WO2010038392A1 - 気泡塔型反応器及び気泡塔型反応器の制御方法 - Google Patents
気泡塔型反応器及び気泡塔型反応器の制御方法 Download PDFInfo
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- WO2010038392A1 WO2010038392A1 PCT/JP2009/004876 JP2009004876W WO2010038392A1 WO 2010038392 A1 WO2010038392 A1 WO 2010038392A1 JP 2009004876 W JP2009004876 W JP 2009004876W WO 2010038392 A1 WO2010038392 A1 WO 2010038392A1
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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
- 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
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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
- B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
- B01J2208/00141—Coils
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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
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00203—Coils
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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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/0061—Controlling the level
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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 bubble column reactor for synthesizing hydrocarbons by a chemical reaction using a catalyst, and a control method for the bubble column reactor.
- a liquid fuel synthesis system using a bubble column reactor has been developed as one method for synthesizing liquid fuel from natural gas.
- natural gas is reformed to produce syngas mainly composed of hydrogen gas (H 2 ) and carbon monoxide gas (CO), and this syngas is used as a raw material gas to produce Fischer-Tropsch.
- FT synthesis reaction a synthesis reaction
- synthesis gas is blown from the bottom of the slurry containing the catalyst, and the synthesis gas rises in the slurry as bubbles. Then, while rising in the slurry, the synthesis gas dissolves in the liquid in the slurry and comes into contact with the catalyst particles to cause an FT synthesis reaction to generate gas, liquid hydrocarbons, and the like.
- synthesis gas that has not reacted in the bubble column reactor and gaseous hydrocarbons and the like flow out from the top of the bubble column reactor and are separated.
- the gaseous hydrocarbons blown into the bubble column reactor are liquefied by cooling in the downstream process to become liquid fuel.
- catalyst particles with a small particle diameter are used to improve the flow and mixing state of the slurry, the catalyst particles scatter upward from the liquid level of the slurry together with unreacted synthesis gas and gaseous hydrocarbons. Since it is discharged from the gas outlet through the top of the tower reactor and the gaseous hydrocarbons are liquefied with the catalyst particles mixed in, the product quality deteriorates and stays in equipment and piping. ⁇ There was a problem of blockage.
- the present invention has been made in view of such problems, and provides a bubble column reactor in which catalyst particles are prevented from being mixed into the flowing gaseous hydrocarbon.
- a first aspect of the bubble column reactor of the present invention includes a reactor main body that contains a slurry formed by suspending solid catalyst particles in a liquid, and is provided at the bottom of the reactor main body. Is a gas synthesized by a chemical reaction between the synthesis gas and the slurry, which is provided at the inlet of the synthesis gas mainly containing carbon monoxide gas and hydrogen gas and at the top of the reactor main body. A flow outlet for allowing hydrocarbons and unreacted synthesis gas to flow out, and a vertical distance between the liquid level of the slurry and the outlet is 1.4 m or more and 10 m or less.
- the synthesis gas that has flowed into the liquid slurry in the reactor body from the inlet provided in the reactor body rises as bubbles in the slurry by the catalyst particles contained in the slurry. It becomes a hydrocarbon through chemical reaction. Some of the catalyst particles may come out of the liquid level of the slurry along with the synthesized gaseous hydrocarbon and unreacted synthesis gas in the slurry, and flow out from the outlet provided at the top of the tower.
- the vertical distance between the slurry level and the outlet is set to be 1.4 m or more and 10 m or less.
- this distance By setting this distance to 1.4 m or more, most of the catalyst particles popping upward will fall back to the slurry contained in the reactor body before reaching the outlet due to the effect of gravity acting on itself. It becomes. Therefore, it is possible to suppress the catalyst particles from being mixed into the hydrocarbons flowing out from the outlet. In addition, by setting this distance to 10 m or less, it is possible to prevent the bubble column reactor from becoming excessive and increase in cost, and it becomes difficult to incorporate the bubble column reactor into, for example, a liquid fuel synthesis system. Can be prevented.
- the gas superficial velocity of the synthesis gas that flows into the reactor main body may be 0.04 m / sec or more and 0.3 m / sec or less.
- the gas superficial velocity by setting the gas superficial velocity to 0.3 m / sec or less, it is possible to suppress the velocity of hydrocarbons jumping upward from the liquid surface of the slurry and to prevent catalyst particles from being mixed into the hydrocarbons flowing out from the outlet. It can be surely suppressed.
- the gas superficial velocity to 0.04 m / sec or more, the catalyst particles settle down below the slurry, so that the catalyst stays in the reactor and the efficiency of the chemical reaction between the synthesis gas and the slurry. A decrease can be prevented.
- a second aspect of the bubble column reactor of the present invention is a reactor main body that contains a slurry in which solid catalyst particles are suspended in a liquid, and is provided at the bottom of the reactor main body.
- Carbonization gas which is a gas synthesized by a chemical reaction between the synthesis gas and the slurry, provided at the inlet of the synthesis gas mainly containing carbon monoxide gas and hydrogen gas, and at the top of the reactor main body. Captures the catalyst particles that are disposed between the outflow port through which hydrogen, unreacted synthesis gas, and the like flow out, and the liquid level of the slurry in the reactor main body and the outflow port, and pass through the inside of the reactor. And a demister section.
- the synthesis gas that has flowed into the slurry containing the catalyst in the reactor main body from the inlet provided in the reactor main body rises as bubbles in the slurry and is contained in the slurry.
- the chemical reaction results in hydrocarbons.
- Some of the catalyst particles may be accompanied by the synthesized gaseous hydrocarbon and unreacted synthesis gas in the slurry, jumping upward from the surface of the slurry, and flowing out from the outlet provided at the top.
