WO2007069317A1 - 気泡塔型フィッシャー・トロプシュ合成スラリー床反応システム - Google Patents
気泡塔型フィッシャー・トロプシュ合成スラリー床反応システム Download PDFInfo
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- WO2007069317A1 WO2007069317A1 PCT/JP2005/022975 JP2005022975W WO2007069317A1 WO 2007069317 A1 WO2007069317 A1 WO 2007069317A1 JP 2005022975 W JP2005022975 W JP 2005022975W WO 2007069317 A1 WO2007069317 A1 WO 2007069317A1
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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
- B01J8/224—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 the particles being subject to a circulatory movement
- B01J8/228—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 the particles being subject to a circulatory movement externally, i.e. the particles leaving the vessel and subsequently re-entering it
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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
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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
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/007—Separating solid material from the gas/liquid stream by sedimentation
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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
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/085—Feeding reactive fluids
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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
- B01J8/1818—Feeding of the fluidising gas
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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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- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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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
- B01J2208/00123—Fingers
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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
- B01J2208/00539—Pressure
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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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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
- C10G2300/805—Water
Definitions
- the present invention relates to a bubble column type slurry bed reaction system for converting a synthesis gas comprising hydrogen and carbon monoxide to a liquid hydrocarbon product in the presence of a suspended Fischer's Tropsch synthesis catalyst, and Relates to the device.
- Fischer-Tropsch synthesis reaction is a reaction of hydrogen and a certain synthesis gas such as carbon monoxide in the presence of a solid catalyst, resulting in a relatively wide molecular weight distribution! Paraffin and olefin hydrocarbons. To give a mixture of In particular, liquid hydrocarbons are attracting attention as clean automobile fuel.
- the Fischer-Tropsch synthesis reaction is characterized by being extremely exothermic.
- the calorific value per kg of carbon monoxide is about 40 McAl.
- the slurry bed reaction system is a fluidized reaction system in which three phases of solid, liquid, and gas that introduce synthesis gas into a suspension of a liquid medium and catalyst particles coexist, and the temperature control is uniform. This is a significant advantage over other fixed bed systems.
- Filtration separation in the main body for example, see Patent Documents 3 and 4
- filtration separation in a separate container connected to the reactor main body by a conduit for example, see Patent Document 5
- high-mouth cyclone separation for example, Patent Documents 6
- Patent Document 1 European Patent No. 0,450,860
- Patent Document 2 U.S. Patent No. 6,348,510
- Patent Document 3 US Patent No. 6,462,098
- Patent Document 4 U.S. Patent No. 5,844,006
- Patent Document 5 US Patent No. 5,770,629
- Patent Document 6 US Pat. No. 6,121,333
- a combination of a coil cooling pipe and a downcomer pipe is disclosed in order to further achieve temperature uniformity. Equal heat removal in the vertical axis direction is achieved, further complicating the system configuration.
- Patent Document 6 in the case of separation of the cyclone and id-mouth cyclone, the slurry force also uses external power such as a pump when separating and deriving the catalyst and the liquid hydrocarbon product.
- external power such as a pump
- the catalyst particles became dusty, leading to performance degradation and the production efficiency of FT synthetic oil decreased, there was a problem.
- the running cost required for external power is large and it is difficult to reduce the cost.
- Patent Document 6 is a slurry bed reactor suitable for efficiently removing reaction heat, but its cooling mechanism is not disclosed.
- the present invention synthesizes liquid hydrocarbons by means of a Bech Fischer's Tropsch synthesis reaction to solve such problems, and separates the catalyst and the liquid hydrocarbon product from the slurry consisting of a gas-liquid solid three-phase. It is an object of the present invention to provide a bubble column type slurry bed reaction system and apparatus in which the operation system to be derived is simple and the deterioration due to pulverization of catalyst particles can be suppressed.
- the present invention also provides a liquid hydrocarbon by a Fischer-Tropsch synthesis reaction in a state of maintaining a uniform temperature distribution in the vertical axis direction and the radial direction separately from or in addition to the above object. It is an object of the present invention to provide a bubble column type slurry bed reaction system and apparatus capable of synthesizing.
