JP4644804B2 - Carbon dioxide recovery method and apparatus for recovering carbon dioxide in exhaust gas - Google Patents

Description

In the present invention, by utilizing the cold heat of LNG (liquefied natural gas), exhaust gas and ice are brought into contact with each other at a low temperature to generate carbon dioxide gas hydrate, and carbon dioxide (CO ₂ ) in the exhaust gas is gasified. The present invention relates to a carbon dioxide separation and recovery system for concentrating and fixing in a hydrate and thus recovering carbon dioxide in exhaust gas.

  Recently, a method for recovering carbon dioxide contained in exhaust gas has been developed from the viewpoint of global environmental conservation. Examples of these methods include a chemical absorption method, a physical adsorption method, and a membrane separation method.

  The chemical absorption method is a method for separating and recovering carbon dioxide by utilizing the property of an amine absorbing solution that absorbs carbon dioxide at 40 ° C. to 50 ° C. and releases carbon dioxide at 100 ° C. to 120 ° C.

  The physical adsorption method is a method for separating and recovering carbon dioxide by utilizing the property of zeolite that adsorbs carbon dioxide when pressure is applied and desorbs when pressure is reduced. The membrane separation method is a method for membrane separation of carbon dioxide using a porous hollow fiber membrane.

  However, the chemical absorption method or the physical adsorption method requires regeneration of the absorbent and the adsorbent and consumes a large amount of energy, so that it is not necessarily suitable as a carbon dioxide separation method for fixing carbon dioxide. .

  On the other hand, the membrane separation method is a method of separation based on the size of the molecules, but since the sizes of the nitrogen molecules and carbon dioxide molecules contained in the combustion exhaust gas are approximately the same, it is difficult to separate them. There is a problem that the purity of the recovered carbon dioxide is low.

In addition, a separation method using gas hydrate has been proposed (see, for example, Patent Document 1 and Patent Document 2).
JP 2001-96133 A Japanese Patent Laid-Open No. 5-38429

  However, in any case, the gas hydrate separation method is difficult to generate a gas hydrate containing carbon dioxide at a high concentration from exhaust gas with a low carbon dioxide content, such as gas turbine exhaust gas. It was.

  On the other hand, recent gas hydrate research shows that, for example, about 60 to 80% of carbon dioxide is concentrated in gas hydrate produced at a low temperature of -70 ° C to -100 ° C. It has also been confirmed in scale experiments.

  The present invention has been made on the basis of the above research and experimental results, and generally accelerates the gas hydrate formation reaction at a low temperature where the production speed is extremely low, and is used as a fuel in a combined cycle power generation facility. An object of the present invention is to provide a carbon dioxide recovery method and apparatus that consumes less energy by recovering unused cold heat that has been discarded when gasifying LNG, and effectively using the cold heat.

  In order to solve the above problems, the present invention is configured as follows.

The carbon dioxide recovery method for recovering carbon dioxide in exhaust gas according to claim 1 is the carbon dioxide recovery method for recovering carbon dioxide in exhaust gas by gas hydrate conversion, wherein the exhaust gas is discharged from the carbon dioxide recovery step. an exhaust gas precooling step of precooling to a predetermined temperature by utilizing the cold energy of the exhaust gas, the particle size by spraying with water by utilizing the cold of liquefied natural gas within a predetermined fine ice generator cooled to a temperature recooling but the fine ice generating step of generating 0.1~10μm fine ice, said pre cooled exhaust gas exhaust precooling process using the cold energy of the liquefied natural gas to -70 ℃ ~-100 ℃ and re-cooling step, mechanically stirred to carbon dioxide hydrate while introducing and re-cooled exhaust gas -70 ℃ ~-100 ℃ in the fine ice and the re-cooling step in the gas hydrate generator to generate a And a carbon dioxide recovery process.

A carbon dioxide recovery device for recovering carbon dioxide in exhaust gas according to claim 2 is a carbon dioxide recovery device for generating carbon dioxide hydrate by reacting carbon dioxide in exhaust gas with water, wherein the water and assist gas are used. A two-fluid spray nozzle for atomizing the water and fine water droplets sprayed from the two-fluid spray nozzle by using cold heat of liquefied natural gas and having a particle diameter of 0.1 to 10 μm A fine ice generator for producing carbon dioxide , and a horizontal oblong that produces carbon dioxide hydrate by introducing the fine ice and exhaust gas cooled to −70 ° C. to −100 ° C. using the cold heat of liquefied natural gas , and , Ri Do and a reaction vessel having a stirrer, Note and has a configuration that connecting the reaction vessel into a plurality zigzag.