- the demister portion is provided between the slurry and the outlet, the catalyst particles are captured by the demister portion when passing through the inside of the demister portion. Therefore, it is possible to suppress the catalyst particles from being mixed into the hydrocarbons flowing out from the outlet.
- the bubble column reactor may further include a heating unit that heats the demister unit.
- a heating unit that heats the demister unit.
- the heating means supplies a heating pipe at least partially disposed in the demister section and a heating medium for heating the heating pipe to the heating pipe.
- Heating medium distribution means since the heating pipe is disposed in the demister section, the demister section can be heated more reliably by flowing a heating medium in the heating pipe. Further, for example, the demister portion can be efficiently heated by circulating the water vapor generated in the process of performing heat exchange with the slurry generated by the FT synthesis reaction, which is an exothermic reaction, in the heating pipe.
- the gas superficial velocity of the synthesis gas that flows into the reactor main body may be 0.04 m / sec or more and 0.3 m / sec or less.
- the gas superficial velocity by setting the gas superficial velocity to 0.3 m / sec or less, it is possible to suppress the velocity of hydrocarbons jumping upward from the liquid surface of the slurry and to prevent catalyst particles from being mixed into the hydrocarbons flowing out from the outlet. It can be surely suppressed.
- the gas superficial velocity to 0.04 m / sec or more, the catalyst particles settle down below the slurry, so that the catalyst stays in the reactor and the efficiency of the chemical reaction between the synthesis gas and the slurry. A decrease can be prevented.
- the bubble column reactor control method of the present invention includes a reactor main body that contains a slurry in which solid catalyst particles are suspended in a liquid, a reactor main body that is provided in the reactor main body, and is provided in the slurry.
- a gas hydrocarbon which is provided at the inlet of a synthesis gas mainly composed of carbon oxide gas and hydrogen gas, and is provided at the top of the reactor main body, and is synthesized by a chemical reaction between the synthesis gas and the slurry;
- a bubble column reactor control method comprising an outlet for allowing unreacted synthesis gas or the like to flow out, wherein a vertical distance between the liquid level of the slurry and the outlet is less than 1.4 m. In this case, there is a step of reducing the amount of the slurry accommodated in the reactor main body.
- the synthesis gas that has flowed into the liquid slurry in the reactor main body from the inflow port rises as bubbles in the slurry and chemically reacts with the catalyst particles contained in the slurry to become hydrocarbons.
- Synthesized gaseous hydrocarbons and unreacted synthesis gas in the slurry jump out upward from the upper surface of the slurry together with the catalyst particles, but the vertical distance between the liquid level of the slurry and the outlet is less than 1.4 m In this case, the distance is controlled to be 1.4 m or more by reducing the amount of slurry contained in the reactor body, that is, by lowering the slurry liquid level to a predetermined position.
- the bubble column reactor and the control method of the bubble column reactor of the present invention it is possible to suppress the catalyst particles from being mixed into the gaseous hydrocarbon that flows out. Further, by heating the demister portion by the heating means, it is possible to prevent the slurry from solidifying and closing the demister portion and preventing gaseous hydrocarbons from flowing into the demister portion.
- FIG. 1 is a schematic diagram showing the overall configuration of a liquid fuel synthesis system in which the bubble column reactor according to the first embodiment of the present invention is used.
- FIG. 2 is a partial cross-sectional view showing the overall configuration of the bubble column reactor according to the first embodiment of the present invention.
- FIG. 3 is a schematic diagram showing the overall configuration of a liquid fuel synthesis system in which the bubble column reactor according to the second embodiment of the present invention is used.
- FIG. 4 is a partial cross-sectional view showing the overall configuration of the bubble column reactor according to the second embodiment of the present invention.
- FIG. 5 is a cross-sectional view taken along line AA in FIG.
- FIG. 1 is a schematic diagram showing the overall configuration of the liquid fuel synthesizing system 1
- FIG. 2 is a partial cross-sectional view showing the overall configuration of the bubble column reactor 30.
- the 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 5, and a product purification unit 7.
- the synthesis gas generation unit 3 reforms natural gas, which is a hydrocarbon raw material, to generate synthesis gas mainly composed of carbon monoxide gas and hydrogen gas.
- the FT synthesis unit 5 generates hydrocarbons from the generated synthesis gas by an 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 main pipe connecting the decarbonator 20 or the gas-liquid separator 18 and the bubble column reactor 30.
- the hydrogen separator 26 can be constituted by, for example, a hydrogen PSA (Pressure Swing Adsorption) apparatus 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 flow control device 33, a bubble column reactor 30, a gas-liquid separator 34, a separator 36, and a gas-liquid separator 38.
- the first fractionator 40 is mainly provided.
- the flow rate control device 33 adjusts the flow rate of the synthesis gas G flowing into the bubble column reactor 30 to be constant.
- the bubble column reactor 30 generates hydrocarbons by subjecting the synthesis gas produced in the synthesis gas production unit 3 to an FT synthesis reaction with catalyst particles contained in a slurry contained in the synthesis gas, and will be described later.
- a liquid level gauge 39 is provided.
- 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 slurry containing catalyst particles from the liquid hydrocarbon product.
- the gas-liquid separator 38 is connected to the bubble column reactor 30, cools unreacted synthesis gas and gaseous hydrocarbon product, and returns the unreacted synthesis gas to the bubble column reactor 30.
- the gaseous hydrocarbon product is cooled to a liquid.
- 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.
- a buffer device that has a tank for temporarily storing the slurry therein and that adjusts the amount of the slurry stored in the bubble column reactor 30 may be installed outside the bubble column reactor 30.
- the bubble column reactor 30 functions as an FT synthesis reactor for synthesizing hydrocarbons by an FT synthesis reaction between a slurry in which solid catalyst particles are suspended in a liquid and a synthesis gas.
