sodium hexadecyl sulfate, sodium dodecylbenzene sulfonate, xylenesulfonate, sodium oleate, 4-n-decylbenzenesulfonate, 4-n-decylbenzenesulfonate Sodium laurate, 4-dodecylbenzenesulfonic acid, dodecylamine hydrochloride, dodecyltrimethylammonium chloride, 4-n-octylbenzenesulfonate (4-n-Octylbenzene sulfonate), ethoxylated sulfonate, Decylbenzenesulfonate, Potassium oleate, n-decylbenzene Sulfonate (n-Decylbenzene sulfonate), alkyltrimethylammonium bromide (C10-C16 chains), dodecyl amine, tetradecyltrimethylammonium chloride, dodecyl polysaccharide glycoside (dodecyl polysaccharide glycosides, cyclodextrins, glycolipids, lipoprotein-lipopeptides, phospholipides, para-toluene sulfonic acid, trisiloxane It is possible to use ice slurry of a surfactant such as (trisiloxane) and triton (X-100).

The amount of the potential seed hydrate aqueous solution mentioned above is sufficient in a small amount, such as within 5% of the total volume of the surfactant solution.

The potential seed hydrate solution forms seed hydrate directly with the gas injected in the cooled reactor (eg methane gas 35-100 bar).

The gas may be introduced before or after the potential aqueous seed hydrate solution is injected into the reactor, or may be injected simultaneously.

Cooling of the reactor may occur before gas enters the reactor, before the potential seed hydrate aqueous solution enters the reactor, or before the surfactant solution enters the reactor.

The cooling temperature of the reactor is preferably -5 ° C to 5 ° C, and the pressurized pressure of the injected gas is preferably 10 to 50 bar or more than the equilibrium pressure of the gas hydrate. That is, the reaction is performed at relatively mild temperature and pressure conditions.

The injected gas may be any gas capable of forming a hydrate such as methane, ethane, propane, carbone dioxide or a mixture thereof.

When the aqueous solution containing the surfactant is injected into the reactor in which the seed hydrate is formed, the gas hydrate is formed immediately without any induction time. In other words, the surfactant solution forms a porous gas hydrate that rises along the reactor wall when in contact with the gas, which not only makes the gas easily accessible to the unreacted aqueous solution, but also dissipates the heat of reaction by easily dispersing the gas. This results in an increase in gas storage density and conversion yield.

The aqueous surfactant solution used at this time is sodium dodecyl sulfate (SDS), diisoctyl sodium sulfosuccinate (DSS), sodium tetradecyl sulfate, sodium hexadecyl sulfate (sodium hexadecyl sulfate, sodium dodecylbenzene sulfonate, xylenesulfonate, sodium oleate, 4-n-decylbenzenesulfonate, sodium lauric Sodium laurate, 4-dodecylbenzenesulfonic acid, dodecylamine hydrochloride, dodecyltrimethylammonium chloride, 4-n-octylbenzenesulfonate (4 -n-Octylbenzene sulfonate, Ethoxylated sulfonate, Decylbenzenesulfonate, Potassium oleate, n-decylbenzene sulfonate N-Decylbenzene sulfonate, alkyltrimethylammonium bromide (C10-C16 chains), dodecyl amine, tetradecyltrimethylammonium chloride, dodecyl polysaccharide glycoside (dodecyl polysaccharide) glycosides, cyclodextrins, glycolipids, lipoprotein-lipopeptides, phospholipides, para-toluene sulfonic acid, trisiloxane trisiloxane, triton (triton) may include any one or more compounds selected from X-100, the concentration is preferably about 50 to 2000 ppm.

Meanwhile, the gas hydrate manufacturing method of the present invention may be applied to a batch type manufacturing method, and in this case, the batch type gas hydrate manufacturing method of the present invention is i) injecting a surfactant solution into a reactor. First step ii) pressurizing the gas into the reactor into which the surfactant solution of the first step is injected, and iii) potential seed hydrate into the reactor into which the gas of the second step is injected. It consists of a third step of injecting an aqueous fresh solution containing a feed hydrate (aqueous fresh solution).

