WO2007114274A1 - 液体燃料合成システム - Google Patents
液体燃料合成システム Download PDFInfo
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- WO2007114274A1 WO2007114274A1 PCT/JP2007/056918 JP2007056918W WO2007114274A1 WO 2007114274 A1 WO2007114274 A1 WO 2007114274A1 JP 2007056918 W JP2007056918 W JP 2007056918W WO 2007114274 A1 WO2007114274 A1 WO 2007114274A1
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- WIPO (PCT)
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- gas
- liquid
- synthesis
- reactor
- liquid fuel
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Classifications
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- 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
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
- C10G2/342—Apparatus, reactors with moving solid catalysts
- C10G2/344—Apparatus, reactors with moving solid catalysts according to the "fluidised-bed" technique
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
Definitions
- the present invention relates to a liquid fuel synthesis system.
- FT synthesis reaction Fischer-Tropsch synthesis reaction
- the synthesized gas as raw material gas
- GTL Gas To Liquid
- the above intermediate product separated for each boiling point by this rectification column becomes a product after further hydrogenation and purification in a hydrogenation reactor, but before being introduced into this hydrogenation reactor.
- a predetermined temperature range for example, 100 to 400 ° C.
- a heat transfer oil is used as a heating medium in order to perform heating to the above temperature range.
- the present invention has been made in view of such problems, and an object thereof is to provide a liquid fuel synthesis system capable of improving the thermal efficiency of the entire liquid fuel synthesis system.
- the liquid fuel synthesizing system of the present invention includes a reformer for reforming a hydrocarbon raw material to generate a syngas mainly composed of carbon monoxide gas and hydrogen gas; A reactor for synthesizing liquid hydrocarbons from contained carbon monoxide gas and hydrogen gas; a purification treatment apparatus for performing a predetermined purification treatment on the liquid hydrocarbons synthesized in the reactor; and the purification treatment Heating means for heating the liquid hydrocarbon introduced into the apparatus using the gas discharged from the reformer as a heat source.
- the reformer reforms the hydrocarbon raw material to produce a synthesis gas mainly composed of carbon monoxide gas and hydrogen gas
- the reactor is a synthesis gas.
- Liquid fuel is synthesized using the raw material as a raw material
- the refining treatment device performs a predetermined refining treatment on the mixture of the above-described plurality of types of liquid fuel
- the heating means heats the liquid fuel introduced into the refining treatment device. To do.
- this high-temperature gas can be directly used as a heating medium. As a result, the thermal efficiency of the entire liquid fuel synthesis system can be improved.
- the refining treatment apparatus hydrogenates the rectification tower for fractionating the liquid hydrocarbon into a plurality of types of liquid fuels having different boiling points, or the liquid hydrocarbon. It may be at least one of the hydrogenation reactors.
- the heating means may be, for example, a heat exchanger capable of exchanging heat between gas liquids.
- liquid fuel synthesized in the reactor may be a mixture of a plurality of types of liquid fuels having different boiling points.
- the thermal efficiency of the entire liquid fuel synthesis system can be improved.
- 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 heating means of the liquid fuel synthesizing system according to the embodiment of the present invention. Explanation of symbols
- FIG. 1 is a schematic diagram showing an overall configuration of a liquid fuel synthesizing system 1 that is useful in the present embodiment.
- the liquid fuel synthesizing 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 produces liquid hydrocarbons by the synthesis gas force Fischer's Tropsch synthesis reaction (hereinafter referred to as “FT synthesis reaction”).
- the product refining unit 7 hydrolyzes and refines the liquid hydrocarbons produced by this FT synthesis reaction to produce liquid fuel products (fusa, kerosene, light oil, wax, etc.).
- liquid fuel products frusa, 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 composed of 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 decarboxylation device 20 also removes carbon dioxide gas from the absorption tower 22 that removes carbon dioxide gas using the absorption liquid, and the carbon dioxide gas from the absorption liquid containing the carbon dioxide gas. It has a regeneration tower 24 for regeneration.
