WO2009113620A1 - フィッシャー・トロプシュ合成粗油からの触媒の選択的除去方法、および除去された触媒のリサイクル方法 - Google Patents
フィッシャー・トロプシュ合成粗油からの触媒の選択的除去方法、および除去された触媒のリサイクル方法 Download PDFInfo
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- WO2009113620A1 WO2009113620A1 PCT/JP2009/054779 JP2009054779W WO2009113620A1 WO 2009113620 A1 WO2009113620 A1 WO 2009113620A1 JP 2009054779 W JP2009054779 W JP 2009054779W WO 2009113620 A1 WO2009113620 A1 WO 2009113620A1
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- separator
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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
- 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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- 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
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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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
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Definitions
- the present invention relates to a finely divided catalyst in a Fischer-Tropsch synthetic crude oil, a method for selectively removing a reduced activity catalyst, and a method for recycling a highly active catalyst in a Fischer-Tropsch synthetic crude oil.
- the catalysts of the FT synthesis method using carbon monoxide and hydrogen as raw materials are iron-based solid catalysts, but in recent years, cobalt-based solid catalysts have also been developed because of their high activity.
- the reaction form of the FT synthesis method is often an embodiment of a slurry in which a solid catalyst is suspended in a product hydrocarbon. Therefore, in addition to obtaining a FT synthetic crude oil that does not contain a catalyst, it is necessary to recover and reuse the catalyst in the slurry in order to reduce the cost of the process.
- the FT synthetic crude oil obtained by the FT synthesis reaction contains a considerable amount of residual catalyst.
- the obtained crude FT synthetic oil is subjected to a purification process such as distillation and hydrotreating to become a product such as a fuel oil, but the residual catalyst affects subsequent processing steps, for example, the purification process. It is necessary to sufficiently remove the residual catalyst from the crude oil.
- a slurry in which the catalyst is suspended is obtained from the FT synthesis reactor, it is preferable to collect and reuse the catalyst while recovering the crude FT synthesis oil not containing the catalyst.
- the catalyst since the catalyst repeatedly collides and pulverizes inside the FT synthesis reactor to become fine particles, the flow state of the slurry inside the FT synthesis reactor may change. Therefore, the finely divided catalyst particles are selectively and actively removed to maintain the fluidity in the FT synthesis reactor and to reduce the catalyst remaining in the FT synthesis crude oil. There is a need to.
- the catalyst may be oxidized by oxygenates inside the FT synthesis reactor.
- coke deposition may occur on the catalyst due to the FT synthesis reaction.
- the activity of the catalyst is reduced, thereby reducing the efficiency of the catalyst. Therefore, even if the catalyst is recovered and reused, it is desirable to discard the catalyst with reduced activity and to recover and reuse only the highly active catalyst.
- the present invention has been made in view of the above circumstances. Since a catalyst having a reduced reaction activity is weak in magnetism, the FT synthetic crude oil can be effectively selected based on the magnitude of magnetism. It is an object of the present invention to provide a method for selectively removing a finely divided catalyst and a catalyst having a reduced activity, and a method for recycling a highly active catalyst in an FT synthetic crude oil.
- a first aspect of the method for selectively removing a catalyst from a Fischer-Tropsch synthetic crude oil of the present invention is a slurry containing a Fischer-Tropsch synthetic crude oil obtained by a Fischer-Tropsch synthetic reaction and a magnetic Fischer-Tropsch catalyst.
- the catalyst separated from the slurry by the first solid-liquid separator is returned to the Fischer-Tropsch synthesis reactor and reused, and the catalyst separated from the slurry by the second solid-liquid separator. Is discharged out of the system.
- the average particle size of the catalyst discharged out of the system is smaller than the average particle size of the catalyst in the slurry at the outlet of the Fischer-Tropsch synthesis reactor.
- the first solid-liquid separation device is a high gradient magnetic separator
- the second solid-liquid separation device is the high gradient magnetic separation. You may select from other than a vessel.
- the second solid-liquid separation device may be the high gradient magnetic separator
- the first solid-liquid separation device may be selected from other than the high gradient magnetic separator.
- the high gradient magnetic separator discharges the cleaning liquid from the separator, and a cleaning liquid introduction path for cleaning the inside of the separator. And a cleaning liquid discharge path.
- the magnetic particles captured inside the separator are washed intermittently.
- the solid-liquid separation device selected from other than the high gradient magnetic separator is a filtration separator, a gravity sedimentation separator, a cyclone, or a centrifuge. It may be at least one of them.
- the second aspect of the method for selectively removing a catalyst from a Fischer-Tropsch synthetic crude oil of the present invention is a slurry comprising a Fischer-Tropsch synthetic crude oil obtained by a Fischer-Tropsch synthetic reaction and a magnetic Fischer-Tropsch catalyst. Extracting from the Fischer-Tropsch synthesis reactor, separating the strong magnetic catalyst from the slurry using a first high gradient magnetic separator, and separating the catalyst from the separated slurry. Separating the weakly magnetic catalyst that has not been separated by the first high gradient magnetic separator using a filtering device. The strong magnetic catalyst separated from the slurry by the first high gradient magnetic separator is recycled back to the Fischer-Tropsch synthesis reactor. The weakly magnetized catalyst separated from the slurry by the filtration device is discharged out of the system.
- the magnetism of the catalyst separated from the slurry by the filtration device is such that the magnetism in the slurry at the outlet of the Fischer-Tropsch synthesis reactor is It may be weaker than the magnetism of the catalyst.
- the Fischer-Tropsch catalyst recycling method of the present invention comprises a step of extracting a slurry containing a Fischer-Tropsch synthetic crude oil obtained by a Fischer-Tropsch synthesis reaction and a magnetic Fischer-Tropsch catalyst from a Fischer-Tropsch synthesis reactor; Separating the strong magnetic catalyst from the slurry using a first high gradient magnetic separator; and the first high gradient magnetic separator from the slurry from which the strong magnetic catalyst has been separated. Separating the catalyst that was not separated by using a second high gradient magnetic separator. The strong magnetic catalyst separated from the slurry by the first high gradient magnetic separator is recycled back to the Fischer-Tropsch synthesis reactor. The catalyst separated from the slurry by the second high gradient magnetic separator is discharged out of the system.
- the magnetism of the catalyst separated from the slurry by the first high gradient magnetic separator is such that the catalyst in the slurry at the outlet of the Fischer-Tropsch synthesis reactor. It may be stronger than the magnetism.
- the treatment of the slurry discharged from the FT reactor is provided with a plurality of separation steps, and the first treatment
- an effective particle size catalyst is recovered from the slurry and returned to the FT reactor for reuse.
- the FT synthetic crude oil with reduced catalyst residue is recovered by removing the finely divided catalyst.
- the finely divided catalyst can be efficiently recovered from the FT synthetic crude oil in which fine fine particles are easily contained.
- the catalyst particles having low reaction activity are selectively separated and removed from the Fischer-Tropsch synthetic crude oil, and the rest is recycled.
- the efficiency of the FT synthesis process can be improved.
- most of the residual catalyst with high magnetism and high activity is separated and removed from the Fischer-Tropsch synthetic crude oil, and the rest is almost low. Since it is an active catalyst, the residual catalyst can be discarded in the step of separation using a filtration device.
- FIG. 1 is a schematic diagram showing a fuel production plant for explaining an embodiment of the present invention.
- FIG. 2 is a schematic diagram showing a high gradient magnetic separator used in the present invention.
- a synthesis gas containing carbon monoxide gas and hydrogen gas is supplied to an FT synthesis reactor 10 through a line 1 as a synthesis gas supply pipe, and liquid carbonization is performed by an FT synthesis reaction in the FT synthesis reactor 10.
- Hydrogen is produced.
- the synthesis gas can be obtained by, for example, hydrocarbon reforming as appropriate. Typical hydrocarbons include methane, natural gas, LNG (liquefied natural gas), and the like.
- As reforming methods partial oxidation reforming method (POX) using oxygen, autothermal reforming method (ATR), which is a combination of partial oxidation reforming method and steam reforming method, carbon dioxide gas reforming method, etc. are utilized. You can also
- the FT synthesis reaction system includes an FT synthesis reactor 10.
- the reactor 10 is an example of a reactor that synthesizes synthesis gas to form liquid hydrocarbons, and functions as a reactor for FT synthesis that synthesizes liquid hydrocarbons from synthesis gas by an FT synthesis reaction.
- the reactor 10 can be a bubble column reactor, for example.
- the main body of the reactor 10 is a substantially cylindrical metal container having a diameter of about 1 to 20 m, preferably about 2 to 10 m.
- the height of the reactor body is about 10 to 50 m, preferably about 15 to 45 m.
- a slurry in which solid catalyst particles are suspended in liquid hydrocarbon (product of FT synthesis reaction) is accommodated inside the reactor main body.
- a part of the slurry accommodated in the reactor 10 is introduced from the trunk portion of the reactor 10 into the separator 20 through the line 3 as a slurry delivery pipe. Unreacted synthesis gas and the like are discharged from the top of the reactor 10 through a line 2 as a synthesis gas discharge pipe, and a part thereof is returned to the reactor 10 through the line 1.
