WO2007110947A1 - Procede de production d'hydrate de gaz et appareil correspondant - Google Patents

Procede de production d'hydrate de gaz et appareil correspondant Download PDF

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Publication number
WO2007110947A1
WO2007110947A1 PCT/JP2006/306480 JP2006306480W WO2007110947A1 WO 2007110947 A1 WO2007110947 A1 WO 2007110947A1 JP 2006306480 W JP2006306480 W JP 2006306480W WO 2007110947 A1 WO2007110947 A1 WO 2007110947A1
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WIPO (PCT)
Prior art keywords
gas
hydrate
gas hydrate
reactor
temperature
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PCT/JP2006/306480
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English (en)
Japanese (ja)
Inventor
Masujiro Hisatani
Kazuyoshi Matsuo
Junya Miyata
Original Assignee
Mitsui Engineering And Shipbuilding Co., Ltd.
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Application filed by Mitsui Engineering And Shipbuilding Co., Ltd. filed Critical Mitsui Engineering And Shipbuilding Co., Ltd.
Priority to PCT/JP2006/306480 priority Critical patent/WO2007110947A1/fr
Publication of WO2007110947A1 publication Critical patent/WO2007110947A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/108—Production of gas hydrates

Definitions

  • the present invention relates to a method and apparatus for producing gas hydrate, which is a solid hydrate of gas.
  • Natural gas mainly composed of methane is conventionally used as clean energy.
  • this natural gas is generally transported and stored in the state of liquefied liquefied natural gas (LNG) including the place to be transported or stored.
  • LNG liquefied liquefied natural gas
  • LNG needs to cool natural gas to a cryogenic temperature of -160 ° C or lower, requires a large-scale and high-priced liquefaction device, and transport ships also have a cooling facility that can maintain a cryogenic temperature.
  • a special transport ship must be used, which requires very large transportation and storage costs. For this reason, methods for transporting and storing natural gas without liquefaction have been studied, and in recent years, attention has been paid to transporting and storing natural gas in a hydrated manner, and research for practical application has been actively conducted. ing.
  • Natural Gas Hydrate is a crystal of water in the form of a bowl.
  • This NGH is produced as ice-like particles by blowing natural gas into water with a pressure of several MPa to 10 MPa and a temperature of about 0 to 10 ° C.
  • a particle size adjusting agent such as polyvinyl pyrrolidone or polyvinyl caprolatatam is added to raw water of methane hydrate to produce methane hydrate with a particle size of 1 ⁇ m to 5 mm. It describes a method for producing methane hydrate that prevents methane hydrate from adhering to heat transfer surfaces and piping.
  • Gasoline and idrate are produced by reacting a raw material gas such as natural gas or methane gas with water in a low-temperature and high-pressure vessel, and a large amount of unreacted gas hydrate is produced in the vessel.
  • a raw material gas such as natural gas or methane gas
  • a large amount of unreacted gas hydrate is produced in the vessel.
  • Patent Document 2 a slurry of gas hydrate and water extracted from a production vessel is guided to a double-structure screw press-type dehydrator having a meshed inner cylinder and physically dehydrated. Gas hydrate adhesion with screw type dehydrator By hydrating the water and the raw material gas, the attached water is hydrated to obtain a product gas hydrate with less attached water.
  • the gas hydrate production apparatus described in Patent Document 3 controls the concentration of gas hydrate discharged from the physical dehydrator and hydration dehydrator.
  • natural gas hydrate has a relationship as shown in FIG. 4 between the generation temperature (reaction temperature between gas and water) and the gas hydrate conversion rate. That is, the lower the production temperature of natural gas, the higher the hydrate yield rate, and the higher the production temperature, the lower the hydrate rate.
  • the relationship between the generation temperature of natural gas hydrate and the particle size of the generated gas hydrate is as shown in FIG. That is, natural gas hydrate has a higher particle size and higher self-storing property as the production temperature is higher, and the self-preserving property is lower and lower as the product temperature is lowered.
  • Patent Document 1 uses the methane hydrate, which has a low self-preserving property, during the transportation of methane hydrate from the production site to a destination such as a consumption place. As dissociation progresses and the residual rate of methane gas at the destination declines, transportation efficiency decreases and transportation costs increase. Patent Documents 2 and 3 do not describe any self-preserving property.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-72615
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-55675
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-64385
  • the present invention was made to eliminate the above-mentioned drawbacks of the prior art, and the residual rate of gas in the gas hydrate during transportation and storage, that is, the gas remains as hydrate.
  • the problem is to improve the ratio.
  • the present invention provides a product in which the hydrate yield rate, which is the ratio of gas hydrate in the product obtained in the reaction process between the raw material gas and water, is X and the gas hydrate is transported to the destination.
  • the gas residual rate of the gas hydrate in the gas is y
  • the evaluation function J when generating the gas hydrate is
  • the inventors have come up with the idea of controlling the gas hydrate generation conditions so that the evaluation function J is maximized.
  • the evaluation function # ⁇ indicates the amount of gas that can be conveniently consumed after transportation of gasno and idrate.
  • the method for producing a gas hydrate according to the present invention is a method for producing a gas hydrate by producing a gas hydrate and an hydrate by hydrating a raw material gas and water.
  • the residual characteristic representing the relationship with the gas residual rate in the gas hydrate that decreases in advance is obtained in advance, and the gas hydrate corresponding to the particle size of the gas hydrate in the product in the process of generating the gas hydrate is obtained.
