WO2010038399A1 - 炭化水素合成反応装置及び炭化水素合成反応システム、並びに炭化水素合成方法 - Google Patents
炭化水素合成反応装置及び炭化水素合成反応システム、並びに炭化水素合成方法 Download PDFInfo
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- WO2010038399A1 WO2010038399A1 PCT/JP2009/004894 JP2009004894W WO2010038399A1 WO 2010038399 A1 WO2010038399 A1 WO 2010038399A1 JP 2009004894 W JP2009004894 W JP 2009004894W WO 2010038399 A1 WO2010038399 A1 WO 2010038399A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/002—Nozzle-type elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00026—Controlling or regulating the heat exchange system
- B01J2208/00035—Controlling or regulating the heat exchange system involving measured parameters
- B01J2208/0007—Pressure measurement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
- B01J2208/00274—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00548—Flow
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
Definitions
- the present invention relates to a hydrocarbon synthesis reaction apparatus for synthesizing a hydrocarbon compound by blowing a synthesis gas mainly composed of carbon monoxide gas and hydrogen gas into a slurry obtained by suspending solid catalyst particles in a liquid, and the same. And a hydrocarbon synthesis method.
- Patent Document 1 As a hydrocarbon synthesis reaction system for producing a liquid fuel using this GTL technology, as shown in Patent Document 1 below, an FT of synthesis gas and a slurry in which solid catalyst particles are suspended in a liquid are used.
- a configuration including a hydrocarbon synthesis reaction apparatus that synthesizes a hydrocarbon compound by a chemical reaction such as a synthesis reaction is known.
- Pressurized gas pressurized gas
- the pressurized gas for example, an inert gas such as nitrogen gas obtained by vaporizing nitrogen stored in a cooling facility or the like is preferably used from the viewpoint of suppressing catalyst deterioration.
- nitrogen gas is supplied from outside the synthesis system for synthesizing the hydrocarbon compound. Therefore, as the nitrogen gas is used, the manufacturing cost of the apparatus for the nitrogen gas increases. In addition, a large amount of energy is required to synthesize the hydrocarbon compound, which increases the running cost. That is, first, in order to use nitrogen gas, a storage facility such as a cooling / heating facility for storing the nitrogen gas is separately required. In the case of a large amount of nitrogen gas, a large-capacity storage facility is required, and it takes production costs when manufacturing this storage facility. In addition, a large amount of cooling and heating is required when synthesizing hydrocarbon compounds by operating the device. Energy is required and running cost increases.
- this nitrogen gas is mixed with a combustible gas or the like generated in the course of the FT synthesis reaction and incinerated as a flare gas.
- This process requires the use of an incinerator such as a flare stack, so if the gas to be incinerated is large, a large-capacity incinerator is required. Since a large amount of energy is required for incineration, the running cost increases as a result.
- the present invention has been made in view of the above-described circumstances, and the object thereof is to suppress the amount of pressurized gas supplied from outside the synthesis system for synthesizing the hydrocarbon compound, and to reduce the device manufacturing cost. It is another object of the present invention to provide a hydrocarbon synthesis reaction apparatus and a hydrocarbon synthesis method capable of synthesizing a hydrocarbon compound with energy saving and low cost, and a hydrocarbon synthesis reaction system including the hydrocarbon synthesis reaction apparatus.
- the hydrocarbon synthesis reaction apparatus synthesizes a hydrocarbon compound by a chemical reaction between a synthesis gas mainly composed of hydrogen and carbon monoxide and a slurry in which solid catalyst particles are suspended in a liquid.
- a hydrocarbon synthesis reaction apparatus comprising: a reactor in which the synthesis gas and the slurry are in contact; and a component that constitutes the hydrocarbon synthesis reaction apparatus by pressurizing an unreacted gas after being derived from the reactor. Unreacted gas supply means for supplying.
- the hydrocarbon synthesis method according to the present invention synthesizes a hydrocarbon compound by a chemical reaction between a synthesis gas mainly composed of hydrogen and carbon monoxide and a slurry in which solid catalyst particles are suspended in a liquid.
- a synthesis gas mainly composed of hydrogen and carbon monoxide
- a slurry in which solid catalyst particles are suspended in a liquid the unreacted gas is led out from the reactor and then pressurized and supplied to the components constituting the hydrocarbon synthesis reaction apparatus.
- the unreacted gas refers to an unreacted synthesis gas that has been introduced into the reactor but has not chemically reacted with the slurry, and a gas generated in the course of the chemical reaction in the reactor (for example, having 4 carbon atoms). Gas containing the following hydrocarbon gas as a main component).
- the hydrocarbon synthesis reaction apparatus and hydrocarbon synthesis method of the present invention after the unreacted gas led out from the reactor is pressurized by the unreacted gas supply means, the hydrocarbon synthesis reaction apparatus is configured. Since it is supplied to the component equipment, this unreacted gas can be used as a pressurized gas. This makes it possible to reduce the amount of pressurized gas supplied from outside the synthesis system for synthesizing the hydrocarbon compound, reduce the manufacturing cost of this hydrocarbon synthesis reactor, and save energy and reduce the cost of the hydrocarbon. Compounds can be synthesized.
- the component device may be a meter inserted in another component device in which the slurry is stored or distributed, and the unreacted gas supply means supplies the unreacted gas to the meter.
- the connecting portion between the instrument and the other component device may be sealed.
- connection portion between the instrument and other components can be sealed by the unreacted gas, accurate measurement by the instrument is possible.
- the instrument is not sealed, there is a possibility that measurement by the instrument cannot be performed accurately, for example, due to the catalyst particles in the slurry adhering to or blocking from the connecting portion.
- the component device may be a storage drum that stores at least one fluid of the slurry and the hydrocarbon compound and communicates with the other component device and delivers the fluid to the other component device.
- the unreacted gas supply means may supply the fluid from the storage drum to the other component device by supplying the unreacted gas to the storage drum.
- the fluid in the storage drum can be sent to other components by the unreacted gas.
- the storage drum may store the hydrocarbon compound
- the other component device may be a mixed fluid separation unit that separates a mixed fluid of the hydrocarbon compound and the catalyst particles, and the unreacted unit.
- the gas supply unit may supply the unreacted gas to the storage drum, thereby sending the hydrocarbon compound stored in the storage drum as a cleaning liquid for cleaning the mixed fluid separation unit.
- the mixed fluid separation means can be maintained in a clean state. For this reason, since the hydrocarbon compound and the catalyst particles can be separated smoothly, the hydrocarbon compound or the catalyst particles can be efficiently separated from the mixed fluid. If the mixed fluid separation means is not washed, for example, the catalyst particles in the slurry may adhere to the inside of the mixed fluid separation means, and separation may not be performed smoothly.
- the unreacted gas supply means includes a pressurization unit that pressurizes the unreacted gas, a first flow unit that extracts the unreacted gas in the reactor and supplies the unreacted gas to the pressurization unit, and the pressurization unit And a second circulation part that supplies the unreacted gas pressurized by the component device to the component device.