- the present inventors have provided a slurry external circulation method between a bubble column type slurry bed reactor (Fitzer-Tropsch synthesis reactor) and a separation vessel, and a bubble column type slurry single bed.
- a bubble column type slurry bed reactor Frazier-Tropsch synthesis reactor
- a separation vessel Separates the separation vessel
- a bubble column type slurry single bed We have intensively studied the cooling method of the reactor, and used the bubble column type slurry bed reaction system of the present invention. I came to get.
- the first aspect of the present invention is as follows.
- Fischer-Tropsch synthesis reaction in which a synthesis gas comprising hydrogen and carbon monoxide and catalyst particles is in contact with each other to produce a liquid hydrocarbon.
- bubbles that generate liquid hydrocarbons, gaseous hydrocarbons, and water through contact between the synthesis gas continuously supplied from the bottom of the reactor and catalyst particles suspended in the liquid component
- a slurry in which a slurry slurry of the liquid product and catalyst particles produced in the tower-type slurry bed Fischer's Tropsch synthesis reaction process and the G 0 Fischer's Tropsch synthesis reaction process is suspended between the reactor and the lower part of the separation vessel.
- the process moves to the lower part of the separation vessel by the installed downward inclined transfer pipe to separate the catalyst particles and the liquid product, and (iii) the gas product generated in the Fisher's top push synthesis reaction process
- the second aspect of the present invention is (2) a plurality of bayonet type cooling pipes installed vertically from the top of the bubble column type slurry bed reactor and comprising a cooling medium introduction inner pipe and a heat exchange outer pipe.
- the bubble column type slurry according to the first aspect is characterized by having a process for controlling the temperature in the reactor and enabling uniform heat removal in the radial direction in the reactor. This is a floor reaction system.
- the pressure of the reactor is 1 to 4 MPaG, and the gas superficial velocity is 0.05 to 0.2 mZ second.
- the catalyst particles introduced from the reactor into the lower part of the separation vessel 99% or more of the catalyst particles having a particle diameter of 20 m or more are circulated to the reactor.
- the bubble column type slurry bed reactor is connected to the reactor by a downward inclined transfer pipe, and the catalyst is connected to the reactor.
- the catalyst In the separation container of the present invention having a slurry outlet pipe (slurry circulation path) for circulating the concentrated slurry, the catalyst concentrated slurry disposed in the slurry outlet pipe (slurry circulation path) between the separation vessel and the reactor.
- the reaction tube cooling process of the present invention in which the temperature in the reactor is controlled by a plurality of bayonet type cooling tubes, water (for example, boiler water) is introduced into the inner tube to control the temperature in the reactor.
- water for example, boiler water
- the outlet power of the cooling pipe is characterized by obtaining steam at a temperature of 200 ⁇ 270 ° C and pressure of 2 ⁇ 6MPaG!
- the third aspect of the present invention is (3) liquid hydrocarbon, gas carbonization by bringing the suspended catalyst particles into contact with the synthesis gas that continuously supplies the gas disperser force installed at the bottom of the reactor.
- a Fischer 'Tropsch synthesis reactor equipped with a bubble column type slurry bed Fischer-Tropsch synthesis reactor that produces hydrogen and water
- the bottom of the reactor is used without external power for circulation.
- the liquid hydrocarbon product and the gaseous hydrocarbon product produced without the use of external power for separation which is operated by the driving force (airlift) of the synthesis gas introduced and lifted in the slurry bed reactor.
- This is a Fischer-Tropsch synthesis reactor characterized by comprising a circulation separation mechanism for separating and deriving water.
- the circulation separation mechanism includes: (i) a slurry in which the reactor, the liquid product produced in the reactor and the catalyst particles are suspended, are placed between the reactor and the lower part of the separation vessel.