  • a gas residual ratio is determined based on the residual characteristics, and an evaluation function value expressed as a product of the gas residual ratio determined above and a hydrate ratio, which is a ratio of the gas and idrate in the product, is obtained. It is characterized by controlling the generation temperature of the gas hydrate so as to be maximized.
  • the evaluation balance expressed as (hydrate yield rate X) X (gas residual rate y) corresponds to the net amount of gas that can be used after transportation of the generated gas hydrate. Therefore, by controlling the generation temperature so that the evaluation function J is maximized, the net amount of gas in the gas hydrate after the transportation of the gas hydrate is increased. For this reason, the transportation efficiency of natural gas can be maximized, and the transportation cost of natural gas can be reduced. In addition, since the gasno and idrate are manufactured so that the evaluation comfort is maximized, the efficiency of the gas hydrate toy can be substantially improved.
  • the particle size of gasno and idrate is smaller than 0.5 mm, the self-preserving property deteriorates rapidly.
  • the limiting condition is that the temperature of the idrate particle diameter is 0.5 mm or more.
  • a gasnoid and idlate production apparatus for carrying out the gas hydrate production method described above includes a reactor for producing a gas hydrate by hydrating a raw material gas and water, and the reaction described above.
  • a cooling unit that removes the heat of reaction between the water and the gas by supplying cold to the vessel, and the particle size during the production of the gas hydrate and decreases with the passage of time after the production
  • a residual rate storage unit that stores in advance a residual characteristic representing a relationship with a gas residual rate of the gas hydrate, a temperature detection unit that detects a temperature in the reactor, and a product generated in the reactor
  • a hydrate slag detector for detecting a hydrate slag that is a ratio of the gas and idrate in the gas
  • a particle size detector for detecting a particle size of the gas hydrate generated in the reactor
  • a residual rate calculating unit for obtaining a gas residual rate of the generated gas hydrate based on the particle diameter detected by the particle size detecting unit and the stored contents of the residual rate storage unit!
  • An evaluation function calculation unit that calculates the evaluation function represented, a control target temperature calculation unit that calculates a generation temperature that maximizes the value of the evaluation function calculated by the evaluation function calculation unit, and the control target temperature calculation unit And a control unit that controls the generated temperature to the control target temperature via the cooling unit based on the control target temperature and the generated temperature detected by the temperature detecting unit.
  • the reactor is generated by the first reactor that generates a slurry containing gas hydrate by hydrating the raw material gas and water, and the first reactor. It is possible to include a second reactor that introduces the gas hydrate that has been introduced and hydrates the water adhering to the gas hydrate with the raw material gas to generate gas hydrate.
  • the cooling unit circulates and supplies the cooled raw material gas to the second reactor, and the temperature detector detects the temperature in the second reactor, The hydrate recovery rate detection unit detects a hydration rate in the product generated in the second reactor, and the particle size detection unit generates in the second reactor. The particle size of the gas hydrate is detected, and the control unit controls the generation temperature in the second reactor to the control target temperature via the cooling unit.
  • the second reactor includes a cylindrical container having an axial line disposed horizontally, and a rotating shaft provided in the cylindrical container along the axial direction and having a plurality of knotted wings attached thereto.
  • the gas hydrate generated by the first reactor is provided at one end of the cylindrical vessel, and the gas hydrate outlet is provided at the other end of the cylindrical vessel. .
  • the second reactor includes a cylindrical vertical container into which the gas hydrate and raw material gas supplied from the first reactor are introduced, and the vertical container.
  • a perforated plate provided between a position where the gas hydrate is introduced and a bottom, and a discharger for discharging the gas hydrate above the perforated plate, and the cooling unit
  • a circulation gas blower that communicates with the upper part of the vertical container and sucks the raw material gas at the upper part of the vertical container and circulates it to the bottom of the vertical container through a cooler can be provided.
  • the gas hydrate production apparatus includes a reactor for producing a slurry containing gas hydrate by hydrating a raw material gas and water, and an upper portion of the reactor.
  • a gas circulation device for extracting the raw material gas from the bottom of the reactor and diffusing the gas into the reactor, and extracting the slurry containing gas hydrate from the bottom of the reactor, and passing the reaction through the cooler.
  • a slurry circulating device that returns to the top of the reactor, a slurry transfer pump that transports a slurry containing gas hydrate from the bottom of the reactor to a dehydrating device, and a honey degree of the circulating slurry circulated by the slurry circulating device, The amount of circulating gas circulated by the gas circulating device, the amount of circulating slurry of the slurry circulating device, and the circulating slurry temperature so that the detected slurry density falls within a set range.
  • Constituting a control means to control at least one.
  • the hydration reaction is promoted by increasing the circulation amount of the raw material gas diffused into the slurry in the reactor, so that the gas hydrate concentration in the slurry can be controlled. Also, since the hydration reaction is exothermic and the hydration reaction depends on the degree of supercooling (the difference between the equilibrium temperature for gas hydrate formation and the temperature in the reactor), the slurry temperature in the reactor is By controlling, the gas hydrate concentration in the slurry can be controlled.
  • the gas hydrate concentration in the slurry can be detected by detecting the honey degree of the circulating slurry.