- the unreacted gas in the reactor supplied to the pressurizing part through the first circulation part can be pressurized by the pressurization part, and can be supplied to the component equipment through the second circulation part.
- the installation position of the pressurizing section can be set freely, and the degree of freedom in design can be improved.
- the hydrocarbon synthesis reaction system according to the present invention includes the hydrocarbon synthesis reaction apparatus according to the present invention, a hydrocarbon raw material reformed to generate the synthesis gas, and the synthesis gas supplied to the reactor.
- a synthesis gas generation unit and a product purification unit that purifies liquid fuel from the hydrocarbon compound are provided.
- the hydrocarbon synthesis reaction system according to the present invention includes a hydrocarbon synthesis reaction apparatus that can synthesize a hydrocarbon compound at a low cost while reducing the apparatus manufacturing cost. It is possible to synthesize liquid fuel at low energy and cost while reducing the cost of manufacturing the system.
- the hydrocarbon synthesis reaction apparatus and the hydrocarbon synthesis method according to the present invention the amount of pressurized gas supplied from outside the synthesis system for synthesizing the hydrocarbon compound is suppressed, the apparatus manufacturing cost is reduced, and the energy is saved.
- a hydrocarbon compound can be synthesized at a low cost.
- the liquid synthesis of the liquid fuel can be synthesized at low energy and cost while reducing the cost of manufacturing the hydrocarbon synthesis reaction system. be able to.
- FIG. 1 is a diagram showing an overall configuration of a liquid fuel synthesizing system according to an embodiment of the present invention.
- FIG. 2 is a schematic view showing the main part of the unreacted gas supply means in the FT synthesis unit shown in FIG.
- FIG. 3 is a schematic diagram showing a main part of the unreacted gas supply means, which is a modification of the FT synthesis unit according to the embodiment of the present invention.
- FIG. 1 is a diagram showing an overall configuration of a liquid fuel synthesis system 1 according to the present embodiment.
- a liquid fuel synthesis system 1 is a plant facility that executes a GTL process for converting a hydrocarbon raw material such as natural gas into liquid fuel.
- the liquid fuel synthesis system 1 includes a synthesis gas generation unit 3, an FT synthesis unit (hydrocarbon synthesis reaction apparatus) 5, and a product purification unit 7.
- the synthesis gas generation unit 3 reforms natural gas that is a hydrocarbon raw material to generate synthesis gas containing carbon monoxide gas and hydrogen gas.
- the FT synthesis unit 5 generates liquid hydrocarbons (hydrocarbon compounds) from the generated synthesis gas by a Fischer-Tropsch synthesis reaction (chemical 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 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 recovers the exhaust heat of the synthesis gas generated in the reformer 12 and generates high-pressure steam.
- the gas-liquid separator 16 separates water heated by heat exchange with the synthesis gas in the exhaust heat boiler 14 into a gas (high-pressure steam) and a 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 decarboxylation device 20.
- the decarboxylation device 20 uses an absorption liquid from the synthesis gas supplied from the gas-liquid separator 18 to remove the carbon dioxide gas, and regenerates the carbon dioxide gas from the absorption liquid containing the carbon dioxide gas for regeneration.
- Tower 24 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 provided depending on circumstances.
- the reformer 12 reforms natural gas using carbon dioxide and steam by, for example, the steam / carbon dioxide reforming method represented by the following chemical reaction formulas (1) and (2).
- a high-temperature synthesis gas mainly composed of carbon monoxide gas and hydrogen gas is generated.
- the reforming method in the reformer 12 is not limited to the steam / carbon dioxide reforming method described above, but includes, for example, a steam reforming method, a partial oxidation reforming method (POX) using oxygen, and a partial oxidation method.
- An autothermal reforming method (ATR), a carbon dioxide gas reforming method, or the like, which is a combination of the reforming method and the steam reforming method, can also be used.
- the hydrogen separator 26 is provided on a branch line branched from a pipe connecting the decarbonator 20 or the gas-liquid separator 18 and the bubble column reactor (reactor) 30.
- This hydrogen separator 26 can be constituted 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, alumina, silica gel, etc.) in a plurality of adsorption towers (not shown) arranged in parallel, and hydrogen is added to each adsorption tower.
- adsorbent zeolite adsorbent, activated carbon, alumina, silica gel, etc.
- 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, and for example, a hydrogen storage alloy adsorption method, a membrane separation method, or a combination thereof. There may be.
- the hydrogen storage alloy method is, for example, a hydrogen storage alloy having the property of adsorbing / releasing hydrogen by being cooled / heated (TiFe, LaNi 5 , TiFe 0.7 to 0.9 Mn 0.3 to 0.1 , Alternatively, TiMn 1.5 or the like) is used to separate hydrogen gas.
- a plurality of adsorption towers containing hydrogen storage alloys are provided, and in each of the adsorption towers, hydrogen adsorption by cooling the hydrogen storage alloys and hydrogen release by heating the hydrogen storage alloys are alternately repeated, so that the inside of the synthesis gas Of hydrogen 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. Further, the separation membrane has no driving device and has a wide stable operation range, so that there is an advantage that maintenance management is easy.
- the FT synthesis unit 5 includes, for example, a bubble column reactor 30, a gas-liquid separator 34, a separator (mixed fluid separation means) 36, a gas-liquid separator 38, and a first rectifying tower 40.
- the bubble column reactor 30 generates a liquid hydrocarbon by performing an FT synthesis reaction of the synthesis gas produced by the synthesis gas production unit 3, that is, carbon monoxide gas and hydrogen gas.
- the gas-liquid separator 34 separates water heated through circulation in the heat transfer tube 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 receives unreacted synthesis gas (CO and H 2 ) and gaseous hydrocarbon products, which are unreacted gases in the bubble column reactor 30. Cool down.
- the first rectifying column 40 distills the liquid hydrocarbons supplied from the bubble column reactor 30 through the separator 36 and the gas-liquid separator 38, and separates and purifies each fraction according to the boiling point.
- the bubble column reactor 30 is an example of a reactor that synthesizes synthesis gas into liquid hydrocarbons, and functions as a reactor for FT synthesis that synthesizes liquid hydrocarbons from synthesis gas by FT synthesis reaction.
- the bubble column reactor 30 is constituted by, for example, a bubble column type slurry bed type reactor in which a slurry composed 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 an 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 catalyst and medium oil. Then, as shown in the chemical reaction formula (3) below, the hydrogen gas and the carbon monoxide gas cause a synthesis reaction in the suspended state.
- the bubble column reactor 30 has a heat exchanger type in which a heat transfer tube 32 is disposed, and supplies, for example, water (BFW: Boiler Feed Water) as a refrigerant.
- BFW Boiler Feed Water
- the heat of reaction of the FT synthesis reaction can be recovered as medium pressure steam by heat exchange between the slurry and water.
- the unreacted synthesis gas and the gaseous hydrocarbon product, which are unreacted gases in the bubble column reactor 30, are heated and raised by the heat generated by the FT synthesis reaction, and are supplied to the gas-liquid separator 38.
- liquid hydrocarbon is used as the medium oil for the slurry.