- a separation vessel that is moved by a downward inclined transfer pipe connected between them to separate the catalyst particles and the liquid product, and (ii 0 the gas product produced in the reactor is installed above the downward inclined transfer pipe (Iv) a liquid product outlet for discharging a liquid product from the separation container; and (V) the separation container.
- a circulation path section for leading out the slurry in which the catalyst particles are concentrated from the bottom of the reactor and circulating it to the bottom of the reactor.
- Reaction pressure force of ⁇ 4MPaG, gas superficial velocity adjusted to the range of 0.05-0.2mZ seconds It is characterized by being able to.
- 99% or more of the catalyst particles having a particle diameter of 20 ⁇ m or more introduced into the lower part of the separation container can be circulated to the reactor.
- the fourth aspect of the present invention provides (4) a heat removal mechanism that controls the temperature in the reactor and enables uniform heat removal in the radial direction and the vertical axis direction in the reactor.
- a Fischer-Tropsch synthesis reaction apparatus according to the third aspect, characterized by comprising.
- the heat removal mechanism includes a plurality of cooling pipes that are vertically installed from the upper part of the reactor, and that includes a cooling medium introduction inner pipe and a heat exchange outer pipe.
- Pipe inlet force Water is introduced, flows through the inner pipe, flows through the outer pipe in the opposite direction, and flows out the outer pipe outlet force at the top of the reactor so that the reaction temperature in the reactor is 210-280 °. It is characterized by being able to adjust to C, and to adjust to obtain steam at a temperature of 200 to 270 ° C and a pressure of 2 to 6 MPaG from the outlet of the outer tube.
- the temperature in the reactor can be controlled by adjusting the fluctuation range of the reaction temperature in the reactor within a range of ⁇ 2 ° C.
- the driving of the synthesis gas that is introduced from the bottom of the reactor and rises in the slurry bed reactor without using external power for circulation Because it can be operated by force (air lift) and the generated liquid hydrocarbon product and gaseous hydrocarbon product can be separated and led without using external power for separation V, It is possible to suppress performance degradation that is difficult to cause catalyst particle dust (physical destruction). In addition, because it is difficult for powdery soot to occur, it is not limited to only specific catalysts that emphasize strength, and any available Fischer 'Tropsch synthesis catalyst can be arbitrarily selected and used. Can do. It is also possible to grasp the circulation state In addition to its simple internal structure, it can quickly respond to abnormalities. Furthermore, maintenance during troubles is easy. Further, it is not necessary to use a filter or external power, the device configuration and operation system can be simplified, and the running cost can be reduced.
- the temperature in the reactor is controlled by a plurality of cooling pipes comprising a cooling medium introduction inner pipe and a heat exchange outer pipe, In addition to the vertical axis direction, it has a process that enables uniform heat removal in the radial direction. As a result, it is also possible to adjust the fluctuation range of the reaction temperature in the reactor within the range of ⁇ 2 ° C (see Table 1 in the examples).
- a reactor can be provided. Furthermore, by gravity separation (sedimentation separation) of the catalyst particles using the difference in density between the catalyst particles and the liquid hydrocarbon product, the catalyst particles are introduced from the upper part of the bubble column type slurry bed reactor to the lower part of the separation vessel. Of the catalyst particles, 99% or more of the catalyst particles having a particle diameter of 20 m or more can be circulated to the reactor.
- FIG. 1 is a schematic configuration diagram showing an example of a bubble column type Fischer-Tropsch synthesis slurry bed reactor used in the present invention.
- FIG. 1 is a schematic configuration diagram showing an example of a bubble column type Fischer Tropsch (hereinafter referred to as FT) synthetic slurry bed reaction apparatus used in the present invention.
- FT Fischer Tropsch
- a synthesis gas having a hydrogen Z-acid-carbon molar ratio suitable for FT synthesis is installed at the bottom of a bubble column type slurry bed FT synthesis reactor 11.
- the gas is continuously supplied from the gas disperser 21 to be bubbled and dispersed into the reactor 11.