- the bubble column reactor 30 includes a reactor main body 30a that stores the slurry S, an inlet 30b that is provided at the bottom of the reactor main body 30a and allows the synthesis gas G to flow into the slurry S, An outlet 30c provided at the top of the reactor main body 30a and allowing gaseous hydrocarbons and unreacted synthesis gas to flow out of the reactor main body 30a.
- the reactor main body 30a is formed of a cylindrical barrel portion 30e having a circular cross section, and a substantially hemispherical upper lid portion 30f and a lower lid portion 30g provided to be connected to both ends of the barrel portion 30e, respectively. Yes. In this way, the reactor main body 30a is arranged at the bottom of the lower lid 30g where the inlet 30b is located below and at the top of the upper lid 30f where the outlet 30c is located above. .
- the synthesis gas G from which carbon dioxide gas has been removed is supplied from the decarboxylation device 20 to the inflow port 30b, and the gas-liquid separator 38 described above is connected to the outflow port 30c.
- the level gauge 39 detects the position of the upper part of the slurry S accommodated in the bubble column reactor 30, that is, the liquid level of the slurry S.
- the synthesis gas G that the above-described flow rate control device 33 flows into the slurry S will be evaluated at a gas superficial velocity below.
- the body portion 30e has a circular cross section.
- the slurry is mainly composed of catalyst particles and liquid hydrocarbons produced by the FT synthesis reaction, and the liquid hydrocarbons contain a WAX fraction that becomes solid when the temperature falls below a certain temperature.
- the synthesis gas G which is a raw material gas, is supplied as bubbles from the inlet 30b of the bubble column reactor 30 and passes through the slurry S.
- the hydrogen gas and the carbon monoxide gas cause a synthesis reaction.
- 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, for example, as intermediate pressure steam by heat exchange between the slurry and water.
- 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, Gas-liquid separators 56, 58, 60, a second rectifying column 70, and a naphtha stabilizer 72 are provided.
- the WAX fraction hydrocracking reactor 50 is connected to the bottom 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 liquid hydrocarbons of the naphtha fraction supplied from the gas-liquid separator 60 and the second rectifying column 70, and discharges butane and lighter components than butane as flare gas, Ingredients of 5 or more are separated and recovered as product naphtha.
- 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 G from which the carbon dioxide gas has been separated in the decarboxylation device 20 passes through the flow rate control device 33 to the bottom of the reactor main body 30a of the bubble column reactor 30 as shown in FIG. It flows in from the provided inlet 30b and rises as bubbles in the liquid slurry S stored in the reactor main body 30a.
- the gas superficial velocity of the synthesis gas G is adjusted by the flow rate control device 33 so as to be a constant value of 0.04 m / sec or more and 0.3 m / sec or less.
- the gas superficial velocity is more preferably 0.1 m / sec or more and 0.2 m / sec or less.
- the carbon monoxide gas and the hydrogen gas contained in the synthesis gas G react with each other by the above-described FT synthesis reaction to generate gas or liquid hydrocarbon.
- the position of the liquid level of the slurry S is always detected by the liquid level gauge 39, the distance L in the vertical direction V between the liquid level of the slurry S and the outlet 30c is 1.4 m or more, and the separator 36. It is controlled so that the liquid level of the slurry S comes upward from the outlet 36a of the pipe toward the pipe. That is, when the distance L becomes smaller than 1.4 m, the flow rate of the slurry S flowing out to the separator 36 is temporarily increased, or the gas is stored in the reactor main body 30a by decreasing the gas superficial velocity. The amount of slurry S to be produced may be reduced. Further, the above-described buffer device may be installed outside the reactor main body 30a to temporarily supply a part of the slurry S.
- the position of the liquid level of the slurry S is temporarily decreased by temporarily reducing the flow rate of the slurry S flowing out to the separator 36 or increasing the gas superficial velocity. May be high.
- the above-described buffer device may be installed outside the reactor main body 30a and the slurry S stored therein may be supplied to the reactor main body 30a.
- the catalyst particles contained in the slurry S move upward from the liquid level of the slurry S together with the fine droplets generated by the bubbles composed of the unreacted synthesis gas G and the gas hydrocarbon synthesized in the slurry S. Jump out to the.
- the gas superficial velocity and the distance L of the synthesis gas G are adjusted as described above, most of the catalyst particles that jump out upward fall before reaching the outlet 30c due to the influence of gravity acting on them.
- the slurry returns to the slurry S accommodated in the reactor main body 30a.
- 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 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.
- Separator 36 separates the slurry containing catalyst particles into a liquid hydrocarbon product.
- the separated slurry is returned to the bubble column reactor 30, and the liquid hydrocarbon product is supplied to the first fractionator 40.
- unreacted synthesis gas, synthesized hydrocarbon gas, and the like are introduced into the gas-liquid separator 38 from the outlet 30 c provided at the top of the bubble column reactor 30.
- the gas-liquid separator 38 cools these gases, separates some of the condensed liquid hydrocarbons, and introduces them into the first fractionator 40.
- the unreacted synthesis gas (CO and H 2 ) is reintroduced into the bottom of the bubble column reactor 30 and reused for the FT synthesis reaction.
- exhaust gas mainly composed of hydrocarbon gas having a low carbon number (C 4 or less) that is not a product target is introduced into an external combustion facility (not shown) and burned into the atmosphere. Released.
- 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 less than about 150 ° C), kerosene / light oil fraction (boiling point about 150-350 ° C), WAX fraction (boiling point about 350 ° C) Separated and purified.
- 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 carbon atoms supplied from the bottom of the first fractionator 40 from the hydrogen separator 26.
- the hydrogen number is reduced by using 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.
- a C 10 or less hydrocarbon (boiling point is less than about 150 ° C.)
