Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
  • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen

Definitions

• the present invention relates to a liquid fuel synthesis system that synthesizes liquid fuel from a hydrocarbon raw material such as natural gas.
• FT synthesis reaction Fischer-Tropsch synthesis reaction
• synthesis gas as raw material gas
• GTL Gas To Liquid
• the possible hydrocarbon gas is, for example, at least 2% or more in terms of product.
• all of these exhaust gases are combusted and discarded, so that the hydrocarbon fraction that can be used in the product is wasted, and the exhaust gas combustion is not only low in product yield.
• the accompanying CO emissions will also increase.
• the present invention has been made in view of the above problems, and can recover a hydrocarbon component having a desired number of carbon atoms contained in the exhaust gas, thereby improving the product yield, and reducing CO emissions. Sharpening It is an object of the present invention to provide a liquid fuel synthesis system that can be reduced. Means for solving the problem
• a liquid fuel synthesizing system of the present invention includes a reformer that reforms a hydrocarbon raw material to generate a syngas mainly composed of carbon monoxide and hydrogen gas; and included in the syngas
• a reactor for synthesizing liquid hydrocarbons from carbon monoxide gas and hydrogen gas; a rectifying column for rectifying the liquid hydrocarbons and separating liquid hydrocarbons having a predetermined number of carbons or more;
• a cooling device that liquefies by cooling at least one of the exhaust gas discharged from the reactor force or the rectifying tower force discharged from the rectifying column, and contained in the liquefied exhaust gas The hydrocarbon gas having the predetermined carbon number or more is recovered.
• the exhaust gas discharged from the reactor or the exhaust gas discharged from the rectification tower is cooled by the cold heat of the refrigerant, whereby the predetermined exhaust gas is contained in the predetermined exhaust gas. It is possible to recover the hydrocarbon gas having a carbon number equal to or greater than that of the liquid. For this reason, hydrocarbon gas having a predetermined number of carbon atoms or more can be commercialized to improve the product yield, and the exhaust gas emissions can be reduced to reduce the CO emissions associated with exhaust gas combustion.
• the cooling device may cool the exhaust gas by using cold heat of a refrigerant supplied from an external device.
• the hydrocarbon raw material is natural gas
• the external device is a natural gas production facility that vaporizes liquefied natural gas and supplies the vaporized natural gas to the liquid fuel synthesis system.
• surplus cooling heat generated in the natural gas production facility can be effectively used for cooling the exhaust gas by the cooling device in the liquid fuel synthesis system. Accordingly, the overall thermal efficiency of the combined natural gas production facility and liquid fuel synthesis system can be greatly improved.
• the hydrocarbon raw material is natural gas
• the external device is a liquefied natural gas production facility for liquefying natural gas collected from a gas field
• the refrigerant is supplied to the liquefied natural gas production facility. It may be a refrigerant used for the natural gas liquid.
• surplus cooling heat contained in the refrigerant used in the liquefied natural gas production facility can be effectively utilized for cooling the exhaust gas by the cooling device in the liquid fuel synthesis system. Therefore The overall thermal efficiency of the combined natural gas production facility and liquid fuel synthesis system can be greatly improved.
• the exhaust gas discharged from the reactor or the exhaust gas discharged from the top of the rectification tower is cooled, so that a hydrocarbon component having a predetermined number of carbon atoms or more is obtained. Can be recovered to improve product yield and reduce CO emissions associated with exhaust gas combustion
• FIG. 1 is a schematic diagram showing an overall configuration of a liquid fuel synthesis system according to an embodiment of the present invention.
• FIG. 2 is a block diagram showing an outline of product recovery from exhaust gas in a liquid fuel synthesizing system using a refrigerant produced by a liquid natural gas production facility that can be used in an embodiment of the present invention. .