The carbon dioxide recovery device for recovering carbon dioxide in the exhaust gas according to claim 3 is a low-temperature / low-pressure exhaust gas that has been expanded to near atmospheric pressure after separating and recovering the exhaust gas discharged from the gas turbine combined cycle power generation facility. An exhaust gas precooler precooled at
An exhaust gas compressor that pressurizes the low-temperature exhaust gas after pre-cooling to the pressure required for generating gas hydrate with the exhaust gas pre-cooler;
An exhaust gas recooler for recooling the exhaust gas compressed by the exhaust gas compressor with low temperature and high pressure exhaust gas after carbon dioxide separation and recovery;
An exhaust gas expander that expands the high-pressure exhaust gas heated by the exhaust gas recooler to atmospheric pressure, and a low-temperature gas hydrate generator composed of the following devices:
The low-temperature gas hydrate generator, a generated water pump that pressurizes the generated water to a pressure required for the reaction;
An assist gas compressor that pressurizes a part of the exhaust gas to an assist gas pressure necessary for spraying produced water;
A spray nozzle for atomizing the produced water by introducing the produced water and the assist gas;
A fine ice generator for producing fine ice by freezing the water droplets atomized by the spray nozzle by the cold heat of liquefied natural gas;
A gas hydrate generator comprising a plurality of reaction vessels connected in series for introducing and reacting the fine ice and the remaining exhaust gas cooled by the cold heat of liquefied natural gas; and
A circulation loop that connects the plurality of reaction vessels in a ring shape and a circulation gas cooler that cools the exhaust gas circulating through these reaction vessel groups with liquefied natural gas are configured.

  As described above, the invention according to claim 1 is a carbon dioxide recovery method for recovering carbon dioxide in exhaust gas by gas hydrate, and recovering the exhaust gas from liquefied natural gas in a facility using liquefied natural gas as fuel. A step of cooling to a predetermined temperature using cold heat, a step of generating fine ice by spraying water into a fine ice generator cooled to a predetermined temperature using the cold heat of the liquefied natural gas, and Since it is composed of a step of introducing fine ice and exhaust gas after cooling to a predetermined temperature into a gas hydrate generator, and reacting fine ice and carbon dioxide in the exhaust gas to generate carbon dioxide hydrate, Under a low temperature, for example, at a low temperature of about −70 ° C. to −100 ° C., the ice, which has been said to be difficult to be gas hydrated, is made into fine ice (for example, 0.1 to 10 μm) for a relatively short time. With fine ice It could be a gas hydrate of to the core.

  As a result, it was possible to efficiently recover the exhaust gas, particularly carbon dioxide in the gas turbine exhaust gas having a carbon dioxide content of about 3 to 4%.

  In addition, according to this method, carbon dioxide hydride can be recovered by a novel method that consumes less energy than before by recovering unused cold energy that was discarded when LNG was gasified and effectively using the cold energy. The rate can be recovered efficiently.

  On the other hand, the invention described in claim 3 is a carbon dioxide recovery device that generates carbon dioxide hydrate by reacting carbon dioxide in exhaust gas with water, the spray nozzle spraying the water, and the spray nozzle A fine ice generator that generates fine ice by freezing the sprayed particulate water droplets using the cold heat of liquefied natural gas, and an exhaust gas cooled by the cold heat of the fine ice and liquefied natural gas are introduced. Since it is composed of a gas hydrate generator that generates carbon dioxide hydrate, it is said that it is difficult to make a gas hydrate at a low temperature, for example, at a low temperature of about -70 ° C to -100 ° C, as in the method invention. By making the ice that had been used fine, it was possible to gas hydrate to the core of the fine ice in a relatively short time. As a result, it was possible to efficiently recover the exhaust gas, particularly carbon dioxide in the gas turbine exhaust gas having a carbon dioxide content of about 3 to 4%.

  In addition, according to this method, carbon dioxide hydride can be recovered by a novel method that consumes less energy than before by recovering unused cold energy that was discarded when LNG was gasified and effectively using the cold energy. The rate can be recovered efficiently.

  The invention according to claim 4 circulates a part of the exhaust gas in the gas hydrate generator and cools the circulating exhaust gas using the cold heat of liquefied natural gas, so that the gas hydrate generator The inside can be maintained at a predetermined temperature, and generation of gas hydrate in the gas hydrate generator can be promoted.