- the product purification unit 7 includes, for example, a WAX fraction hydrocracking reactor 50, a kerosene / light oil fraction hydrocracking reactor 52, a naphtha fraction hydrocracking reactor 54, and gas-liquid separators 56, 58. , 60, a second rectifying tower 70, and a naphtha stabilizer 72.
- the WAX fraction hydrocracking reactor 50 is connected to the lower part of the first fractionator 40.
- the kerosene / light oil fraction hydrotreating reactor 52 is connected to the center of the first fractionator 40.
- the naphtha fraction hydrotreating reactor 54 is connected to the upper part of the first fractionator 40.
- the gas-liquid separators 56, 58 and 60 are provided corresponding to the hydrogenation reactors 50, 52 and 54, respectively.
- the second rectification 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 butane and components lighter than butane as flare gas, and has 5 carbon atoms. The above components are separated and recovered as naphtha of the product.
- the liquid fuel synthesis system 1 is supplied with natural gas (main component is CH 4 ) as a hydrocarbon feedstock from an external natural gas supply source (not shown) 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 containing carbon monoxide gas and hydrogen gas as main components).
- 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 sulfur contained in natural gas using the hydrogen gas, for example, with a ZnO catalyst.
- a ZnO catalyst By desulfurizing the natural gas in advance in this way, it is possible to prevent the activity of the catalyst used in the reformer 12 and the bubble column reactor 30 or the like from being reduced by sulfur.
- the natural gas (which may contain carbon dioxide) desulfurized in this way is generated in carbon dioxide (CO 2 ) gas supplied from a carbon dioxide supply source (not shown) and the exhaust heat boiler 14. After being mixed with water vapor, it is supplied to the reformer 12.
- the reformer 12 reforms the natural gas using carbon dioxide and steam by the steam / carbon dioxide reforming method described above, so that the reformer 12 has a high temperature mainly composed of carbon monoxide gas and hydrogen gas. Generate 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 that is endothermic by the combustion heat of the fuel gas in the burner. The reaction heat necessary for the gas reforming reaction is covered.
- the high-temperature synthesis gas (for example, 900 ° C., 2.0 MPaG) generated in the reformer 12 in this manner is supplied to the exhaust heat boiler 14 and is exchanged by heat exchange with the water flowing in the exhaust heat boiler 14. It is cooled (for example, 400 ° C.) and the exhaust heat is recovered. At this time, the water heated by the synthesis gas in the exhaust heat boiler 14 is supplied to the gas-liquid separator 16, and the gas component from the gas-liquid separator 16 is reformed as high-pressure steam (for example, 3.4 to 10.0 MPaG). The water in the liquid is returned to the exhaust heat boiler 14 after being supplied to the vessel 12 or other external device.
- high-temperature synthesis gas for example, 900 ° C., 2.0 MPaG
- the synthesis gas cooled in the exhaust heat boiler 14 is supplied to the absorption tower 22 or the bubble column reactor 30 of the decarboxylation device 20 after the condensed liquid is separated and removed in the gas-liquid separator 18.
- 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 by, for example, steam and stripped. To the reformer 12 and reused in 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 subjected to an FT synthesis reaction 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 an appropriate pressure (for example, about 3.6 MPaG).
- the hydrogen separator 26 separates the hydrogen gas contained in the synthesis gas by adsorption and desorption (hydrogen PSA) using the pressure difference as described above.
- the separated hydrogen is subjected to various hydrogen utilization reactions in which a predetermined reaction is performed using hydrogen in the liquid fuel synthesizing system 1 from a gas holder (not shown) or the like via a compressor (not shown). It supplies continuously to the apparatus (for example, desulfurization reactor 10, WAX fraction 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 in the decarboxylation device 20 flows from the bottom of the bubble column reactor 30 and rises in the catalyst slurry stored in the bubble column reactor 30. To do.
- the carbon monoxide and hydrogen gas contained in the synthesis gas react with each other by the above-described FT synthesis reaction 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. Become.
- the water liquefied by 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 slurry containing 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 taken slurry into a catalyst (solid content) and 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 gas is introduced into the gas-liquid separator 38 from the top of the bubble column reactor 30.
- the gas-liquid separator 38 cools the unreacted gas, separates some condensed liquid hydrocarbons, and introduces them into the first fractionator 40.
- a part of the gas separated by the gas-liquid separator 38 is reintroduced into the bottom of the bubble column reactor 30 and reused for the FT synthesis reaction. Further, the remaining part is used as a pressurized gas, which will be described later, and the remaining part is introduced into an external combustion facility (not shown) as flare gas, burned, and released into the atmosphere.
- the first rectifying column 40 heats the 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. Fractionation using the difference in boiling point, naphtha fraction (boiling point is lower than about 150 ° C), kerosene / light oil fraction (boiling point is about 150-350 ° C), WAX fraction (boiling point is about 350 ° C) And then purify.
- the first fractionator 40 WAX fraction of liquid hydrocarbons withdrawn from the bottom of the (mainly C 21 or more) are transferred to the WAX fraction hydrocracking reactor 50, the central portion of the first fractionator 40
- the liquid hydrocarbon (mainly C 11 to C 20 ) of the kerosene / light oil fraction taken out is transferred to the kerosene / light oil fraction hydrotreating reactor 52 and taken out from the upper part of the first rectifying tower 40.
- Liquid hydrocarbons (mainly C 5 -C 10 ) are transferred to the naphtha fraction hydrotreating reactor 54.
- the WAX fraction hydrocracking reactor 50 is supplied with liquid hydrocarbons (approximately C 21 or more) of the WAX fraction having a large number of carbons supplied from the lower part of the first fractionator 40 from the hydrogen separator 26.
- the hydrogen gas is hydrocracked using the hydrogen gas to reduce the carbon number to 20 or less.
- this hydrocracking reaction using a catalyst and heat, the C—C bond of a hydrocarbon having a large number of carbon atoms is cleaved to generate a low molecular weight hydrocarbon having a small number of carbon atoms.
- the product containing liquid hydrocarbon hydrocracked by the WAX fraction hydrocracking reactor 50 is separated into a gas and a liquid by a gas-liquid separator 56, and the liquid hydrocarbon is separated into a 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.
- the kerosene / light oil fraction hydrotreating reactor 52 is a liquid hydrocarbon (approximately C 11 to C 20 ) of the kerosene / light oil fraction having a medium carbon number supplied from the center of the first fractionator 40. Is hydrorefined using the hydrogen gas supplied from the hydrogen separator 26 through the WAX fraction hydrocracking reactor 50. In this hydrorefining reaction, in order to obtain mainly a side chain saturated hydrocarbon, the liquid hydrocarbon is isomerized, and hydrogen is added to the unsaturated bond of the liquid hydrocarbon to be saturated.
- the hydrorefined liquid hydrocarbon-containing product is separated into a gas and a liquid by the gas-liquid separator 58, and the liquid hydrocarbon is transferred to the second rectifying column 70, where the gas component (hydrogen Gas is reused) in the hydrogenation reaction.