- the synthesis gas supplied to the reactor 10 through the line 1 is injected into the slurry inside the reactor 10 from a synthesis gas supply port (not shown).
- a liquid hydrocarbon synthesis reaction (FT synthesis reaction) is performed by a contact reaction in which the synthesis gas and the catalyst particles come into contact with each other.
- FT synthesis reaction a liquid hydrocarbon synthesis reaction
- hydrogen gas and carbon monoxide gas cause a synthesis reaction.
- synthesis gas is introduced into the bottom of the reactor 10 and rises in the slurry stored in the reactor 10.
- carbon monoxide and hydrogen gas contained in the synthesis gas react with each other by the above-described FT synthesis reaction to generate hydrocarbons. Since heat is generated during this synthesis reaction, heat is removed by an appropriate cooling means.
- the metal catalyst includes a supported type and a deposited type, but in any case, it is a solid magnetic particle containing an iron group metal. An appropriate amount of metal is contained in the solid particles, but the solid particles may be 100% metal.
- the iron group metal is exemplified by iron, and cobalt having high activity is preferable.
- synthesis gas supplied to the reactor 10 is pressurized to a pressure (for example, 3.6 MPaG) appropriate for the FT synthesis reaction by an appropriate compressor (not shown). However, in some cases, it is not necessary to provide the compressor.
- the liquid hydrocarbon synthesized in the reactor 10 as described above is taken out from the reactor 10 through a line 3 connected to the body of the reactor 10 as a slurry in which catalyst particles are suspended, and the catalyst is separated. , Supplied to the recovery process.
- two separators 20 and 30 are arranged in series.
- a catalyst having a predetermined diameter or more is separated and recovered from the slurry.
- the recovered catalyst is circulated to the reactor 10 through the line 21 and reused.
- the predetermined diameter can be set as appropriate.
- the catalyst particle diameter (prepared diameter) at the initial stage of the reaction may be set, or the appropriate diameter of the particle diameter that decreases with time may be set as appropriate. That is, the diameter of the catalyst to be separated and recovered is appropriately set from the viewpoint of returning to the reaction system and reusing it.
- the catalyst separated and recovered by the separator 20 Since the catalyst separated and recovered by the separator 20 has a large particle size and can be reused in the reactor 10, it is returned to the reaction system through the line 21 and reused. The remaining slurry from which the large particles are separated and removed is introduced into the next separator 30 through the line 22.
- the reusable catalyst is separated and recovered, so that the catalyst remaining in the slurry is an unnecessary catalyst having a small particle size.
- This residual catalyst is removed in the second solid-liquid separation step by the separator 30. Specifically, the catalyst having an average particle diameter of the catalyst discharged from the separator 30 is separated from the average particle diameter of the catalyst in the slurry at the outlet of the reactor 10. The separated catalyst is discharged out of the system through the line 31. The resulting FT synthetic crude oil can be recovered through line 32.
- the separator 30 Since the catalyst separated and recovered by the separator 30 is pulverized, it is discharged out of the reaction system and discarded without being reused. Either of the separators 20 and 30 can be a magnetic separator, but the case where the separator 20 is a magnetic separator will be described below.
- the first solid-liquid separation process by the high gradient magnetic separator 20 will be described.
- the magnetic particles contained in the extracted FT synthetic crude oil are separated and removed from the FT synthetic crude oil by the high gradient magnetic separator 20.
- the FT synthetic crude oil is magnetically processed by the high gradient magnetic separator 20 to separate and remove the magnetized catalyst particles.
- the iron group metal as the FT synthesis catalyst whether iron or cobalt, has a certain magnetic susceptibility and exhibits paramagnetism, so that removal by magnetic separation is considerably effective.
- a ferromagnetic filler is disposed in a uniform high magnetic field space generated by an external electromagnetic coil, and usually 1000 to 20000 Gauss / Solid magnetic particles such as catalyst particles are separated from the liquid component containing liquid hydrocarbons by attaching ferromagnetic or paramagnetic particles to the surface of the packing with a high magnetic field gradient of cm. The filling is washed to remove the adhered particles.
- a commercial machine known as a registered trademark “FEROSEP” can be used as a registered trademark “FEROSEP” can be used.
- ferromagnetic filler an aggregate of ferromagnetic fine wires such as steel wool or steel net having a diameter of 1 to 1000 ⁇ m, expanded metal, and shell-like metal strips are usually used.
- metal stainless steel having excellent corrosion resistance, heat resistance and strength is preferable.
- the ratio of R to the maximum thickness d of the plate-like body, that is, R / d is in the range of 5 to 20, and the plate-like body is mainly composed of Fe, Cr is 5 to 25 wt%, Si In an amount of 0.5 to 2 wt% and C in an amount of 2 wt% or less.
- the slurry is introduced into the magnetic field space of the high gradient magnetic separator 20, and the magnetic particles are put into the ferromagnetic packing placed in the magnetic field space. By adhering, the magnetic particles are removed from the slurry.
- the ferromagnetic filler adhering to the magnetic particles is washed, and the magnetic particles are removed from the filler with a washing liquid. There is a limit to the amount of magnetic particles that can be captured by a packing with a constant surface area.
- the magnetic particles are removed from the packing by cutting off the magnetic field, and then the packing is washed with the cleaning liquid, and the magnetic particles are magnetically combined with the cleaning liquid. Drain out of separator.
- the magnetic separation conditions for the magnetic particles contained in the slurry and the washing and removal conditions for the magnetic particles attached to the packing will be described below.
- the magnetic field strength is preferably 2000 gauss or more, and more preferably 3000 gauss or more.
- the liquid temperature (treatment temperature) in the separator is preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 100 ° C. or higher and 300 ° C. or lower, and particularly preferably 100 ° C. or higher and 200 ° C. or lower.
- the liquid residence time (residence time) is preferably 15 seconds or longer, and more preferably 20 seconds or longer.
- the “liquid residence time” is obtained by dividing the volume of the filling tank to which the magnetic field is applied by the inflow amount of the liquid introduced into the filling tank (that is, FT synthetic crude oil containing magnetic particles). It is expressed by the following formula.
- the removal rate of the magnetic particles by the packing decreases as the amount of the magnetic particles trapped by the packing increases. Therefore, in order to maintain the removal rate, it is necessary to perform a washing and removing step for discharging the magnetic particles trapped in the packing after the magnetic separation operation is continued for a certain period of time to the outside of the magnetic separator.
- the liquid containing magnetic particles may bypass the magnetic separator during this washing and removing process. However, if the time required for washing is long, the amount of magnetic particles flowing into the next process increases and the removal rate decreases, so a preliminary separator for switching may be provided as necessary.
- magnetically separated FT synthetic crude oil can be used as the cleaning liquid.
- the cleaning liquid linear velocity is 1 to 10 cm / sec, preferably 2 to 6 cm / sec.
- FIG. 2 is a schematic simplified diagram of the high gradient magnetic separator 20.
- the separation part of the high gradient magnetic separator 20 forms a vertical packed column, and the column is filled with a ferromagnetic packing.
- the filling tank 26 filled with the packing is magnetized by the magnetic field lines generated by the electromagnetic coil 23 installed outside the tower to form a high-gradient magnetic separation part. This portion is a uniform high magnetic field space generated by the external electromagnetic coil 23.
- the slurry heated to an appropriate operating temperature is introduced into the bottom of the magnetic separator 20 through the line 3 and flows from the bottom to the top at a predetermined flow rate in the column, preferably at a flow rate such that the residence time in the magnetic separation unit is 15 seconds or more. It passes through and is discharged through the line 22 from the top of the tower. While the slurry passes through the magnetic separation part, the magnetic particles contained in the slurry adhere to the surface of the packing.
- the cleaning liquid bypasses the magnetic separator 20 through a cleaning oil bypass line (not shown).
- the cleaning liquid is introduced into the magnetic separator 20 through the line 24.
- the slurry can bypass the magnetic separator 20 through a slurry bypass line (not shown) and can be sent to a subsequent solid-liquid separation device, for example, the separator 30. In this way, it is possible to perform switching between removal operation, cleaning operation, and repeated continuous operation.
- the washing and removing step can be performed with reference to the method described in JP-A-6-200260.
- the liquid component from which the catalyst particles have been separated in the first solid-liquid separation step is introduced into the separator 30 through the line 22.
- the separator 30 further separates the catalyst from the liquid component separated in the first solid-liquid separation step.
- the average particle size is smaller than the average particle size of the catalyst in the slurry at the outlet of the reactor 10.
- the separated catalyst is discharged out of the system through the line 31, and the clean crude FT synthetic oil with reduced catalyst residues is extracted from the separator 30 through the line 32, and is supplied to the next step, for example, the rectifying column 40. be introduced.
- the method for measuring the average particle diameter is not particularly limited.
- an average particle diameter ( ⁇ m) measured by a particle size distribution measuring apparatus using a laser diffraction method, a dynamic light scattering method, or a standard sieving method can be preferably exemplified.