  Further, the invention according to claim 5 removes the heat of reaction generated in the gas hydrate generator by cooling the generator using the cold of liquefied natural gas. It became possible to enhance the reaction.

The invention according to claim 6 is an exhaust gas precooler for precooling exhaust gas discharged from a gas turbine combined cycle power generation facility with carbon dioxide separation and recovery, and with low temperature / low pressure exhaust gas expanded to near atmospheric pressure, and the exhaust gas Exhaust gas compressor that pressurizes low-temperature exhaust gas after pre-cooling to a pressure required for gas hydrate generation with a pre-cooler, and exhaust gas compressed by the exhaust gas compressor is re-cooled with low-temperature and high-pressure exhaust gas after carbon dioxide separation and recovery Composed of an exhaust gas recooler, an exhaust gas expander that expands the high-pressure exhaust gas heated by the exhaust gas recooler to atmospheric pressure, and a low-temperature gas hydrate generator composed of the following devices:
The low-temperature gas hydrate generating device, a generated water pump that pressurizes the generated water to a pressure required for the reaction, an assist gas compressor that pressurizes a part of the exhaust gas to an assist gas pressure required for spraying the generated water, A spray nozzle that atomizes the generated water by introducing the generated water and the assist gas, and a fine ice generator that generates fine ice by freezing the water droplets atomized by the spray nozzle by the cold heat of the liquefied natural gas; A gas hydrate generator in which a plurality of reaction vessels for introducing and reacting the fine ice and the remaining exhaust gas cooled by the cold heat of the liquefied natural gas are connected in series, and the ring of the plurality of reaction vessels is connected Since it consists of a circulation loop and a circulation gas cooler that cools the exhaust gas that circulates through these reaction vessel groups with liquefied natural gas, For example, at a low temperature of about −70 ° C. to −100 ° C., gas hydrate can be made to the core of fine ice in a relatively short time by making the ice, which was said to be difficult to gas hydrate, into fine ice. I was able to. As a result, it was possible to efficiently recover the exhaust gas, particularly carbon dioxide in the gas turbine exhaust gas having a carbon dioxide content of about 3 to 4%.

  In addition, according to this method, carbon dioxide hydride can be recovered by a novel method that consumes less energy than before by recovering unused cold energy that was discarded when LNG was gasified and effectively using the cold energy. The rate can be recovered efficiently.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  In this embodiment, a large gas turbine combined cycle power generation facility is taken as an example, but the present invention is not limited to this example.

  FIG. 1 is a block diagram of a carbon dioxide separation and recovery system according to the present invention. This carbon dioxide separation and recovery system mainly includes a large gas turbine combined cycle power generation facility 10, an exhaust gas precooler 11, an exhaust gas compressor 12, The exhaust gas recooler 13, the exhaust gas hydrate generator (carbon dioxide separation and recovery device) 14, and the exhaust gas expander 15 are configured.

  Accordingly, the exhaust gas 1a having a relatively low carbon dioxide content discharged from the gas turbine combined cycle power generation facility 10 (eg, 3 to 4%) and a predetermined temperature and pressure (eg, 100 ° C., 0 MPa). Is introduced into the exhaust gas precooler 11 and separated and recovered from the carbon dioxide discharged from the exhaust gas hydrate generator 14 by the exhaust gas precooler 11, and further to near atmospheric pressure (for example, 0 MPa) by the exhaust gas expander 15. Precooled by the expanded low temperature / low pressure exhaust gas 1e.

  The low-temperature exhaust gas 1c that has been pre-cooled by the exhaust gas pre-cooler 11 is boosted to a pressure necessary for generating gas hydrate using the exhaust gas compressor 12 (for example, 2 MPa). Further, the exhaust gas 1d compressed by the exhaust gas compressor 12 is introduced into the exhaust gas recooler 13 and is discharged at a low temperature and high pressure (for example, 2 MPa, −70 ° C.) after carbon dioxide separation and recovery discharged from the exhaust gas hydrate generator 14. )) Is re-cooled using the exhaust gas 1b.

  The high-pressure / low-temperature (for example, 2 MPa, −70 ° C.) exhaust gas 1 f re-cooled by the exhaust gas re-cooler 13 reacts with fine ice generated by using the cold heat of LNG to react with exhaust gas hydrate (dioxide dioxide). Carbon gas hydrate).