In addition, the batch type gas hydrate manufacturing method of the present invention comprises: i) a first step of injecting a surfactant solution into a reactor, ii) a potential seed in a reactor into which the first step of surfactant solution is injected; A second step of injecting an aqueous fresh solution containing a potential feed hydrate, and iii) pressurizing a gas into a reactor into which a pure aqueous solution containing a potential seed hydrate of said second step is injected; The third step is made.

In addition, the batch type gas hydrate manufacturing method of the present invention comprises: i) a first step of injecting a surfactant solution into a reactor, and ii) a gas into a reactor into which the surfactant solution of the first step is injected. This is followed by a second step of simultaneous injection of aqueous fresh solution containing pressurize and potential feed hydrate.

In addition, the batch type gas hydrate manufacturing method of the present invention comprises: i) a first step of pressurizing a gas into a reactor, and ii) a surfactant solution in a reactor into which the gas of the first step is pressurized. a second step of injecting a surfactant solution, and iii) injecting an aqueous fresh solution containing a potential feed hydrate into the reactor into which the second solution of the surfactant solution is injected. This is done in a third step.

The surfactant solution and potential seed hydrate aqueous solution which can be used in the batch gas hydrate manufacturing method are the same as those used in the semibatch production method mentioned above. In a batch preparation method, seed hydrate is formed on the first injected surfactant solution.

That is, if a potential aqueous seed hydrate solution entering the reactor forms a seed hydrate with the gas injected in the cooled reactor (eg methane gas 35-100 bar), the seed hydrate is already injected into the reactor. The gas hydrate is formed immediately without any induction time with the surfactant present.

The gas may be introduced before or after the potential seed hydrate solution is injected into the reactor, or simultaneously, and the cooling of the reactor may occur before the gas enters the reactor, before the potential seed hydrate solution enters the reactor, or at the interface. The activator solution may be made before entering the reactor.

At this time, it is preferable that the cooling temperature of the reactor is -5 ℃ to 5 ℃, and the pressurized pressure of the injected gas is 10 to 50 bar or more than the equilibrium pressure of the gas hydrate like the semi-batch production method.

2 is an experimental apparatus using the manufacturing method of the present invention, in which gas is supplied from a gas tank 1 through a pipe 3 and a mass flow meter 2 is installed therein so that a gas injection amount according to gas hydrate formation is measured. The surfactant solution is supplied to the reactor via the liquid injection line 4 to the high pressure liquid pump 5. A gas discharge line 6 hangs on the top of the reactor 9. The coolant lines 10 connect the reactor with the cooler 11 to which the temperature controller is attached to lower the temperature of the reactor.

Hereinafter, an embodiment of the present invention will be described.

<Example 1>

Table 1 below is an experimental result of using a pure THF solution as the seed hydrate forming solution. First, 0.02 liters of 500 ppm SDS and 4 wt% THF solution are fed to the reactor. The reactor temperature is then lowered via an external cooler near 0 ° C. and methane gas is charged to the reactor at 50 bar. One liter of 500 ppm SDS aqueous solution is then injected into the reactor to produce a gas hydrate.

In this experiment, methane gas was stored at a temperature of 173 times at a pressure of 0 ° C and 1 atmosphere per unit volume of methane hydrate. When the reactor was heated after the experiment, it can be seen that methane hydrate was formed through the reaction wall.

Reactor Volume  5 L Pure Seed THF Solution  0.02 L (THF 4wt% + SDS 500ppm) Methane consumption ^{(Nm 3) (Methane Gas Consumption} )  193 Aqueous SDS Solution  1.0 Aqueous SDS Solution Injection Time  100 Initial Reaction Temperature / Pressure  0.1 ℃ / 50bar Volumetric Gas Storage Per Hydrate (v / v)  173 Induction time (min) for methane hydrates  0

Fed-batch Hydrate Formation From Fresh THF solution

<Example 2>

Table 2 below shows the results of using a pure CP solution as a seed hydrate forming solution. The storage density of methane is somewhat lower than the above experiments, but optimizing the reaction temperature, pressure, liquid injection rate, etc. can maximize gas storage.

