CN107684932A - Slurry bed system Co based Fischer-Tropsch synthesis catalyst regenerated offline method and its device - Google Patents

Slurry bed system Co based Fischer-Tropsch synthesis catalyst regenerated offline method and its device Download PDF

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CN107684932A
CN107684932A CN201710941247.7A CN201710941247A CN107684932A CN 107684932 A CN107684932 A CN 107684932A CN 201710941247 A CN201710941247 A CN 201710941247A CN 107684932 A CN107684932 A CN 107684932A
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catalyst
slurry
bed reactor
heating
fluidized
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Inventor
刘倩倩
宋德臣
海国良
李昌元
程凤
汪大闪
李程根
宋侃
詹晓东
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/34—Apparatus, reactors
    • C10G2/342—Apparatus, reactors with moving solid catalysts
    • C10G2/344—Apparatus, reactors with moving solid catalysts according to the "fluidised-bed" technique

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process and its device, method to comprise the following steps：1) gas-liquid separation and filtration treatment；2) mink cell focus separating treatment and heating air lift removing hydrocarbon；3) heating and oxidation is handled, and heating and oxidation finishing temperature is 300~400 DEG C；4) heating reduction is handled, and heating reduction finishing temperature is 300~400 DEG C；5) catalyst after reduction is transferred in slurry commanding tank from fluidized-bed reactor, carried out with mink cell focus with slurry.In the present invention, mink cell focus separation, heating air lift removing hydrocarbon, oxidation and reduction treatment are completed in same fluidized-bed reactor, equipment investment cost is low, it is not related to mechanical agitation completely in whole regenerative process, the transfer of catalyst need not be carried out, reduces the loss and abrasion of catalyst, regeneration efficiency is high, technical process is simply easily controllable, easy to operate.

Description

Slurry bed system Co based Fischer-Tropsch synthesis catalyst regenerated offline method and its device
Technical field
The present invention relates to catalyst regeneration techniques, in particular to a kind of slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process And its device.
Background technology
Cobalt-base catalyst is the catalyst that F- T synthesis technical field is widely used in paste state bed reactor, is turned with one way Rate is high, heavy hydrocarbon-selective is good, long lifespan, convenience add the advantage such as low with displacement, running cost.But F- T synthesis is anti- After a period of time should being carried out, because catalyst poisoning, surface form carbon distribution, metallic cobalt is oxidized, cobalt granule sintering is grown up Reason, makes catalytic activity and selectivity declines that (wherein inactivation can not pass through regeneration caused by catalyst poisoning, it is necessary to regenerated Activity recovery).By catalyst regeneration techniques, it on the one hand can extend the service life of catalyst, reduce the use of catalyst Cost, it on the other hand can also save the consumption of Precious Metals Resources and reduce environmental pollution.
For a long time, substantial amounts of Patent document data shows that Co based Fischer-Tropsch synthesis catalyst can recover to turn by regenerating It is combined to the ability of gas.The regeneration of slurry bed system Co based Fischer-Tropsch synthesis catalyst can be divided into reactor in situ according to reproduction position Regeneration and the outer major class of regenerated offline two of reactor.In-situ regeneration in reactor, this original as disclosed in United States Patent (USP) 5973012 Position regeneration method must interrupt the operation of paste state bed reactor, change process conditions, and this regeneration influences plant running Stability.The outer regenerated offline technology of reactor is a lot, such as US 8921252, WO 02/085508, WO2008/139407, CN 101844093rd, the renovation process disclosed in CN 101703937, is mainly included the following steps that：(1) dewax：From slurry reactor The catalyst of inactivation and the slurries of wax liquor composition are extracted in device, it is removed by way of sedimentation concentration, solvent extraction, air lift In hydrocarbon compound, obtain the catalyst granules that can be flowed freely；(2) aoxidize：Hydrocarbonization is further removed by oxidation Compound, while active metal simple substance is oxidized to oxidation state；(3) reduce：With hydrogen reducing activated catalyst；(4) it is with slurry：Use wax Liquid by catalyst granules it is with slurry after send back in reactor.The general dewaxing of this kind of method and oxidation, reduction process are each single Completed in equipment, equipment cost is high；The cobalt layers on dewaxing rear catalyst surface are exposed, are easily oxidized, are urged for safe transfer Agent need to be passivated processing, so result in recovery time extension, running cost improves to oxidation furnaces.