  As a result, 60 to 80% of carbon dioxide is taken into the exhaust gas hydrate, and the concentration of carbon dioxide in the exhaust gas discharged from the chimney 16 described later decreases accordingly. 1 g of exhaust gas after separation and recovery of carbon dioxide heated by the exhaust gas recooler 15 is discharged into the atmosphere from the chimney 16.

  Next, it demonstrates more concretely using FIG.

  As shown in FIG. 2, this carbon dioxide separation and recovery system includes a large gas turbine combined cycle power generation facility 10, an exhaust gas precooler 11, an exhaust gas compressor 12, an exhaust gas recooler 13, a low temperature gas hydrate generator 14, The exhaust gas expander 15 is configured.

  And this low-temperature gas hydrate production | generation apparatus 14 produces | generates the cold heat of the product water pump 20, the assist gas compressor 21, the fluid spray nozzle 22, the fine ice generator 23, the gas hydrate generator 24, the circulation loop 25, and LNG. The circulating gas cooler 26 is used.

  On the other hand, the exhaust gas supply pipe 28 for supplying the exhaust gas 1a discharged from the gas turbine combined cycle power generation facility 10 reaches the fine ice generator 23 via the exhaust gas precooler 11, the exhaust gas compressor 12, and the exhaust gas recooler 13. Yes. An exhaust gas supply branch pipe 29 branched from the exhaust gas supply pipe 28 is connected to the circulation loop 25. The exhaust gas discharge pipe 30 connected to the circulation loop 25 is connected to a chimney (not shown) through the exhaust gas recooler 13, the exhaust gas expander 15, and the exhaust gas precooler 11.

  A water supply pipe 31 is connected to the fine ice generator 23. Further, a water recovery pipe 32 that recovers water generated in the exhaust gas precooler 11 is connected to the water supply pipe 31.

  The gas turbine combined cycle power generation facility 10 includes a generator 35, an intake compressor 36, an exhaust gas expander 37, a combustor 38, and a waste heat boiler 39, and is driven by the exhaust gas expander 37. The generator 35 generates power.

  The exhaust gas 1 discharged from the exhaust gas expander 37 is recovered by the waste heat boiler 39 and then becomes an exhaust gas 1a having a relatively low temperature (for example, 373 ° K (100 ° C.)) and normal pressure (0 MPa). It is supplied to the precooler 11.

  The exhaust gas 1a supplied to the exhaust gas precooler 11 is a low temperature that has been separated and recovered from the carbon dioxide discharged from the low temperature gas hydrate generator 14 and expanded to near atmospheric pressure (for example, 0 MPa) by the exhaust gas expander 15. -Precooling is performed using the low-pressure exhaust gas 1e.

The low-temperature exhaust gas 1c after being pre-cooled by the exhaust gas pre-cooler 11 (for example, about −40 ° C. to −50 ° C. ) is used up to a pressure (for example, about 2 MPa) necessary for generating gas hydrate using the exhaust gas compressor 12. Boosted.

  The exhaust gas 1d compressed by the exhaust gas compressor 12 is introduced into the exhaust gas recooler 13, and is discharged at a low temperature / high pressure (for example, 203 ° K ( -70 ° C)) · 2 MPa) of the exhaust gas 1b.

  The low temperature / low pressure exhaust gas 1e is discharged into the atmosphere through a chimney (not shown) after the exhaust gas 1d compressed by the exhaust gas compressor 12 is re-cooled. At this time, the pressure of 1 g of the released gas is, for example, 0 MPa.

  In the present invention, the exhaust gas compressor 12 and the generator 17 are driven by the exhaust gas expander 15, and the generator 17 generates power.

  As described above, the low temperature gas hydrate generator 14 includes the generated water pump 20, the assist gas compressor 21, the fluid spray nozzle 22, the fine ice generator 23, the gas hydrate generator 24, the circulation loop. 25, a circulating gas cooler 26.

  The produced water w for producing exhaust gas hydrate (for producing carbon dioxide gas hydrate) is pressurized by the produced water pump 20 to a pressure required for the reaction.

  On the other hand, a part of the exhaust gas 1f recooled by the exhaust gas recooler 13 is pressurized by the assist gas compressor 21 to an assist gas pressure (for example, 2.3 MPa) necessary for spraying the generated water w.

  The fine ice generator 23 includes a two-fluid spray nozzle 22 therein. The two-fluid spray nozzle 22 sprays generated water w in the form of fine particles from a nozzle hole (not shown) opened by introduction of an assist gas (for example, 2.3 MPa) 1 h.