• FIG. 3 is a block diagram showing an outline of product recovery from exhaust gas in a liquid fuel synthesizing system using a refrigerant produced by a natural gas production facility that makes use of an embodiment of the present invention. Explanation of symbols
• Kerosene ⁇ Gas oil fraction hydrotreating reactor, 54 ⁇ Naphtha fraction hydrotreating reactor, 56, 58, 60 ⁇ Gas-liquid separator, 70... Second fractionator, 72 ... Naphtha's stabilizer, 73 ... Exhaust passage, 80 ... First cooling device, 82 ... Second cooling device, 83, 84 ... Piping, 85 ... Recovery route, 90 ... Liquefied natural Gas production equipment, 91 ... Gas field, 92 ... Heat exchange, 94 ... Refrigerant supply source, 96 LNG tank , 100.. Natural gas production facility, 102 LNG tank, 104 ... heat ⁇ , 106 ... heat medium supply source, 110 ... combustion equipment BEST MODE FOR CARRYING OUT THE INVENTION
• FIG. 1 is a schematic diagram showing an overall configuration of a liquid fuel synthesizing system 1 that is useful in the present embodiment.
• a liquid fuel synthesis system 1 is a plant facility that executes a GTL process for converting a hydrocarbon feedstock such as natural gas into liquid fuel.
• the liquid fuel synthesizing system 1 includes a syngas generating unit 3, an FT synthesizing unit 5, and a product refining unit 7.
• the synthesis gas generation unit 3 reforms the natural gas, which is a hydrocarbon raw material, to generate synthesis gas containing carbon monoxide gas and hydrogen gas.
• the FT synthesis unit 5 also generates liquid hydrocarbons by the Fischer's Tropsch synthesis reaction (hereinafter referred to as “FT synthesis reaction”).
• the product refining unit 7 produces liquid fuel products (naphtha, kerosene, light oil, wax, etc.) by hydrogenating and refining the liquid hydrocarbons produced by the FT synthesis reaction.
• liquid fuel products nophtha, kerosene, light oil, wax, etc.
• the synthesis gas generation unit 3 mainly includes, for example, a desulfurization reactor 10, a reformer 12, an exhaust heat boiler 14, gas-liquid separators 16 and 18, a decarboxylation device 20, and a hydrogen separation device 26.
• the desulfurization reactor 10 is constituted by a hydrodesulfurization device or the like, and removes sulfur components from natural gas as a raw material.
• the reformer 12 reforms the natural gas supplied from the desulfurization reactor 10 to generate a synthesis gas containing carbon monoxide gas (CO) and hydrogen gas (H 2) as main components.
• the exhaust heat boiler 14 is produced in the reformer 12.
• High pressure steam is generated by recovering the exhaust heat of the synthesized gas.
• the gas-liquid separator 16 separates water heated by heat exchange with the synthesis gas in the exhaust heat boiler 14 into gas (high-pressure steam) and liquid.
• the gas-liquid separator 18 removes the condensate from the synthesis gas cooled by the exhaust heat boiler 14 and supplies the gas to the decarbonator 20.
• the decarbonation device 20 includes an absorption tower 22 that removes carbon dioxide gas using the absorption liquid as well as the syngas power supplied from the gas-liquid separator 18. And a regeneration tower 24 that regenerates the carbon dioxide gas by releasing the carbon dioxide gas from the absorbing solution.
• the hydrogen separation device 26 separates a part of the hydrogen gas contained in the synthesis gas from the synthesis gas from which the carbon dioxide gas has been separated by the decarbonation device 20.
• the decarboxylation device 20 may not be required in some cases.
• the reformer 12 uses, for example, carbon dioxide and steam by the steam 'carbonate gas reforming method represented by the following chemical reaction formulas (1) and (2). Natural gas is reformed to produce high-temperature synthesis gas mainly composed of carbon monoxide gas and hydrogen gas.
• the reforming method in the reformer 12 is not limited to the above-mentioned steam 'carbon dioxide reforming method, for example, a water vapor reforming method, a partial oxidation reforming method (POX) using oxygen, Autothermal reforming (ATR), which is a combination of partial oxidation reforming and steam reforming, or carbon dioxide reforming can also be used.
• the hydrogen separator 26 is provided in a branch line branched from a main piping force that connects the decarbonator 20 or the gas-liquid separator 18 and the bubble column reactor 30.
• the hydrogen separator 26 can be constituted by, for example, a hydrogen PSA (Pressure Swing Ads orption) device that performs adsorption and desorption of hydrogen using a pressure difference.