- 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 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 on a branch line branched from the main piping force connecting the decarbonator 20 or the gas-liquid separator 18 and the bubble column reactor 30.
- the hydrogen separator 26 can be configured by, for example, a hydrogen PSA (Pressure Swing Adsorption) device that performs adsorption and desorption of hydrogen using a pressure difference.
- This hydrogen PSA apparatus has an adsorbent (zeolite adsorbent, activated carbon, aluminum) in a plurality of adsorption towers (not shown) arranged in parallel.
- the purity of hydrogen gas is increased (for example, about 99.999%) by repeating the steps of pressurization, adsorption, desorption (decompression), and purge in order in each adsorption tower. However, it can be continuously fed to the reactor.
- the hydrogen gas separation method in the hydrogen separator 26 is not limited to 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 hydrogen storage alloy method is, for example, a hydrogen storage alloy (TiFe, LaNi, TiFe, Mn, or TiMn that has the property of adsorbing and releasing hydrogen by being cooled and heated by Z.
- a hydrogen storage alloy TiFe, LaNi, TiFe, Mn, or TiMn that has the property of adsorbing and releasing hydrogen by being cooled and heated by Z.
- a plurality of adsorption towers containing hydrogen storage alloys are provided, and in each adsorption tower, hydrogen adsorption by cooling the hydrogen storage alloy and hydrogen release by heating the hydrogen storage alloy are alternately repeated to synthesize Hydrogen gas in the gas can be separated and recovered.
- the membrane separation method is a method of separating hydrogen gas having excellent membrane permeability from a mixed gas using a membrane made of a polymer material such as aromatic polyimide. Since this membrane separation method does not involve a phase change, the energy required for operation is small, and the running cost is low. Further, since the structure of the membrane separation apparatus is simple and compact, the equipment cost is low and the required area of the equipment is small. Furthermore, the separation membrane has the advantage of easy maintenance because it has a wide stable operating range.
- 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 FT synthesis reaction by synthesizing the synthesis gas produced by the synthesis gas production unit 3, that is, carbon monoxide gas and hydrogen gas, by FT synthesis reaction.
- 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 through the separator 36 and the gas-liquid separator 38, and produces each product according to the boiling point. Separation and purification of fractions.
- 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 has a heat exchange type with a heat transfer tube 32 disposed therein, and for example, water (BFW: Boiler) Feed
- 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 and 60 are provided corresponding to the hydrogenation reactors 50, 52 and 54, respectively.
- 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 side, and has 5 or more carbon atoms. These components are separated and recovered as product naphtha.
- liquid fuel synthesizing system 1 configured as described above is used to produce liquid fuel such as natural gas.
- the process of synthesis (GTL process) will be described.
- natural gas main component is CH 2
- an external natural gas supply source such as a natural gas field or a natural gas plant.
- the synthesis gas generation unit 3 reforms the natural gas to produce a synthesis gas (a mixed gas mainly composed of carbon monoxide gas 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. By desulfurizing natural gas in this way, it is possible to prevent the activity of the catalyst used in the reformer 12, the bubble column reactor 30, etc. from being reduced by sulfur.
- the natural gas desulfurized in this way (which may contain diacid carbon) is a diacid carbon (CO 2) gas supplied from a carbon dioxide supply source (not shown).
- CO 2 diacid carbon
- the raw steam is mixed and supplied to the reformer 12.
- the reformer 12 reforms natural gas using carbon dioxide and water vapor by the above-described steam 'carbon dioxide gas reforming method, and contains carbon monoxide gas and hydrogen gas as main components. Produces hot synthesis gas.
- the reformer 12 is supplied with, for example, fuel gas and air for the burner included in the reformer 12, and the steam 'carbonic acid gas reforming reaction is performed by the combustion heat of the fuel gas in the burner.