- kerosene (boiling point is about 150 to 250 ° C.)
- light oil (boiling point is about 250 to 350 ° C.)
- WAX fraction hydrocracking reactor 50 And purified into an undecomposed WAX fraction (boiling point greater than about 350 ° C.).
- Light oil is taken out from the lower part of the second fractionator 70, and kerosene is taken out from the center.
- a hydrocarbon gas having a carbon number of 10 or less is 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 FT synthesis reaction is caused by the catalyst particles contained in the slurry S to rise to gas or liquid hydrocarbons while rising in the slurry S as bubbles.
- a part of the catalyst particles may jump out from the liquid surface of the slurry S to the top of the tower together with the synthesis gas G that has not reacted in the slurry S or the synthesized gaseous hydrocarbon, etc.
- the control unit 33 adjusts the gas superficial velocity to be a constant value of 0.04 m / sec or more and 0.3 m / sec or less, and the liquid level gauge 39 adjusts the vertical direction between the liquid level of the slurry S and the outlet 30c.
- the distance L is adjusted to be 1.4 m or more and 10 m or less.
- the gas superficial velocity By setting the gas superficial velocity to 0.3 m / sec or less, the speed of the hydrocarbons jumping upward from the liquid surface of the slurry S is suppressed, and the catalyst particles are mixed into the hydrocarbons flowing out from the outlet 30c. It can be surely suppressed. Further, by setting the gas superficial velocity to 0.04 m / sec or more, catalyst particles settle down below the slurry S, and the catalyst stays in the reactor main body 30a and the synthesis gas G and the slurry S are mixed. It is possible to prevent a decrease in the efficiency of the chemical reaction.
- the vertical distance L between the liquid level of the slurry S and the outlet 30c is 1.4 m or more, most of the catalyst particles jumping upward are affected by gravity acting on the catalyst particles before reaching the outlet 30c. Falls into the slurry contained in the reactor body. Therefore, it is possible to suppress the catalyst particles from being mixed into the hydrocarbons flowing out from the outlet 30c.
- the distance L is set to 10 m or less, it is possible to suppress the bubble tower reactor 30 from becoming excessively large and increasing the cost, and the bubble tower reactor 30 is incorporated into the liquid fuel synthesis system 1. It can be prevented from becoming difficult.
- this distance L is 1.4 m or more and 10 m or less, and it is more preferable that it is 1.8 m or more and 7 m or less.
- this distance L is 1.4 m or more and 10 m or less, and it is more preferable that it is 1.8 m or more and 7 m or less.
- Table 1 shows the test results when the inner diameter of the body 30e of the reactor main body 30a is 250 mm. In Examples and Comparative Examples, the outflow amount of catalyst particles was measured when the bubble column reactor 30 was operated for a certain period of time.
- the outflow amount of the catalyst particles per hour is 0.0037 g / h. It was.
- the distance L shown in the comparative example is 0.7 m
- the outflow amount is 0.0875 g / h, which is 20 times or more that of the example.
- the catalyst particles are 1. in the vertical direction V above the position where the liquid surface of the slurry S is located on the inner wall surface of the body portion 30e. It was found to be attached to a range of up to 3 m.
- the body 30e has a circular cross section, but may have other shapes such as an oval, a quadrangle, or a hexagon.
- the distance L of the vertical direction V of the liquid level of the slurry S and the outflow port 30c becomes smaller than 1.4 m, the quantity of the slurry S accommodated in the reactor main body 30a is set. Decrease. However, instead of this, a warning sound may be sounded or the operation of the liquid fuel synthesis system 1 may be stopped.
- the demister part which captures the catalyst particle
- the demister portion is formed, for example, by knitting a thin metal line to form a large number of fine communication gaps.
- FIG. 3 is a schematic diagram showing the overall configuration of the liquid fuel synthesis system 1
- FIG. 4 is a partial cross-sectional view showing the overall configuration of the bubble column reactor.
- the 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 5, and a product purification unit 7.
- the synthesis gas generation unit 3 reforms natural gas, which is a hydrocarbon raw material, to generate synthesis gas mainly composed of carbon monoxide gas and hydrogen gas.
- the FT synthesis unit 5 generates hydrocarbons from the generated synthesis gas by an 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.
- the components of the synthesis gas generation unit 3 and the product purification unit 7 are the same as those in the first embodiment.
- the FT synthesis unit 5 having a configuration different from that of the first embodiment will be described below.
- the FT synthesis unit 5 includes, for example, a flow control device 33, 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 flow rate control device 33 adjusts the flow rate of the synthesis gas flowing into the bubble column reactor 30 to be constant.
- the bubble column reactor 30 generates hydrocarbons by subjecting the synthesis gas produced by the synthesis gas production unit 3 to an FT synthesis reaction.
- 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 particles extracted from the bubble column reactor 30 and the liquid hydrocarbon product.
- the gas-liquid separator 38 is connected to the top of the bubble column reactor 30, cools the unreacted synthesis gas and the gaseous hydrocarbon product, and converts the unreacted synthesis gas into the bubble column reactor 30. Return and cool the gaseous hydrocarbon product to a liquid.
- 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 functions as an FT synthesis reactor for synthesizing hydrocarbons by an FT synthesis reaction between a slurry in which solid catalyst particles are suspended in a liquid and a synthesis gas.
- the bubble column reactor 30 includes a reactor main body 30 a that stores the slurry S, and an inlet 30 b that is provided at one end of the reactor main body 30 a and flows the synthesis gas G into the slurry S. And an outlet 30c provided at the other end of the reactor main body 30a for allowing hydrocarbons to flow out of the reactor main body 30a, and disposed between the liquid level of the slurry S and the outlet 30c in the reactor main body 30a.
- a demister section 30d for capturing the catalyst particles passing through the interior of the apparatus.