- the average particle diameter of the discarded FT catalyst is not particularly limited as long as it is smaller than the average particle diameter of the FT catalyst in the slurry at the outlet of the FT reactor 10.
- the average particle size of the FT catalyst in the slurry at the FT reactor outlet is preferably 5% or less, more preferably 10% or more, and even more preferably 20% or more.
- the lower limit is not particularly limited. Usually, it depends on the separation ability in the second-stage solid-liquid separation step.
- a known technique can be adopted for the separation means, and a filter using an appropriate filter such as a sintered metal filter, gravity It is selected from sedimentation separators, cyclones, centrifuges and the like.
- a sedimentation tank gravitation sedimentation separator
- Gravity sedimentation separators are advantageous because of their simple structure. These can be used either continuously or batchwise.
- a magnetic separator is adopted as the first-stage separator 20, and separation means other than the magnetic separator is adopted as the second-stage separator 30.
- separation means other than the magnetic separator may be employed for the first stage separator 20 and a magnetic separator may be employed for the second stage separator 30.
- the FT synthetic crude oil from which the magnetic particles have been separated by the separators 20 and 30 is introduced into the rectification column 40 through the line 32 and rectified, and subjected to various purification processes such as hydrogenation.
- the FT synthetic crude oil obtained through the two-stage solid-liquid separation step is introduced into the rectification column 40 and fractionated.
- a naphtha fraction (boiling point less than about 150 ° C.) is fractionated through line 41
- an intermediate fraction (boiling point is about 150 to 350 ° C.) is fractionated through line 42
- Greater than ° C. is fractionated through line 43.
- Example 1 A synthesis gas containing carbon monoxide and hydrogen gas obtained by reforming natural gas as main components is introduced into a bubble column type hydrocarbon synthesis reactor (FT synthesis reactor) 10 through a line 1, and an FT catalyst.
- FT synthesis reactor bubble column type hydrocarbon synthesis reactor
- Liquid hydrocarbons were synthesized by reacting in a slurry in which particles (average particle size of 100 ⁇ m, cobalt as an active metal was supported by 30% by weight) were suspended.
- the liquid hydrocarbon synthesized in the FT synthesis reactor 10 is taken out from the reactor 10 through the line 3 as a slurry containing FT catalyst particles.
- the taken slurry is led to an electromagnet type high gradient magnetic separator 20 (FEROSEP (registered trademark)) provided in the first solid-liquid separation step disposed at the subsequent stage of the FT synthesis reactor, and the treatment described in Table 1 Under conditions, it is separated into particles having a relatively large particle size and a liquid component (liquid A).
- FEROSEP electromagnet type high gradient magnetic separator 20
- the catalyst particles separated in the first solid-liquid separation step are returned to the synthesis reactor 10 through the line 21.
- a liquid component (liquid A) containing catalyst particles that cannot be captured by the high gradient magnetic separator 20 is passed through a line 22 to a separator 30 (a sintered metal filter having an opening of 10 ⁇ m) provided in the second solid-liquid separation step. Then, it is further separated into catalyst particles which are solid and liquid (liquid B).
- the high gradient magnetic separator 20 used in the first solid-liquid separation step has a cleaning liquid introduction line 24 for internal cleaning and a line 25 for discharging the cleaning liquid, and is separated from the FT synthetic crude oil. The catalyst particles thus obtained are washed intermittently every 2 hours and returned to the synthesis reactor 10.
- the catalyst particles separated in the second solid-liquid separation step are discharged out of the system.
- the liquid fraction (liquid B) is led to the rectification column 40, the naphtha fraction (boiling point is less than about 150 ° C.) is fractionated through line 41, and the middle fraction (boiling point is about 150 to 350 ° C.) is passed through line 42.
- the wax fraction (boiling point greater than about 350 ° C.) was fractionated through line 43.
- the average particle diameter of the catalyst particles in the slurry at the outlet of the synthesis reactor 10 was 72.5 ⁇ m, and the average particle diameter of the catalyst particles discharged out of the system was 57 ⁇ m.
- the average particle size of the catalyst particles is a value measured using a laser diffraction particle size distribution analyzer SALD-3100 manufactured by Shimadzu Corporation (the same applies hereinafter).
- Example 2 The same treatment as in Example 1 was performed except that the treatment conditions of the first solid-liquid separation step were changed as shown in Table 1. At this time, the average particle diameter of the catalyst particles discharged out of the system was 28 ⁇ m.
- Example 3 The same treatment as in Example 1 was performed except that the treatment conditions of the first solid-liquid separation step were changed as shown in Table 1. At this time, the average particle diameter of the catalyst particles discharged out of the system was 39 ⁇ m.
- Example 4 The same treatment as in Example 1 was performed except that the treatment conditions of the first solid-liquid separation step were changed as shown in Table 1. At this time, the average particle diameter of the catalyst particles discharged out of the system was 25 ⁇ m.
- Example 5 A synthesis gas containing carbon monoxide and hydrogen gas obtained by reforming natural gas as main components is introduced into a bubble column type hydrocarbon synthesis reactor (FT synthesis reactor) 10 through a line 1, and an FT catalyst.
- FT synthesis reactor a bubble column type hydrocarbon synthesis reactor
- Liquid hydrocarbons were synthesized by reacting in a slurry in which particles (average particle size of 100 ⁇ m, cobalt as an active metal was supported by 30% by weight) were suspended.
- the liquid hydrocarbon synthesized in the FT synthesis reactor 10 is taken out from the reactor 10 through the line 3 as a slurry containing FT catalyst particles.
- the taken slurry is guided to a separator 20 (sintered metal filter having an opening of 10 ⁇ m) provided in the first solid-liquid separation step disposed at the subsequent stage of the FT synthesis reactor 10, and has a relatively large particle size. It separates into particles and a liquid component (liquid A).
- the catalyst particles separated in the first solid-liquid separation step are returned to the synthesis reactor 10 through the line 21, and a liquid component (liquid A) containing catalyst particles that cannot be captured by the separator 20 such as a sintered metal filter is obtained. It is led to an electromagnet type high gradient magnetic separator 30 (FEROSEP (registered trademark)) provided in the second solid-liquid separation step, and further separated into catalyst particles and liquid (liquid B) which are solid contents.
- FEROSEP electromagnet type high gradient magnetic separator
- the high-gradient magnetic separator 30 used in the second solid-liquid separation step has a cleaning liquid introduction line 24 for internal cleaning and a line 25 for discharging the cleaning liquid. Rinse periodically and discharge outside the system.
- the liquid fraction (liquid B) is led to the rectification column 40, the naphtha fraction (boiling point is less than about 150 ° C.) is fractionated through line 41, and the middle fraction (boiling point is about 150 to 350 ° C.) is passed through line 42.
- the wax fraction (boiling point greater than about 350 ° C.) was fractionated through line 43.
- the hydroisomerization apparatus and hydrocracking apparatus were mixed in the line, introduced into a second rectification tower (not shown), and fractionated to obtain a diesel fuel base material.
- the average particle diameter of the catalyst particles in the slurry at the outlet of the synthesis reactor 10 was 72.5 ⁇ m, and the average particle diameter of the catalyst particles discharged out of the system was 25 ⁇ m.
- a synthesis gas containing carbon monoxide and hydrogen gas obtained by reforming natural gas as main components is introduced into a bubble column type hydrocarbon synthesis reactor (FT synthesis reactor) 10 through a line 1, and an FT catalyst.
- Liquid hydrocarbons were synthesized by reacting in a slurry in which particles (average particle size of 100 ⁇ m, cobalt as an active metal was supported by 30% by weight) were suspended.
- the liquid hydrocarbon synthesized in the FT synthesis reactor 10 is taken out from the reactor 10 through the line 3 as a slurry containing FT catalyst particles.
- the taken slurry is guided to a separator 20 (sintered metal filter having an opening of 10 ⁇ m) provided in a solid-liquid separation step disposed at the subsequent stage of the FT synthesis reactor, and separated into catalyst particles and a liquid component.
- a separator 20 sintered metal filter having an opening of 10 ⁇ m
- the solid-liquid separator 20 is a single stage, and the magnetic separator 30 is not provided.
- the catalyst particles separated by the single-stage separator 20 are discharged out of the system.
- the liquid is led to the rectification column 40, the naphtha fraction (boiling point less than about 150 ° C.) is fractionated through line 41, and the middle fraction (boiling point is about 150-350 ° C.) is fractionated through line 42, A wax fraction (boiling point greater than about 350 ° C.) was fractionated through line 43.
- the average particle diameter of the catalyst particles discharged out of the system was 72.5 ⁇ m.
- an electromagnetic high gradient magnetic separator 20 is disposed as the first solid-liquid separation step, and a separator 30 such as a metal filter is disposed as the second solid-liquid separation step (Example 1 to 4)
- the separator 20 such as a metal filter
- the electromagnet type high gradient magnetic separator 30 is disposed as the second solid-liquid separation step
- the catalyst discharged outside the system The average particle diameter (weight basis) showed a value smaller than that of Comparative Example 1 in any case. That is, it can be seen that the catalyst particles having a reduced particle size can be selectively removed from the slurry.