• This hydrogen PSA apparatus has adsorbents (zeolite-based adsorbent, activated carbon, alumina, silica gel, etc.) in a plurality of adsorbing towers (not shown) arranged in parallel. By repeating the steps of pressurization, adsorption, desorption (decompression), and purge in order, high purity hydrogen gas (eg, about 99.999%) separated from synthesis gas is continuously supplied to the reactor. can do.
• adsorbents zeolite-based adsorbent, activated carbon, alumina, silica gel, etc.
• the hydrogen gas separation method in the hydrogen separator 26 is not limited to the example of the pressure fluctuation adsorption method such as the hydrogen PSA device described above.
• the hydrogen storage alloy adsorption method, the membrane separation method, or these Combinations may be used.
• the FT synthesis unit 5 mainly includes, for example, a bubble column reactor 30, a gas-liquid separator 34, a separator 36, a gas-liquid separator 38, and a first rectifying column 40.
• the bubble column reactor 30 generates liquid hydrocarbons by FT synthesis reaction of the synthesis gas generated in the synthesis gas generation unit 3, that is, carbon monoxide gas and hydrogen gas. To do.
• the gas-liquid separator 34 separates the water heated through the heat transfer tubes 32 disposed in the bubble column reactor 30 into water vapor (medium pressure steam) and liquid.
• the separator 36 is connected to the center of the bubble column reactor 30 and separates the catalyst and the liquid hydrocarbon product.
• the gas-liquid separator 38 is connected to the upper part of the bubble column reactor 30 and cools the unreacted synthesis gas and the gaseous hydrocarbon product.
• the first rectification column 40 distills liquid hydrocarbons supplied from the bubble column reactor 30 via the separator 36 and the gas-liquid separator 38, and separates and purifies each product fraction according to the boiling point. To do.
• the bubble column reactor 30 is an example of a reactor that synthesizes synthesis gas into liquid hydrocarbons, and is an FT synthesis reactor that synthesizes liquid hydrocarbons from synthesis gas by FT synthesis reaction. Function.
• the bubble column reactor 30 is constituted by, for example, a bubble column type slurry bed type reactor in which a slurry made of a catalyst and a medium oil is stored inside a column type container.
• the bubble column reactor 30 generates liquid hydrocarbons from synthesis gas by FT synthesis reaction.
• the synthesis gas which is a raw material gas, is supplied as bubbles from the dispersion plate at the bottom of the bubble column reactor 30, and passes through the slurry composed of the catalyst and the medium oil.
• hydrogen gas and carbon monoxide gas undergo a synthesis reaction as shown in chemical reaction formula (3) below.
• the bubble column reactor 30 is a heat exchanger type in which a heat transfer tube 32 is disposed inside, and water (BFW: Boiler Feed Watt) is used as a refrigerant. er), and the heat of reaction of the FT synthesis reaction can be recovered as an intermediate pressure steam by heat exchange between the slurry and water.
• BFW Boiler Feed Watt
• Product refining unit 7 includes, for example, W AX fraction hydrocracking reactor 50, kerosene / light oil fraction hydrotreating reactor 52, naphtha fraction hydrotreating reactor 54, and gas-liquid separator 56, 58. , 60, a second rectification tower 70, and a naphtha 'stabilizer 72.
• the WAX fraction hydrocracking reactor 50 is connected to the lower part of the first rectification column 40.
• the kerosene / light oil fraction hydrotreating reactor 52 is connected to the center of the first rectifying column 40.
• the naphtha fraction hydrotreating reactor 54 is connected to the upper part of the first rectifying column 40.
• the gas-liquid separators 56, 58, 60 are the same as those of the hydrogenation reactors 50, 52, 54. It is provided corresponding to each.
• the second rectifying column 70 separates and purifies the liquid hydrocarbons supplied from the gas-liquid separators 56 and 58 according to the boiling point.