Reactor Volume  5 L Fresh Seed CP Solution  0.02 L (CP 4wt% + SDS 500ppm) Methane consumption ^{(Nm 3) (Methane Gas Consumption} )  181 Aqueous SDS Solution  1.0

Aqueous SDS Solution Injection Time  100 Initial Reaction Temperature / Pressure  0.3 ℃ / 50bar Volumetric Gas Storage Per Hydrate (v / v)  163 Induction time (min) for methane hydrates  0

Fed-Batch Hydrate Formation From Fresh CP solution

In both examples, the seed hydrate was formed during the pressurization and cooling process before the SDS aqueous solution was injected, and the gas hydrate was immediately formed while the SDS aqueous solution was injected.

The technical spirit of the present invention is not limited to the above specific embodiments and descriptions, and any person having ordinary knowledge in the technical field to which the present invention belongs without departing from the gist of the present invention claimed in the claims. Various modifications can be made from the technology, and it can be seen that such modifications fall within the protection scope of the present invention.

Figure 1 shows the structure of the gas hydrate molecules of the si, sII type.

2 is a detailed view of a gas hydrate manufacturing apparatus using the gas hydrate manufacturing method of the present invention.

                         [Drawing symbol]

1) Gas Tank 2) Mass Flow Meter (MFC)

3) gas injection line 4) aqueous solution injection line

5) liquid pump 6) gas vent line

7) Thermocouple 8) Aqueous Tank

9) Reactor 10) Refrigerant In and Out

11) Chiller 12) Data Link

13) PC 14) Data Acquisition Board

Claims (35)