- FIG. 1 A second embodiment of the present invention will be described with reference to FIGS.
- two separators 20 and 30 are arranged in series.
- a high gradient magnetic separator is used as the separator 20
- a filter is used as the separator 30.
- the high gradient magnetic separator 20 separates strong magnetic catalyst particles. Since the strong magnetic catalyst particles are still highly reactive particles, they are returned to the reactor 10 through the line 21 and reused.
- the magnetism of the particles to be returned to the reactor 10 can be arbitrarily set in advance.
- the slurry before being introduced into the high gradient magnetic separator 20 may be extracted from the reactor 10, and particles having higher magnetic properties than the catalyst particles in the slurry may be captured, separated, and recycled.
- the slurry from which the strong magnetic particles are separated and removed is supplied to the second solid-liquid separation step by the filter 30 through the line 22.
- the magnetic field strength is preferably 15000 gauss or more, and more preferably 30000 gauss or more.
- the liquid temperature (treatment temperature) in the separator is preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 100 ° C. or higher and 300 ° C. or lower, and particularly preferably 100 ° C. or higher and 200 ° C. or lower.
- the liquid residence time is preferably 15 seconds or longer, and more preferably 50 seconds or longer.
- the high gradient magnetic separator 20 can separate particles by magnetism by appropriately setting the separation conditions.
- a second solid-liquid separation process using the filter 30 using an appropriate filter such as a sintered metal filter will be described.
- the liquid component from which the catalyst particles have been separated in the second solid-liquid separation step is introduced into the filter 30 through the line 22.
- a known technique can be adopted for the filter 30, and it is selected from a gravity sedimentation separator, a cyclone, a centrifugal separator and the like in addition to the above-described filter.
- a gravity sedimentation separator for example, a sedimentation tank (gravity sedimentation separator) that fills with a liquid and is allowed to stand for a certain period of time to allow solid particles in the liquid to spontaneously settle can be used.
- Gravity sedimentation separators are advantageous because of their simple structure. These can be used either continuously or batchwise.
- the filter 30 in the second solid-liquid separation step weakly magnetic particles, that is, low activity catalysts are introduced. Therefore, use a filter with the smallest possible opening.
- the separated catalyst is discharged out of the system without being recycled and is preferably discarded. That is, the catalyst particles discharged out of the system in the second solid-liquid separation step have a magnetism smaller than that of the FT catalyst in the slurry at the outlet of the reactor 10. Accordingly, such catalyst particles are discharged out of the system through the line 31.
- the magnetic measurement method is not particularly limited, but a magnetic susceptibility (emu / g) measured by, for example, SQUID (superconducting quantum interference device) can be preferably mentioned.
- the magnetism of the catalyst particles to be discarded is not particularly limited as long as it is smaller than the magnetism of the FT catalyst in the slurry at the outlet of the reactor 10.
- the magnetism of the discarded catalyst particles is 98% or less, preferably 97% or less of the magnetic susceptibility of the FT catalyst in the slurry at the outlet of the reactor 10.
- a clean FT synthetic crude oil with reduced catalyst residue can be obtained by a conventional filtration operation, so that a FT catalyst having low magnetism and low activity can be selectively removed.
- the FT synthetic crude oil from which the magnetic particles have been separated by the separators 20 and 30 is introduced into the rectification column 40 through the line 32 and rectified, and subjected to various purification processes such as hydrogenation. To become a product.
- Example 6 A synthesis gas containing carbon monoxide and hydrogen gas obtained by reforming natural gas as main components is introduced into a bubble column type hydrocarbon synthesis reactor (FT synthesis reactor) 10 through a line 1, and an FT catalyst. Liquid hydrocarbons were synthesized by reacting in a slurry in which particles (average particle size of 100 ⁇ m, cobalt as an active metal was supported by 30% by weight) were suspended. The liquid hydrocarbon synthesized in the FT synthesis reactor 10 is taken out from the reactor 10 through the line 3 as a slurry containing FT catalyst particles.
- the taken slurry was led to an electromagnet type high gradient magnetic separator 20 (FEROSEP (registered trademark)) provided in the first solid-liquid separation step disposed at the subsequent stage of the FT synthesis reactor 10 and described in Table 2. Under the processing conditions, a part of the catalyst particles and a liquid component (liquid A) are separated.
- FEROSEP electromagnet type high gradient magnetic separator 20
- the catalyst particles separated in the first solid-liquid separation step are returned to the synthesis reactor 10 through the line 21.
- a liquid component (liquid A) containing catalyst particles that cannot be captured by the high gradient magnetic separator 20 is filtered through a line 22 in a second solid-liquid separation step (sintered metal filter having an opening of 10 ⁇ m). ) And further separated into solid catalyst particles and liquid (liquid B).
- the catalyst particles separated in the second solid-liquid separation step are discharged out of the system. Then, the liquid (liquid B) is guided to the rectification column 40, and the naphtha fraction (boiling point is less than about 150 ° C) is fractionated through the line 41, and the middle fraction (boiling point is about 150 to 350 ° C) is lined.
- the wax fraction (boiling point greater than about 350 ° C.) was fractionated through line 43. Further, after the middle distillate is processed in a hydroisomerization apparatus (not shown) and the wax fraction is processed in a hydrocracking apparatus (not shown), the hydroisomerization apparatus and hydrocracking apparatus The effluent was mixed in the line, introduced into a second rectification tower (not shown), and fractionated to obtain a diesel fuel base material.
- the magnetic susceptibility of the catalyst particles in the slurry at the outlet of the synthesis reactor 10 was 7.30 emu / g, and the magnetic susceptibility of the catalyst particles discharged out of the system and discarded was 7.13 emu / g.
- the magnetic susceptibility of the catalyst particles is a value measured using a SQUID (superconducting quantum interference device) magnetometer (MPMS-5 manufactured by Quantum Design) (the same applies hereinafter).
- Example 7 The same processing as in Example 6 was performed except that the processing conditions of the high gradient magnetic separator 20 were changed as shown in Table 2.
- Table 2 shows the average magnetic susceptibility of the FT catalyst particles discarded in each example.
- Comparative Example 2 The same process as in Example 6 was performed except that the high gradient magnetic separator 20 was not used for the separation process of the FT catalyst particles from the slurry.
- the magnetic susceptibility of the FT catalyst particles discarded in Comparative Example 2 is shown in Table 2.
- the FT catalyst particles discharged to the outside of the system through the separation step by the high gradient magnetic separator 20 and the filter 30 are lower in magnetism than the FT catalyst particles in the slurry at the outlet of the reactor 10, and the activity decreases. I understand that. On the other hand, when the FT catalyst particles are removed and discarded only with the filter 30, the relatively strong catalyst is also discarded.
- FIG. 1 A third embodiment of the present invention will be described with reference to FIGS.
- two separators 20 and 30 are arranged in series.
- high gradient magnetic separators are used as the separators 20 and 30.
- the operating conditions of both are made different so that the magnetism of the catalyst separated and recovered by each separator is different.
- the first high gradient magnetic separator 20 separates strong magnetic catalyst particles. Since the strong magnetic catalyst particles are still highly reactive particles, they are returned to the reactor 10 through the line 21 and reused.
- the degree of magnetism of the particles to be returned to the reactor 10 can be arbitrarily set in advance. For example, the magnetism of the catalyst particles removed from the slurry by the high gradient magnetic separator 20 and returned to the reactor 10 can be greater than the magnetism of the FT catalyst in the slurry at the outlet of the reactor 10. As a result, only the FT catalyst having strong magnetism and high reaction activity can be selectively recycled to the FT reactor.
- the magnetic measurement method is not particularly limited, but a magnetic susceptibility (emu / g) measured by, for example, SQUID (superconducting quantum interference device) can be preferably mentioned.
- the magnetism of the FT catalyst returned to the FT reactor is not particularly limited as long as it is larger than the magnetism of the FT catalyst in the slurry at the outlet of the reactor 10.
- the magnetic susceptibility of the FT catalyst in the slurry at the outlet of the reactor 10 is larger by 0.5% or more and 1.0% or more.
- the catalyst separated and recovered from the initial high gradient magnetic separator 20 treatment is still highly active as described above, it is returned to the reactor 10 via line 21 for reuse.
- the slurry from which the strong magnetic particles are separated and removed is supplied to the second solid-liquid separation step by the second high gradient magnetic separator 30 through the line 22.
- the catalyst separated and recovered from the slurry by the high gradient magnetic separator 30 is weak in magnetism and has a reduced activity, and is discharged out of the system through the line 31.
- the magnetic field strength is preferably 5000 gauss or more, and more preferably 15000 gauss or more.
- the liquid temperature (treatment temperature) in the separator is preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 100 ° C. or higher and 300 ° C. or lower, and particularly preferably 100 ° C. or higher and 200 ° C. or lower.
- the liquid residence time is preferably 10 seconds or more, and more preferably 50 seconds or more.
- the high gradient magnetic separator 20 can separate particles by magnetism by appropriately setting the above-described separation conditions.