• the naphtha stabilizer 72 rectifies the liquid hydrocarbons of the naphtha fraction supplied from the gas-liquid separator 60 and the second rectifying column 70, and discharges lighter components than butane to the flare gas (exhaust gas) side, Ingredients whose number is C or more
• This naphtha stabilizer 72 is a rectifying tower that rectifies liquid hydrocarbons according to the present embodiment and separates liquid fuel having a predetermined number of carbons or more (rectifying tower that discharges exhaust gas (carbon number is less than C)). It is configured as an example, but the details
• the liquid fuel synthesizing system 1 includes natural gas (main component is CH 2) as a hydrocarbon feedstock from an external natural gas supply source (not shown) such as a natural gas field or a natural gas plant.
• natural gas main component is CH 2
• an external natural gas supply source not shown
• the synthesis gas generation unit 3 reforms the natural gas to produce a synthesis gas (a mixed gas mainly composed of carbon monoxide and hydrogen gas).
• the natural gas is supplied to the desulfurization reactor 10 together with the hydrogen gas separated by the hydrogen separator 26.
• the desulfurization reactor 10 hydrodesulfurizes the sulfur content contained in the natural gas using, for example, a ZnO catalyst using the hydrogen gas.
• the natural gas desulfurized in this manner is a diacid-carbon (CO 2) gas supplied from a carbon dioxide supply source (not shown).
• CO 2 diacid-carbon
• the reformer 12 After the raw steam is mixed, it is supplied to the reformer 12.
• the reformer 12 reforms natural gas using carbon dioxide and water vapor by the steam 'carbon dioxide gas reforming method described above, and generates high-temperature components mainly composed of carbon monoxide gas and hydrogen gas. Generate synthesis gas.
• fuel gas and air for a burner provided in the reformer 12 are supplied to the reformer 12, and the steam / CO reforming which is an endothermic reaction by the combustion heat of the fuel gas in the burner. The heat of reaction necessary for quality reaction is covered!
• the high-temperature synthesis gas thus produced in the reformer 12 (eg, 900 ° C, 2. OMPa G) is supplied to the exhaust heat boiler 14, cooled (for example, 400 ° C.) by heat exchange with water circulating in the exhaust heat boiler 14, and recovered as exhaust heat.
• water heated by the synthesis gas in the exhaust heat boiler 14 is supplied to the gas-liquid separator 16, and the gas component is reformed as high-pressure steam (for example, 3.4 to 10. OMPaG).
• the water in the liquid is returned to the waste heat boiler 14 after being supplied to the vessel 12 or other external device.
• the synthesis gas cooled in the exhaust heat boiler 14 is separated and removed in the gas-liquid separator 18 by the condensate, and then the absorption tower 22 of the decarboxylation device 20 or the bubble column reactor. Supplied to 30.
• the absorption tower 22 separates carbon dioxide from the synthesis gas by absorbing the carbon dioxide contained in the synthesis gas in the stored absorption liquid.
• the absorption liquid containing carbon dioxide gas in the absorption tower 22 is introduced into the regeneration tower 24, and the absorption liquid containing carbon dioxide gas is heated by, for example, steam and subjected to the stripping process. It is sent to the reformer 12 and reused for the reforming reaction.
• the synthesis gas produced by the synthesis gas production unit 3 is supplied to the bubble column reactor 30 of the FT synthesis unit 5.
• the synthesis gas supplied to the bubble column reactor 30 is FT by a compressor (not shown) provided in a pipe connecting the decarbonation device 20 and the bubble column reactor 30.
• the pressure is increased to a pressure suitable for the synthesis reaction (eg, 3.6 MPaG).
• a part of the synthesis gas from which the carbon dioxide gas has been separated by the decarbonation device 20 is also supplied to the hydrogen separation device 26.
• the hydrogen separator 26 separates hydrogen gas contained in the synthesis gas by adsorption and desorption (hydrogen PSA) using a pressure difference as described above.
• the separated hydrogen is supplied through various compressors (not shown) such as a gas holder (not shown) and various hydrogens that perform a predetermined reaction using hydrogen in the liquid fuel synthesis system 1.
• reactors eg desulfurization reactor 10, WAX hydrocracking reactor 50, kerosene / light oil fraction hydrotreating reactor 52, naphtha fraction hydrotreating reactor 54, etc.
• the FT synthesis unit 5 synthesizes liquid hydrocarbons from the synthesis gas produced by the synthesis gas production unit 3 by an FT synthesis reaction.