  Further, the fine ice generator 23 has a cooling jacket 27 on the outer side thereof, and fine water droplets are frozen by using the cold heat of LNG (liquefied natural gas) by the spray nozzle 22, and fine ice (for example, 0. 1 to 10 μm) i is generated. The cooling jacket 27 uses the refrigerant a that has been cooled to a predetermined temperature using the cold heat of LNG. Here, if the particle size of fine ice exceeds 10 μm, it takes time to gas hydrate up to the core of fine ice, so it is safer to avoid it industrially.

  The gas hydrate generator 24 includes a plurality of reaction vessels 41a to 41d. Although these reaction vessels 41a to 41d are apparently arranged in parallel, the adjacent reaction vessels 41 have their rear end portion (downstream end) and front end portion (upstream end) connected to each other by a communication pipe 42. Therefore, they are connected in series.

  In the figure, the uppermost reaction vessel 41a has its left end (upstream end) connected to the outlet of the fine ice generator 23 via the communication pipe 42a, and the lowermost reaction vessel 41d has its left end ( A discharge pipe 43 is provided at the downstream end.

  On the other hand, the circulation loop 25 circulates the exhaust gas 1f along the plurality of reaction vessels 41a to 41d described above, and one end of the loop forming pipe 45 connected to the exhaust gas supply branch pipe 29 is the uppermost stage. The other end of the reaction vessel 41a is connected to the right end of the lowermost reaction vessel 41d. Further, the uppermost reaction vessel 41a and the second reaction vessel 41b are connected at the left end by a communication pipe 46a, and the second reaction vessel 41b and the third reaction vessel 41c are connected at the right end. The parts are in communication with each other through the communication pipe 46b, and the left end of the third-stage reaction container 41c and the lowermost-stage reaction container 41d are in communication with each other through the communication pipe 46c.

  The reaction vessels 41a to 41d are each provided with a stirrer 47, and the fine ice i in the reaction vessels 41a to 41d is stirred to promote the reaction with the exhaust gas 1f.

  Accordingly, the exhaust gas 1a having a relatively low carbon dioxide content discharged from the gas turbine combined cycle power generation facility 10 (eg, 3 to 4%) and a predetermined temperature and pressure (eg, 100 ° C., 0 MPa). Is introduced into the exhaust gas precooler 11, and after the separation and recovery of carbon dioxide discharged from the exhaust gas hydrate generator 14 in the exhaust gas precooler 11, and near the atmospheric pressure (for example, 0 MPa) by the exhaust gas expander 15. It is pre-cooled using the low-temperature and low-pressure exhaust gas 1e expanded to

  The low-temperature exhaust gas 1c that has been pre-cooled by the exhaust gas pre-cooler 11 is boosted to a pressure necessary for generating gas hydrate using the exhaust gas compressor 12 (for example, 2 MPa). The exhaust gas 1d compressed by the exhaust gas compressor 12 is introduced into the exhaust gas recooler 13, and the exhaust gas recooler 13 discharges the exhaust gas hydrate from the exhaust gas hydrate generator 14 at a low temperature and high pressure (for example, 2 MPa, −70 ° C.) and the exhaust gas 1b.

  The high-pressure / low-temperature (for example, 2 MPa, −70 ° C.) exhaust gas 1 f recooled by the exhaust gas recooler 13 is boosted to a predetermined pressure (for example, 2.3 MPa) by the assist gas compressor 21.

  When the assist gas 1f is supplied to the two-fluid spray nozzle 22, as already described, the valve or valve built in the two-fluid spray nozzle 22 is opened and the generated water pressurized by the generated water pump 20 is opened. w is sprayed to form fine water droplets. Since the inside of the fine ice generator 23 is cooled to a predetermined temperature (for example, −30 to −50 ° C.) by the cooling jacket 27, the fine particulate water droplets are instantly frozen and fine ice i It becomes.

  The fine ice i is supplied to the upstream end of the uppermost reaction vessel 41 a of the exhaust gas hydrate generator 24 and then transferred to the downstream end while being stirred by the stirrer 47. On the other hand, the remaining exhaust gas 1f supplied to the loop forming pipe 45 via the exhaust gas supply branch pipe 29 is supplied to a predetermined temperature (for example, 203 ° K (−) by the circulating gas cooler 26 using the cold heat of LNG (b). 70 ° C.) and 2 MPa), and then supplied to the downstream end of the uppermost reaction vessel 41a.