- the magnetism of the FT catalyst removed from the slurry by the high gradient magnetic separator 20 and returned to the FT reactor can be greater than the magnetism of the FT catalyst in the slurry at the outlet of the reactor 10.
- the high gradient magnetic separator 30 magnetically separates particles having weak magnetism. As described above, since the strong magnetic catalyst particles have already been separated and removed by the high gradient magnetic separator 20, the catalyst remaining in the FT synthetic crude oil introduced into the high gradient magnetic separator 30 is magnetic. Weak and low activity. The high-gradient magnetic separator 30 is required to separate such low-magnetization and low-activity catalyst particles as much as possible and discharge them out of the system.
- the magnetic field strength is preferably 15000 gauss or more, and more preferably 20000 gauss or more.
- the liquid temperature (treatment temperature) in the separator is preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 100 ° C. or higher and 300 ° C. or lower, and particularly preferably 100 ° C. or higher and 200 ° C. or lower.
- the liquid residence time is preferably 50 seconds or more.
- the catalyst particles separated and removed by the high gradient magnetic separator 30 have weak magnetism and low activity. Therefore, such catalyst particles are discharged out of the system through the line 31 without being recycled to the reactor 10, and are preferably discarded.
- the FT synthetic crude oil from which the magnetic particles have been separated is introduced into the rectification column 40 through the line 32.
- many residual catalysts can be removed by appropriately adjusting the operating conditions. Thereby, the FT synthetic crude oil from which the residual catalyst has been removed can be obtained.
- the FT synthetic crude oil from which the magnetic particles have been separated by the separators 20 and 30 is introduced into the rectification column 40 through the line 32 and rectified, and subjected to various purification processes such as hydrogenation. To become a product.
- Example 10 A synthesis gas containing carbon monoxide and hydrogen gas obtained by reforming natural gas as main components is introduced into a bubble column type hydrocarbon synthesis reactor (FT synthesis reactor) 10 through a line 1, and an FT catalyst.
- FT synthesis reactor a bubble column type hydrocarbon synthesis reactor
- Liquid hydrocarbons were synthesized by reacting in a slurry in which particles (average particle size of 100 ⁇ m, cobalt as an active metal was supported by 30% by weight) were suspended.
- the liquid hydrocarbon synthesized in the FT synthesis reactor 10 is taken out from the reactor 10 through the line 3 as a slurry containing FT catalyst particles.
- a first electromagnet type high gradient magnetic separator 20 (FEROSEP (registered trademark)) provided in a first solid-liquid separation process in which the extracted slurry (FT catalyst concentration: 100 mass ppm) is disposed in the subsequent stage of the synthesis reactor 10 is used. Trademark)), and under the processing conditions shown in Table 3, a part of the catalyst particles (which are stronger in magnetism than the FT catalyst particles in the slurry at the outlet of the reactor 10) and the liquid component (liquid A) And to separate.
- FEROSEP registered trademark
- the highly active catalyst particles separated in the first solid-liquid separation step are returned to the synthesis reactor 10 through the line 21. Then, the liquid component (liquid A) containing catalyst particles that cannot be captured by the high gradient magnetic separator 20 is led to the second high gradient magnetic separator 30 provided in the second solid-liquid separation step through the line 22, 3 is further separated into FT catalyst particles, which are solid components, and a liquid component (liquid B). The low activity catalyst particles separated in the second solid-liquid separation step are discharged out of the system through the line 31.
- the liquid (liquid B) is guided to the rectification column 40, and the naphtha fraction (boiling point is less than about 150 ° C) is fractionated through the line 41, and the middle fraction (boiling point is about 150 to 350 ° C) is lined.
- the wax fraction (boiling point greater than about 350 ° C.) was fractionated through line 43.
- the middle fraction is treated with a hydroisomerization apparatus (not shown), the wax fraction is treated with a hydrocracking apparatus (not shown), and then mixed in the line to be a second fractionator. (Not shown) and fractionated to obtain a diesel fuel base material.
- the magnetic susceptibility of the catalyst particles in the slurry at the outlet of the synthesis reactor 10 is 7.30 emu / g, separated and removed by the high gradient magnetic separator 20, and recycled to the FT reactor 10 through the line 21.
- the magnetic susceptibility of the catalyst particles was 7.36 emu / g.
- the catalyst concentration of liquid B at the outlet of the high gradient magnetic separator 30 was 9.6 ppm by mass.
- the magnetic susceptibility of the catalyst particles is a value measured using a SQUID (superconducting quantum interference device) magnetometer (MPMS-5 manufactured by Quantum Design) (the same applies hereinafter).