The content of the invention
, should present invention aim to provide a kind of slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process and its device Method to catalyst without being shifted, and process is easily controlled, and the performance of the catalyst after regeneration can reach fresh catalyst Performance level, and regeneration cost is low.
To achieve the above object, the technical solution adopted by the present invention is：A kind of slurry bed system Co based Fischer-Tropsch synthesis catalyst is again Generation method, comprise the following steps：
1) slurries containing gas phase come out from paste state bed reactor are subjected to gas-liquid separation processing, obtained containing mink cell focus Decaying catalyst slurries；
2) decaying catalyst slurries are put into progress mink cell focus separating treatment in fluidized-bed reactor, then using indifferent gas The hydrocarbon of body heating air lift Removal of catalyst particle surface, heating air lift finishing temperature are 120~200 DEG C；
3) with after the air lift that heated up in the dilution oxygen heating and oxidation Removal of catalyst particle that percent by volume is 0.1~5% Remaining hydrocarbon, and the metal simple substance cobalt on catalyst is oxidizing to oxidation state, heating and oxidation finishing temperature is 300~ 400℃；
4) after heating and oxidation process terminates, reducing gas heating reduction catalyst is passed through, heating reduction finishing temperature is 300 ~400 DEG C；
5) catalyst after reduction is transferred in slurry commanding tank from fluidized-bed reactor, carried out with mink cell focus with slurry.
Further, in the step 2), mink cell focus separating treatment comprises the following steps：
A, decaying catalyst slurries being heated to 80~220 DEG C in fluidized-bed reactor, control pressure is 0.5~ 3MPa, and stirring of inert gas is passed through, first time solid-liquor separation then is carried out by filtering, removes liquid phase mink cell focus, consolidate Phase catalyst；
B, the solvent naphtha of low viscosity is added in solid-phase catalyst to the weight that is adhered between catalyst granules and in duct Matter oil carries out one or many extraction removings, is passed through stirring of inert gas in extraction process, until catalyst reaches can free flow Dynamic fluidisation state, second of solid-liquor separation then is carried out by filtering, further removes liquid phase mink cell focus；Extraction temperature be 65~ 220 DEG C, pressure is 0.5~3MPa.
Further, in the step b, solvent naphtha is using one or more of in C7~C20 alkane derivative Combination, solvent naphtha are 1~6 with decaying catalyst slurry volume ratio:1.
Further, in the step 2), during the air lift that heats up, catalyst layer is made with 0.5~2 DEG C/min speed 120~200 DEG C of heating air lift finishing temperature is warming up to, and is incubated 2~10h, heating air lift pressure is 0.5~1.5MPa, heating Air lift gas empty bed speed is 0.5~5cm/s, and air speed GHSV is 0.5~3L/ (gh).
Further, in the step 3), during heating and oxidation, catalysis is made with 0.5~2.0 DEG C/min heating rate Agent bed is warming up to 300~400 DEG C of heating and oxidation finishing temperature, and keeps 2~20h, is then cooled to 100~150 DEG C；Fluidisation The empty bed speed of gas is 2~10cm/s in bed, and pressure is 0.5~3.0MPa, and air speed GHSV is 1.0~4.0L/ (gh).
Further, in the step 4), using pure hydrogen heating reduction, reaction bed temperature is with 0.5~2.0 DEG C/min Heating rate be warming up to 350~400 DEG C of heating reduction finishing temperature, and be incubated 2~10h, be then cooled to 180~200 DEG C； The empty bed speed of gas is 2~10cm/s in fluid bed, and pressure is 0.5~3.0MPa, and air speed GHSV is 1.0~4.0L/ (gh).