  • the gas hydrate concentration in the slurry can be set to a desired value by controlling at least one of the circulating gas amount, the circulating slurry amount, and the circulating slurry temperature so that the honey level of the circulating slurry falls within the set range. Ff3 ⁇ 4 can be controlled accurately.
  • the gas hydrate transferred by the slurry transfer pump A first dehydrator for physically dehydrating by introducing a slurry containing a rate, and a high-concentration gas by hydrating the water adhering to the gas hydrate dehydrated by the first dehydrator with the source gas It is desirable to provide a second dehydrator that generates hydrate.
  • the first dehydrator discharges a cylindrical vertical container into which a slurry containing a gas hydrate transferred by the slurry transfer pump is introduced at the bottom, and a gas hydrate at the top of the container.
  • the drainage chamber force can be configured to include a control means for controlling the drainage amount to be drained.
  • the second dehydrator includes a cylindrical vertical container into which the gas hydrate discharged from the discharger of the first dehydrator and the raw material gas are introduced, and the vertical container
  • the perforated plate provided between the position where the gas hydrate is introduced and the bottom, and the upper part of the vertical container are connected to the upper part of the vertical container to suck the raw material gas and pass through the cooler to
  • a circulating gas blower that is circulated to the bottom of the mold vessel, a discharger that discharges the gas hydrate above the perforated plate, and a load amount of the discharger is detected, so that the detected load amount falls within a set range.
  • Control means for controlling at least one of the circulating gas amount circulated by the circulating gas blower, the temperature of the circulating gas, and the discharge amount of the discharger can be provided.
  • the second dehydrating device fluidizes the gas hydrate discharged from the first dehydrating device with the raw material gas to form a fluidized bed, and the adhering water of the gas hydrate is obtained by the fluidized bed reaction.
  • the concentration of gas hydrate can be increased to the required concentration level.
  • FIG. 1 is an explanatory diagram of a gas hydrate production apparatus according to a first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a second reactor according to the first embodiment.
  • FIG. 3 is an explanatory diagram of an operation control apparatus according to the first embodiment.
  • FIG. 4 is a conceptual diagram showing the relationship between the gas hydrate generation temperature and the hydrate yield rate.
  • FIG. 5 is a conceptual diagram showing the relationship between the gas hydrate formation temperature and the average particle size of the gas hydrate.
  • FIG. 6 is a diagram illustrating a method for producing a gas hydrate according to the present invention.
  • FIG. 7 is an overall configuration diagram of a hydrate slurry production apparatus according to another embodiment of the present invention.
  • FIG. 1 is an explanatory diagram showing an outline of a gas hydrate production apparatus according to an embodiment of the present invention.
  • the production of natural gas hydrate (NGH) will be described as an example.
  • the hydrate generation unit 12 in the gas hydrate production apparatus 10, the hydrate generation unit 12 includes a first reactor 14 and a second reactor 16.
  • a gas supply source 20 is connected to the first reactor 14 via a gas supply pipe 18, and a generated water supply source 24 is connected via a generated water supply pipe 22.
  • the interior of the first reactor 14 is maintained at a high pressure of several to lOMPa when the gas hydrate is generated, and the natural gas that is the raw material gas reacts with the generated water (water). Therefore, supply pumps 26 and 28 are installed in the gas supply pipe 18 and the generated water supply pipe 22 so that high-pressure gas and high-pressure water can be supplied to the first reactor 14. Yes.
  • the raw material gas is natural gas mainly composed of methane gas.
  • the first reactor 14 includes a publishing mechanism and a stirrer (not shown) so that the gas and water can be brought into contact efficiently.
  • the first reactor 14 is provided with a line for externally circulating and cooling the internal water.
  • the cooling unit 30 is connected to the cooling line so that the circulating water can be cooled with the refrigerant. It is. By circulating the internal water to the outside and cooling with the refrigerant, the reaction heat when the gas and water react to form gas hydrate is removed, and the inside of the first reactor 14 is brought to 0-10 ° C. Cooling.
  • a second reactor 16 is arranged below the first reactor 14, and the gas and idrate generated in the first reactor 14 are water. (Adhesive water) flows in.
  • the second reactor 16 is usually set to have the same internal pressure as that of the first reactor 14.
  • the second reactor 16 has a cooling medium flow path on its peripheral surface, and the heat of reaction when the gas hydrate is generated is removed by the refrigerant supplied from the cooling unit 32, so that the inside is zero. Hold at ⁇ 10 ° C. Further, the second reactor 16 is supplied with gas from a gas supply source 20 (not shown), and the water (adhesion water) flowing from the first reactor 14 is described in detail later. ) And gas to increase the gas hydrate content in the product (gas hydrate, adhering water, and powerful product).
  • the second reactor 16 includes a cylindrical container 34 whose axis is disposed horizontally, and the rotating shaft 36 passes through the center of the cylindrical container 34.
  • the rotary shaft 36 is rotatably supported by the cylindrical container 34, and a drive motor 38 is connected to one end thereof and is rotated by the drive motor 38.
  • the cylindrical container 34 is provided with an inflow port 40 at the upper part on one end side, and a discharge port 42 at the lower part on the other end side.
  • the inlet 40 is connected to the first reactor 14, and the gas hydrate product 45 composed of the gas hydrate and adhering water flows into the first reactor 14.
  • the discharge port 42 is connected to the hydrate cooling device 44, and supplies the gas hydrate product 95 generated in the second reactor 16 to the noise rate cooling device 44. To do.