- the catalyst concentration (mass ppm) of the liquid B is a value calculated on the basis of the weight of the treated oil based on the measurement result of the laser diffraction particle size distribution analyzer SALD-3100 manufactured by Shimadzu Corporation ( The same applies below).
- Example 11 to 14 The same processing as in Example 10 was performed except that the processing conditions of the first high gradient magnetic separator 20 and the second high gradient magnetic separator 30 were changed as shown in Table 3.
- Table 3 shows the magnetic susceptibility of the recycled FT catalyst particles and the catalyst concentration at the outlet of the second high gradient magnetic separator 30 in each example.
- Example 3 For the separation process of the FT catalyst particles from the slurry, a sintered metal filter having an opening of 10 ⁇ m was used instead of the first high gradient magnetic separator 20 and the second high gradient magnetic separator 30. The same treatment as in Example 10 was performed. Table 3 shows the magnetic susceptibility of the recycled FT catalyst particles and the catalyst concentration in the treated oil at the filter outlet. The catalyst concentration in the treated oil at the filter outlet is shown in the column of catalyst concentration at the outlet of the second magnetic separator 30 in Table 3.
- the FT catalyst concentration in the liquid B at the outlet of the second magnetic separator 20 is reduced to less than 10 ppm by mass. It can be seen that the fine particle removal effect is equal to or higher than that of Comparative Example 3 using only the above.
- the present invention relates to a finely divided catalyst in a Fischer-Tropsch synthetic crude oil, a method for selectively removing a reduced activity catalyst, and a method for recycling a highly active catalyst in a Fischer-Tropsch synthetic crude oil.
- the pulverization catalyst can be efficiently recovered from the FT synthetic crude oil in which fine fine particles are easily generated.
- a highly magnetic and highly active residual catalyst can be selectively reused.
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Abstract
Description
本願は、2008年3月14日に出願された特願2008-65773号、特願2008-65778号、および特願2008-65780号について優先権を主張し、その内容をここに援用する。
そして、FT合成反応によって得られるFT合成粗油中には、相当量の残留触媒が含まれる。得られたFT合成粗油は、蒸留及び水素化処理等の精製処理を施されて燃料油等の製品になるが、残留触媒が、後の処理工程、たとえば精製処理に影響するため、FT合成粗油から残留触媒を十分に除去する必要がある。
しかし、触媒は、FT合成反応器の内部で衝突、粉砕等を繰り返し、微粉粒子となることから、FT合成反応器内部のスラリーの流動状態が変化することがある。
そのため、微粉化した触媒粒子は、FT合成反応器内の流動性を維持するためにも、FT合成粗油中に残留する触媒を低減させるためにも、選択的、かつ積極的にこれらを除去する必要がある。
したがって、触媒を回収して再使用するとしても、活性の低下した触媒は廃棄し、活性の高い触媒のみを回収して再使用することが望ましい。
前記第一の固液分離装置によって前記スラリーから分離された前記触媒は、前記フィッシャー・トロプシュ合成反応器に戻して再利用され、前記第二の固液分離装置によって前記スラリーから分離された前記触媒は、系外に排出される。前記系外に排出される前記触媒の平均粒径は、前記フィッシャー・トロプシュ合成反応器の出口における前記スラリー中の前記触媒の平均粒径よりも小さい。
前記第一の高勾配磁気分離器によって前記スラリーから分離された前記磁性の強い触媒は、前記フィッシャー・トロプシュ合成反応器に戻して再利用される。前記ろ過装置によって前記スラリーから分離された磁性の弱い前記触媒は、系外に排出される。
前記第一の高勾配磁気分離器によって前記スラリーから分離された前記磁性の強い触媒は、前記フィッシャー・トロプシュ合成反応器に戻して再利用される。前記第二の高勾配磁気分離器によって前記スラリーから分離された前記触媒は、系外に排出される。
そして、第一の高勾配磁気分離器を使用して分離する工程では、磁性が大きく、高活性な残留触媒の大部分がフィッシャー・トロプシュ合成粗油から分離、除去されており、残りはほとんど低活性な触媒なので、ろ過装置を使用して分離する工程では、残留触媒を廃棄することができる。
20、30…分離器
40…精留塔
本発明の第一の実施形態を図1および図2を参照して説明する。
図1に示すように、一酸化炭素ガスと水素ガスを含む合成ガスを、合成ガス供給管としてのライン1を通じてFT合成反応器10に供給し、FT合成反応器10におけるFT合成反応により液体炭化水素が生成される。合成ガスは、たとえば適宜に炭化水素の改質等により得ることができる。代表的な炭化水素としては、メタンや天然ガス、LNG(液化天然ガス)等を挙げる事ができる。改質方法としては、酸素を用いた部分酸化改質法(POX)、部分酸化改質法と水蒸気改質法の組合せである自己熱改質法(ATR)、炭酸ガス改質法などを利用することもできる。
FT合成反応システムは、FT合成反応器10を備える。反応器10は、合成ガスを合成して液体炭化水素とする反応器の一例であり、FT合成反応により合成ガスから液体炭化水素を合成するFT合成用反応器として機能する。反応器10は、たとえば気泡塔型反応器とすることができる。
反応器10に収容されたスラリーの一部は、反応器10の胴部から、スラリー配送管としてのライン3を通じて分離器20に導入される。未反応の合成ガス等は、反応器10の塔頂から合成ガス排出管としてのライン2を通じて排出され、一部はライン1を通じて反応器10に戻される。
金属触媒には担持型や沈積型等があるが、いずれにしろ、鉄族金属を含む固体の磁性粒子である。固体粒子中に金属は適宜の量が含まれるが、固体粒子は100%金属でも良い。鉄族金属としては鉄が例示されるほか、活性の高いコバルトが好ましい。
分離器20による第一の固液分離工程では、スラリー中から所定の径以上の触媒を分離、回収する。回収された触媒は、ライン21を通じて反応器10に循環され、再使用される。
前記所定の径は適宜に設定することができる。たとえば、反応初期の触媒粒径(仕込み径)を設定してもよいし、経時的に減少する粒子径の適当な時期の径を適宜に設定してもよい。つまり、分離、回収すべき触媒の径は、反応系に戻して再利用する観点から適宜に設定される。
粒径の大な粒子が分離除去された残りのスラリーは、ライン22を通じて次の分離器30に導入される。
分離器20、30のいずれかを磁気分離器とすることができるが、以下では、分離器20を磁気分離器とする場合について説明する。
次に、充填物に付着した磁性粒子を洗浄除去する工程では、磁性粒子が付着した強磁性充填物を洗浄し、磁性粒子を洗浄液によって充填物から除去する。表面積が一定の充填物が捕捉できる磁性粒子の量には限界がある。そこで、磁性粒子の捕捉量が一定量又は限界量に達したならば、磁場を断って磁性粒子を充填物から脱離させたうえで、充填物を洗浄液によって洗浄し、磁性粒子を洗浄液とともに磁気分離器外に排出する。スラリー中に含有される磁性粒子の磁気分離条件、ならびに充填物に付着した磁性粒子の洗浄除去条件を以下に述べる。
なお、本発明において「液滞留時間」とは、磁場を印加する充填槽の体積を、充填槽に導入される液(すなわち磁性粒子を含むFT合成粗油)の流入量で除することで得られる時間を意味し、以下のような式で表される。
図2は、高勾配磁気分離器20の模式簡略図である。高勾配磁気分離器20の分離部は縦型充填塔をなし、該塔内に強磁性充填物が充填されている。充填物が充填されている充填槽26は、塔の外部に設置された電磁コイル23により発生する磁力線により磁化されて高勾配の磁気分離部を形成する。この部分が、外部の電磁コイル23により発生する均一な高磁場空間である。操作適温に加熱されたスラリーは、ライン3を通じて磁気分離器20の底部に導入され、塔内を所定の流速、好ましくは磁気分離部での滞留時間が15秒以上となる流速で下から上に通過し、塔頂部からライン22を通じて排出される。スラリーが磁気分離部を通過する間に、スラリーに含まれる磁性粒子が充填物の表面に付着する。
第一の固液分離工程において触媒粒子を分離された液体分は、ライン22を通じて分離器30に導入される。分離器30で、第一の固液分離工程において分離された液体分からさらに触媒を分離する。その平均粒径は、反応器10の出口におけるスラリー中の触媒の平均粒径よりも小さい。分離された触媒はライン31を通じて系外へ排出され、触媒残渣の低減された清浄なFT合成粗油は、ライン32を通じて分離器30から抜き出され、次の工程、たとえば、精留塔40に導入される。
すなわち、二段階の固液分離工程を経て得られたFT合成粗油は精留塔40に導入されて分留される。そして、たとえばナフサ留分(沸点が約150℃未満)がライン41を通じて分留され、中間留分(沸点が約150~350℃)がライン42を通じて分留され、ワックス留分(沸点が約350℃より大)がライン43を通じて分留される。なお、図1では三つの留分に分留されるが、二つの留分に分留されてもよいし、三つ以上の留分に分留されても良い。また、特に蒸留されずに次の精製工程に供することもできる。
天然ガスを改質して得られた一酸化炭素と水素ガスとを主成分として含む合成ガスを、ライン1を通じて気泡塔型炭化水素合成反応器(FT合成反応器)10に導入し、FT触媒粒子(平均粒径100μm、活性金属としてコバルトを30重量%担持)を懸濁させたスラリー内で反応させて液体炭化水素を合成した。