- the naphtha fraction hydrotreating reactor 54 supplies liquid hydrocarbons (generally C 10 or less) of the naphtha fraction with a small number of carbons supplied from the upper part of the first rectification column 40 from the hydrogen separator 26 to the WAX fraction. Hydrorefining is performed using the hydrogen gas supplied through the hydrocracking reactor 50. As a result, 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 transferred to the naphtha stabilizer 72, where the gas component (hydrogen gas is removed). Is reused in the hydrogenation reaction.
- liquid hydrocarbons generally C 10 or less
- 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 to obtain a carbon number.
- Light oil is taken out from the lower part of the second fractionator 70, and kerosene is taken out from the center.
- hydrocarbons having a carbon number of 10 or less are taken out from the top of the second rectifying column 70 and supplied to the naphtha stabilizer 72.
- the naphtha stabilizer 72 distills hydrocarbons having a carbon number of 10 or less supplied from the naphtha fraction hydrotreating reactor 54 and the second rectifying tower 70 to obtain naphtha (C 5 as a product). ⁇ C 10 ) is separated and purified. Thereby, high-purity naphtha is taken out from the lower part of the naphtha stabilizer 72. Meanwhile, from the top of the naphtha stabilizer 72, the exhaust gas carbon number of target products composed mainly of hydrocarbons below predetermined number (C 4 or less) (flare gas) is discharged.
- the process of the liquid fuel synthesis system 1 has been described above.
- This GTL process makes natural gas easy and economical to clean liquid fuels such as high-purity naphtha (C 5 to C 10 ), kerosene (C 11 to C 15 ) and light oil (C 16 to C 20 ).
- liquid fuels such as high-purity naphtha (C 5 to C 10 ), kerosene (C 11 to C 15 ) and light oil (C 16 to C 20 ).
- the steam / carbon dioxide reforming method is adopted in the reformer 12
- carbon dioxide contained in natural gas as a raw material is effectively used, and the FT synthesis is performed.
- FIG. 2 for convenience of explanation, main components among the components of the liquid fuel synthesizing system 1 illustrated in FIG. 1 are illustrated, and some of the components are not illustrated.
- the FT synthesis unit 5 includes a pressure gauge (instrument) 80 inserted in the bubble column reactor 30 and an oil supply drum for backwashing that contains liquid hydrocarbons, in addition to the components described above. 82 (accommodating drum).
- the pressure gauge 80 measures the pressure (or differential pressure) in the bubble column reactor 30.
- the pressure gauge 80 has a nozzle portion 30a (one portion of the gauge connected to the other components) projecting from the outer surface of the bubble column reactor 30 toward the outside in the radial direction. ).
- the pressure gauge 80 measures the pressure of the fluid that reaches the pressure gauge 80 from the inside to the outside of the bubble column reactor 30 through the nozzle portion 30a.
- the nozzle part 30a is opened toward the inside of the bubble column reactor 30, and a plurality (four in the illustrated example) are provided at intervals in the height direction of the bubble column reactor 30.
- the pressure gauge 80 is inserted in each nozzle part 30a.
- the reverse cleaning oil supply drum 82 is in communication with the separator 36.
- a first flow path 84 that is a pipe through which liquid hydrocarbons flow from the separator 36 to the backwashing oil supply drum 82;
- a second flow path 86 which is a pipe for circulating liquid hydrocarbons from the backwashing oil supply drum 82 to the separator 36, is provided.
- the first flow path 84 and the second flow path 86 are provided with flow rate adjusting valves 84a and 86a for adjusting the flow rate of the liquid hydrocarbons in the flow paths 84 and 86, respectively.
- the separator 36 is provided with the filter part 36a which isolate
- the filter part 36a filters (filters) catalyst particles from a mixed fluid composed of liquid hydrocarbons and catalyst particles that pass through the filter part 36a.
- the filter unit 36 a is disposed in the separator 36 so that the mixed fluid sent from the bubble column reactor 30 passes through to the connection port between the separator 36 and the first flow path 84. .
- the mixed fluid delivered from the separator 36 is separated from the catalyst particles by the filter part 36a before reaching the connection port, and only liquid hydrocarbons are present in the connection port and the backwashing oil supply drum 82. Supplied.
- the direction in which the mixed fluid sent from the bubble column reactor 30 passes through the filter portion 36a is referred to as a normal flow path direction.
- the connection port between the second flow path 86 and the separator 36 is connected to the separator 36 by the liquid hydrocarbon supplied through the second flow path 86 from the backwashing oil supply drum 82 to the filter portion 36a. Is disposed so as to pass in the reverse flow direction that is the direction opposite to the normal flow direction.
- the liquid hydrocarbons supplied from the backwashing oil supply drum 82 can wash (backwash) the catalyst particles in the slurry accumulated on the surface of the filter portion 36a.
- the FT synthesis unit 5 is an unreacted gas supply means that pressurizes the unreacted gas in the bubble column reactor 30 after being led out from the bubble column reactor 30 and supplies the pressurized gas to components constituting the FT synthesis unit 5. It has.
- the FT synthesis unit 5 has unreacted unreacted gas supply means, first unreacted gas supply means 90A for supplying unreacted gas to each pressure gauge 80, and backwashing oil supply drum 82.
- Second unreacted gas supply means 90B for supplying gas is provided.
- the unreacted gas supply units 90A and 90B have the same schematic configuration, the configuration, operation, and effect of the first unreacted gas supply unit 90A will be described first.
- the first unreacted gas supply means 90A seals the pressure gauge 80 with the unreacted gas supplied to each pressure gauge 80.
- the first unreacted gas supply means 90A includes a pressurizing unit 92A that pressurizes the unreacted gas, and a first unit that extracts the unreacted gas in the bubble column reactor 30 and supplies the unreacted gas to the pressurizing unit 92A.
- 1 circulation part 94A and the 2nd circulation part 96A which supplies the unreacted gas pressurized by the pressurization part 92A to each pressure gauge 80 are provided.
- the pressurizing unit 92A can adjust the pressure applied to the unreacted gas, and is configured by, for example, an axial flow compressor.
- the first flow part 94A communicates the bubble column reactor 30 and the pressurizing part 92A.
- the gas-liquid separator 38 described above is provided in the first flow section 94A from the bubble column reactor 30 to the pressurizing section 92A.
- the first flow section 94A includes pipes that respectively connect the bubble column reactor 30 and the gas-liquid separator 38, and the gas-liquid separator 38 and the pressurizing section 92A. The reactor 30 and the pressurizing part 92A are communicated.
- the second flow part 96A communicates the pressurizing part 92A and each nozzle part 30a in which the pressure gauge 80 is inserted.
- the second flow part 96A is connected to the common pipe 98 communicating with the pressurizing part 92A, and branched from the common pipe 98 corresponding to each nozzle part 30a, and the common pipe 98 and the nozzle part 30a communicate with each other.
- a plurality of branch pipes 100 Each branch pipe 100 is provided such that unreacted gas flowing through the inside of the branch pipe 100 is supplied from the outside to the inside of the bubble column reactor 30 at the nozzle portion 30 a communicating with the branch pipe 100.
- each branch pipe 100 is provided with a flow rate adjusting valve 100a so that the flow rate of the unreacted gas flowing inside can be adjusted.