  • a plurality of scissors wings 46 are attached to the rotary shaft 36.
  • Each stirring blade 46 has a portal shape.
  • These agitating blades 46 are arranged so as to form a spiral along the axis of the rotary shaft 36, and a part thereof is inclined with respect to the tangential direction of the rotary shaft 36. Therefore, the second reactor 16 agitates the gas hydrate product 45 flowing in from the inlet 40 in the gas by the stirring blade 46 rotating integrally with the rotating shaft 36, and reacts the adhering water and the gas. It is sent toward the discharge port 42 and is put into the next hydrate cooling device 44.
  • the idrate cooling device 44 cools the gas hydrate product 95 flowing from the second reactor 16 to about 20 ° C. with the supplied brine 62.
  • a depressurization device 64 is connected to the discharge port 97 of the hydrate cooling device 44.
  • the depressurizer 64 can depressurize the gas / idrate product 96 that has been cooled and maintained at a high pressure to atmospheric pressure.
  • the gas hydrate product 96 depressurized by the depressurizer 64 is transferred to the depressurizer 64.
  • the gasnoid and idrate product 96 stored in the storage tank 66 is sent to a pellets bowl device as necessary, and is made into spherical pellets having a diameter of about 2 cm, for example, for easy handling.
  • the cylindrical container 34 has a coolant channel 48 formed on the peripheral surface thereof, so that the inside can be cooled by the coolant 50 supplied from the cooling unit 32. Further, the cylindrical container 34 is provided with a sensor insertion part 52 for inserting a plurality of (three in the case of the present embodiment) temperature sensors along the axis, and is inserted into the cylindrical container 34 from the sensor insertion part 52.
  • the temperature in the cylindrical container 34 (generation temperature) can be detected by a temperature sensor that is a temperature detection unit.
  • the detection signal of the temperature sensor 54 inserted into the sensor insertion portion 52 of the cylindrical container 34 is input to the arithmetic / control device 60 described later in detail.
  • detection signals from the moisture sensor 56 and the particle size sensor 58 are input to the calculation / control device 60.
  • the moisture sensor 56 constitutes a hydrate ratio detection unit, and the gas hydrate product 95 or gas hydrate product generated and cooled in the second reactor 16 or the hydrate cooling device 44.
  • the 96 is irradiated with laser, infrared rays, or X-rays, and the ratio of adhering water (ice) in the product is detected.
  • the particle size sensor 58 constitutes a particle size detection unit, and the gas hydrate product 95 or the gas hydrate product 96 discharged from the second reactor 16 or the hydrate cooling device 44 has a laser or the like.
  • the particle size of gas hydrate products 95 and 96 is measured.
  • the water content and particle size of the product by the moisture sensor 56 and the particle size sensor 58 are measured by the gas and idrate discharged from the outlet 42 of the second reactor 16 or the outlet 97 of the hydrate cooling device 44.
  • the products 95 and 96 may be measured directly in-line by irradiating them with a laser or the like.
  • the second reactor 16 or hydrate cooling device 44 may be used to sample the gas and idrate products 95 and 96 that have also been discharged. You may measure with
  • the calculation / control device 60 is connected to the moisture sensor 56 and, together with the moisture sensor 56, constitutes a hydrate yield rate detection unit 70.
  • the unit 72 and the particle size sensor 58 have a particle size calculation unit 76 that constitutes a particle size detection unit 74.
  • the particle size calculator 76 is connected to the particle size sensor 58 on the input side, and the particle size sensor 58 detects the particle size.
  • the particle size of the gas hydrate product 95 or gas hydrate 96 is calculated.
  • the calculation / control apparatus 60 includes an evaluation function / control target temperature calculation unit 78, a remaining rate calculation unit 80, a control unit 82, a manufacturing / transport condition setting unit 84, and a remaining data storage unit 86.
  • the residual rate calculation unit 80 is connected to the output side of the particle size calculation unit 76 and inputs the particle size obtained by the particle size calculation unit 76.
  • the remaining rate calculation group 80 is connected to the manufacturing / transport condition setting unit 84 and the remaining data storage unit 86, and the gas hydrate manufacturing conditions and transport conditions set in the manufacturing / transport condition setting unit 84 are input. It is supposed to be.
  • the gas hydrate with respect to the grain size of the gas hydrate product 95 or the gas hydrate product 96 corresponding to the gasno and idrate production conditions and transport conditions determined in advance is stored.
  • the data of the gas remaining rate is recorded.
  • the data of the gas residual rate is read out when the residual rate calculating unit 80 calculates the gas residual rate in the gas hydrate based on the particle diameter obtained by the particle size calculating unit 76.
  • Control target temperature calculation unit 78 has an evaluation function calculation unit and a control target temperature calculation unit (not shown), and the input side has a hydrate ratio calculation unit 72 and a remaining rate calculation unit.
  • the evaluation function calculation unit calculates the evaluation interval J based on the nod rate increase rate X and the gas residual rate y obtained by these. Further, the evaluation function / control target temperature calculation unit 78 obtains the gas hydrate generation temperature at which the control target temperature calculation unit maximizes the value of the evaluation function J and outputs it to the control unit 82.
  • the control unit 82 The temperature of the second reactor 16 is controlled via the cooling unit 32 so that the generated temperature obtained by the function 'control target temperature calculator 78 is obtained.