FT合成反応器10で合成された液体炭化水素は、FT触媒粒子を含むスラリーとしてライン3を通じて反応器10から取り出される。
なお、第一の固液分離工程で用いた高勾配磁気分離器20は、内部洗浄をするための洗浄液導入ライン24と洗浄液を排出するためのライン25とを有し、FT合成粗油から分離された触媒粒子を2時間おきに間欠的に洗浄して合成反応器10へと戻す。
なお、触媒粒子の平均粒径は、(株)島津製作所製レーザ回折式粒度分布測定装置 SALD-3100を用いて測定した値である(以下同様)。
第一の固液分離工程の処理条件を表1に記載の通りに変更した以外は、実施例1と同様の処理を行った。このとき、系外へ排出された触媒粒子の平均粒径は28μmであった。
第一の固液分離工程の処理条件を表1に記載の通りに変更した以外は、実施例1と同様の処理を行った。このとき、系外へ排出された触媒粒子の平均粒径は39μmであった。
第一の固液分離工程の処理条件を表1に記載の通りに変更した以外は、実施例1と同様の処理を行った。このとき、系外へ排出された触媒粒子の平均粒径は25μmであった。
天然ガスを改質して得られた一酸化炭素と水素ガスとを主成分として含む合成ガスを、ライン1を通じて気泡塔型炭化水素合成反応器(FT合成反応器)10に導入し、FT触媒粒子(平均粒径100μm、活性金属としてコバルトを30重量%担持)を懸濁させたスラリー内で反応させて液体炭化水素を合成した。
FT合成反応器10で合成された液体炭化水素は、FT触媒粒子を含むスラリーとしてライン3を通じて反応器10から取り出される。
第一の固液分離工程において分離された触媒粒子を、ライン21を通じて合成反応器10に戻し、焼結金属フィルターなどの分離器20では捕捉できない触媒粒子を含む液体分(液体A)を、第二の固液分離工程に設けられた電磁石型高勾配磁気分離器30(FEROSEP(登録商標))に導き、さらに固形分である触媒粒子と液体分(液体B)とに分離する。
液体分(液体B)を精留塔40へと導き、ナフサ留分(沸点が約150℃未満)がライン41を通じて分留され、中間留分(沸点が約150~350℃)がライン42を通じて分留され、ワックス留分(沸点が約350℃より大)がライン43を通じて分留された。さらに、中間留分を水素化異性化装置(図示せず)で処理し、ワックス留分を水素化分解装置(図示せず)で処理した後、水素化異性化装置および水素化分解装置からの流出物をライン内で混合して第2の精留塔(図示せず)に導入して分留し、ディーゼル燃料基材とした。
このとき、合成反応器10の出口におけるスラリー中の触媒粒子の平均粒径は72.5μmであり、系外へ排出された触媒粒子の平均粒径は25μmであった。
天然ガスを改質して得られた一酸化炭素と水素ガスとを主成分として含む合成ガスを、ライン1を通じて気泡塔型炭化水素合成反応器(FT合成反応器)10に導入し、FT触媒粒子(平均粒径100μm、活性金属としてコバルトを30重量%担持)を懸濁させたスラリー内で反応させて液体炭化水素を合成した。
FT合成反応器10で合成された液体炭化水素は、FT触媒粒子を含むスラリーとしてライン3を通じて反応器10から取り出される。
取り出されたスラリーを、FT合成反応器の後段に配置した固液分離工程に設けられた分離器20(目開きが10μmの焼結金属フィルター)に導き、触媒粒子と液体分とに分離する。ここで、固液分離器20は単段であって、磁気分離器30は設けていない。
FT合成反応器の後段に、第一の固液分離工程として電磁石型高勾配磁気分離器20を、第二の固液分離工程として金属フィルターなどの分離器30を配した場合(実施例1~4)、および第一の固液分離工程として金属フィルターなどの分離器20を、第二の固液分離工程として電磁石型高勾配磁気分離器30を配した場合、系外へ排出された触媒の平均粒径(重量基準)は、いずれの場合でも上記比較例1より小さな値を示した。つまり、粒径が小さくなった触媒粒子が、スラリー中から選択的に除去できることが分かる。
本発明の第二の実施形態を図1および図2を参照して説明する。
本実施形態の触媒分離、回収工程では、図1に示すように、二基の分離器20、30が直列に配列されている。第一の固液分離工程では、分離器20として高勾配磁気分離器を使用し、第二の固液分離工程では、分離器30としてろ過器を使用する。
本実施形態では、高勾配磁気分離器20は、上記分離条件を適宜に設定することにより磁性による粒子の分離が可能である。
第二の固液分離工程において触媒粒子を分離された液体分は、ライン22を通じてろ過器30に導入される。第二の固液分離工程では、ろ過器30に公知の技術を採用することができ、上記のろ過器以外にも、重力沈降分離器、サイクロン、遠心分離器等から選択される。重力沈降分離器としては、たとえば、液体分を満たし、その液体中の固体粒子を自然沈降させるべく一定時間放置する沈降槽(重力沈降分離器)を利用することができる。重力沈降分離器は構造が簡単であるので有利である。これらは、連続式、またはバッチ式のいずれも使用することができる。
磁性の測定法については特に限定は無いが、たとえばSQUID(超伝導量子干渉素子)等で測定される磁化率(emu/g)を好ましく挙げることができる。また、廃棄される触媒粒子の磁性は、反応器10の出口におけるスラリー中のFT触媒の磁性よりも小さければ、特に限定されるものではない。磁化率に関して検討した場合、廃棄される触媒粒子の磁性は、反応器10の出口におけるスラリー中のFT触媒の磁化率の98%以下、好ましくは97%以下である。
上記のように常法のろ過操作により、触媒残渣の低減された清浄なFT合成粗油が得られるので、磁性が小さく活性の低いFT触媒を選択的に除去することができる。
天然ガスを改質して得られた一酸化炭素と水素ガスとを主成分として含む合成ガスを、ライン1を通じて気泡塔型炭化水素合成反応器(FT合成反応器)10に導入し、FT触媒粒子(平均粒径100μm、活性金属としてコバルトを30重量%担持)を懸濁させたスラリー内で反応させて液体炭化水素を合成した。
FT合成反応器10で合成された液体炭化水素は、FT触媒粒子を含むスラリーとしてライン3を通じて反応器10から取り出される。
第二の固液分離工程において分離された触媒粒子を系外へ排出する。そして、液体分(液体B)を精留塔40へと導き、ナフサ留分(沸点が約150℃未満)がライン41を通じて分留され、中間留分(沸点が約150~350℃)がライン42を通じて分留され、ワックス留分(沸点が約350℃より大)がライン43を通じて分留された。さらに、中間留分を水素化異性化装置(図示せず)で処理し、ワックス留分を水素化分解装置(図示せず)で処理した後、水素化異性化装置および水素化分解装置からの流出物をライン内で混合して第2の精留塔(図示せず)に導入して分留し、ディーゼル燃料基材とした。
なお、触媒粒子の磁化率は、SQUID(超伝導量子干渉素子)磁束計(カンタム・デザイン社製 MPMS-5)を用いて測定した値である(以下同様)。
高勾配磁気分離器20の処理条件を表2に記載の通りに変更した以外は、実施例6と同様の処理を行った。各実施例において廃棄されたFT触媒粒子の平均磁化率を表2に記す。
スラリーからのFT触媒粒子の分離処理に、高勾配磁気分離器20を使用しないこと以外は、実施例6と同様の処理を行った。比較例2において廃棄されたFT触媒粒子の磁化率を表2に記す。
高勾配磁気分離器20およびろ過器30による分離工程を経て、系外へ排出されたFT触媒粒子は、反応器10の出口におけるスラリー中のFT触媒粒子よりも磁性が低く、活性が低下していることが分かる。一方、ろ過器30のみでFT触媒粒子を除去して廃棄した場合は、比較的磁性の強い触媒も廃棄されている。
本発明の第三の実施形態を図1および図2を参照して説明する。
本実施形態の触媒分離、回収工程では、図1に示すように、二基の分離器20、30が直列に配列されている。本実施形態では、分離器20、30として高勾配磁気分離器を使用する。第1の高勾配磁気分離器20、および第2の高勾配磁気分離器30においては、各分離器によって分離、回収する触媒の磁性が異なるように、双方の操作条件等を異ならせる。
磁性の測定法については特に限定は無いが、たとえばSQUID(超伝導量子干渉素子)等で測定される磁化率(emu/g)を好ましく挙げることができる。また、FT反応器に戻すFT触媒の磁性は、反応器10の出口におけるスラリー中のFT触媒の磁性よりも大きければ、特に限定されるものではない。磁化率に関して検討した場合、反応器10の出口におけるスラリー中のFT触媒の磁化率を基準として0.5%以上、1.0%以上大きいことが好ましい。
磁性の強い粒子を分離除去されたスラリーは、第2の高勾配磁気分離器30による第二の固液体分離工程にライン22を通じて供給される。
本実施形態では、高勾配磁気分離器20は、上記の分離条件を適宜に設定することにより、磁性による粒子の分離が可能である。例えば、高勾配磁気分離器20によりスラリー中から取り除かれ、FT反応器に戻されるFT触媒の磁性を、反応器10の出口におけるスラリー中のFT触媒の磁性よりも大きくすることが可能である。
高勾配磁気分離器30の分離条件としては、磁場強度は15000ガウス以上が好ましく、20000ガウス以上がさらに好ましい。分離器内の液温度(処理温度)は100℃以上400℃以下が好ましく、100℃以上300℃以下がさらに好ましく、100℃以上200℃以下が特に好ましい。液滞留時間は、50秒以上が好ましい。
高勾配磁気分離器30によって分離、除去された触媒粒子は磁性が弱く活性が低い。従って、このような触媒粒子は反応器10にリサイクルされることなく、ライン31を通じて系外へ排出され、好ましくは廃棄される。
磁性粒子が分離されたFT合成粗油は、ライン32を通じて精留塔40に導入される。
なお、第二の磁気分離工程における高勾配磁気分離器30では、適宜に操作条件を調節することにより、その多くの残渣触媒を除去することが可能である。これにより、残留触媒を除去されたFT合成粗油を取得することができる。
天然ガスを改質して得られた一酸化炭素と水素ガスとを主成分として含む合成ガスを、ライン1を通じて気泡塔型炭化水素合成反応器(FT合成反応器)10に導入し、FT触媒粒子(平均粒径100μm、活性金属としてコバルトを30重量%担持)を懸濁させたスラリー内で反応させて液体炭化水素を合成した。
FT合成反応器10で合成された液体炭化水素は、FT触媒粒子を含むスラリーとしてライン3を通じて反応器10から取り出される。
第二の固液分離工程において分離された低活性の触媒粒子を、ライン31を通じて系外へ排出する。そして、液体分(液体B)を精留塔40へと導き、ナフサ留分(沸点が約150℃未満)がライン41を通じて分留され、中間留分(沸点が約150~350℃)がライン42を通じて分留され、ワックス留分(沸点が約350℃より大)がライン43を通じて分留された。さらに、中間留分を水素化異性化装置(図示せず)で処理し、ワックス留分を水素化分解装置(図示せず)で処理した後、ライン内で混合して第2の精留塔(図示せず)に導入して分留し、ディーゼル燃料基材とした。
また、高勾配磁気分離器30の出口における液体Bの触媒濃度は9.6質量ppmであった。
また、液体Bの触媒濃度(質量ppm)は、(株)島津製作所製レーザ回折式粒度分布測定装置SALD-3100の測定結果に基づき、処理油の重量を基準にして算出された値である(以下同様)。
第1の高勾配磁気分離器20および第2の高勾配磁気分離器30の処理条件を表3に記載の通りに変更した以外は、実施例10と同様の処理を行った。各実施例においてリサイクルされたFT触媒粒子の磁化率、および第2の高勾配磁気分離器30出口における触媒濃度を表3に記す。
スラリーからのFT触媒粒子の分離処理に、第1の高勾配磁気分離器20および第2の高勾配磁気分離器30の代わりに、目開きが10μmの焼結金属フィルターを用いたこと以外は、実施例10と同様の処理を行った。リサイクルされたFT触媒粒子の磁化率、およびフィルター出口における処理油中の触媒濃度を表3に記す。なお、フィルター出口における処理油中の触媒濃度を、表3中の第2の磁気分離器30の出口における触媒濃度の欄に記載した。
比較例3のように、フィルターでFT触媒粒子を除去してリサイクルした場合は、磁性が弱く低活性の触媒もFT反応器に戻されていることが分かる。一方、各実施例のように、第1の高勾配磁気分離器20によって分離され、反応器10に戻されたFT触媒粒子は、いずれも反応器10の出口におけるスラリー中のFT触媒粒子よりも磁性が高く、触媒活性の高いことが分かる。