• the synthesis gas produced by the synthesis gas production unit 3 is a bubble column reaction.
• the bottom force of the vessel 30 is also introduced, and the catalyst slurry stored in the bubble column reactor 30 rises.
• the carbon monoxide and hydrogen gas contained in the synthesis gas react with each other by the FT synthesis reaction described above to generate hydrocarbons.
• water is circulated through the heat transfer tube 32 of the bubble column reactor 30 to remove the reaction heat of the FT synthesis reaction, and the water heated by this heat exchange evaporates to form water. It becomes steam.
• the water that has been liquefied in the gas-liquid separator 34 is returned to the heat transfer tube 32, and the gas component is supplied to the external device as medium-pressure steam (for example, 1.0 to 2.5 MPaG).
• the liquid hydrocarbon synthesized in the bubble column reactor 30 is taken out from the center of the bubble column reactor 30 and introduced into the separator 36.
• the separator 36 separates the catalyst (solid content) in the removed slurry into a liquid content containing a liquid hydrocarbon product. A part of the separated catalyst is returned to the bubble column reactor 30, and the liquid is supplied to the first rectifying column 40.
• unreacted synthesis gas and the synthesized hydrocarbon gas are introduced into the gas-liquid separator 38.
• the gas-liquid separator 38 cools these gases, separates some condensed liquid hydrocarbons, and introduces them into the first fractionator 40.
• the unreacted synthesis gas CO and H
• the unreacted synthesis gas is reintroduced into the bottom of the bubble column reactor 30 and reused for the FT synthesis reaction.
• the main component is a hydrocarbon gas with a low carbon number (C or less) that is not covered by the product.
• Exhaust gas (flare gas) is introduced into an external combustion facility (not shown) via a first cooling device 80 (details will be described later), and is released into the atmosphere after being combusted.
• the first rectification column 40 is a liquid hydrocarbon (having various carbon numbers) supplied from the bubble column reactor 30 through the separator 36 and the gas-liquid separator 38 as described above. ) And fractionate using the difference in boiling point, naphtha fraction (boiling point is less than about 315 ° C), kerosene 'light oil fraction (boiling point is about 315 to 800 ° C), WAX fraction Separation and purification (boiling point greater than about 800 ° C).
• the liquid hydrocarbons (mainly C or more) of WAX taken out from the bottom of the first rectifying column 40 are
• Kerosene and liquid hydrocarbons (mainly C to C) of kerosene / light oil fraction transferred to WAX fraction hydrocracking reactor 50 and taken out from the center of first fractionator 40
• the liquid hydrocarbon (mainly C to C) of the naphtha fraction which is transferred to the reactor 52 and from which the upper force of the first rectifying column 40 is also taken out is transferred to the naphtha fraction hydrotreating reactor 54.
• the WAX fraction hydrocracking reactor 50 removes the liquid hydrocarbon (approximately C or more) having a large number of carbon atoms supplied from the lower column of the first rectifying column 40 from the hydrogen separator 26. Supplied
• the catalyst and heat are used to cleave C C bonds of hydrocarbons with a large number of carbons to produce low molecular weight hydrocarbons with a small number of carbons.
• the product containing liquid hydrocarbons hydrocracked by this WAX hydrocracking reactor 50 is separated into gas and liquid by gas-liquid separator 56, of which liquid hydrocarbons are separated by the second rectification fraction.
• the gas component (including hydrogen gas) is transferred to the tower 70 and transferred to the kerosene / light oil fraction hydrotreating reactor 52 and the naphtha fraction hydrotreating reactor 54.
• Kerosene ⁇ Gas oil fraction hydrotreating reactor 52 is a liquid hydrocarbon of kerosene 'light oil fraction (generally C to C) with a medium carbon number, which is also supplied with the central force of the first fractionator 40. ), Hydrogen content
• Hydrotreating is performed using hydrogen gas supplied from the separation device 26 through the WAX hydrocracking reactor 50.
• This hydrorefining reaction is a reaction in which hydrogen is added to the unsaturated bond of the liquid hydrocarbon to saturate to produce a linear saturated hydrocarbon.