  • the hydrate ratio which is the ratio of the gas hydrate in the product obtained in the process of reacting the raw material gas and water, and the gas in the gas hydrate with the passage of time after generation That is, the particle size of the gas hydrate product 95 or the gas hydrate product 96 in which the gas residual rate of the gas hydrate product 95 or the gas hydrate product 96 obtained in the reaction process of gas and water is maximized ( In the case of the embodiment, an average particle diameter) relationship (gas residual rate data) is obtained in advance. This gas residual rate data is simulated by considering the difference in the gas residual rate depending on the gas hydrate production conditions and transportation conditions, corresponding to the production conditions and the transportation conditions. -Ask for it with a Chillon.
  • the previously obtained gas residual ratio data is stored in the particle diameter storage unit 84 of the calculation / control apparatus 60.
  • the temperature in the second reactor 16 that is, the generation temperature (reaction temperature) and the generated gas hydrate product
  • the relationship with the particle size of 95 is obtained in advance.
  • the feed pumps 26 and 28 use the feed gas 26 to supply the raw material gas (natural gas mainly composed of methane gas) from the gas supply source 20 and the generated water supply source 24 to water (product water). ) Is supplied to the first reactor 14 constituting the hydrate generation unit 12.
  • the first reactor 14 includes a publishing mechanism and a stirrer, and is contained in the generated water in the first reactor 14.
  • the raw material gas is published, water and gas are mixed, and further stirred to react both efficiently.
  • a part of the gas supplied to the first reactor 14 is taken into a crystal of water in the form of a cage, and becomes a gas hydrate that is a clathrate compound.
  • the hydrate yield in the gas hydrate product 95 or the gas hydrate product 96 generated and cooled in the second reactor 16 or the hydrate cooling device 44 is about 90%.
  • Gas with which the particle size of the gas hydrate product 95 or gas hydrate product 96 produced and cooled in the second reactor 16 or the hydrate cooling device 44 is 0.5 mm or more.
  • Hydrate generation conditions are set. Specifically, the internal pressure of the first reactor 14 and the second reactor 16 is set so as to be around 5 MPa, for example.
  • the internal liquid is circulated to the outside, and cooling is supplied by cooling with a cooling medium in the cooling unit 30, and in the second reactor 16, cooling heat is supplied by the refrigerant of the cooling unit 32 power. Is supplied, and the heat of reaction in the hydration of water and gas is removed, and the inside is brought to a temperature of, for example, 0 to 5 ° C.
  • the gas / idrate product 45 produced in the first reactor 14 is a mixture of gas hydrate and water (adhesion water), and the ratio of gas hydrate in the mixture (hydrate yield rate). ) Is usually around 40% and moisture is around 60%.
  • the gas hydrate product 45 generated in the first reactor 14 is supplied to the second reactor 16 in a sherbet-like or slurry-like state.
  • the second reactor 16 is supplied with the gas hydrate product 45 in the first reactor 14 and the raw material gas.
  • the gas supplied from the first reactor 14 is rotated by rotating the stirring blade 46 by the drive motor 38.
  • the idrate product 45 is stirred and reacted with the gas and sent to the outlet 42.
  • Gasoline / idrate product 45 supplied with 14 forces of first reactor is agitated in the gas by stirring blade 46, and the water adhering to gasno / idleate product 45 reacts with the gas, resulting in a hydrate yield rate.
  • the gas hydrate product 95 with a force of about 90% is sent to the hydrate cooler 44.
  • the temperature sensor 54 attached to the second reactor 16 detects the reaction temperature in the second reactor 16 and inputs it as a feedback signal to the control unit 82 of the calculation / control apparatus 60. Based on the detection signal of the temperature sensor 54, the control unit 82 controls the amount of cold given to the second reactor 16 via the cooling unit 32 so that the reaction temperature is a predetermined temperature.
  • the moisture sensor 56 constituting the hydrate ratio detection unit 70 irradiates the gas hydrate product 95 generated in the second reactor 16 with laser, infrared rays, or X-rays to generate gas hydrate.
  • the ratio of the adhering water (ice) contained in the object 95 is detected and input to the hydrate ratio calculation unit 72 of the calculation / control device 60.
  • the hydrate yield ratio calculation unit 72 is a ratio of gas hydrate in the gas hydrate product 95 discharged from the second reactor 16 (hydrate yield ratio) x Is input to the evaluation function 'control target temperature calculator 78.
  • the particle size sensor 58 constituting the particle size detection unit 74 irradiates the gas hydrate product 95 discharged from the second reactor 16 with a laser to detect the particle size of the product. Input to the particle size calculator 76 of the control device 60.
  • the particle size calculation unit 76 calculates the particle size of the gas hydrate product 95 detected by the particle size sensor 58 (including the average particle size in the embodiment) and sends it to the residual rate calculation unit 80.
  • the remaining rate calculation unit 80 reads the manufacturing condition and the transportation condition set in the manufacturing / transport condition setting unit 84. Based on the particle size obtained by the particle size calculator 76, the remaining data storage unit 86 is examined, and the relationship between the particle size and the remaining rate corresponding to the read manufacturing conditions and transportation conditions is read, and the generated gas hydride is read. Evaluation function for target gas residual rate y ⁇ Control target temperature Output to operation unit 78.