- the hydrogen Z-carbon oxide molar ratio of the synthesis gas suitable for FT synthesis is preferably 1.9 to 2.1. If the hydrogen Z-acid-carbon molar ratio is within the above range, almost the entire amount is subjected to the FT synthesis reaction of the above general formula (1) and converted to the target liquid hydrocarbon product (FT synthetic oil). Efficiency (FT synthetic oil production efficiency) can be increased.
- the composition of the synthesis gas may contain hydrogen gas and carbon monoxide gas, as well as hydrocarbon gas such as methane gas and nitrogen as shown in Table 1 of the examples. Furthermore, depending on the raw material of the synthesis gas and production conditions, carbon dioxide may be included, and depending on the operating conditions, it may be removed as necessary.
- the flow rate of the synthesis gas necessary for operating the apparatus is that of the synthesis gas introduced from the bottom of the reactor and rising in the slurry bed reactor without using external power for circulation.
- the flow rate is not particularly limited as long as it can be operated by driving force (air lift).
- driving force air lift
- the gas superficial velocity conditions described later are satisfied, and the reaction efficiency by contact with the catalyst particles is excellent while the synthesis gas rises in the reactor according to the size and internal shape of the reactor. It is desirable to determine appropriately.
- the bubble size of the mixed gas supplied with the gas distributor force is not particularly limited as long as a desired synthesis gas driving force (air lift) is obtained for the same reason. It is desirable that it is appropriately determined so as to satisfy the superficial velocity conditions.
- the gas distributor 21 is not particularly limited as long as it can be supplied uniformly to the cross section of the reactor and a conventionally known one can be used as appropriate.
- the dispersed synthesis gas comes into contact with the catalyst particles suspended in the medium liquid while rising in the reactor 11 to generate a reaction product containing liquid hydrocarbons.
- the operating conditions of the reactor are pressure l ⁇ 4MPaG, temperature 210 ⁇ 280 ° C, gas superficial velocity 0. 05-0. It is about 20mZ seconds.
- FT synthetic oil liquid hydrocarbon product
- the catalyst particles are not particularly limited as long as they do not affect the intended use of the liquid hydrocarbon product and further the FT synthesis reaction. It is sufficient that the slurry can be suspended to form a slurry. This initially charged medium oil is replaced with liquid hydrocarbon products (FT synthetic oil) that are sequentially produced in the course of continuous operation.
- a conventionally known Fischer-Tropsch synthesis catalyst can be appropriately used as long as it is particulate and can be suspended in a medium solution to form a slurry. Details will be described later.
- the reaction pressure is less than IMPaG
- the catalytic activity may be insufficient, and if it exceeds 4 MPaG, it may increase the cost of the reactor. There is sex. If the reaction temperature is less than 210 ° C, the catalytic activity may be insufficient.If it exceeds 280 ° C, it depends on the catalyst used, but is not suitable for the FT synthesis reaction. Often.
- the concentration of the catalyst (solid component) in the slurry in the operating conditions is specific limitation usually 10 to 40 weight 0/0, preferably 20 to It is in the range of 30% by mass. If the catalyst concentration in the slurry is less than 10% by mass, the reactor may become unnecessarily large relative to the production volume.
- the slurry 42 in which the liquid hydrocarbons and catalyst particles generated by the FT synthesis reaction are suspended is supplied to the lower part of the separation vessel 12 via the downward inclined transfer pipe 25 installed in the upper part of the reactor. Is done.
- the slant angle of the descending inclined transfer pipe 25 is preferably 30 to 45 °, and the slurry transfer speed is preferably about 0.4 to 1.6 mZ seconds.
- FIG. 1 shows an embodiment in which one separation container 12 is provided.
- the present invention is not limited to this, and a plurality of separation containers 12 may be provided. However, from the viewpoint of simplifying the device and operation system, it is better to use one unit.
- a single downward inclined transfer pipe is provided between the reactor and the separation vessel is shown, a plurality of pipes may be provided without being limited thereto. However, one is sufficient from the viewpoint of simplifying the equipment and operation system.