- the unreacted gas is supplied to the pressure gauge 80 located on the uppermost side in the height direction of the bubble column reactor 30 among the plurality of pressure gauges 80. Will be described as an example.
- the unreacted gas in the bubble column reactor 30 flows through the gas-liquid separator 38 of the first flow unit 94A as described above, and is then supplied to the pressurizing unit 92A.
- the pressurizing unit 92A pressurizes the supplied unreacted gas and sends it to the second flow unit 96A.
- the flow rate adjustment valve of the branch pipe 100 communicated with the nozzle part 30a in which the pressure gauge 80 located on the uppermost side is inserted.
- 100a is opened and the flow rate adjustment valve 100a of the other branch pipe 100 is closed.
- the unreacted gas flows only inside the branch pipe 100 communicating with the nozzle portion 30a located on the uppermost side.
- the branch pipe 100 is provided so that unreacted gas flowing through the inside of the branch pipe 100 is supplied from the outside to the inside of the bubble column reactor 30 at the nozzle portion 30 a communicating with the branch pipe 100. Therefore, no fluid flows from the inside to the outside of the bubble column reactor 30 into the nozzle portion 30a supplied with the unreacted gas, that is, the nozzle portion 30a is sealed with the unreacted gas.
- the unreacted gas led out from the bubble column reactor 30 is pressurized by the first unreacted gas supply means 90A. Thereafter, the unreacted gas can be used as a pressurized gas because it is supplied to the pressure gauge 80 which is a component device constituting the FT synthesis unit 5. For this reason, it becomes possible to suppress the usage amount of the pressurized gas supplied from outside the synthesis system for synthesizing the liquid hydrocarbon, thereby reducing the production cost of the FT synthesis unit 5 and reducing the carbonization of the liquid at low energy and cost. Hydrogen can be synthesized.
- the bubble column type is formed after the unreacted gas seals the pressure gauge 80. Even when it is mixed with the slurry and the liquid hydrocarbon in the reactor 30, the influence on the process of synthesizing the liquid hydrocarbon can be extremely reduced.
- the nozzle part 30a which is a connection part of the pressure gauge 80 and the bubble column reactor 30 can be sealed by unreacted gas, accurate measurement by the pressure gauge 80 is possible. If the nozzle portion 30a is not sealed, catalyst particles suspended in the slurry adhere to the nozzle portion 30a and block the opening of the nozzle portion 30a. There is a risk that it will not be performed accurately.
- an optimum environment for synthesizing liquid hydrocarbons in the bubble column reactor 30 can be constructed, so that excessive energy is not required, and energy saving and low power can be achieved. Liquid hydrocarbons can be synthesized at low cost.
- the first and second circulation portions 94A and 96A are provided, the installation position of the pressurizing portion 92A can be freely set, and the degree of freedom in design can be improved.
- the FT synthesizing unit 5 capable of synthesizing liquid hydrocarbons at low energy and at low cost is provided. It is possible to synthesize liquid fuel at low energy and low cost while reducing the device manufacturing cost of the liquid fuel synthesizing system 1.
- the second unreacted gas supply means 90B will be described.
- the second unreacted gas supply means 90B will be described only with respect to differences from the first unreacted gas supply means 90A.
- the reference numerals indicating the pressurizing part, the first circulation part, and the second circulation part of the second unreacted gas supply means 90B are the reference numerals (92A, 94A, 96A) of the respective components in the first unreacted gas supply means 90A.
- the last alphabet A is changed to alphabet B (92B, 94B, 96B).
- the second unreacted gas supply means 90B sends out the liquid hydrocarbons stored in the backwash oil supply drum 82 as a wash liquid for cleaning the separator 36 by the unreacted gas supplied to the backwash oil supply drum 82.
- the second flow part 96B of the second unreacted gas supply means 90B supplies the unreacted gas pressurized by the pressurizing part 92B to the backwashing oil supply drum 82.
- the second circulation part 96B is a pipe that connects the pressurization part 92B and the top of the oil supply drum 82 for backwashing, and the unreacted gas supplied from the second circulation part 96B is reversed. It is supplied to the gas phase part of the cleaning oil supply drum 82.
- the operation of supplying unreacted gas to the backwashing oil supply drum 82 in the second unreacted gas supply means 90B will be described.
- the unreacted gas in the bubble column reactor 30 flows through the inside of the first flow part 94B and is supplied to the pressurizing part 92B.
- the pressurizing unit 92B pressurizes the supplied unreacted gas and sends it to the second flow unit 96B.
- the flow path adjustment valve 84a of the first flow path 84 is closed in advance, and the flow path adjustment valve 86a of the second flow path 86 is opened.
- the unreacted gas supplied to the backwashing oil supply drum 82 pressurizes the liquid hydrocarbon stored in the drum 82 from the gas phase side, and the liquid hydrocarbon is supplied to the second flow path 86.
- the liquid hydrocarbon introduced through the second flow path 86 from the back washing oil supply drum 82 flows through the filter portion 36a of the separator 36 in the reverse flow direction as described above and back washed.
- the second unreacted gas supply means 90B sends out the liquid hydrocarbons stored in the reverse cleaning oil supply drum 82 as a cleaning liquid for cleaning the separator 36.
- the same operational effects as those provided with the first unreacted gas supply means 90A are obtained.
- the liquid hydrocarbon in the backwashing oil supply drum 82 can be sent to the separator 36 by the unreacted gas.
- liquid hydrocarbons can be removed by using unreacted gas. The amount of pressurized gas supplied from outside the synthesis system to be synthesized can be greatly suppressed.
- the separator 36 can be maintained in a clean state. For this reason, liquid hydrocarbons and catalyst particles can be separated smoothly, so that liquid hydrocarbons can be efficiently separated from the mixed fluid. In the case where the separator 36 is not washed, there is a possibility that the separation cannot be performed smoothly, for example, because catalyst particles in the slurry adhere to the filter portion 36a. Further, the separator 36 requires a large amount of cleaning liquid in order to constantly operate the separator 36 in the process of producing liquid fuel, and is supplied from outside the synthesis system that synthesizes liquid hydrocarbons by using unreacted gas. The amount of pressurized gas used can be greatly reduced.
- natural gas is used as the hydrocarbon raw material supplied to the liquid fuel synthesizing system 1.
- the present invention is not limited to this example, and other hydrocarbon raw materials such as asphalt and residual oil are used. May be.
- liquid hydrocarbon was synthesize
- this invention is not limited to this example.
- the synthesis reaction in the bubble column reactor 30 include oxo synthesis (hydroformylation reaction) “R—CH ⁇ CH 2 + CO + H 2 ⁇ R—CH 2 CH 2 CHO”, methanol synthesis “CO + 2H 2 ⁇ CH 3 OH”. And dimethyl ether (DME) synthesis “3CO + 3H 2 ⁇ CH 3 OCH 3 + CO 2 ”.
- the FT synthesis unit 5 includes both the first unreacted gas supply unit 90A and the second unreacted gas supply unit 90B, but may include only one of them.