- the inlet 30b is arranged at the bottom and the outlet 30c is arranged at the top of the tower. Then, for example, the synthesis gas G from which carbon dioxide gas has been removed is supplied from the decarboxylation device 20 to the inflow port 30b, and the gas-liquid separator 38 described above is connected to the outflow port 30c.
- the slurry S is mainly composed of catalyst particles and liquid hydrocarbons produced by the FT synthesis reaction, and the liquid hydrocarbons contain a WAX fraction that becomes solid when the temperature falls below a certain temperature.
- the demister portion 30d is formed by, for example, knitting a thin metal wire to form a large number of fine communication gaps.
- the synthesis gas G that is introduced into the slurry S by the flow rate control device 33 described above will be evaluated at a gas superficial velocity below.
- the demister section 30 d includes a heating pipe 31 a that is arranged to meander in the demister section 30 d, and a heating pipe 31 a for heating.
- a heating means 31 including a gas-liquid separator (heating medium circulation means) 34 for supplying water vapor (heating medium) for heating the pipe 31a is provided.
- the synthesis gas G which is a raw material gas, is supplied as bubbles from the inlet 30b of the bubble column reactor 30, passes through the slurry S, and is in a suspended state.
- the hydrogen gas and the carbon monoxide gas cause a synthesis reaction.
- 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 G from which the carbon dioxide gas has been separated in the decarboxylation device 20 passes through the flow rate control device 33 to the bottom of the reactor main body 30a of the bubble column reactor 30 as shown in FIG. It flows in from the provided inlet 30b and rises as bubbles in the liquid slurry S stored in the reactor main body 30a.
- the carbon monoxide gas and the hydrogen gas contained in the synthesis gas G react with each other by the above-described FT synthesis reaction to generate gas or liquid hydrocarbon.
- the flow rate control device 33 adjusts the gas superficial velocity of the synthesis gas G so as to be a constant value of 0.04 m / sec or more and 0.3 m / sec or less.
- the gas superficial velocity is more preferably 0.1 m / sec or more and 0.2 m / sec or less.
- the catalyst particles contained in the slurry S move upward from the liquid level of the slurry S together with the fine droplets generated by the bubbles composed of the unreacted synthesis gas G and the gas hydrocarbon synthesized in the slurry S. And pass through a fine gap formed in the demister portion 30d.
- the gas such as the synthesis gas G and the gaseous hydrocarbon passes through a fine gap, but the liquid droplets and the solid catalyst particles contained therein are captured by the demister section 30d, and the slurry S is formed into fine liquid droplets. May adhere to the demister portion 30d, and some of the heat may be lost and solidify.
- the demister portion 30d when the demister portion 30d is heated to a temperature higher than a certain temperature at which the solidified portion of the slurry S dissolves in the heating pipe 31a through which water vapor flows, the slurry S that has become relatively large droplets becomes the reactor body 30a. It returns to the liquid slurry S stored inside.
- water (BFW) is circulated in the heat transfer tube 32 of the bubble column reactor 30 to remove the reaction heat of the FT synthesis reaction, and the water heated by this heat exchange is vaporized. It becomes water vapor.
- the water vapor liquefied by the gas-liquid separator 34 is returned to the heat transfer pipe 32, and the water vapor is transferred to an external device such as the above-described heating pipe 31a as medium-pressure steam (for example, 1.0 to 2.5 MPaG). It may be supplied.
- medium-pressure steam for example, 1.0 to 2.5 MPaG
- the liquid hydrocarbon synthesized in the bubble column reactor 30 is taken out from the center of the bubble column reactor 30 and sent to the separator 36.
- the separator 36 separates the catalyst (solid content) in the extracted slurry into a liquid content containing the liquid hydrocarbon product. A part of the separated catalyst is returned to the bubble column reactor 30 as a slurry together with liquid hydrocarbons, and the liquid is supplied to the first rectifying column 40.
- unreacted synthesis gas, synthesized hydrocarbon gas, and the like are introduced into the gas-liquid separator 38 from the outlet 30 c provided at the top of the bubble column reactor 30.
- the gas-liquid separator 38 cools these gases, separates the hydrocarbon condensed as a part of the liquid, and introduces it into the first rectifying column 40.
- the unreacted synthesis gas CO and H 2
- exhaust gas mainly composed of hydrocarbon gas having a small number of carbon atoms (C 4 or less) that is not a product target is used as fuel gas for the reformer 12 or external combustion equipment (not shown). ) And then released to the atmosphere.
- the FT synthesis reaction is caused by the catalyst particles contained in the slurry S to rise into gas and liquid hydrocarbons while rising in the slurry S as bubbles.
- a part of the catalyst particles may jump out from the liquid surface of the slurry S to the top of the tower together with the synthesis gas G that has not reacted in the slurry S or the synthesized gaseous hydrocarbons.
- the demister portion 30d is provided between S and the outlet 30c, the catalyst particles are captured by the demister portion 30d when passing through the inside of the demister portion 30d. Therefore, it is possible to suppress the catalyst particles from being mixed into the hydrocarbons flowing out from the outlet 30c, and to improve the quality and yield of the hydrocarbon as a product.
- the demister section 30d is provided with the heating means 31 including the heating pipe 31a and the gas-liquid separator 34, a part of the slurry S adheres to the demister section 30d, and the hydrocarbons in the slurry are removed. Even when the contained WAX fraction is cooled and solidified, the solidified portion of the slurry S can be heated and melted by the heating means 31 and dropped back into the slurry S accommodated in the reactor main body 30a. . Therefore, it is possible to prevent the slurry S from being solidified and blocked in the demister section 30d and the gaseous hydrocarbons from not flowing. This makes it possible to improve the operating rate of the bubble column reactor 30.