- the slurry supplied to the lower part of the separation container 12 is a liquid product 4 in which most or all of the catalyst particles are separated due to the density difference between the catalyst particles and the liquid product in the separation container 12. 3 and the catalyst particle concentrated slurry 44 are separated by gravity.
- the liquid product 43 is installed in the middle of the separation vessel 12 (below the liquid level fluctuation range during stable operation of the device) while adjusting the liquid level of the separation vessel 12 with the liquid level control valve 28. It is sent from pipe 34 (liquid product outlet) to a separate process such as liquid hydrocarbon separation and purification equipment.
- the gravity-separated catalyst particle-concentrated slurry 44 is circulated to the bottom of the reactor 11 via the slurry circulation path 27 and the flow rate control valve 26, and is reused as the FT synthesis reaction catalyst. It is preferable that the slurry circulation speed is about 0.4 to 1.6 mZ seconds.
- the upper gas phase space of the reactor 11 and the upper gas phase space of the separation vessel 12 are connected by a horizontal connecting pipe 23, and further connected to the descending inclined transfer pipe 25 by a connecting vertical pipe 57.
- the pressure difference between the gas phase space and the upper gas phase space of the separation vessel 12 is adjusted by the differential pressure control valve 24.
- the gaseous product and unreacted synthesis gas components separated by the reactor 11, the separation vessel 12, and the descending inclined transfer pipe 25 are sent out of the system through the outlet 33 installed at the top of the separation vessel 12.
- the flow rate is adjusted by the gas component outflow control valve 61.
- the connecting pipe is a pipe in which the gas product generated in the reactor is connected between the gas phase part of the reactor and the separation vessel. What is necessary is just to be transferred to a separation container through. Therefore, in addition to the pipe (horizontal pipe 23) connected horizontally between the reactor 11 and the separation vessel 12 shown in FIG. Not particularly limited.
- the separation method of the catalyst particles and the liquid hydrocarbon product characterized by the bubble column type slurry bed reaction system of the present invention is such that, in the gravity separation in the separation vessel 12, the majority of the catalyst particles are subjected to V-tanking.
- the ascending rate of the separated liquid product 43 in the container is adjusted to 0.4 times or less of the terminal sedimentation rate of the catalyst particles with a particle size of 20 ⁇ m.
- catalyst particles with a particle size of 20 m or more The separation efficiency of 99% or more is achieved. This eliminates the use of filtration filters and power, and leads to catalyst stability (prolonging the life) that is difficult for catalyst dust (physical destruction) to occur. Therefore, there is a possibility that performance degradation can be suppressed and costs can be reduced.
- catalyst particles having a particle diameter of 20 ⁇ m or more by classification or the like it is desirable to use catalyst particles having a particle diameter of 20 ⁇ m or more by classification or the like. That is, when many catalyst particles with a particle diameter of less than 20 m are contained, the catalyst particles having a small particle diameter are reduced by gravity even if the rising speed of the liquid product in the container is adjusted as described above. This is because it is difficult to separate. As a result, a liquid product in which the catalyst particles are separated by gravity (sedimentation separation) can be derived. However, during continuous operation, a small amount of catalyst particles may be pulverized and mixed into the liquid product derivation liquid, so a filter is added to the liquid product outlet. It may be installed in
- the rising speed of the liquid product 43 in the container is controlled by the control valves 24, 26 and 28, the slurry circulation flow control valve 26 and the liquid product derivation control valve 28 which are substantially low differential pressure operation ball valves.
- the rising speed of the product oil (liquid hydrocarbon product) in the separation vessel 12 is adjusted by the operation, and is maintained at 0.4 times or less of the terminal sedimentation speed in the catalyst particle having a particle diameter of 20 m. . Further, the rising speed of the product oil (liquid hydrocarbon product) in the separation vessel 12 also indicates the flow rate of the product oil derived from the outlet pipe 34.
- the particle diameter is 20 m or more. It is difficult to achieve a catalyst particle separation efficiency of 99% or more. That is, catalyst particles and liquid hydrocarbon products are It may be difficult to carry out using gravity separation instead of such filtration separation.