- the FT synthesis unit 5 includes unreacted gas supply means 90A and 90B, but does not include means for supplying pressurized gas from outside the synthesis system for synthesizing liquid hydrocarbons.
- a configuration in which both are used may be used.
- the pressure gauge 80 and the oil supply drum 82 for backwashing were shown as a component apparatus to which unreacted gas supply means 90A, 90B is supplied, the kind and quantity provided Etc. are not limited to those shown in the above embodiment.
- the component device may not be the pressure gauge 80 but may be a gauge that measures a temperature other than the pressure.
- the instrument may be provided in addition to the bubble column reactor 30.
- the component device may be a storage drum that stores at least one of the slurry and the liquid hydrocarbon and communicates with the other component device and delivers the fluid to the other component device.
- Examples of the storage drum include a slurry concentration adjusting drum for adjusting the concentration of the slurry in the bubble column reactor 30 when the FT synthesis unit 5 is started or operated.
- the slurry concentration adjusting drum accommodates the slurry therein and communicates with the bubble column reactor 30.
- Examples of the slurry concentration adjusting drum include an FT slurry adjusting drum that adjusts the concentration when the FT synthesis unit 5 is started up, and an FT slurry makeup drum that adjusts the concentration during the operation of the FT synthesis unit 5.
- the plurality of unreacted gas supply means 90A and 90B are provided with different pressurizing units 92A and 92B, respectively.
- the first unreacted gas supply unit 112A includes a pressurizing unit 114, a first circulation unit 116, and a second circulation unit 118A.
- the first flow part 116 is shared by a part of the flow path of the unreacted gas that is separated by the gas-liquid separator 38 and re-entered into the bottom of the bubble column reactor 30.
- the pressure unit 114 is provided in a portion of the flow path that is located closer to the bubble column reactor 30 than the gas-liquid separator 38.
- the second circulation part 118A is branched from the flow path at a portion of the flow path that is located closer to the bubble column reactor 30 than the pressurizing part 114.
- the second unreacted gas supply means 112B has a pressurization part and a first circulation part common to the pressurization part 114 and the first circulation part 116 of the first unreacted gas supply means 112A, and further a second circulation. Part 118B.
- a part located on the pressurizing part 114 side is a common part common to the second circulation part 118A of the first unreacted gas supply means 112A, and from the end of this common part, respectively. Is branched off towards components that supply unreacted gas.
- the second flow part 118A of the first unreacted gas supply means 112A is provided with a flow rate adjusting valve 118Aa on the pressure gauge 80 side from the end, and the second flow of the second unreacted gas supply means 112B.
- the part 118B is provided with a flow rate adjusting valve 118Ba on the back cleaning oil supply drum 82 side from the end.
- the unreacted gas supply means 112A and 112B are provided with a common pressurization section 114, the unreacted gas supply means 112A and 112B have different pressurization sections. Compared with the case where the apparatus is provided, the device manufacturing cost can be further reduced.
- the hydrocarbon synthesis reaction apparatus and the hydrocarbon synthesis method of the present invention, and the hydrocarbon synthesis reaction system equipped with this hydrocarbon synthesis reaction apparatus, can reduce the amount of pressurized gas supplied from outside the synthesis system for synthesizing a hydrocarbon compound. Therefore, it is possible to synthesize a hydrocarbon compound with low energy and low cost while reducing the cost of manufacturing the apparatus.
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Abstract
Description