- the reaction heat necessary for the The liquid fuel synthesizing system 1 according to this embodiment is characterized in that it uses an exhaust gas of about 1000 to 1200 ° C. generated by the combustion heat of the combustion gas in this burner. This will be explained in detail below.
- the high-temperature synthesis gas (for example, 900 ° C, 2. OMPa G) generated in the reformer 12 in this way is supplied to the exhaust heat boiler 14 and is circulated in the exhaust heat boiler 14. It is cooled (for example, 400 ° C) by heat exchange with the heat and recovered. At this time, 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.
- high-temperature synthesis gas for example, 900 ° C, 2. OMPa G
- the synthesis gas cooled in the exhaust heat boiler 14 has a condensate component as a gas-liquid separator 1. After being separated and removed in 8, it is supplied to the absorption tower 22 of the decarboxylation device 20 or the bubble column reactor 30.
- the absorption tower 22 removes 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 sent to the regeneration tower 24, and the absorption liquid containing carbon dioxide gas is heated with, for example, steam and subjected to a stripping process. It is sent to the reformer 12 and reused for the reforming reaction.
- the synthesis gas produced in 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 decarboxylation device 20 and the bubble column reactor 30.
- the pressure is increased to a pressure appropriate for the synthesis reaction (eg, about 3.6 MPaG).
- a part of the synthesis gas from which the carbon dioxide gas has been separated by the decarbonator 20 is also supplied to the hydrogen separator 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 from which the carbon dioxide gas has been separated by the decarboxylation device 20 flows from the bottom of the bubble column reactor 30 and is stored in the bubble column reactor 30. Ascends in the catalyst slurry.
- carbon monoxide and hydrogen gas contained in the synthesis gas react to generate hydrocarbons by the above-described FT synthesis reaction.
- water is circulated through the heat transfer tube 32 of the bubble column reactor 30 to remove the heat of reaction of the FT synthesis reaction, and the water heated by this heat exchange is vaporized and vaporized. It becomes.
- the water vapor liquefied by the gas-liquid separator 34 is returned to the heat transfer tube 32.
- the gas component is supplied to the external device as medium-pressure steam (for example, gas pressure 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 sent to 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.
- the exhaust gas is generally introduced into an external combustion facility (not shown) as flare gas, burned, and then released into the atmosphere.
- the first rectifying 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 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 CC bonds of hydrocarbons with many carbon atoms to produce low molecular weight hydrocarbons with few carbon atoms.
- This WAX fraction hydrocracking reaction The product containing the hydrocracked liquid hydrocarbons is separated into gas and liquid by the gas / liquid separator 56, and the liquid hydrocarbons are transferred to the second rectification column 70 and gas The fraction (including hydrogen gas) is transferred to kerosene / light oil fraction hydrotreating reactor 52 and naphtha fraction hydrotreating reactor 54.
- Kerosene ⁇ Gas oil fraction hydrotreating reactor 52 is a liquid hydrocarbon of kerosene 'light oil fraction (approximately C to C ), 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 carbon atoms 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 hydrorefined liquid hydrocarbon-containing product is separated into a gas and a liquid by the gas-liquid separator 60, and the liquid hydrocarbon is separated into a naphtha stabilizer 72, which is a kind of rectification column.
- the gas component (including hydrogen gas) is transferred and reused for the hydrogenation reaction.
- 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)
- diesel oil (boiling point approx. 450-800 ° C).
- Gas oil is taken out from the lower force of the second fractionator 70, and kerosene is taken out from the central force.
- hydrocarbon gas having a carbon number of C or less is taken out from the top of the second rectifying column 70 and is supplied to the naphtha stabilizer 72.
- 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. Of naphtha (C to C). This allows the bottom of the naphtha stabilizer 72
- 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 sent to an external combustion facility (not shown), burned, and 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,
- FIG. 2 is a block diagram showing the heating means of the liquid fuel synthesizing system useful for this embodiment.