  • Evaluation function ⁇ Control target temperature calculation unit 78 is configured so that the evaluation function calculation unit calculates the hydrate ratio X determined by the hydrate ratio calculation unit 72 and the hydrate gas residual rate y calculated by the remaining rate calculation unit 80. Based on the above, the evaluation function 3 ⁇ 4J is calculated. In the case of the embodiment, the evaluation function 3 ⁇ 4J is obtained as a product of the hydrate toy ratio X and the residual gas ratio y. That is, the evaluation function 3 ⁇ 4J is
  • the evaluation function “target temperature calculation unit 78 obtains the gas hydrate generation temperature at which the control target temperature calculation unit maximizes the evaluation function J.
  • the optimum gas hydrate formation temperature that maximizes the evaluation function J varies depending on the composition of the gas components. Therefore, the optimum generation temperature is recorded as data of the current value and past history of evaluation function # ⁇ and the generation temperature at that time, and the generation temperature that maximizes evaluation function J is estimated from this data group. Ask. Specifically, the following method is used.
  • the relationship shown in FIG. 6 exists among the hydrate yield rate x, the gas residual rate y, the evaluation function J, and the noise rate production temperature T at a certain hydrate production pressure. Therefore, first, the temperature is set so that the particle diameter is 0.5 mm. (At temperatures below this, the residual gas ratio drops extremely, so this temperature is taken as the minimum line.) Gradually raise the temperature while calculating the evaluation comfort. As the temperature rises, the particle size increases and the gas residual rate y increases. Since the hydrate yield rate X decreases, the evaluation function J should reach a local maximum (maximum value) somewhere. The maximum temperature Tm is controlled. When the value of the evaluation function J decreases, the direction in which the temperature is changed is determined according to the change in the particle diameter and the hydrate ratio X, the temperature is changed in that direction, and the evaluation function J To the maximum point.
  • the optimum generation temperature obtained by the evaluation function and the control target temperature calculation unit 78 is given to the control unit 82 as the control target temperature.
  • the control unit 82 reads the generation temperature in the second reactor 16 detected by the temperature sensor 54, and cools down so that the generation temperature becomes the optimum generation temperature obtained by the evaluation function 'control target temperature calculation unit 78'. Controls the amount of cold supplied by unit 32 to second reactor 16. [0053] This makes it possible to maximize the value of the evaluation interval J, which is obtained as the product of the No. and Idle ratio x and the gas residual rate y. Therefore, in the embodiment, since the net amount of gas after transportation of the generated gas hydrate increases, transportation efficiency and storage efficiency can be improved, and transportation cost of natural gas can be reduced.
  • the amount of water and the particle diameter contained in the gas hydrate product 95 at the outlet of the second reaction B16 sent from the second reactor 16 to the hydrate cooling device 44 are detected.
  • the detection of the amount of water and the particle diameter described in the example may be performed on the gas hydrate product 96 at the outlet of the hydrate cooling device 44 after being cooled in the idle cooling device 44.
  • the force described for the generation of gas hydrate in the second reactor 16 may be applied to the generation of gas hydrate in the first reactor 14.
  • FIG. 7 shows an overall configuration diagram of a hydrate slurry production apparatus according to another embodiment of the present invention.
  • this embodiment shows an example of producing a hydrate of natural gas (hereinafter abbreviated as NGH), the present invention is not limited to natural gas and can be applied to hydrate production of other raw material gases.
  • NGH natural gas
  • the hydrate production apparatus of the present embodiment includes a reactor 101 that generates NGH slurry, and water is separated from the NGH slurry generated in the reactor 101 to increase the concentration.
  • a first dehydrator that includes a dehydration tower 102 that produces NGH, and a fluidized bed reaction tower 103 that reacts the NGH adhering water dehydrated in the dehydration tower 102 with natural gas to increase the NGH concentration to the product level.
  • a second dehydrator and a hopper 104 for storing the product NGH are provided.
  • These reactors 101, dehydration tower 102, fluidized bed reaction tower 103 and hopper 104 Are maintained at a predetermined high pressure (for example, 3 to: LOMPa).
  • Reactor 101 is formed of a cylindrical container, and a certain amount of high-pressure source gas (natural gas) and high-pressure water is supplied from a supply device (not shown) and introduced into reactor 101. Natural gas and water react under low temperature conditions (eg, 1-5 ° C) to produce NGH. In order to accelerate the NGH production reaction, the water in the reactor 101 is agitated by the agitator 111, and the natural gas at the top of the reactor 101 is extracted by the circulating gas blower 112, and is discharged from the nozzle 113 at the bottom of the reactor 101. A gas circulation system that diffuses into the water of the reactor 101 is provided! The amount of circulating gas is controlled by a flow control valve 114 equipped with a gas flow meter.
  • a flow control valve 114 equipped with a gas flow meter.
  • NGH generation is accompanied by heat generation
  • the NGH slurry containing NGH generated from the bottom of the reactor 101 is extracted by the circulating slurry pump 115
  • a slurry circulation system is provided that is cooled with a refrigerant by a cooler 116 and returned to the top of the reactor 101.
  • the amount of slurry circulating is controlled by a flow control valve 117 equipped with a slurry flow meter.
  • the amount of refrigerant in the cooler 116 is controlled so that the temperature of the circulating slurry is detected by a thermometer 118 provided in the slurry circulation system, and the detected value matches the set temperature T2.
  • the NGH slurry produced in the reactor 101 is continuously extracted by the slurry transfer pump 120 by the bottom force of the reactor 101 and supplied to the bottom of the dehydration tower 102.