i) injecting an aqueous fresh solution containing a potential seed hydrate into the reactor; ii) pressurizing a gas into a reactor into which a pure aqueous solution containing the potential seed hydrate of said first stage is injected; And iii) a third step of injecting a surfactant solution into the reactor into which the gas of the second step is injected; Fed-batch type gas hydrate manufacturing method comprising a. i) pressurizing the gas into the reactor; ii) a second step of injecting an aqueous fresh solution containing a potential feed hydrate into the reactor into which the gas of the first step is injected; And iii) a third step of injecting a surfactant solution into the reactor into which the pure aqueous solution containing the potential seed hydrate of the second step is injected; Fed-batch type gas hydrate manufacturing method comprising a. i) simultaneously injecting an aqueous fresh solution containing pressurize and seed feed hydrate into the reactor; And ii) a second step of injecting a surfactant solution into a reactor into which an aqueous fresh solution containing the pressurize of the first step and a seed feed hydrate are simultaneously injected; Fed-batch type gas hydrate manufacturing method comprising a. 4. The method of claim 1 or 3, further comprising the step of cooling down the reactor prior to injecting the gas into the reactor. The method of claim 4, wherein the cooling temperature of the reactor is -5 ℃ to 5 ℃. 4. The method of claim 1 or 3, further comprising the step of cooling down the reactor before injecting an aqueous fresh solution containing potential seed hydrate into the reactor. Process for preparing fed-batch type gas hydrates. 7. The method of claim 6, wherein the cooling temperature of the reactor is -5 ° C to 5 ° C. 4. The method of claim 1 or 3, further comprising the step of cooling down the reactor prior to injecting the surfactant solution into the reactor. 9. The method of claim 8, wherein the cooling temperature of the reactor is -5 ° C to 5 ° C. 4. The fed batch according to claim 1 or 3, wherein the gas injected into the reactor is methane, ethane, propane, carbone dioxide or a mixture thereof. batch type) Method for preparing gas hydrates. The method of claim 10, wherein the pressurized pressure of the injection gas is 10 to 50 bar or more than the equilibrium pressure of the gas hydrate. 4. The semi-batch according to claim 1 or 3, wherein the latent seed hydrate is a salt which forms a sI, sII, sH hydrate former or semi-clathrate compound. fed-batch type) Process for preparing gas hydrates. The salt of claim 12, wherein the salt forming the si, sII, sH hydrate former or semi-clathrate compound is tetrahydrofuran (THF), 1,3-di. Oxolane (1,3-dioxolane), tetrahydropyran, cyclopentane, acetone, difluoromethane (HFC-32), isobutane, isobutyl Iso-butylene, n-butane, propane, LPG (C3 + C4), methylcyclohexane, methylcyclopetane, neo-hexane neohexane, methyltertbutyl ether, adamantine, tetra-nbutylammonium bromide, tetra-n-butylammonium fluoride and tetra selected from n-butyl ammonium chloride (tetra-nbutylammonium chloride) A method for producing a fed-batch type gas hydrate, characterized in that any one or more compounds. The method of claim 1, wherein the potential seed hydrate is sodium dodecyl sulfate (SDS), diisoctyl sodium sulfosuccinate (DSS), sodium tetradecyl sulfate (sodium tetradecyl sulfate) sulfate, sodium hexadecyl sulfate, sodium dodecylbenzene sulfonate, xylenesulfonate, sodium oleate, 4-n-decylbenzenesulfonate (4 -n-Decylbenzenesulfonate, sodium laurate, 4-dodecylbenzenesulfonic acid, dodecylamine hydrochloride, dodecyltrimethylammonium chloride, 4 4-n-octylbenzenesulfonate, ethoxylated sulfonate, decylbenzenesulfonate, potassium oleate Potassium oleate, n-decylbenzene sulfonate, alkyltrimethylammonium bromide (C10-C16 chains), dodecyl amine, tetradecyltrimethylammonium chloride, dodecyltrimethylammonium chloride Dodecyl polysaccharide glycosides, cyclodextrins, glycolipids, lipoprotein-lipopeptides, phospholipides, para-toluene sulfonic acid (para-) Method for producing a fed-batch type gas hydrate, characterized in that the ice slurry of any one or more compounds selected from toluene sulfonic acid, trisiloxane, triton X-100. . The method of claim 1, wherein the volume of the pure aqueous solution containing the potential seed hydrate is within 5% of the total volume of the surfactant solution. . The method according to claim 1 or 3, wherein the surfactant is sodium dodecyl sulfate (SDS), diisoctyl sodium sulfosuccinate (DSS), sodium tetradecyl sulfate ), Sodium hexadecyl sulfate, sodium dodecylbenzene sulfonate, xylenesulfonate, sodium oleate, 4-n-decylbenzenesulfonate (4- n-Decylbenzenesulfonate, sodium laurate, 4-dodecylbenzenesulfonic acid, dodecylamine hydrochloride, dodecyltrimethylammonium chloride, 4- n-octylbenzenesulfonate, ethoxylated sulfonate, decylbenzenesulfonate, potassium oleate oleate, n-decylbenzene sulfonate, alkyltrimethylammonium bromide (C10-C16 chains), dodecyl amine, tetradecyltrimethylammonium chloride, dodecyl Polysaccharide glycosides, cyclodextrins, glycolipids, lipoprotein-lipopeptides, phospholipides, para-toluene sulfonic acid Method for producing a fed-batch type gas hydrate, characterized in that any one or more compounds selected from sulfonic acid), trisiloxane, triton (triton) X-100. 