本発明によれば、微細な微粒子の発生しやすいFT合成粗油から微粉化触媒を効率よく回収することができる。さらに、磁性が強く高活性な残留触媒を選択的に再使用することができる。
Claims (9)
- フィッシャー・トロプシュ合成反応器からのフィッシャー・トロプシュ触媒の選択的除去方法であって、
フィッシャー・トロプシュ合成反応により得られるフィッシャー・トロプシュ合成粗油と磁性を有するフィッシャー・トロプシュ触媒とを含むスラリーを、フィッシャー・トロプシュ合成反応器から抜き出す工程と、
前記スラリーから、所定の径以上の触媒を、第一の固液分離装置を使用して分離する工程と、
前記所定の径以上の触媒を分離された前記スラリーから、前記第一の固液分離装置によっては分離されなかった触媒を、第二の固液分離装置を使用して分離する工程とを備え、
前記第一の固液分離装置によって前記スラリーから分離された前記触媒は、前記フィッシャー・トロプシュ合成反応器に戻して再利用され、
前記第二の固液分離装置によって前記スラリーから分離された前記触媒は、系外に排出され、
前記系外に排出される前記触媒の平均粒径は、前記フィッシャー・トロプシュ合成反応器の出口における前記スラリー中の前記触媒の平均粒径よりも小さいフィッシャー・トロプシュ触媒の選択的除去方法。 - 請求項1に記載のフィッシャー・トロプシュ触媒の選択的除去方法であって、
前記第一の固液分離装置は、高勾配磁気分離器であり、
前記第二の固液分離装置は、前記高勾配磁気分離器以外から選択されるフィッシャー・トロプシュ触媒の選択的除去方法。 - 請求項1に記載のフィッシャー・トロプシュ触媒の選択的除去方法であって、
前記第二の固液分離装置は、高勾配磁気分離器であり、
前記第一の固液分離装置は、前記高勾配磁気分離器以外から選択されるフィッシャー・トロプシュ触媒の選択的除去方法。 - 請求項2または3に記載のフィッシャー・トロプシュ触媒の選択的除去方法であって、
前記高勾配磁気分離器は、同分離器の内部を洗浄するための洗浄液導入経路と、前記洗浄液を前記分離器から排出する洗浄液排出経路とを有し、
前記分離器内部で捕捉した磁性粒子を間欠的に洗浄するフィッシャー・トロプシュ触媒の選択的除去方法。 - 請求項2または3に記載のフィッシャー・トロプシュ触媒の選択的除去方法であって、
前記高勾配磁気分離器以外から選択される固液分離装置が、ろ過分離器、重力沈降分離器、サイクロン、遠心分離器の少なくともいずれかひとつであるフィッシャー・トロプシュ触媒の選択的除去方法。 - フィッシャー・トロプシュ合成反応器からのフィッシャー・トロプシュ触媒の選択的除去方法であって、
フィッシャー・トロプシュ合成反応により得られるフィッシャー・トロプシュ合成粗油と磁性を有するフィッシャー・トロプシュ触媒とを含むスラリーを、フィッシャー・トロプシュ合成反応器から抜き出す工程と、
前記スラリーから、磁性の強い触媒を、第一の高勾配磁気分離器を使用して分離する工程と、
前記触媒を分離された前記スラリーから、前記第一の高勾配磁気分離器によっては分離されなかった磁性の弱い触媒を、ろ過装置を使用して分離する工程とを備え、
前記第一の高勾配磁気分離器によって前記スラリーから分離された前記磁性の強い触媒は、前記フィッシャー・トロプシュ合成反応器に戻して再利用され、
前記ろ過装置によって前記スラリーから分離された磁性の弱い前記触媒は、系外に排出されるフィッシャー・トロプシュ触媒の選択的除去方法。 - 請求項6に記載のフィッシャー・トロプシュ触媒の選択的除去方法であって、
前記ろ過装置によって前記スラリーから分離された前記触媒の磁性が、前記フィッシャー・トロプシュ合成反応器の出口における前記スラリー中の前記触媒の磁性よりも弱いフィッシャー・トロプシュ触媒の選択的除去方法。 - フィッシャー・トロプシュ触媒のリサイクル方法であって、
フィッシャー・トロプシュ合成反応により得られるフィッシャー・トロプシュ合成粗油と磁性を有するフィッシャー・トロプシュ触媒とを含むスラリーを、フィッシャー・トロプシュ合成反応器から抜き出す工程と、
前記スラリーから、磁性の強い触媒を、第一の高勾配磁気分離器を使用して分離する工程と、
前記磁性の強い触媒が分離された前記スラリーから、前記第一の高勾配磁気分離器によっては分離されなかった触媒を、第二の高勾配磁気分離器を使用して分離する工程とを備え、
前記第一の高勾配磁気分離器によって前記スラリーから分離された前記磁性の強い触媒は、前記フィッシャー・トロプシュ合成反応器に戻して再利用され、
前記第二の高勾配磁気分離器によって前記スラリーから分離された前記触媒は、系外に排出されるフィッシャー・トロプシュ触媒のリサイクル方法。 - 請求項8に記載のフィッシャー・トロプシュ触媒のリサイクル方法であって、
前記第一の高勾配磁気分離器によって前記スラリーから分離された前記触媒の磁性が、前記フィッシャー・トロプシュ合成反応器の出口における前記スラリー中の前記触媒の磁性よりも強いフィッシャー・トロプシュ触媒のリサイクル方法。
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EP09719232A EP2261306A1 (en) | 2008-03-14 | 2009-03-12 | Method for selectively removing catalysts from fischer-tropsch synthetic crude oil and method for recycling removed catalysts |
BRPI0909149-1A BRPI0909149A2 (pt) | 2008-03-14 | 2009-03-12 | Método de remoção seletiva de catalisador de óleo cru sintético fischer-tropsch e método de reciclagem do catalisador removido |
AU2009224349A AU2009224349B2 (en) | 2008-03-14 | 2009-03-12 | Method for selectively removing catalysts from Fischer-Tropsch synthetic crude oil and method for recycling removed catalysts |
US12/736,106 US20110281960A1 (en) | 2008-03-14 | 2009-03-12 | Method of selectively removing catalyst from fischer-tropsch synthetic crude oil and method of recycling removed catalyst |
CN2009801085165A CN101970605A (zh) | 2008-03-14 | 2009-03-12 | 选择性地除去来自费-托合成粗油的催化剂的方法以及被除去的催化剂的回收再利用方法 |
CA2718164A CA2718164C (en) | 2008-03-14 | 2009-03-12 | Method of selectively removing catalyst from fischer-tropsch synthetic crude oil and method of recycling removed catalyst |
EA201070959A EA201070959A1 (ru) | 2008-03-14 | 2009-03-12 | Способ селективного удаления катализатора из синтетической сырой нефти фишера-тропша и способ повторного использования удаленного катализатора |
ZA2010/06512A ZA201006512B (en) | 2008-03-14 | 2010-09-10 | Method for selctively removing catalyst from fischer-tropsch synthetic crude oil and method for recycling removed catalysts |
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JP2008065773A JP5294662B2 (ja) | 2008-03-14 | 2008-03-14 | Ft合成油中の微粉化したft触媒の選択的除去方法 |
JP2008-065778 | 2008-03-14 | ||
JP2008065780A JP5294664B2 (ja) | 2008-03-14 | 2008-03-14 | Ft合成油中の失活したft触媒の選択的除去方法 |
JP2008-065780 | 2008-03-14 | ||
JP2008065778A JP5294663B2 (ja) | 2008-03-14 | 2008-03-14 | Ft合成油中のft触媒をリサイクルする方法 |
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JP5764307B2 (ja) * | 2010-08-19 | 2015-08-19 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 炭化水素油の製造方法及び炭化水素油の製造システム |
EP3153776A1 (en) * | 2015-10-08 | 2017-04-12 | Improbed AB | Bed management cycle for a fluidized bed boiler and corresponding arrangement |
CN110628454B (zh) * | 2018-06-21 | 2021-11-05 | 国家能源投资集团有限责任公司 | 费托合成系统及分离费托合成油气产物中催化剂细粉的方法 |
CN111187638A (zh) * | 2018-11-15 | 2020-05-22 | 国家能源投资集团有限责任公司 | 分离费托合成渣蜡中废催化剂的系统和方法 |
CN111187636A (zh) * | 2018-11-15 | 2020-05-22 | 国家能源投资集团有限责任公司 | 分离费托合成重质蜡中催化剂的系统和方法 |
CN111187639A (zh) * | 2018-11-15 | 2020-05-22 | 国家能源投资集团有限责任公司 | 分离费托合成渣蜡中废催化剂的装置和方法 |
CN111187637A (zh) * | 2018-11-15 | 2020-05-22 | 国家能源投资集团有限责任公司 | 分离费托合成渣蜡中废催化剂的系统和方法 |
CN116179240A (zh) * | 2021-11-29 | 2023-05-30 | 国家能源投资集团有限责任公司 | 分离费托合成重质蜡与催化剂的系统和方法 |
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ZA201006512B (en) | 2011-12-28 |
BRPI0909149A2 (pt) | 2015-08-25 |
EA201070959A1 (ru) | 2011-02-28 |
US20110281960A1 (en) | 2011-11-17 |
CA2718164A1 (en) | 2009-09-17 |
CN101970605A (zh) | 2011-02-09 |
AU2009224349B2 (en) | 2012-09-06 |
CA2718164C (en) | 2013-09-17 |
EP2261306A1 (en) | 2010-12-15 |
AU2009224349A1 (en) | 2009-09-17 |
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