- the demister section 30d can be heated more reliably by flowing heating steam through the heating pipe 31a. Then, the water vapor heated in the heat transfer tube 32 and separated in the gas-liquid separator 34 is circulated in the heating pipe 31a, so that the demister unit 30d can be made efficient without newly producing a heating medium using electric power or the like. Heating is possible.
- the gas superficial velocity is adjusted by the flow rate control device 33 so as to be a constant value of 0.04 m / sec or more and 0.3 m / sec or less.
- the speed of the hydrocarbons jumping upward from the liquid surface of the slurry S is suppressed, and the catalyst particles are mixed into the hydrocarbons flowing out from the outlet 30c. It can be surely suppressed.
- the gas superficial velocity is set to 0.04 m / sec or more, catalyst particles settle down below the slurry S, and the catalyst stays in the reactor main body 30a and the synthesis gas G and the slurry S are mixed. It is possible to prevent a decrease in the efficiency of the chemical reaction.
- Table 2 shows test results in the case where the central portion of the reactor main body 30a has a cylindrical shape with an inner diameter of 250 mm.
- the outflow amount of the catalyst particles when the distance between the liquid level of the slurry S and the outlet 30c in the vertical direction is constant at 0.7 m and the bubble column reactor 30 is operated for a certain period of time. Is measured.
- the demister portion 30d When the demister portion 30d is provided between the liquid level of the slurry S and the outlet 30c shown in the example, it was found that the outflow amount of the catalyst particles per hour was 0.00023 g / h. . On the other hand, when the demister part 30d shown in the comparative example is not provided, the outflow amount of the catalyst particles is 0.0875 g / h, which is several hundred times that when the demister part 30d is provided. When these measurement results and calculation results are converted into the catalyst concentration in the liquid hydrocarbon supplied from the bubble column reactor 30 to the first rectification column 40, the demister portion 30d is 0.03 wt. It was found that when ppm and the demister portion 30d are not provided, this corresponds to 50 wt.ppm.
- the second embodiment of the present invention has been described in detail with reference to the drawings, but the specific configuration is not limited to this embodiment, and includes changes in the configuration and the like without departing from the gist of the present invention. It is.
- the steam separated by the gas-liquid separator 34 is caused to flow through the heating pipe 31a, but the steam obtained by a separately provided steam generating means may be allowed to flow.
- the heating unit 31 including the heating pipe 31a and the gas-liquid separator 34 is used.
- a heater or the like may be used as the heating unit.
- the demister unit 30d may not include the heating unit 31.
- the demister portion 30d is a braided metal thin line.
- the demister section 30d may be configured such that, for example, a labyrinth-like or louver-like flow path through which gaseous hydrocarbons pass is formed by combining plates, and the catalyst particles jumping upward from the slurry S are captured.