- the features of the present invention include the bubble force of the synthesis gas supplied from the bottom of the reactor 11, the driving force (air lift) generated when rising in the slurry, and the separation from the reactor 11.
- the slurry in which the catalyst particles and liquid product are suspended is naturally circulated between the reactor 11 and the separation vessel 12 without using external power such as a pump due to the difference in density of the fluid staying inside each container 12.
- the circulating speed of the slurry to be applied is adjusted to about 0.4 to 1.6 mZ seconds by the low differential pressure operation ball valve 26 and the flow meter 29 installed in the vertical portion of the slurry circulation path 27.
- the present invention provides a bubble column type slurry single bed reaction system that enables stable operation for a long period of time without causing abrasion and crushing of catalyst particles by performing slurry circulation operation by natural circulation. Furthermore, the bubble column type slurry bed reaction system of the present invention provides a catalyst column force separation / derivation of liquid hydrocarbon products without using external power, and provides a low column operation type bubble column type slurry bed reaction system. It is also what you do.
- the slurry circulation flow rate is controlled by the slurry circulation flow rate control valve 26 installed in the vertical part of the circulation path 27 so that the slurry circulation rate is about 0.4 to 1.6 mZ seconds. .
- Le 45 it is preferable to install Le 45 in multiple places on the circulation path 27 as necessary.
- This aeration gas is constantly or intermittently injected in order to increase the slurry circulation driving force, and is used particularly at the start of slurry circulation with a large inertial resistance.
- a differential pressure regulating valve 24 for controlling the differential pressure between the two columns is installed.
- the differential pressure control valve 24 is a low differential pressure operation ball valve.
- the flow rate control valve 24 appropriately maintains the difference in liquid level between the reactor 11 and the separation vessel 12, thereby realizing stable natural circulation operation of the slurry.
- the horizontal connecting pipe 23 and The descending inclined transfer pipe 25 is connected by a connecting vertical pipe 57. This vertical pipe 57 prevents the slurry from overflowing from the horizontal connection pipe 23 to the separation container 12 due to excessive rise of the slurry liquid level on the reactor 11 side, and air bubbles mixed into the descending inclined transfer pipe 25. Gas-liquid separation, which facilitates the gravity separation of catalyst particles, liquid products and gaseous components in the separation vessel 12.
- the FT synthesis catalyst used in the bubble column type slurry bed reaction system of the present invention is particulate and can be suspended in a medium oil to form a slurry.
- a medium oil for example, cobalt Or a ruthenium-based catalyst is preferably used.
- the particle size of the FT synthesis catalyst is 20 m or more, preferably in the range of 50 to 150 ⁇ m in average particle size.
- the heat transfer tube 22 is inserted into the reactor 11 in order to remove a large amount of heat generated by the FT synthesis reaction.
- the cooling method using the heat transfer tube is not particularly limited, but in Fig. 1 it is a bayonet type cooling tube with excellent temperature distribution control. In the embodiment shown in FIG. 1, the temperature inside the reactor is controlled, and further, uniform heat removal in the radial direction and the vertical axis direction in the reactor is possible. A plurality of bayonet type cooling pipes are installed vertically in the upper part of the reactor.
- the structure consists of an outer pipe 51 and an inner pipe 52, which are arranged on each tube sheet 53, 54 at an appropriate pitch (preferably triangular pitch), and are provided with a boiler water inlet 31 and boiler water and steam outlet 32. have.
- the boiler water inlet force is also supplied to the inner pipe 52 of each tube via the inner pipe header 55, and the cooling water is supplied from a part of the boiler water due to the heat generated by the FT synthesis reaction when passing through the outer pipe 51.
- Steam is generated, and the mixed phase fluid of steam and water is sent from the outlet 32 through the outer pipe header 56, and the generated steam is recovered as plant steam.
- the operating conditions are pressure 2.0 to 6.