Further, in the step a, during first time solid-liquor separation, control in fluidized-bed reactor filter top and The pressure difference of bottom is 0.05~0.1MPa.
Further, in the step b, when carrying out second of solid-liquor separation, control in fluidized-bed reactor on filter The pressure difference of portion's pressure and low pressure is 0.05~0.3MPa.
Further, in the step 2), the inert gas that heating air lift uses is one kind in nitrogen and methane or two Kind.
Further, in the step 3), the concentration of volume percent of oxygen is 0.1~1.0% in dilution oxygen；Oxygen Beds are made to be warming up to 300~400 DEG C with 0.5~1.0 DEG C/min heating rate during change.
A kind of slurry bed system Co based Fischer-Tropsch synthesis catalyst regenerating unit, including paste state bed reactor, in addition to gas-liquid separation Tank, fluidized-bed reactor and slurry commanding tank, the serum outlet of the paste state bed reactor and the slurry inlet of knockout drum connect, The liquid-phase outlet of the knockout drum is connected with the slurry inlet of the fluidized-bed reactor, and the fluidized-bed reactor is urged Agent outlet is connected with the slurry commanding tank, and the slurry commanding tank communicates with the heavy oil export of the paste state bed reactor.
Further, gas feed, solvent oil inlet and offgas outlet are also provided with the fluidized-bed reactor.
Further, air inlet pipe is connected with the gas feed of the fluidized-bed reactor, the air inlet pipe is matched somebody with somebody with described Starch tank connection.
Compared with prior art, the present invention has advantages below：
First, in the present invention, mink cell focus separation, heating air lift removing hydrocarbon, oxidation and reduction treatment are same Completed in one fluidized-bed reactor, equipment investment cost is low, is not related to mechanical agitation completely in whole regenerative process, without entering The transfer of row catalyst, the loss and abrasion of catalyst are reduced, regeneration efficiency is high, and technical process is simply easily controllable, operation It is easy.
Second, can optionally remove particle tiny in catalyst during solid-liquor separation, it is catalyzed after ensureing regeneration The size distribution of agent is consistent with the size distribution of fresh catalyst.
Third, the performance of the catalyst after regeneration can reach the performance level of fresh catalyst.
Fourth, apparatus of the present invention equipment is few, simple to operation, equipment investment and operating cost are significantly reduced.
Brief description of the drawings
Fig. 1 is a kind of slurry bed system Co based Fischer-Tropsch synthesis catalyst regenerating unit.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, is easy to more clearly understand this Invention, but they do not form to the present invention and limited.
Slurry bed system Co based Fischer-Tropsch synthesis catalyst regenerating unit as shown in Figure 1, including paste state bed reactor 1, gas-liquid point From tank 2, fluidized-bed reactor 3 and slurry commanding tank 4, the serum outlet 1-1 and knockout drum 2 of paste state bed reactor 1 slurries enter Mouth 2-1 connections, the liquid-phase outlet 2-2 of knockout drum 2 are connected with the slurry inlet 3-1 of fluidized-bed reactor 3, fluidized-bed reaction The catalyst outlet 3-2 of device 3 is connected with slurry commanding tank 4, and slurry commanding tank 4 communicates with the heavy oil export 1-2 of paste state bed reactor 1.Stream Also it is provided with fluidized bed reactor 3 for being filled with inert gas, dilution oxygen and the also gas feed 3-3 of Primordial Qi, solvent oil inlet 3-4 and offgas outlet 3-5.Air inlet pipe 5 is connected with the gas feed 3-3 of fluidized-bed reactor 3, air inlet pipe 5 connects with slurry commanding tank 4 It is logical, it is stirred for being filled with inert gas.The grout outlet of slurry commanding tank 4 is connected with the overfall mouth 1-3 of paste state bed reactor 1.
The course of work of above-mentioned slurry bed system Co based Fischer-Tropsch synthesis catalyst regenerating unit is as follows：
1) gas-liquid separation processing is carried out from the slurries containing gas phase that paste state bed reactor 1 comes out by knockout drum 2, obtained To the decaying catalyst slurries containing mink cell focus.