  • NGH is basically in the form of powder
  • the fluidity is drastically reduced, and it cannot be circulated by the circulating slurry pump 115 and cooled. It becomes difficult to generate NGH.
  • the process of producing the product NGH by stabilizing the process of producing the product NGH by reacting the dehydration treatment and the NGH adhering water with natural gas, which will be described later, is highly accurate! It is desirable to produce a concentrated NGH slurry
  • a density meter 119 of NGH slurry is provided in the slurry circulation system, and the amount of circulating gas and circulation slurry are set so that the detection density falls within a set range (for example, about 20% by weight). At least one of Lee's temperature T2 and circulating slurry volume is controlled.
  • a constant concentration of NGH slurry is continuously generated by continuously controlling the amount of circulating slurry and the amount of circulating gas so that the slurry density is a set density.
  • the amount of refrigerant in the cooler 116 is controlled to control the temperature 2 of the circulating slurry to the set temperature.
  • the NGH concentration of the NGH slurry can be continuously controlled accurately and stably to the desired value.
  • the dehydration tower 102 is formed of a cylindrical vertical container, and a large-diameter drainage part 121 is provided in the middle of the tower.
  • the inner wall of the tower corresponding to the drainage part 121 is, for example, a wire mesh or
  • the porous wall 122 is formed of a porous plate or the like.
  • the water in the NGH slurry introduced into the dehydration tower 102 is separated into the water drainage part 121 through the porous wall 122.
  • the water in the drain section 121 is extracted by the dehydration circulation pump 124 through the flow control valve 123 and returned to the reactor 101.
  • the water level in the drain part 121 is detected by a water level gauge 125, and the flow control valve 123 is adjusted so that the detected water level is maintained at the set water level. Also, one end of a screw conveyor 126 is inserted near the top of the dehydration tower 102. The screw conveyor 126 is provided with an opening in a casing (for example, a lower surface) of a portion located in the tower.
  • the dehydrating tower 102 of the present embodiment when the NGH slurry introduced from the bottom of the tower is pushed up to the top of the tower and reaches the drain section 121, the slurry is removed.
  • the water in the water is separated into the drainage part 121 through the porous wall 122.
  • the water separated in the drain part 121 is extracted by the dehydration circulation pump 124 and returned to the reactor 101.
  • the water in the NGH slurry introduced into the dehydration tower 102 is separated and removed by the water drainage section 121 and reaches the top of the tower as dehydrated NGH slurry having a high NGH concentration.
  • the NGH concentration in the process of reaching the top of the tower varies from a state where the finely packed powdery NGH voids are filled with water to a state where water is attached to the surface of the powdered NGH.
  • the force that holds water in the voids between powdery NGH by capillary action NGH force water is separated as the gravity of water becomes larger than its holding force. Therefore, in the process in which the position force of the drainage part 121 reaches the top of the tower, the moisture of the NGH becomes the same as the moisture adhering to the surface.
  • a screw conveyor 126 driven by a motor 127 and introduced into the fluidized bed reaction tower 103.
  • the concentration of NGH discharged from the dehydration tower 102 is too low, that is, if there is too much water adhering to NGH, the fluidity of NGH in the fluidized bed reaction tower 103 in the next step will decrease, and NG H adhesion will occur. Reaction of water and source gas becomes difficult. Therefore, in this embodiment, the concentration of NGH that is unloaded by the screw con bare 126 (NGHZ (NGH + adhering water)), for example, 4 5-70 0/0, preferably controlled to 50 ⁇ 5 weight 0/0 Like to do.
  • the NGH concentration is controlled by controlling the amount of water withdrawn by the flow rate control valve 123 so that the water level meter 125 maintains the water level at the water draining portion 121 at the set water level.
  • the position at which the water holding force held in the gap between the NGHs by the capillary phenomenon balances with the water strength is such that the water level force of the drain part 121 is also at a certain height.
  • the concentration of NGH carried out by the screen conveyor 126 can be controlled to a desired value by appropriately adjusting the equilibrium position 128 with reference to the water level of the water draining part 121.
  • the concentration of NGH entering the fluidized bed reaction tower 3 can be controlled to improve the fluidity and reaction with the raw material gas in the fluidized bed reaction tower 103. That is, according to the present embodiment, the concentration of NGH discharged from the dehydration tower 102 can be controlled to a desired value accurately and stably, so that the treatment in the fluidized bed reaction tower 103 in the next step can be performed. Stable and final product Improves NGH quality and enables stable production
  • the NGH concentration and the load (torque) of the screw conveyor 126 are correlated, so the current of the motor 127 is The extraction amount by the flow control valve 123 can be controlled so as to be within the set current range. Further, instead of the current of the motor 127, the load torque may be directly detected by a torque detector. In addition, by controlling the amount of water withdrawn by the flow control valve 123, by adjusting the amount of water separated through the porous wall 122 into the water drainage part 121 by changing the opening area of the porous wall 122. Can also be controlled.
  • a cylindrical partition plate is provided so as to be movable from the upper side to the lower side of the porous wall 121 along the porous wall 121. This can be realized by moving the partition plate up and down according to the current of 7.
  • the fluidized bed reaction tower 103 is formed of a cylindrical vertical container, and natural gas as a raw material gas is supplied to the top of the vertical container. Further, a perforated plate 131 is provided at a certain height from the bottom of the vertical container, and NGH conveyed by a screw conveyor 216 is placed on the perforated plate 131. In addition, natural gas, which is a raw material gas, is blown as a fluidized gas from the circulating gas blower 132 through the flow control valve 133 between the bottom and the perforated plate 131. The top of the fluidized bed reactor 103 communicates with the suction port of the circulating gas blower 132 through a cyclone 134.