- the operating condition of the cooling unit is that water (for example, boiler water) is introduced into the inner pipe of the cooling pipe, and pressure 2.0 to 6.
- OMPaG temperature 200 to 270 from the outlet of the outer pipe of the cooling pipe. It is desirable to obtain steam at ° C.
- the control of the temperature in the reactor by this makes the fluctuation range of the reaction temperature in the reactor stable within a range of ⁇ 5 ° C, preferably ⁇ 2 ° C. (See Table 1 in the Examples below.) O
- the results are shown in Table 1. Adjusting the reaction temperature in the reactor to the above temperature range, introducing boiler water into the inner pipes of a plurality of bayonet type cooling pipes, and steam at a temperature of 226 ° C and a pressure of 2450 kPaG from the outlet of the cooling pipe. Adjusted to obtain. Under the operating conditions, the CO conversion rate in the FT synthesis reaction was 89%.
- the temperature of the reactor in Table 1 represents the values of temperature sensors provided at various locations in the reactor. However, the two values shown in the upper, middle, middle, and middle columns represent the values of multiple (two) temperature sensors provided in the same plane of the reactor.
- Insert paper (thin ⁇ ) Applicable to bed reaction systems and equipment.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2005339076A AU2005339076B2 (en) | 2005-12-14 | 2005-12-14 | Bubble column-type Fischer-Tropsch synthesis slurry bed reaction system |
CN2005800522852A CN101351526B (zh) | 2005-12-14 | 2005-12-14 | 鼓泡塔型费-托合成淤浆床反应*** |
PCT/JP2005/022975 WO2007069317A1 (ja) | 2005-12-14 | 2005-12-14 | 気泡塔型フィッシャー・トロプシュ合成スラリー床反応システム |
US12/097,161 US8057744B2 (en) | 2005-12-14 | 2005-12-14 | Bubble column-type Fischer-Tropsch synthesis slurry bed reaction system |
KR1020087014142A KR100989756B1 (ko) | 2005-12-14 | 2005-12-14 | 기포탑형 피셔ㆍ트롭쉬 합성 슬러리상 반응 방법 및 장치 |
EP05816400.5A EP1964908B1 (en) | 2005-12-14 | 2005-12-14 | Fischer-tropsch synthesis process using bubble column type slurry-bed reactor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2005/022975 WO2007069317A1 (ja) | 2005-12-14 | 2005-12-14 | 気泡塔型フィッシャー・トロプシュ合成スラリー床反応システム |
Publications (1)
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WO2007069317A1 true WO2007069317A1 (ja) | 2007-06-21 |
Family
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PCT/JP2005/022975 WO2007069317A1 (ja) | 2005-12-14 | 2005-12-14 | 気泡塔型フィッシャー・トロプシュ合成スラリー床反応システム |
Country Status (6)
Country | Link |
---|---|
US (1) | US8057744B2 (ja) |
EP (1) | EP1964908B1 (ja) |
KR (1) | KR100989756B1 (ja) |
CN (1) | CN101351526B (ja) |
AU (1) | AU2005339076B2 (ja) |
WO (1) | WO2007069317A1 (ja) |
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US20150064070A1 (en) * | 2012-03-28 | 2015-03-05 | Japan Oil, Gas And Metals National Corporation | Catalyst filling apparatus of bubble column slurry bed reactor and catalyst filling method of bubble column slurry bed reactor |
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Also Published As
Publication number | Publication date |
---|---|
US8057744B2 (en) | 2011-11-15 |
AU2005339076A1 (en) | 2007-06-21 |
EP1964908A1 (en) | 2008-09-03 |
CN101351526B (zh) | 2011-11-09 |
CN101351526A (zh) | 2009-01-21 |
AU2005339076B2 (en) | 2010-02-18 |
KR100989756B1 (ko) | 2010-10-26 |
US20090220389A1 (en) | 2009-09-03 |
KR20080096499A (ko) | 2008-10-30 |
EP1964908B1 (en) | 2014-11-26 |
EP1964908A4 (en) | 2012-05-30 |
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