2) catalyst slurry of inactivation enters fluidized-bed reactor 3, first to catalyst in fluidized-bed reactor 3 Slurries carry out mink cell focus separating treatment：A, first slurries are further concentrated, the heavy oil of removing is thin through follow-up removing solid Turn into heavy oil product after powder, then squeeze into solvent naphtha in fluidized-bed reactor 3 through air inlet pipe 5, solvent naphtha and fluidized-bed reaction The volume ratio (abbreviation solvent ratios) of decaying catalyst slurries in device 3 is 1:1~6:1, solvent naphtha C7~C20Alkanes One or more of combinations of compound, preferably Fischer-Tropsch synthetic light oil；B, inert gas through pipeline 6 from fluidized-bed reactor 3 bottoms are passed through beds, and mixing is sufficiently stirred in the form of bubble, with improve extraction effect, extraction temperature be 65~ 220 DEG C, extracting pressure is 0.5~3MPa, and extraction time is 10min~6h.It is anti-by adjusting fluid bed after the completion of single extraction The mode of the filter of device 3 pressure difference up and down is answered, separates solid catalyst and extractant, the pressure difference of filter top and bottom is 0.05~0.3MPa, extraction process may be repeated repeatedly, until the extractant that solid-liquor separation obtains is in a liquid state at normal temperatures.
Then, using the nytron of inert gas heating air lift Removal of catalyst particle surface in fluidized-bed reactor 3 Thing：Inert gas is being passed through to fluidized-bed reactor 3 through pipeline 6, and with 0.5~2 DEG C/min heating rate temperature programming air lifts The hydrocarbon of Removal of catalyst particle surface, temperature programming finishing temperature are 120~200 DEG C, and keep 2 in finishing temperature ~10h.Air lift pressure is 0.5~1.5MPa.Then 100~150 DEG C are cooled to.
3) volumetric concentration is that 0.1~5.0% dilution oxygen enters fluidized-bed reactor 3 through pipeline 6, and with 0.5~2.0 DEG C/min heating rate makes beds temperature programming to 300~400 DEG C, and keeps 2~10h, heating and oxidation removing is urged Remaining hydrocarbon in catalyst particles, while analyze from fluid bed exhaust pipe 7 and discharge O in tail gas2、H2O、CO2With CO's Concentration, to ensure that oxidation is complete, then it is cooled to 100~150 DEG C；Gas pressure is 0.5~3.0MPa in fluid bed.
4) dilution oxygen in pipeline 6 is switched into inert gas purge, until inert gas replaces dilution oxygen Entirely, pure hydrogen then is passed through through pipeline 6, with 0.5~2.0 DEG C/min heating rate temperature programming to 350~400 DEG C, pressure For 0.5~3.0MPa, and 2~20h is kept in finishing temperature, be then cooled to 180~200 DEG C；Empty bed speed is 2~10cm/ S, preferably empty bed speed are 3~8cm/s, and air speed GHSV is 1.0~4.0L/ (gh).
5) using the heavy oil of F- T synthesis generation in paste state bed reactor 1 as liquid phase with slurry, the catalysis in slurry commanding tank 4 is made The concentration of agent particle is consistent with the concentration of the catalyst granules of Fischer-Tropsch synthesis in paste state bed reactor 1, weight used with slurry The finishing temperature that oil temperature cools after terminating with catalyst reduction is consistent, and through overfall mouth 1-3 F- T synthesis is returned to after with slurry Paste state bed reactor 1.
Embodiment 1
1) slurries containing gas phase come out from paste state bed reactor are subjected to gas-liquid separation processing, obtained containing mink cell focus Decaying catalyst slurries；
2) decaying catalyst slurries are put into fluidized-bed reactor, it is 80 to keep slurry temperature in fluidized-bed reactor DEG C, be passed through stirring of inert gas it is uniform after, the pressure difference of controlling filter upper and lower part is 0.1MPa, isolates mink cell focus.