• the hydrogenated and purified product containing liquid hydrocarbons is separated into a gas and a liquid by the gas-liquid separator 58, and the liquid hydrocarbons are transferred to the second rectification column 70 for gas separation. (Including hydrogen gas) is reused in the hydrogenation reaction.
• the naphtha fraction hydrotreating reactor 54 has a small number of carbons supplied by the upper force of the first rectifying column 40! /, And liquid hydrocarbons (approximately C or less) of the naphtha fraction are separated by a hydrogen separator. 26 to WA
• the second fractionator 70 distills the liquid hydrocarbons supplied from the WAX fraction hydrocracking reactor 50 and the kerosene / light oil fraction hydrotreating reactor 52 as described above. Hydrocarbons with a carbon number of C or less (boiling point less than about 315 ° C) and kerosene (boiling point about 315 to 450 ° C)
• the naphtha's stabilizer 72 distills hydrocarbons having a carbon number of C or less supplied from the naphtha fraction hydrotreating reactor 54 and the second rectifying column 70 as a product.
• the main component of the exhaust is hydrocarbons whose main component is a carbon number not exceeding the specified number (C or less).
• Gas (flare gas) is discharged.
• This exhaust gas is introduced into an external combustion facility (not shown) via a second cooling device 82 (details will be described later), and after being combusted, it is released into the atmosphere.
• the reformer 12 adopts the steam / carbon dioxide reforming method described above, so that carbon dioxide contained in the natural gas as a raw material is effectively used,
• hydrocarbons with more than c carbon atoms that can become naphtha products over time are at least produced.
• the hydrocarbon gas that can be used in this product has also been burned and discarded in the combustion facility, which causes a reduction in product yield.
• Tower reactor 30 Exhaust path from top of tower 39 and top of naphtha's stabilizer 72 A first cooling device 80 and a second cooling device 82 for cooling the exhaust gas are provided on the powerful exhaust path 73, respectively.
• FIGS. 2 and 3 show the first cooling device 80 and the second cooling device 82 (hereinafter sometimes simply referred to as “cooling devices 80 and 82”).
• cooling devices 80 and 82 The details of product recovery from the exhaust gas that was stored are described in detail.
• Figures 2 and 3 show the liquid fuel natural gas production equipment 90 or the natural gas production equipment 100 used in the present embodiment. It is a block diagram which shows the outline
• the liquid fuel synthesizing system 1 (GTL plant) is, for example, a liquefied natural gas production facility installed in a region where a gas field 91 exists (such as a natural gas exporting country such as the Middle East). It is located adjacent to the facility 90 (Liquid Natural Gas Production Plant). In the case of FIG. 2, the liquid fuel synthesizing system 1 is supplied with natural gas collected from the gas field 91 as a raw material gas.
• the liquefied natural gas production facility 90 is a facility for producing liquefied natural gas (LNG) by cooling the natural gas collected from the gas field 91.
• the liquefied natural gas production facility 90 includes a heat exchanger 92 that liquefies natural gas, a refrigerant supply source 94 that supplies a refrigerant to the heat exchanger 92, and an LNG tank 96 that stores LNG.
• natural gas from a gas field and the refrigerant from the refrigerant supply source 94 are supplied to the heat exchanger 92, and the heat exchange is performed between the natural gas and the refrigerant.
• the natural gas is cooled to a very low temperature (approximately 1 162 ° C or less) and liquidized to LNG.
• This liquefied LNG is stored in the LNG tank 96 and transported to other areas (such as natural gas importing countries such as Japan) by tankers as necessary.
• a refrigerant for liquidizing natural gas in the liquid natural gas production facility 90 as described above for example, natural gas is used with liquid nitrogen, liquid propane, liquefied methane, liquefied ethylene, or the like. Any material that can be cooled below the critical temperature can be used. In addition, a refrigerant obtained by mixing some of these can also be used as the refrigerant. These refrigerants are used at extremely low temperatures to liquefy natural gas, so even after the temperature has risen somewhat due to heat exchange in heat exchange. Have enough cold. A refrigerant for liquefying the natural gas is supplied to the liquid fuel synthesizing system 1 as a refrigerant for exhaust gas cooling.