本願は、2008年09月30日に日本出願された特願2008-253214に基づいて優先権を主張し、その内容をここに援用する。
ところで従来、この炭化水素合成反応装置を構成する構成機器には、他の構成機器との接続部分からスラリー等が逆流することを抑制する、或いは内部に収容している流体を他の構成機器に送出する等のために、必要に応じて加圧ガス(加圧された気体)が供給される。なお、この加圧ガスとしては、触媒劣化抑制の観点から、例えば冷熱設備等に保管された窒素を気化した窒素ガス等の不活性ガスが好適に利用される。
即ち、まず窒素ガスを使用するためには、この窒素ガスを保管するための冷熱設備等の保管設備が別途必要となる。窒素ガスが大量の場合には大容量の保管設備が必要であり、この保管設備製作時に製作費用がかかる上、装置を稼動させて炭化水素化合物を合成するときに冷却加熱等のための多量のエネルギーが必要となりランニングコストが増加する。
更に、この窒素ガスは、FT合成反応の過程で生じる可燃性ガス等と混合されてフレアガスとして焼却処理されてしまう。この処理には、フレアスタック等の焼却設備を利用する必要があるため、焼却処理されるガスが大量の場合には大容量の焼却設備が必要となり、この焼却設備製作時に製作費用がかかる上、焼却処理のために多量のエネルギーが必要となるため、結果としてランニングコストが増加する。
本発明に係る炭化水素合成反応装置は、水素及び一酸化炭素を主成分とする合成ガスと、液体中に固体の触媒粒子を懸濁させてなるスラリーとの化学反応によって炭化水素化合物を合成する炭化水素合成反応装置であって、前記合成ガスと前記スラリーとが接触する反応器と、未反応ガスを前記反応器から導出した後に加圧して、この炭化水素合成反応装置を構成する構成機器に供給する未反応ガス供給手段とを備える。
本発明に係る炭化水素合成反応装置及び炭化水素合成方法によれば、未反応ガス供給手段によって反応器内から導出された未反応ガスが加圧された後、この炭化水素合成反応装置を構成する構成機器に供給されるので、この未反応ガスを加圧ガスとして利用することができる。このため、炭化水素化合物を合成する合成系外から供給される加圧ガスの使用量を抑制することが可能となり、この炭化水素合成反応装置の製作費用を低減すると共に省エネルギー且つ低コストで炭化水素化合物を合成することができる。
なお、計器をシールしない場合には、例えば前記接続部分にスラリー内の触媒粒子が固着・閉塞する等して、計器による計測が正確に行えない恐れがある。
なお、混合流体分離手段を洗浄しない場合には、例えばその内部でスラリー内の触媒粒子が固着する等して、分離が円滑に行えない恐れがある。
また、本発明に係る炭化水素合成反応システムによれば、この炭化水素合成反応装置を備えるので、炭化水素合成反応システムの装置製作費用を低減した上で、省エネルギー且つ低コストで液体燃料を合成することができる。
CH4+CO2→2CO+2H2 ・・・(2)
気泡塔型反応器30は、上記合成ガス生成ユニット3で生成された合成ガス、即ち、一酸化炭素ガスと水素ガスとをFT合成反応させて液体炭化水素を生成する。気液分離器34は、気泡塔型反応器30内に配設された伝熱管32内を流通して加熱された水を、水蒸気(中圧スチーム)と液体とに分離する。分離器36は、気泡塔型反応器30の中央部に接続され、触媒と液体炭化水素生成物を分離処理する。気液分離器38は、気泡塔型反応器30の上部に接続され、気泡塔型反応器30内の未反応ガスである未反応の合成ガス(COとH2)及び気体炭化水素生成物を冷却処理する。第1精留塔40は、気泡塔型反応器30から分離器36、気液分離器38を介して供給された液体炭化水素を蒸留し、沸点に応じて各留分に分離・精製する。
本実施形態では、FT合成ユニット5は、前述した構成機器に加えて、気泡塔型反応器30に挿設された圧力計器(計器)80と、液体炭化水素を収容する逆洗浄用オイル供給ドラム82(収容ドラム)と、を備えている。
圧力計器80は、気泡塔型反応器30内の圧力(又は、差圧)を計測する。図示の例では、圧力計器80は、その一端が、気泡塔型反応器30の外表面にその径方向の外側に向けて突設されたノズル部30a(計器と他の構成機器との接続部分)に挿設されている。
圧力計器80は、この圧力計器80に、ノズル部30a内を気泡塔型反応器30の内側から外側に向けて流通して達した流体の圧力を計測する。なお、ノズル部30aは、気泡塔型反応器30内に向けて開口すると共に気泡塔型反応器30においてその高さ方向に沿って互いに間隔をあけて複数(図示の例では4つ)設けられており、各ノズル部30aに圧力計器80が挿設されている。
また、第2流路86と分離器36との接続口は、この分離器36に逆洗浄用オイル供給ドラム82から第2流路86を流通して供給された液体炭化水素が、フィルタ部36aを正流路方向の反対方向である逆流路方向に向かって通過するように配設されている。これにより、逆洗浄用オイル供給ドラム82から供給された液体炭化水素は、フィルタ部36aの表面に蓄積したスラリー内の触媒粒子等を洗浄(逆洗浄)できるようになっている。
FT合成ユニット5は、気泡塔型反応器30内の未反応ガスを気泡塔型反応器30から導出した後に加圧して、このFT合成ユニット5を構成する構成機器に供給する未反応ガス供給手段を備えている。図示の例では、FT合成ユニット5には、未反応ガス供給手段として、各圧力計器80に未反応ガスを供給する第1未反応ガス供給手段90Aと、逆洗浄用オイル供給ドラム82に未反応ガスを供給する第2未反応ガス供給手段90Bと、が設けられている。
ここで、各未反応ガス供給手段90A、90Bは、概略構成が同一なので、以下ではまず、第1未反応ガス供給手段90Aについて構成、動作及び効果について説明する。
第1未反応ガス供給手段90Aは、各圧力計器80に供給する未反応ガスによって圧力計器80をシールするものである。図示の例では、第1未反応ガス供給手段90Aは、未反応ガスを加圧する加圧部92Aと、気泡塔型反応器30内の未反応ガスを導出して加圧部92Aに供給する第1流通部94Aと、加圧部92Aによって加圧された未反応ガスを各圧力計器80に供給する第2流通部96Aと、を備えている。
第1流通部94Aは、気泡塔型反応器30と加圧部92Aとを連通している。図示の例では、第1流通部94Aには、気泡塔型反応器30から加圧部92Aに至るまでの間に前述した気液分離器38が設けられている。そして、第1流通部94Aは、気泡塔型反応器30及び気液分離器38と、気液分離器38及び加圧部92Aと、をそれぞれ連通する配管を備えており、これらにより気泡塔型反応器30と加圧部92Aとを連通している。
まず、気泡塔型反応器30内の未反応ガスは、前述したように第1流通部94Aの気液分離器38の内部を流通し、その後加圧部92Aに供給される。
ここで、分岐配管100は、その内部を流通した未反応ガスが、この分岐配管100に連通するノズル部30aにおいて、気泡塔型反応器30の外側から内側に向けて供給されるように設けられているので、未反応ガスが供給されたノズル部30aには気泡塔型反応器30の内側から外側に向けて流体が流入されず、つまりノズル部30aが未反応ガスによりシールされる。
また、第1未反応ガス供給手段90Aによって構成機器に供給される未反応ガスは、液体炭化水素を合成する過程で発生したものなので、この未反応ガスが圧力計器80をシールした後に気泡塔型反応器30内でスラリー及び液体炭化水素と混合される場合であっても、液体炭化水素を合成する過程に与える影響を極めて小さくすることができる。
また、より正確な計測が可能となることで、気泡塔型反応器30内において液体炭化水素を合成する最適な環境を構築することができるので、過剰なエネルギーを必要とせず、より省エネルギー且つ低コストで液体炭化水素を合成することができる。
また、第1、第2流通部94A、96Aを有しているので、加圧部92Aの設置位置を自在とすることができ、設計自由度を向上させることができる。
次に、第2未反応ガス供給手段90Bについて説明する。なお、この第2未反応ガス供給手段90Bについては、第1未反応ガス供給手段90Aと異なる点についてのみ説明する。また、第2未反応ガス供給手段90Bの加圧部、第1流通部、第2流通部を示す符号は、第1未反応ガス供給手段90Aにおける各構成の符号(92A、94A、96A)の末尾のアルファベットAをアルファベットBに変更したもの(92B、94B、96B)とする。
第2未反応ガス供給手段90Bの第2流通部96Bは、加圧部92Bによって加圧された未反応ガスを逆洗浄用オイル供給ドラム82に供給するものである。図示の例では、第2流通部96Bは、加圧部92Bと逆洗浄用オイル供給ドラム82の塔頂とを連通する配管であり、第2流通部96Bから供給される未反応ガスは、逆洗浄用オイル供給ドラム82の気相部に供給される。
まず、第1未反応ガス供給手段90Aと同様に、気泡塔型反応器30内の未反応ガスが第1流通部94Bの内部を流通して、加圧部92Bに供給される。
次に、加圧部92Bは、供給された未反応ガスを加圧して第2流通部96Bに送出する。この際予め、第1流路84の流路調整バルブ84aを閉状態にし、第2流路86の流路調整バルブ86aを開状態にしておく。これにより、逆洗浄用オイル供給ドラム82に供給された未反応ガスが、このドラム82の内部に収容された液体炭化水素を気相部側から加圧し、この液体炭化水素を第2流路86を通して分離器36に送出させる。