3) it is passed through Fischer-Tropsch synthetic light oil C7-C10(solvent ratios 1:1) extracted, 65 DEG C of extraction temperature, pressure 0.5MPa, time 1h, extraction is passed through nitrogen three times, in extraction process makes slurries fully mix；Controlling filter during solid-liquor separation The pressure difference of top and bottom is 0.3MPa.
4) after solid-liquor separation terminates, nitrogen is passed through into fluidized-bed reactor, from extraction temperature with 0.5 DEG C/min speed Temperature programming keeps 10h to 120 DEG C, is then cooled to 100 DEG C；Air lift pressure is 0.5MPa.
5) the oxygen/nitrogen mixed gas that oxygenous percent by volume is 0.1% is passed through, with 0.5 DEG C/min heating Rate program is warming up to 300 DEG C of oxidation 20h, while analyzes O in fluid bed discharge tail gas2、H2O、CO2With CO concentration, ensure oxygen It is complete to change reaction, is then cooled to 100 DEG C；System pressure is 0.5MPa in oxidizing process.
6) switch to nitrogen to purge dilution oxygen, until nitrogen replaces dilution oxygen completely, then pass to pure hydrogen, Air speed 4.0L/ (gh), 350 DEG C are warming up to 0.5 DEG C/min rate program, 10h is kept, pressure 0.5MPa, then cools To 180 DEG C.
7) using the catalyst after reduction in 180 DEG C of heavy oil and step 6) mix it is with slurry after return to paste state bed reactor In.
Embodiment 2
1) slurries containing gas phase come out from paste state bed reactor are subjected to gas-liquid separation processing, obtained containing mink cell focus Decaying catalyst slurries；
2) decaying catalyst slurries are put into fluidized-bed reactor, it is 220 to keep slurry temperature in fluidized-bed reactor DEG C, be passed through stirring of inert gas it is uniform after, the pressure difference of controlling filter upper and lower part is 0.05MPa, isolates mink cell focus.
3) it is passed through Fischer-Tropsch synthetic light oil C18-C20(solvent ratios 6:1) extracted, 220 DEG C of extraction temperature, pressure 3MPa, time 6h, extraction is once.Nitrogen is passed through in extraction process makes slurries fully mix.During solid-liquor separation in controlling filter The pressure difference of portion and bottom is 0.05MPa.
4) after solid-liquor separation terminates, methane is passed through into fluidized-bed reactor, from extraction temperature with 2 DEG C/min speed journey Sequence is warming up to 200 DEG C, and keeps 2h, is then cooled to 150 DEG C.Air lift pressure is 1.5MPa.
5) oxygenous 5% oxygen/nitrogen mixed gas is passed through, with 2.0 DEG C/min heating rate temperature programming extremely 400 DEG C of oxidation 2h, while analyze O in fluid bed discharge tail gas2、H2O、CO2With CO concentration, ensure that oxidation reaction is complete.Then It is cooled to 150 DEG C.System pressure is 3.0MPa in oxidizing process.
6) nitrogen is switched to purge dilution oxygen, until nitrogen replaces dilution oxygen completely.It is passed through pure hydrogen, air speed 1.0L/ (gh), 400 DEG C are warming up to 2.0 DEG C/min rate program, 2h is kept, pressure 3.0MPa, is then cooled to 200 ℃。
7) using the catalyst after reduction in 200 DEG C of heavy oil and step 6) mix it is with slurry after return to paste state bed reactor In.
Embodiment 3
1) slurries containing gas phase come out from paste state bed reactor are subjected to gas-liquid separation processing, obtained containing mink cell focus Decaying catalyst slurries；
2) decaying catalyst slurries are put into fluidized-bed reactor, it is 150 to keep slurry temperature in fluidized-bed reactor DEG C, be passed through stirring of inert gas it is uniform after, the pressure difference of controlling filter upper and lower part is 0.07MPa, isolates mink cell focus.
3) it is passed through Fischer-Tropsch synthetic light oil C11-C15(solvent ratios 3:1) extracted, 120 DEG C of extraction temperature, pressure 2MPa, time 4h, is extracted twice.Nitrogen is passed through in extraction process makes slurries fully mix.During solid-liquor separation in controlling filter The pressure difference of portion and bottom is 0.1MPa.