  The fine ice i is sequentially transferred from the uppermost reaction vessel 41a to the lowermost reaction vessel 41d, and finally discharged from the discharge pipe 43 provided in the lowermost reaction vessel 41d. However, while passing through the plurality of reaction vessels 41a to 41d, it reacts with carbon dioxide contained in the exhaust gas 1f to become carbon dioxide gas hydrate c.

  As a result, 60 to 80% of carbon dioxide is taken into the carbon dioxide gas hydrate c, and the concentration of carbon dioxide in the exhaust gas discharged from the chimney 16 to be described later decreases accordingly.

  On the other hand, the exhaust gas 1f circulates according to the path of the circulation loop 25, but a part thereof is released into the atmosphere through the exhaust gas exhaust pipe 30 already described.

1 is a block diagram of a carbon dioxide separation and recovery system according to the present invention. 1 is a configuration diagram of a carbon dioxide separation and recovery system according to the present invention.

Explanation of symbols

1 exhaust gas 23 fine ice generator b liquefied natural gas c carbon dioxide hydrate i fine ice

Claims (3)

An exhaust gas pre-cooling step of pre- cooling the exhaust gas to a predetermined temperature using cold heat of the exhaust gas discharged from the carbon dioxide recovery step in a carbon dioxide recovery method for recovering carbon dioxide in the exhaust gas by gas hydrate conversion When the fine ice formation process particle size by spraying water into a fine ice generator which is cooled to a predetermined temperature by utilizing the cold of liquefied natural gas to produce a 0.1~10μm fine ice, the A re-cooling step in which the exhaust gas pre-cooled in the exhaust gas pre-cooling step is re-cooled to −70 ° C. to −100 ° C. using the cold of liquefied natural gas; carbon dioxide and re-cooled exhaust gas 100 ° C. to recover the carbon dioxide in the exhaust gas consisting of carbon dioxide recovery step of generating mechanically stirred to carbon dioxide hydrate while introducing into the gas hydrate generator Osamu way. A carbon dioxide recovery device for generating carbon dioxide hydrate by reacting carbon dioxide in exhaust gas with water, the two-fluid spray nozzle for introducing the water and assist gas to atomize the water, and the two fluids A fine ice generator that produces fine ice particles having a particle diameter of 0.1 to 10 μm by utilizing the cold heat of liquefied natural gas from fine water droplets sprayed from a spray nozzle, and the cold heat of the fine ice and liquefied natural gas A horizontally long reaction vessel that introduces an exhaust gas cooled to −70 ° C. to −100 ° C. to produce carbon dioxide hydrate and has a stirrer, and a plurality of the reaction vessels A carbon dioxide recovery device that recovers carbon dioxide in exhaust gas connected in a zigzag pattern. An exhaust gas precooler that precools the exhaust gas discharged from the gas turbine combined cycle power generation facility with carbon dioxide separation and recovery, and with low-temperature and low-pressure exhaust gas expanded to near atmospheric pressure,
An exhaust gas compressor that pressurizes the low-temperature exhaust gas after pre-cooling to the pressure required for generating gas hydrate with the exhaust gas pre-cooler;
An exhaust gas recooler for recooling the exhaust gas compressed by the exhaust gas compressor with low temperature and high pressure exhaust gas after carbon dioxide separation and recovery;
An exhaust gas expander that expands the high-pressure exhaust gas heated by the exhaust gas recooler to atmospheric pressure, and a low-temperature gas hydrate generator composed of the following devices:
The low-temperature gas hydrate generator, a generated water pump that pressurizes the generated water to a pressure required for the reaction;
An assist gas compressor that pressurizes a part of the exhaust gas to an assist gas pressure necessary for spraying produced water;
A spray nozzle for atomizing the produced water by introducing the produced water and the assist gas;
A fine ice generator for producing fine ice by freezing the water droplets atomized by the spray nozzle by the cold heat of liquefied natural gas;
A gas hydrate generator comprising a plurality of reaction vessels connected in series for introducing and reacting the fine ice and the remaining exhaust gas cooled by the cold heat of liquefied natural gas; and
A carbon dioxide recovery device for recovering carbon dioxide in the exhaust gas, comprising a circulation loop that connects the plurality of reaction vessels in a ring shape and a circulation gas cooler that cools the exhaust gas that circulates through these reaction vessel groups with liquefied natural gas .

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