- the reformer 12 is configured to convert the natural gas supplied as a raw material and the carbon dioxide gas, and the carbon monoxide gas having a high temperature of about 1000 ° C.
- This is a device that generates synthesis gas mainly composed of hydrogen gas.
- the fuel gas introduced into the reformer 12 as described above. Must be burned with a burner. Due to the combustion of this fuel gas, the reformer 12 gives about 1000
- the high-temperature exhaust gas discharged from the reformer 12 is directly used as a heating medium, and the thermal efficiency of the entire system is improved as compared with the conventional system. I was able to.
- the liquid fuel The temperature of the mixture should be about 320 ° C.
- the temperature of the liquid fuel mixture taken out of the bubble-type reactor 30 is about 240 ° C, it is necessary to heat the mixture to about 80 ° C up to the above temperature.
- the first fractionator 40 is also supplied with a liquid hydrocarbon component of about 40 ° C. separated as a liquid by the gas-liquid separator 38. This liquid hydrocarbon component also needs to be heated to about 320 ° C.
- heating means such as heat exchange 100 is provided on the inlet side of the first rectifying tower 40, and the high-temperature exhaust gas discharged from the reformer 12 is used. It was decided to supply directly.
- heat exchange lOO a heat exchange capable of exchanging heat between gas and liquid can be used.
- heat exchanges include, for example, plate heat exchangers and finned tube heat exchanges. These heat exchanges are devices that transfer heat between gas and liquid via plates and tubes.
- the liquid fuel mixture produced in the bubble column reactor 30 passes through the heat exchanger 100 provided between the bubble column reactor 30 and the first rectification column 40, and then passes through the heat exchange 100.
- the liquid fuel mixture is supplied to the rectification column 40, but when it passes through the heat exchanger 100, it is heated to about 320 ° C by the high-temperature exhaust gas discharged from the reformer 12 to the heat exchanger 100. Heated.
- the exhaust gas from the reformer 12 that has passed through the heat exchanger 100 is discarded after being subjected to a predetermined treatment.
- the liquid fuel synthesis system uses a high-temperature exhaust gas directly to heat a mixture of a plurality of types of liquid fuels introduced into the first rectification column 40.
- the heat efficiency can be improved, and there is no need to newly install equipment for generating heat transfer oil.
- the mixture of a plurality of types of liquid fuel is fractionated into three types of liquid fuel by the first fractionator 40 based on the difference in boiling point, and purified.
- each of the three types of liquid fuel is used as hydrogenation reactors 50, 52, 54 in the product purification unit 7.
- To hydrogenate liquid fuels containing unsaturated bonds such as C C double bonds and C ⁇ C triple bonds to liquid fuels with only C-C single bonds.
- These three types of liquid fuel need to be heated to about 300 ° C when supplied to the hydrogenation reactors 50, 52 and 54, respectively.
- a heat exchange 102 is provided as a heating means between the first rectifying column 40 and the respective hydrogenation reactors 50, 52, 54, and this heat exchange 102 is modified.
- each hydrogenated liquid fuel is introduced into the second rectifying column 70, where it is separated and purified. Also in this case, each fuel needs to be heated to about 110 to 400 ° C. before being supplied to the second rectification column 70. Also in this case, as shown in FIG. 2, for example, a heat exchange 104 is provided as a heating means between the respective hydrogenation reactors 50, 52, 54 and the second rectification column 70, By supplying exhaust gas discharged from the reformer 12 to the heat exchanger 102, it is possible to efficiently heat the liquid fuel.
- the heat exchange ⁇ 102, 104 can be the same as the heat exchange ⁇ 100 described above.
- the exhaust gas from the reformer 12 that has passed through these heat exchangers 102 and 104 is discarded after being subjected to a predetermined treatment.