4) after solid-liquor separation terminates, the gaseous mixture (volume ratio of the two of methane and nitrogen is passed through into fluidized-bed reactor For 1:1) 160 DEG C, are warming up to from extraction temperature with 1 DEG C/min rate program, and keeps 6h, is then cooled to 120 DEG C.Air lift Pressure is 1.0MPa.
5) oxygenous 2.5% oxygen/nitrogen mixed gas is passed through, with 1.0 DEG C/min heating rate temperature programming To 350 DEG C of oxidation 6h, while analyze O in fluid bed discharge tail gas2、H2O、CO2With CO concentration, ensure that oxidation reaction is complete.So After be cooled to 120 DEG C.System pressure is 2.0MPa in oxidizing process.
6) nitrogen is switched to purge dilution oxygen, until nitrogen replaces dilution oxygen completely.It is passed through pure hydrogen, air speed 2.0L/ (gh), 370 DEG C are warming up to 1.0 DEG C/min rate program, 6h is kept, pressure 2.0MPa, is then cooled to 190 ℃。
7) using the catalyst after reduction in 190 DEG C of heavy oil and step 6) mix it is with slurry after return to paste state bed reactor In.
Embodiment 4
1) slurries containing gas phase come out from paste state bed reactor are subjected to gas-liquid separation processing, obtained containing mink cell focus Decaying catalyst slurries；
2) decaying catalyst slurries are put into fluidized-bed reactor, it is 120 to keep slurry temperature in fluidized-bed reactor DEG C, be passed through stirring of inert gas it is uniform after, the pressure difference of controlling filter upper and lower part is 0.05MPa, isolates mink cell focus.
3) it is passed through Fischer-Tropsch synthetic light oil C15-C18(solvent ratios 2:1) extracted, 160 DEG C of extraction temperature, pressure 1.5MPa, time 3h, is extracted twice.Nitrogen is passed through in extraction process makes slurries fully mix.Controlling filter during solid-liquor separation The pressure difference of top and bottom is 0.3MPa.
4) after solid-liquor separation terminates, nitrogen is passed through into fluidized-bed reactor, from extraction temperature with 1.5 DEG C/min speed Temperature programming keeps 8h to 140 DEG C, is then cooled to 110 DEG C.Air lift pressure is 1.0MPa.
5) oxygenous 4% oxygen/nitrogen mixed gas is passed through, with 1.5 DEG C/min heating rate temperature programming 380 DEG C oxidation 4h, while analyze fluid bed discharge tail gas in O2、H2O、CO2With CO concentration, ensure that oxidation reaction is complete.Then drop Temperature is to 140 DEG C.System pressure is 1.5MPa in oxidizing process.
6) nitrogen is switched to purge dilution oxygen, until nitrogen replaces dilution oxygen completely.It is passed through pure hydrogen, air speed 3.0L/ (gh), 380 DEG C are warming up to 1.5 DEG C/min rate program, 4h is kept, pressure 1.5MPa, is then cooled to 180 ℃。
7) using the catalyst after reduction in 180 DEG C of heavy oil and step 6) mix it is with slurry after return to paste state bed reactor In.
Embodiment 5
1) slurries containing gas phase come out from paste state bed reactor are subjected to gas-liquid separation processing, obtained containing mink cell focus Decaying catalyst slurries；
2) decaying catalyst slurries are put into fluidized-bed reactor, it is 180 to keep slurry temperature in fluidized-bed reactor DEG C, be passed through nitrogen gas stirring it is uniform after, the pressure difference of controlling filter upper and lower part is 0.08MPa, isolates mink cell focus.
3) it is passed through Fischer-Tropsch synthetic light oil C15-C20(solvent ratios 4:1) extracted, 180 DEG C of extraction temperature, pressure 2.5MPa, time 0.5h, is extracted twice.Nitrogen is passed through in extraction process makes slurries fully mix.Filtering is controlled during solid-liquor separation The pressure difference of device top and bottom is 0.15MPa.