- the bubble column reactor and the control method thereof of the present invention it is possible to prevent the catalyst particles from being mixed into the gaseous hydrocarbon flowing out from the bubble column reactor.
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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2008-254813および特願2008-254814に基づいて優先権を主張し、これらの内容をここに援用する。
しかし、スラリーの流動・混合状態を良くするために粒子径の小さな触媒粒子が用いられるので、スラリーの液面から未反応の合成ガスおよび気体の炭化水素等とともに触媒粒子が上方に飛散して気泡塔型反応器の塔頂部を経由してガス排出口から排出され、気体の炭化水素は中に触媒粒子が混入されたまま液化されてしまうため、製品の品質低下、機器・配管内での滞留・閉塞が発生する問題が生じていた。
また、この距離を10m以下に設定することで、気泡塔型反応器が過大となりコスト増となることを抑制することができ、且つ気泡塔型反応器を例えば液体燃料合成システムに組込み難くなるのを防止することができる。
この場合、ガス空塔速度を0.3m/sec以下に設定することにより、スラリーの液面から上方に飛び出す炭化水素の速度を抑え流出口から流出する炭化水素に触媒粒子が混入することをより確実に抑えることができる。
また、ガス空塔速度を0.04m/sec以上に設定することで、スラリーの下方に触媒粒子が沈降することによる、前記反応器内部における触媒の滞留および合成ガスとスラリーとの化学反応の効率低下を防止することができる。
この場合、例えば、デミスタ部に触媒を含むスラリーが付着して冷えて固まった場合であっても、加熱手段により付着したスラリーを加熱して溶かし、反応器本体内に収容された液体のスラリー内に落として戻すことができる。従って、デミスタ部にスラリーが固まることによりデミスタ部が閉塞すること、およびそれに伴って気体の炭化水素が流れなくなることを防止することができる。
この場合、加熱用配管はデミスタ部内に配置されているので、加熱用配管内に加熱媒体を流すことによりデミスタ部をより確実に加熱することができる。また、例えば、発熱反応であるFT合成反応で発熱したスラリーとの熱交換を行う工程で生じる水蒸気を加熱用配管内に流通させることで、デミスタ部を効率的に加熱することが可能となる。
この場合、ガス空塔速度を0.3m/sec以下に設定することにより、スラリーの液面から上方に飛び出す炭化水素の速度を抑え流出口から流出する炭化水素に触媒粒子が混入することをより確実に抑えることができる。
また、ガス空塔速度を0.04m/sec以上に設定することで、スラリーの下方に触媒粒子が沈降することによる、前記反応器内部における触媒の滞留および合成ガスとスラリーとの化学反応の効率低下を防止することができる。
従って、流出口から流出する炭化水素に触媒粒子が混入することを抑えることができる。
また、加熱手段によりデミスタ部を加熱することで、スラリーが固まってデミスタ部が閉塞することおよびデミスタ部に気体の炭化水素が流れなくなることを防止することができる。
以下、本発明に係る第一実施形態の気泡塔型反応器、及びこの気泡塔型反応器が用いられる液体燃料合成システムを、図1及び図2を参照しながら説明する。
図1は液体燃料合成システム1の全体構成を示す概略図、図2は気泡塔型反応器30の全体構成を示す一部断面図である。
脱硫反応器10は、水添脱硫装置等で構成されて原料である天然ガスから硫黄成分を除去する。改質器12は、脱硫反応器10から供給された天然ガスを改質して、一酸化炭素ガス(CO)と水素ガス(H2)とを主成分として含む合成ガスを生成する。排熱ボイラー14は、改質器12にて生成した合成ガスの排熱を回収して高圧スチームを発生する。気液分離器16は、排熱ボイラー14において合成ガスとの熱交換により加熱された水を気体(高圧スチーム)と液体とに分離する。気液分離器18は、排熱ボイラー14にて冷却された合成ガスから凝縮分を除去し気体分を脱炭酸装置20に供給する。脱炭酸装置20は、気液分離器18から供給された合成ガスから吸収液を用いて炭酸ガスを除去する吸収塔22と、当該炭酸ガスを含む吸収液から炭酸ガスを放散させて再生する再生塔24とを有する。水素分離装置26は、脱炭酸装置20により炭酸ガスが分離された合成ガスから、当該合成ガスに含まれる水素ガスの一部を分離する。ただし、上記脱炭酸装置20は場合によっては設けないこともある。
CH4+CO2→2CO+2H2 ・・・(2)
なお、気泡塔型反応器30の外部に、内部にスラリーを一時的に貯留するタンクを有し気泡塔型反応器30に収容されるスラリーの量を調節するバッファー装置を設置してもよい。
図2に示すように、気泡塔型反応器30は、スラリーSを貯留する反応器本体30aと、反応器本体30aの底部に設けられスラリーS内に合成ガスGを流入させる流入口30bと、反応器本体30aの塔頂部に設けられ反応器本体30aからガス状の炭化水素および未反応の合成ガス等を流出させる流出口30cと、を備えている。反応器本体30aは、断面が円形で筒状の胴部30eと、胴部30eの両端部にそれぞれ連接して設けられた略半球状の上蓋部30f及び下蓋部30gと、で形成されている。
このように、反応器本体30aは、流入口30bが下方に配置された下蓋部30gの底部に、流出口30cが上方に配置された上蓋部30fの塔頂部にくるように配置されている。流入口30bには、例えば、炭酸ガスを除去された合成ガスGが脱炭酸装置20から供給され、前述した気液分離器38は流出口30cに接続される。
ここで、前述の流量制御装置33がスラリーS内に流入させる合成ガスGを、以下では、ガス空塔速度で評価することにする。本実施形態では胴部30eの断面は円形となる。
なお、スラリーは主に触媒粒子とFT合成反応により生成する液体炭化水素とからなり、液体炭化水素には一定の温度以下になると固体になるWAX留分が含まれる。
反応器本体30a内では、上述したFT合成反応により、当該合成ガスGに含まれる一酸化炭素ガスと水素ガスとが反応して、気体や液体炭化水素が生成される。
さらに、この合成反応時には、気泡塔型反応器30の伝熱管32内に水を流通させることで、FT合成反応の反応熱を除去し、この熱交換により加熱された水が気化して水蒸気となる。この水蒸気は、気液分離器34で液化した水が伝熱管32に戻されて、気体分が中圧スチーム(例えば1.0~2.5MPaG)として外部装置に供給される。
また、スラリーSの液面と流出口30cとの鉛直方向の距離Lが1.4m以上あるので、上方に飛び出す大部分の触媒粒子は自身に作用する重力の影響により、流出口30cに達する前に落ちて反応器本体に収容されたスラリーに戻ることとなる。従って、流出口30cから流出する炭化水素に触媒粒子が混入することを抑えることができる。また、この距離Lを10m以下に設定することで、気泡塔型反応器30が過大となりコスト増となることを抑制することができ、且つ気泡塔型反応器30が液体燃料合成システム1に組込み難くなるのを防止することができる。