- FIG. 2 shows the case where the exhaust gas discharged from the reformer 12 is supplied to each of the heat exchanges 100, 102, 104 using a common exhaust gas supply path.
- the supply route is not limited to a powerful example, and for example, a dedicated route for each heat exchange 100, 102, 104 may be provided separately.
- the liquid fuel synthesis system 1 directly uses the exhaust gas discharged from the reformer 12 as a heating medium, so that the heat exchange 100, 10 2, 104 of the system 1 is provided.
- the size can be reduced and liquid fuel can be efficiently heated.
- the thermal efficiency of the entire liquid fuel synthesis system can be improved by about 5 to 10% compared to the conventional heating method using heat transfer oil.
- the entire liquid fuel synthesis system 1 can be downsized.
- the hydrocarbon raw material supplied to the liquid fuel synthesizing system 1 is not limited to a powerful example using natural gas, but other carbonization such as asphalt and residual oil, for example.
- a hydrogen raw material may be used.
- 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 relates to a reformer for reforming a hydrocarbon raw material to generate a synthesis gas mainly composed of a mono-acid carbon gas and a hydrogen gas; A reactor that synthesizes liquid hydrocarbons from carbon gas and hydrogen gas; a purification processing device that performs a predetermined purification treatment on the liquid hydrocarbons synthesized in the reactor; and a liquid that is introduced into the purification processing device And a heating means for heating hydrocarbons using the gas discharged from the reformer as a heat source.
- the thermal efficiency of the entire liquid fuel synthesis system can be improved.
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Abstract
Description
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JP2008508620A JP5107234B2 (ja) | 2006-03-30 | 2007-03-29 | 液体燃料合成システム |
AU2007232922A AU2007232922B2 (en) | 2006-03-30 | 2007-03-29 | Liquid fuel synthesis system |
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JP2006-095516 | 2006-03-30 | ||
JP2006095516 | 2006-03-30 |
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JP (1) | JP5107234B2 (ja) |
CN (1) | CN101432391A (ja) |
AU (1) | AU2007232922B2 (ja) |
MY (1) | MY149298A (ja) |
RU (1) | RU2418840C2 (ja) |
WO (1) | WO2007114274A1 (ja) |
ZA (1) | ZA200808242B (ja) |
Cited By (7)
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WO2009041545A1 (ja) * | 2007-09-28 | 2009-04-02 | Japan Oil, Gas And Metals National Corporation | 管式リフォーマーの有効熱利用方法 |
WO2009113714A1 (ja) * | 2008-03-14 | 2009-09-17 | 独立行政法人 石油天然ガス・金属鉱物資源機構 | 天然ガスから液状炭化水素を製造する方法 |
WO2009123247A1 (ja) | 2008-03-31 | 2009-10-08 | 独立行政法人 石油天然ガス・金属鉱物資源機構 | 天然ガスから液状炭化水素を製造する方法 |
JP2010084984A (ja) * | 2008-09-30 | 2010-04-15 | Japan Oil Gas & Metals National Corp | 液体燃料混合システム及び液体燃料合成システム、並びに液体燃料混合方法 |
US8303848B2 (en) | 2008-03-31 | 2012-11-06 | Japan Oil, Gas And Metals National Corporation | Operation method of synthesis gas reformer in GTL plant |
JP2013538772A (ja) * | 2010-07-09 | 2013-10-17 | エコ テクノル プロプライエタリー リミテッド | 膜技術の使用によるシンガスの生成 |