4) after solid-liquor separation terminates, nitrogen is passed through into fluidized-bed reactor, from extraction temperature with 1 DEG C/min speed journey Sequence is warming up to 180 DEG C, and keeps 4h, is then cooled to 140 DEG C.Air lift pressure is 1.2MPa.
5) oxygenous 1.0% oxygen/nitrogen mixed gas is passed through, with 1.0 DEG C/min heating rate temperature programming 320 DEG C of oxidation 8h, while analyze O in fluid bed discharge tail gas2、H2O、CO2With CO concentration, ensure that oxidation reaction is complete.Then It is cooled to 130 DEG C.System pressure is 1.0MPa in oxidizing process.
6) nitrogen is switched to purge dilution oxygen, until nitrogen replaces dilution oxygen completely.It is passed through pure hydrogen, air speed 1.5L/ (gh), 360 DEG C are warming up to 1.0 DEG C/min rate program, 8h is kept, pressure 1.0MPa, is then cooled to 200 ℃。
7) using the catalyst after reduction in 200 DEG C of heavy oil and step 6) mix it is with slurry after return to paste state bed reactor In.
Under identical reaction conditions, the activity and selectivity of the catalyst after fresh catalyst and regeneration, reaction are evaluated Condition is：220 DEG C, reaction pressure 3.0MPa of reaction temperature, synthesis gas composition is V (N2):V(H2):V (CO)=3:2:1, air speed GHSV=10L/ (gh).Reaction operation is as shown in table 1 below to evaluation result during 300h.
Table 1
From table 1 it follows that catalyst, after the present invention regenerates, activity and selectivity is with fresh catalyst without obvious poor It is different, illustrate that the inventive method can make the Co based Fischer-Tropsch synthesis catalyst activity recovery of inactivation, and the activity level after regeneration It is suitable with the activity level of fresh catalyst.

Claims (13)

  1. A kind of 1. slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process, it is characterised in that：Comprise the following steps：
    1) slurries containing gas phase come out from paste state bed reactor are subjected to gas-liquid separation processing, obtain the inactivation containing mink cell focus Catalyst slurry；
    2) decaying catalyst slurries are put into progress mink cell focus separating treatment in fluidized-bed reactor, then using inert gas liter Wet carries the hydrocarbon of Removal of catalyst particle surface, and heating air lift finishing temperature is 120~200 DEG C；
    3) with remaining after the air lift that heated up in the dilution oxygen heating and oxidation Removal of catalyst particle that percent by volume is 0.1~5% Hydrocarbon, and the metal simple substance cobalt on catalyst is oxidizing to oxidation state, heating and oxidation finishing temperature is 300~400 ℃；
    4) after heating and oxidation process terminates, it is passed through reducing gas heating reduction catalyst, heating reduction finishing temperature is 300~ 400℃；
    5) catalyst after reduction is transferred in slurry commanding tank from fluidized-bed reactor, carried out with mink cell focus with slurry.
  2. 2. slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process according to claim 1, it is characterised in that：The step 2) in, mink cell focus separating treatment comprises the following steps：
    A, decaying catalyst slurries being heated to 80~220 DEG C in fluidized-bed reactor, control pressure is 0.5~3MPa, and Stirring of inert gas is passed through, then carries out first time solid-liquor separation by filtering, liquid phase mink cell focus is removed, obtains solid catalysis Agent；
    B, the solvent naphtha of low viscosity is added in solid-phase catalyst to the mink cell focus that is adhered between catalyst granules and in duct One or many extraction removings are carried out, stirring of inert gas are passed through in extraction process, until catalyst reaches free flowable State is fluidized, then second of solid-liquor separation is carried out by filtering, further removes liquid phase mink cell focus；Extraction temperature is 65~220 DEG C, pressure is 0.5~3MPa.
  3. 3. slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process according to claim 2, it is characterised in that：The step In b, solvent naphtha is starched using one or more of combinations in C7~C20 alkane derivative, solvent naphtha with decaying catalyst Liquid volume ratio is 1~6:1.