  • thermometer 136 As a result, natural gas, which is a fluidized gas, is circulated in the fluidized bed reaction column 103.
  • a cooler 135 and a thermometer 136 are provided, and the flow rate of the refrigerant in the cooler 135 is controlled so that the detected temperature of the thermometer 136 is maintained at a set temperature.
  • one end of a screw compressor 138 driven by a motor 137 is inserted into the space above the perforated plate 131.
  • An opening is provided in a casing (for example, the upper surface) of a portion of the screw conveyor 138 located in the fluidized bed reaction tower 103.
  • the other end of the screw conveyor 138 communicates with the upper part of the hopper 104 that stores the product NGH!
  • a torque detector 139 that detects the torque of the output shaft of the motor 137 is provided.
  • the flow control valve 133 is controlled so that the load amount of the screw conveyor 138 detected by the torque detector 139 falls within the set range, and the circulating gas amount, the carry-out amount of the screw conveyor 138, and the refrigerant of the cooler 135 are controlled. It comprises a control means that controls at least one of the flow rates.
  • the current of the motor 137 may be detected to detect the load torque.
  • the porous An NGH fluidized bed is formed on top of the plate 131.
  • the NGH adhering water and natural gas react to generate NGH, and the NGH concentration, which is the gas hydrate yield rate, is increased to, for example, 90% by weight or more.
  • the NGH in which the amount of adhering water has been greatly reduced in this way is transported to the hopper 104 by the star conveyor 138 and stored temporarily.
  • the granular NGH stored in the hopper 104 is appropriately cut out through the gate valve 141 to obtain the product NGH. Or transported to an NGH pellet manufacturing equipment.
  • the inside of the hopper 104 is at a high pressure (for example, 3 to: LOMpa), although not shown, normally, a depressurization device is provided on the downstream side of the gate valve 141.
  • the reactor 101 can continuously generate an NGH slurry with a stable NGH concentration, so that the dehydration treatment and fluidized bed in the subsequent dehydration tower 102 can be performed.
  • the treatment of the attached water in the reaction tower 103 with NGH can be effectively and stably performed.
  • the concentration of NGH dehydrated in the dehydration tower 102 and the fluidized bed reaction tower 103 is also controlled with high precision, there is an effect that a high-quality product NGH can be produced stably and continuously.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production d'un hydrate de gaz par l'intermédiaire d'une réaction d'hydratation entre un gaz de départ et de l'eau, caractérisé en ce que les caractéristiques résiduelles définissant le rapport entre le diamètre de particules au moment de la formation d'hydrate de gaz et le rapport résiduel de gaz dans l'hydrate de gaz qui diminue sur la durée lors du transfert après la formation d'hydrate de gaz sont déterminées à l'avance, et en ce que le rapport résiduel de gaz correspondant au diamètre de particules de l'hydrate de gaz dans le produit lors de la formation de l'hydrate de gaz est déterminé sur la base des caractéristiques résiduelles ci-dessus, et en ce que la température de formation de l'hydrate de gaz est régulée de façon à maximiser la valeur de la fonction de performance représentée sous la forme d'un produit du rapport résiduel de gaz déterminé multiplié par un rapport de conversion d'hydrate défini comme une proportion d'hydrate de gaz dans le produit.
PCT/JP2006/306480 2006-03-29 2006-03-29 Procede de production d'hydrate de gaz et appareil correspondant WO2007110947A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017008019A (ja) * 2015-06-18 2017-01-12 宏祐 名倉 メタンハイドレートの人工製造法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000303083A (ja) * 1999-04-23 2000-10-31 Ishikawajima Harima Heavy Ind Co Ltd ハイドレートスラリ燃料及びその製造方法並びにその製造装置又その保管方法
JP2003105360A (ja) * 2001-09-28 2003-04-09 Mitsui Eng & Shipbuild Co Ltd ハイドレートの濃度測定用指標物質および濃度測定方法
JP2006096865A (ja) * 2004-09-29 2006-04-13 Mitsui Eng & Shipbuild Co Ltd ハイドレートスラリー製造装置およびハイドレート製造プラント
JP2006143771A (ja) * 2004-11-16 2006-06-08 Mitsui Eng & Shipbuild Co Ltd ガスハイドレートの製造方法および装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000303083A (ja) * 1999-04-23 2000-10-31 Ishikawajima Harima Heavy Ind Co Ltd ハイドレートスラリ燃料及びその製造方法並びにその製造装置又その保管方法
JP2003105360A (ja) * 2001-09-28 2003-04-09 Mitsui Eng & Shipbuild Co Ltd ハイドレートの濃度測定用指標物質および濃度測定方法
JP2006096865A (ja) * 2004-09-29 2006-04-13 Mitsui Eng & Shipbuild Co Ltd ハイドレートスラリー製造装置およびハイドレート製造プラント
JP2006143771A (ja) * 2004-11-16 2006-06-08 Mitsui Eng & Shipbuild Co Ltd ガスハイドレートの製造方法および装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017008019A (ja) * 2015-06-18 2017-01-12 宏祐 名倉 メタンハイドレートの人工製造法

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