• the liquid fuel synthesizing system 1 is, for example, a natural gas production facility installed in an area where natural gas is consumed (such as a natural gas importing country such as Japan). It is located adjacent to 100 (natural gas production plant).
• the natural gas production facility 100 includes an LNG tank 102 that stores liquefied natural gas (LNG), a heat exchanger 104 that vaporizes LNG, and a heat medium supply source 106 that supplies a heat medium to the heat exchanger 104.
• LNG liquefied natural gas
• the LNG produced in the liquefied natural gas production facility 90 is transported by a tanker or the like and stored in the LNG tank 102.
• the extremely low temperature (about ⁇ 162 ° C. or lower) LNG stored in the LNG tank 102 and the heat medium from the heat medium supply source 106 are supplied to the heat exchanger 104.
• the heat exchanger 104 heats LNG and vaporizes it into natural gas by performing heat exchange between the LNG and the heat medium.
• the natural gas produced by vaporizing LNG in the natural gas production facility 100 in this way is supplied to the liquid fuel synthesis system 1 as a raw material gas.
• a heat medium for evaporating the LNG for example, power that can use seawater, water, glycol, and the like. These heat mediums are absorbed by cryogenic LNG and cooled to a low temperature.
• the heat medium cooled when evaporating LNG in this way is also supplied to the liquid fuel synthesizing system 1 as a refrigerant for exhaust gas cooling.
• the cryogenic LNG itself stored in the LNG tank 102 can be supplied to the liquid fuel synthesizing system 1 as a refrigerant for exhaust gas cooling (see the broken line arrow 108 in FIG. 3).
• the refrigerant supplied from the liquefied natural gas production facility 90 or the natural gas production facility 100 is used for exhaust gas. I will explain how to cool it.
• the natural gas supplied from the gas field 91 or the natural gas production facility 100 is reformed by the reformer 12 and synthesized.
• the synthesis gas is synthesized into liquid hydrocarbons by the bubble column reactor 30.
• the first rectification column 40, the hydrogenation reactors 50, 52, 54, the second rectification column 70 and naphtha 'stabilizer 72 to convert liquid hydrocarbons into liquid fuel products (naphtha, kerosene, light oil) Purify 'separate.
• the exhaust gas discharged from the top of the bubble column reactor 30 is supplied to the first cooling device 80 via the exhaust path 39, and the top of the naphtha 'stabilizer 72 is supplied.
• the exhaust gas from which power is also discharged is supplied to the second cooling device 82 via the exhaust path 73.
• these cooling devices 80, 82 are connected to the refrigerant used for liquefying the LNG from the liquefied natural gas production facility 90 or the natural gas production facility 100 via the pipes 83, 84, or the LNG
• the low temperature heat medium having the cold generated during the vaporization is supplied as a refrigerant for exhaust gas cooling.
• the cooling devices 80 and 82 include, for example, a heat exchanger (not shown), exchange heat between the exhaust gas supplied as described above and the refrigerant, Cool below temperature.
• This predetermined temperature is, for example, a temperature at which a hydrocarbon gas having a predetermined number of carbons (for example, C or more) that can become a liquid fuel product in the GTL process becomes liquid (for example, a pentagon).
• hydrocarbon gases hydrocarbons with a predetermined number of carbons (for example, c or more) that can be used as products
• the gas is liquid and hydrocarbon gas with less carbon number (eg C or less) does not liquid.
• the temperature condition during exhaust gas cooling by the cooling devices 80 and 82 can be, for example, ⁇ 10 to 10 ° C., and it is possible to select an appropriate type of refrigerant that meets this temperature condition.
• hydrocarbons having a carbon number of C or more liquefied by the second cooling device 82 are supplied to the outside from the second cooling device 82 as naphtha products.
• the hydrocarbon gas having a liquefied and powerful carbon number of a predetermined number or less contains a toxic gas and a combustible gas component.
• exhaust gas to be burned fume gas
• it is introduced into the combustion facility 110 from the cooling devices 80 and 82, burned, and released to the atmosphere.
• the exhaust gas from the bubble column reactor 30 (FT-TAIL gas) and the exhaust gas from the naphtha stabilizer 72 are used as products.
• hydrocarbons in an amount of at least 2% or more in terms of products that were conventionally discarded can be suitably recovered and commercialized, so that the product yield can be improved.