  4. 4. the slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process according to claim 1 or 2 or 3, it is characterised in that：Institute State in step 2), during the air lift that heats up, catalyst layer is warming up to heating air lift with 0.5~2 DEG C/min speed and end 120~200 DEG C of temperature, and be incubated 2~10h, heating air lift pressure be 0.5~1.5MPa, heating air lift gas empty bed speed for 0.5~ 5cm/s, air speed GHSV are 0.5~3L/ (gh).
  5. 5. the slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process according to claim 1 or 2 or 3, it is characterised in that：Institute State in step 3), during heating and oxidation, beds is warming up to heating oxygen with 0.5~2.0 DEG C/min heating rate Change 300~400 DEG C of finishing temperature, and keep 2~20h, be then cooled to 100~150 DEG C；The empty bed speed of gas in fluid bed For 2~10cm/s, pressure is 0.5~3.0MPa, and air speed GHSV is 1.0~4.0L/ (gh).
  6. 6. the slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process according to claim 1 or 2 or 3, it is characterised in that：Institute State in step 4), using pure hydrogen heating reduction, reaction bed temperature is warming up to liter with 0.5~2.0 DEG C/min heating rate Temperature 350~400 DEG C of finishing temperature of reduction, and 2~10h is incubated, then it is cooled to 180~200 DEG C；The empty bed of gas in fluid bed Speed is 2~10cm/s, and pressure is 0.5~3.0MPa, and air speed GHSV is 1.0~4.0L/ (gh).
  7. 7. slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process according to claim 2, it is characterised in that：The step In a, during first time solid-liquor separation, the pressure difference for controlling filter upper and lower part in fluidized-bed reactor is 0.05~0.1MPa.
  8. 8. slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process according to claim 2, it is characterised in that：The step In b, when carrying out second of solid-liquor separation, the pressure difference of filter upper pressure and low pressure in fluidized-bed reactor is controlled to be 0.05~0.3MPa.
  9. 9. the slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process according to claim 1 or 2 or 3, it is characterised in that：Institute State in step 2), the inert gas that heating air lift uses is one or both of nitrogen and methane.
  10. 10. the slurry bed system Co based Fischer-Tropsch synthesis catalyst renovation process according to claim 1 or 2 or 3, it is characterised in that： In the step 3), the concentration of volume percent of oxygen is 0.1~1.0% in dilution oxygen；With 0.5~1.0 in oxidizing process DEG C/min heating rate makes beds be warming up to 300~400 DEG C.
  11. 11. a kind of slurry bed system Co based Fischer-Tropsch synthesis catalyst regenerating unit, including paste state bed reactor (1), it is characterised in that：Also Including knockout drum (2), fluidized-bed reactor (3) and slurry commanding tank (4), the serum outlet (1- of the paste state bed reactor (1) 1) it is connected with the slurry inlet (2-1) of knockout drum (2), liquid-phase outlet (2-2) and the stream of the knockout drum (2) Slurry inlet (3-1) connection of fluidized bed reactor (3), the catalyst outlet (3-2) of the fluidized-bed reactor (3) are matched somebody with somebody with described Tank (4) connection is starched, the slurry commanding tank (4) communicates with the heavy oil export (1-2) of the paste state bed reactor (1).
  12. 12. the slurry bed system Co based Fischer-Tropsch synthesis catalyst regenerating unit according to claim 11, it is characterised in that：The fluidisation Gas feed (3-3), solvent oil inlet (3-4) and offgas outlet (3-5) are also provided with bed reactor (3).
  13. 13. the slurry bed system Co based Fischer-Tropsch synthesis catalyst regenerating unit according to claim 12, it is characterised in that：The fluidisation Air inlet pipe (5) is connected with the gas feed (3-3) of bed reactor (3), the air inlet pipe (5) connects with the slurry commanding tank (4).
CN201710941247.7A 2017-10-11 2017-10-11 Slurry bed system Co based Fischer-Tropsch synthesis catalyst regenerated offline method and its device Pending CN107684932A (en)

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Application publication date: 20180213