WO2023085960A1 (en) * | 2021-11-10 | 2023-05-19 | Qatar Foundation For Education, Science And Community Development | Retrofitting gas to liquids processing utilizing cargen technology |
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JP5804747B2 (ja) * | 2011-03-31 | 2015-11-04 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 合成ガス製造装置への金属混入抑制方法 |
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- 2007-03-29 AU AU2007232922A patent/AU2007232922B2/en not_active Ceased
- 2007-03-29 WO PCT/JP2007/056918 patent/WO2007114274A1/ja active Application Filing
- 2007-03-29 MY MYPI20083819 patent/MY149298A/en unknown
- 2007-03-29 ZA ZA200808242A patent/ZA200808242B/xx unknown
- 2007-03-29 CN CNA2007800156018A patent/CN101432391A/zh active Pending
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WO2009041545A1 (ja) * | 2007-09-28 | 2009-04-02 | Japan Oil, Gas And Metals National Corporation | 管式リフォーマーの有効熱利用方法 |
JP2009084392A (ja) * | 2007-09-28 | 2009-04-23 | Japan Oil Gas & Metals National Corp | 管式リフォーマーの有効熱利用方法 |
US8338495B2 (en) | 2007-09-28 | 2012-12-25 | Japan Oil, Gas And Metals National Corporation | Method for efficient use of heat from tubular reformer |
JP2009221036A (ja) * | 2008-03-14 | 2009-10-01 | Japan Oil Gas & Metals National Corp | 天然ガスからの液状炭化水素製造プロセスにおける合成ガスの製造方法 |
US8268898B2 (en) | 2008-03-14 | 2012-09-18 | Japan Oil, Gas And Metals National Corporation | Production method of liquid hydrocarbons from natural gas |
WO2009113714A1 (ja) * | 2008-03-14 | 2009-09-17 | 独立行政法人 石油天然ガス・金属鉱物資源機構 | 天然ガスから液状炭化水素を製造する方法 |
EA017725B1 (ru) * | 2008-03-14 | 2013-02-28 | Джэпэн Ойл, Гэз Энд Металз Нэшнл Корпорейшн | Способ получения жидких углеводородов из природного газа |
WO2009123247A1 (ja) | 2008-03-31 | 2009-10-08 | 独立行政法人 石油天然ガス・金属鉱物資源機構 | 天然ガスから液状炭化水素を製造する方法 |
JP2009242154A (ja) * | 2008-03-31 | 2009-10-22 | Japan Oil Gas & Metals National Corp | 天然ガスからの液状炭化水素製造プロセスにおける合成ガスの製造方法 |
US8303848B2 (en) | 2008-03-31 | 2012-11-06 | Japan Oil, Gas And Metals National Corporation | Operation method of synthesis gas reformer in GTL plant |
US8354456B2 (en) | 2008-03-31 | 2013-01-15 | Japan Oil, Gas And Metals National Corporation | Production method of liquid hydrocarbons from natural gas |
EA018431B1 (ru) * | 2008-03-31 | 2013-07-30 | Джэпэн Ойл, Гэз Энд Металз Нэшнл Корпорейшн | Способ получения жидких углеводородов из природного газа |
JP2010084984A (ja) * | 2008-09-30 | 2010-04-15 | Japan Oil Gas & Metals National Corp | 液体燃料混合システム及び液体燃料合成システム、並びに液体燃料混合方法 |
JP2013538772A (ja) * | 2010-07-09 | 2013-10-17 | エコ テクノル プロプライエタリー リミテッド | 膜技術の使用によるシンガスの生成 |
WO2023085960A1 (en) * | 2021-11-10 | 2023-05-19 | Qatar Foundation For Education, Science And Community Development | Retrofitting gas to liquids processing utilizing cargen technology |
Also Published As
Publication number | Publication date |
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RU2008141283A (ru) | 2010-04-27 |
RU2418840C2 (ru) | 2011-05-20 |
JPWO2007114274A1 (ja) | 2009-08-13 |
CN101432391A (zh) | 2009-05-13 |
AU2007232922B2 (en) | 2010-12-09 |
AU2007232922A1 (en) | 2007-10-11 |
JP5107234B2 (ja) | 2012-12-26 |
MY149298A (en) | 2013-08-30 |
ZA200808242B (en) | 2010-01-27 |
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