• the amount of exhaust gas combusted by the combustion facility 110 can be reduced to reduce CO emissions from the liquid fuel synthesis system 1.
• the liquid gas natural gas production facility 90 disposed adjacent to the liquid fuel synthesis system 1 is used when the natural gas is liquefied.
• the surplus cooling heat contained in the refrigerant used or the surplus cooling heat contained in the heat medium used for vaporizing LNG in the natural gas production facility 100 is used.
• surplus cold heat generated in the liquefied natural gas production facility 90 or the natural gas production facility 100 can be effectively used for exhaust gas cooling in the liquid fuel synthesis system 1, so the liquid natural gas production facility 90 or natural gas production
• the thermal efficiency of the entire system including the equipment 100 and the liquid fuel synthesis system 1 can be greatly improved.
• the exhaust gas is cooled by using a very low temperature refrigerant of, for example, about 160 ° C, a small amount of hydrocarbons contained in the exhaust gas (hydrocarbons with a carbon number of C or more that can be produced)
• the initial investment in adopting the above recovery mechanism is only the equipment cost of the heat exchanger as the cooling devices 80, 82, and this equipment cost is the cost of the gas fuel for burning the exhaust gas (running cost). ) Can be recovered sufficiently.
• the hydrocarbon raw material supplied to the liquid fuel synthesizing system 1 is not limited to a powerful example using natural gas, and other carbonization such as asphalt and residual oil, for example.
• a hydrogen raw material may be used.
• the synthesis reaction in the bubble column reactor 30 is FT synthesis.
• liquid hydrocarbons were synthesized by reaction, the present invention is not limited to powerful examples.
• the cooling source of the exhaust gas cooling in the liquid fuel synthesis system 1 the excess cooling heat in the liquefied natural gas manufacturing facility 90 or the natural gas manufacturing facility 100 is used.
• the present invention is not limited to this example, and powerful cold energy such as other plant equipment capable of supplying the refrigerant used in the cooling process may be used as the cold heat source.
• an example of the naphtha stabilizer 72 that separates naphtha is given as an example of a rectifying column that distills liquid hydrocarbons and separates liquid fuel having a predetermined number of carbons or more.
• the present invention is not limited to a powerful example, and may be, for example, a distillation column for separating various liquid fuels such as kerosene, light oil, alcohol, and DME.
• a bubble column type slurry bed type reactor is used as a reactor for synthesizing synthesis gas into liquid hydrocarbons.
• the present invention is not limited to a powerful example.
• FT synthesis reaction may be performed using a fixed bed reactor.
• the present invention includes a reformer that reforms a hydrocarbon raw material to generate a synthesis gas mainly composed of carbon monoxide gas and hydrogen gas; and a carbon monoxide gas contained in the synthesis gas; A reactor for synthesizing liquid hydrocarbons from hydrogen gas; a rectifying column for rectifying the liquid hydrocarbons to separate liquid hydrocarbons having a predetermined carbon number or more; exhaust gas discharged from the reactor; Or a cooling device that liquefies by cooling at least one of the exhaust gas discharged from the rectifying column, and the hydrocarbon having the predetermined number of carbons or more contained in the liquid exhaust gas.
• the present invention relates to a liquid fuel synthesis system for recovering gas.
• a hydrocarbon component having a desired carbon number contained in the exhaust gas can be recovered to improve the product yield, and CO emissions can be reduced.

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• 2007
  • 2007-03-29 MY MYPI20083785 patent/MY148262A/en unknown
  • 2007-03-29 CN CNA2007800155922A patent/CN101432402A/zh active Pending
  • 2007-03-29 AU AU2007232926A patent/AU2007232926B2/en not_active Ceased
  • 2007-03-29 WO PCT/JP2007/056924 patent/WO2007114277A1/ja active Application Filing
  • 2007-03-29 ZA ZA200808234A patent/ZA200808234B/xx unknown
  • 2007-03-29 RU RU2008140160/05A patent/RU2415904C2/ru not_active IP Right Cessation
  • 2007-03-29 JP JP2008508622A patent/JPWO2007114277A1/ja active Pending

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