そして、逆洗浄用オイル供給ドラム82から第2流路86を流通して導入された液体炭化水素は、前述したように分離器36のフィルタ部36aを逆流路方向に向かって流通して逆洗浄する。つまり、第2未反応ガス供給手段90Bは、逆洗浄用オイル供給ドラム82に収容された液体炭化水素を分離器36を洗浄する洗浄液として送出する。
また、未反応ガスによって逆洗浄用オイル供給ドラム82内の液体炭化水素を分離器36に送出することができる。なお、逆洗浄用オイル供給ドラム82のような流体を収容する収容ドラムから流体を送出するためには大量の加圧ガスが必要であるため、未反応ガスを利用することで、液体炭化水素を合成する合成系外から供給される加圧ガスの使用量を大きく抑制することができる。
なお、分離器36を洗浄しない場合には、例えばフィルタ部36aにスラリー内の触媒粒子が固着する等して、分離が円滑に行えない恐れがある。また、分離器36は、液体燃料を製造する過程で分離器36を常時稼動するために大量の洗浄液が必要であり、未反応ガスを利用することで液体炭化水素を合成する合成系外から供給される加圧ガスの使用量を大きく抑制することができる。
また、上記実施形態では、FT合成ユニット5は、未反応ガス供給手段90A、90Bを備えている一方で、液体炭化水素を合成する合成系外から加圧ガスを供給する手段を備えていない構成としているが、両者を併用する構成としても構わない。
例えば、前記構成機器は、圧力計器80ではなく、圧力以外の温度等を計測する計器でも良い。また、計器は、気泡塔型反応器30以外に設けていても構わない。
また、前記構成機器は、スラリー及び液体炭化水素のうち少なくともいずれか一方の流体を収容すると共に他の構成機器と連通され、他の構成機器に前記流体を送出する収容ドラムであっても良い。この収容ドラムの例としては、FT合成ユニット5の起動時若しくは運転時に、気泡塔型反応器30内のスラリーの濃度を調整するためのスラリー濃度調整ドラム等が挙げられる。スラリー濃度調整ドラムは、内部にスラリーを収容すると共に、気泡塔型反応器30と連通されるものである。このスラリー濃度調整ドラムとしては、例えばFT合成ユニット5のスタートアップ時に濃度を調整するFTスラリー調整ドラムや、FT合成ユニット5の運転中に濃度を調整するFTスラリーメイクアップドラム等が挙げられる。
図3に示すFT合成ユニット110では、第1未反応ガス供給手段112Aは、加圧部114と、第1流通部116と、第2流通部118Aと、を備えている。図示の例では、第1流通部116は、気液分離器38で分離されて気泡塔型反応器30の底部に再投入される未反応ガスの流路の一部分と共通となっており、加圧部114は、前記流路において気液分離器38より気泡塔型反応器30側に位置する部分に設けられている。また、第2流通部118Aは、前記流路において加圧部114より気泡塔型反応器30側に位置する部分で前記流路から分岐されている。
図3に示すFT合成ユニット110によれば、複数の未反応ガス供給手段112A、112Bが共通の加圧部114を備えているので、各未反応ガス供給手段112A、112Bに互いに異なる加圧部を備える場合に比べて、より一層装置製作費用を低減することができる。
3 合成ガス生成ユニット
5、110 FT合成ユニット(炭化水素合成反応装置)
7 製品精製ユニット
30 気泡塔型反応器(反応器、他の構成機器)
30a ノズル部(他の構成機器との接続部分)
36 分離器(混合流体分離手段)
80 圧力計器(計器)
82 逆洗浄用オイル供給ドラム(収容ドラム)
90A、112A 第1未反応ガス供給手段(未反応ガス供給手段)
90B、112B 第2未反応ガス供給手段(未反応ガス供給手段)
92A、92B、114 加圧部
94A、94B、116 第1流通部
96A、96B、118A、118B 第2流通部
Claims (7)
- 水素及び一酸化炭素を主成分とする合成ガスと、液体中に固体の触媒粒子を懸濁させてなるスラリーとの化学反応によって炭化水素化合物を合成する炭化水素合成反応装置であって、
前記合成ガスと前記スラリーとが接触する反応器と、
未反応ガスを前記反応器から導出した後に加圧して、この炭化水素合成反応装置を構成する構成機器に供給する未反応ガス供給手段と、
を備える炭化水素合成反応装置。 - 請求項1に記載の炭化水素合成反応装置であって、
前記構成機器は、前記スラリーが収容される若しくは流通する他の構成機器に挿設された計器であり、
前記未反応ガス供給手段が、前記未反応ガスを前記計器に供給することによって、前記計器と前記他の構成機器との接続部分をシールする炭化水素合成反応装置。 - 請求項1に記載の炭化水素合成反応装置であって、
前記構成機器は、前記スラリー及び前記炭化水素化合物のうち少なくともいずれか一方の流体を収容すると共に他の構成機器と連通され、前記他の構成機器に前記流体を送出する収容ドラムであり、
前記未反応ガス供給手段が、前記未反応ガスを前記収容ドラムに供給することによって、前記収容ドラムから前記他の構成機器に前記流体を送出する炭化水素合成反応装置。 - 請求項3に記載の炭化水素合成反応装置であって、
前記収容ドラムは、前記炭化水素化合物を収容し、
前記他の構成機器は、前記炭化水素化合物と前記触媒粒子との混合流体をそれぞれに分離する混合流体分離手段であり、
前記未反応ガス供給手段が、前記未反応ガスを前記収容ドラムに供給することによって、前記収容ドラムに収容された前記炭化水素化合物を、前記混合流体分離手段を洗浄する洗浄液として送出する炭化水素合成反応装置。 - 請求項1から4のいずれか1項に記載の炭化水素合成反応装置であって、
前記未反応ガス供給手段は、
前記未反応ガスを加圧する加圧部と、
前記反応器内の前記未反応ガスを導出して前記加圧部に供給する第1流通部と、
前記加圧部によって加圧された前記未反応ガスを前記構成機器に供給する第2流通部と、
を有する炭化水素合成反応装置。 - 請求項1から5のいずれか1項に記載の炭化水素合成反応装置と、
炭化水素原料を改質して前記合成ガスを生成し、該合成ガスを前記炭化水素合成反応装置の前記反応器に供給する合成ガス生成ユニットと、
前記炭化水素化合物から液体燃料を精製する製品精製ユニットと、
を備えている炭化水素合成反応システム。 - 水素及び一酸化炭素を主成分とする合成ガスと、液体中に固体の触媒粒子を懸濁させてなるスラリーとの化学反応によって炭化水素化合物を合成する炭化水素合成方法であって、
未反応ガスを前記反応器から導出した後に加圧して、この炭化水素合成反応装置を構成する構成機器に供給する炭化水素合成方法。
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JP2010531726A JP5364716B2 (ja) | 2008-09-30 | 2009-09-25 | 炭化水素合成反応装置及び炭化水素合成反応システム、並びに炭化水素合成方法 |
CA2738126A CA2738126C (en) | 2008-09-30 | 2009-09-25 | Hydrocarbon synthesis reaction apparatus, hydrocarbon synthesis reaction system, and hydrocarbon synthesizing method |
US12/998,187 US8569386B2 (en) | 2008-09-30 | 2009-09-25 | Hydrocarbon synthesis reaction apparatus, hydrocarbon synthesis reaction system, and hydrocarbon synthesizing method |
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CN2009801380382A CN102165038B (zh) | 2008-09-30 | 2009-09-25 | 烃合成反应装置、烃合成反应系统以及烃合成方法 |
AU2009299346A AU2009299346B2 (en) | 2008-09-30 | 2009-09-25 | Hydrocarbon synthesis reaction apparatus, hydrocarbon synthesis reaction system, and hydrocarbon synthesizing method |
BRPI0919428-2A BRPI0919428B1 (pt) | 2008-09-30 | 2009-09-25 | Aparelho de reação de síntese de hidrocarboneto, sistema de reação de síntese de hidrocarboneto e método de síntese de hidrocarboneto |
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EA201170498A1 (ru) | 2011-12-30 |
AU2009299346A1 (en) | 2010-04-08 |
EP2351815A1 (en) | 2011-08-03 |
US20110196048A1 (en) | 2011-08-11 |
EA020378B1 (ru) | 2014-10-30 |
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