4. The method of claim 1 or 3, wherein the concentration of the surfactant solution is 50 to 2000 ppm. i) injecting a surfactant solution into the reactor; ii) pressurizing a gas into the reactor into which the surfactant solution of the first step is injected; And iii) a third step of injecting an aqueous fresh solution containing a potential feed hydrate into the reactor into which the gas of the second step is injected; Batch type gas hydrate manufacturing method comprising a. i) injecting a surfactant solution into the reactor; ii) a second step of injecting an aqueous fresh solution containing a potential feed hydrate into the reactor into which the surfactant solution of the first step is injected; And iii) pressurizing a gas into a reactor into which a pure aqueous solution containing the potential seed hydrate of said second step is injected; Batch type gas hydrate manufacturing method comprising a. i) injecting a surfactant solution into the reactor; And ii) a second step of simultaneously injecting an aqueous fresh solution containing a pressurize and a potential feed hydrate into the reactor into which the surfactant solution of the first step is injected; Batch type gas hydrate manufacturing method comprising a. i) pressurizing the gas into the reactor; ii) a second step of injecting a surfactant solution into the reactor into which the gas of the first step is pressurized; And iii) a third step of injecting an aqueous fresh solution containing a potential feed hydrate into the reactor into which the surfactant solution of the second step is injected; Batch type gas hydrate manufacturing method comprising a. 22. The method of claim 18 or 21, further comprising the step of cooling down the reactor prior to injecting gas into the reactor. The method of claim 22, wherein the cooling temperature of the reactor is -5 ℃ to 5 ℃. 22. The method of claim 18 or 21, further comprising the step of cooling down the reactor prior to injecting the pure aqueous solution containing the potential seed hydrates to the reactor. 25. The method of claim 24, wherein the cooling temperature of the reactor is -5 ° C to 5 ° C. 22. The method of claim 18 or 21, further comprising the step of cooling down the reactor prior to injecting the surfactant solution into the reactor. 27. The method of claim 26, wherein the cooling temperature of the reactor is -5 ° C to 5 ° C. 22. The batch type of claim 18 or 21, wherein the gas injected into the reactor is methane, ethane, propane, carbone dioxide, or mixtures thereof. ) Gas hydrate manufacturing method. 29. The method of claim 28, wherein the pressurized pressure of the injection gas is 10-50 bar or more above the equilibrium pressure of the gas hydrate. 22. The batch of claim 18 or 21, wherein the potential seed hydrate is a salt that forms a sI, sII, sH hydrate former or semi-clathrate compound. type) gas hydrate manufacturing method. 31. The salt of claim 30, wherein the salts forming sI, sII, sH hydrate former or semi-clathrate compounds are tetrahydrofuran (THF), 1,3-di Oxolane (1,3-dioxolane), tetrahydropyran, cyclopentane, acetone, difluoromethane (HFC-32), isobutane, isobutyl Iso-butylene, n-butane, propane, LPG (C3 + C4), methylcyclohexane, methylcyclopetane, neohexane neohexane, methyltertbutyl ether, adamantine, tetra-nbutylammonium bromide, tetra-n-butylammonium fluoride and tetra selected from n-butyl ammonium chloride (tetra-nbutylammonium chloride) Batch type gas hydrate manufacturing method, characterized in that any one or more compounds. 22. The method of claim 18 or 21, wherein the potential seed hydrate is sodium dodecyl sulfate (SDS), diisoctyl sodium sulfosuccinate (DSS), sodium tetradecyl sulfate sulfate, sodium hexadecyl sulfate, sodium dodecylbenzene sulfonate, xylenesulfonate, sodium oleate, 4-n-decylbenzenesulfonate (4 -n-Decylbenzenesulfonate, sodium laurate, 4-dodecylbenzenesulfonic acid, dodecylamine hydrochloride, dodecyltrimethylammonium chloride, 4 4-n-octylbenzenesulfonate, ethoxylated sulfonate, decylbenzenesulfonate, potassium oleic acid (Potassium oleate), n-Decylbenzene sulfonate, Alkyltrimethylammonium bromide (C10-C16 chains), Dodecyl amine, Tedecyltrimethylammonium chloride, Dodecyl polysaccharide glycoside, cyclodextrins, glycolipids, lipoprotein-ipopeptides, phospholipides, para-toluene sulfonic acid (para-toluene sulfonic acid) Batch type gas hydrate manufacturing method characterized in that the ice particles (ice slurry) of any one or more compounds selected from -toluene sulfonic acid), trisiloxane, triton (triton) X-100. 22. The method of claim 18, wherein the volume of the pure aqueous solution containing the potential seed hydrate is within 5% of the total volume of the surfactant solution. 22. The method of claim 18, wherein the surfactant is sodium dodecyl sulfate (SDS), diisoctyl sodium sulfosuccinate (DSS), sodium tetradecyl sulfate (sodium tetradecyl sulfate) ), Sodium hexadecyl sulfate, sodium dodecylbenzene sulfonate, xylenesulfonate, sodium oleate, 4-n-decylbenzenesulfonate (4- n-Decylbenzenesulfonate, sodium laurate, 4-dodecylbenzenesulfonic acid, dodecylamine hydrochloride, dodecyltrimethylammonium chloride, 4- n-octylbenzenesulfonate, ethoxylated sulfonate, decylbenzenesulfonate, potassium oleate oleate, n-decylbenzene sulfonate, alkyltrimethylammonium bromide (C10-C16 chains), dodecyl amine, tetradecyltrimethylammonium chloride, dodecyl Polysaccharide glycosides, cyclodextrins, glycolipids, lipoprotein-lipopeptides, phospholipides, para-toluene sulfonic acid (para-) Toluene sulfonic acid), trisiloxane (trisiloxane), triton (triton) A process for producing a batch gas hydrate, characterized in that any one or more compounds selected from triton (X-100). 22. The method of claim 18 or 21, wherein the concentration of the surfactant solution is from 50 to 2000 ppm.

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