実施例と比較例は、気泡塔型反応器30をそれぞれ一定時間稼働した時の、触媒粒子の流出量を測定した。
また、実施例の試験を行った反応器本体30aを分解して目視で観察すると、触媒粒子は胴部30eの内壁面に、スラリーSの液面があった位置から鉛直方向V上方に1.3mまでの範囲に付着していることが分かった。
例えば、上記第一実施形態では胴部30eの断面を円形としたが、楕円形、4角形又は6角形等他の形状であってもよい。
また、上記第一実施形態では、スラリーSの液面と流出口30cとの鉛直方向Vの距離Lが1.4mより小さくなった場合には反応器本体30aに収容されるスラリーSの量を減少させる。しかし、これに代えて警告音を鳴らしたり、液体燃料合成システム1の運転を停止させたりしてもよい。
また、反応器本体30a内においてスラリーSと流出口30cとの間に、自身の内部を通過する触媒粒子を捕らえるデミスタ部を設けてもよい。デミスタ部は、例えば金属の細い線を編んで細かい連通する隙間を数多く形成したものである。
以下、本発明に係る第二実施形態の気泡塔型反応器、及びこの気泡塔型反応器が用いられる液体燃料合成システムを、図3から図5を参照しながら説明する。
図3は液体燃料合成システム1の全体構成を示す概略図、図4は気泡塔型反応器の全体構成を示す一部断面図である。
図4に示すように、気泡塔型反応器30は、スラリーSを貯留する反応器本体30aと、反応器本体30aの一方の端に設けられスラリーS内に合成ガスGを流入させる流入口30bと、反応器本体30aの他方の端に設けられ反応器本体30aから炭化水素を流出させる流出口30cと、反応器本体30a内においてスラリーSの液面と流出口30cとの間に配置され、自身の内部を通過する触媒粒子を捕らえるデミスタ部30dと、を備えている。反応器本体30aにおいては、流入口30bが底部に、流出口30cが塔頂部に配置される。そして、流入口30bには、例えば、炭酸ガスを除去された合成ガスGが脱炭酸装置20から供給され、前述した気液分離器38は流出口30cに接続される。
なお、スラリーSは主に触媒粒子とFT合成反応により生成する液体炭化水素とからなり、液体炭化水素には一定の温度以下になると固体になるWAX留分が含まれる。また、デミスタ部30dは、本実施形態では、例えば金属の細い線を編んで細かい連通する隙間を数多く形成したものが用いられている。
また、前述の流量制御装置33がスラリーS内に流入させる合成ガスGを、以下では、ガス空塔速度で評価することにする。
この気泡塔型反応器30では、原料ガスである合成ガスGは、気泡塔型反応器30の流入口30bから気泡となって供給されてスラリーS内を通過し、懸濁状態の中で上記化学反応式(3)に示すように水素ガスと一酸化炭素ガスとが合成反応を起こす。
また、加熱用配管31aの一部はデミスタ部30d内に配置されているので、加熱用配管31a内に加熱用の水蒸気を流すことによりデミスタ部30dをより確実に加熱することができる。そして、伝熱管32内で加熱され気液分離器34で分離された水蒸気を加熱用配管31a内に流通させることで、新たに電力等を用いて加熱媒体を製造することなくデミスタ部30dを効率的に加熱することが可能となる。
実施例と比較例は、スラリーSの液面と流出口30cとの鉛直方向の距離を0.7mと一定にし、気泡塔型反応器30をそれぞれ一定時間稼働した時の、触媒粒子の流出量を測定したものである。
例えば、上記第二実施形態では、加熱用配管31aには気液分離器34で分離された水蒸気を流したが、別に設けた水蒸気発生手段で得られた水蒸気を流してもよい。
また、上記第二実施形態では、加熱用配管31aと気液分離器34とを備えた加熱手段31を用いたが、加熱手段としてヒータ等を用いてもよい。
また、上記第二実施形態では、デミスタ部30dに加熱手段31は備えられていなくてもよい。付着するスラリーSの量に対してデミスタ部30dが充分大きい場合には、スラリーSを加熱して溶かしデミスタ部30dから落とす必要が無いからである。
また、上記第二実施形態では、デミスタ部30dは金属の細い線を編んだものとした。しかし、デミスタ部30dは、例えば板を組み合わせて気体の炭化水素が通るラビリンス状またはルーバー状の流路を形成し、スラリーSから上方に飛び出す触媒粒子を捕捉するように構成したものでもよい。
30a 反応器本体
30b 流入口
30c 流出口
30d デミスタ部
31 加熱手段
31a 加熱用配管
34 気液分離器(加熱媒体流通手段)
39 液面計
G 合成ガス
S スラリー
Claims (7)
- 液体中に固体の触媒粒子を懸濁させてなるスラリーを収容する反応器本体と、
該反応器本体の底部に設けられ、前記スラリー内に一酸化炭素ガス及び水素ガスを主成分とする合成ガスを流入させる流入口と、
前記反応器本体の塔頂部に設けられ、前記合成ガスと前記スラリーとの化学反応によって合成される気体である炭化水素、及び未反応の前記合成ガス等を流出させる流出口と、
を備え、
前記スラリーの液面と前記流出口との鉛直方向の距離が1.4m以上10m以下である気泡塔型反応器。 - 請求項1に記載の気泡塔型反応器であって、
前記反応器本体内へ流入させる前記合成ガスのガス空塔速度が、0.04m/sec以上0.3m/sec以下である気泡塔型反応器。 - 液体中に固体の触媒粒子を懸濁させてなるスラリーを収容する反応器本体と、
該反応器本体の底部に設けられ、前記スラリー内に一酸化炭素ガス及び水素ガスを主成分とする合成ガスを流入させる流入口と、
前記反応器本体の塔頂部に設けられ、前記合成ガスと前記スラリーとの化学反応によって合成される気体である炭化水素、及び未反応の前記合成ガス等を流出させる流出口と、
前記反応器本体内の前記スラリーの液面と前記流出口との間に配置され、自身の内部を通過する前記触媒粒子を捕らえるデミスタ部と、
を備える気泡塔型反応器。 - 請求項3に記載の気泡塔型反応器であって、
前記デミスタ部を加熱する加熱手段がさらに備えられている気泡塔型反応器。 - 請求項4に記載の気泡塔型反応器であって、
前記加熱手段は、
少なくとも一部が前記デミスタ部内に配置された加熱用配管と、
該加熱用配管に当該加熱用配管を加熱するための加熱媒体を供給する加熱媒体流通手段と、
を備える気泡塔型反応器。 - 請求項3から5のいずれかに記載の気泡塔型反応器であって、
前記反応器本体内へ流入させる前記合成ガスのガス空塔速度が、0.04m/sec以上0.3m/sec以下である気泡塔型反応器。 - 液体中に固体の触媒粒子を懸濁させてなるスラリーを収容する反応器本体と、
該反応器本体に設けられ、前記スラリー内に一酸化炭素ガス及び水素ガスを主成分とする合成ガスを流入させる流入口と、
前記反応器本体の塔頂部に設けられ、前記合成ガスと前記スラリーとの化学反応によって合成される気体の炭化水素、及び未反応の前記合成ガス等を流出させる流出口と、
を備える気泡塔型反応器の制御方法であって、
前記スラリーの液面と前記流出口との鉛直方向の距離が1.4m未満となった場合には、前記反応器本体に収容される前記スラリーの量を減少させる工程を有する気泡塔型反応器の制御方法。
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