CN1219569C - Method of separating and reclaiming spent cobalt based catalyst and heavy hydrocarbon throuth Fishcher-Tropsch synthesis in slurry bed - Google Patents
Method of separating and reclaiming spent cobalt based catalyst and heavy hydrocarbon throuth Fishcher-Tropsch synthesis in slurry bed Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title abstract description 6
- 239000010941 cobalt Substances 0.000 title abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract description 6
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Abstract
The present invention relates to a separation recovery method of a fluid bed Fischer-Tropsch synthesis waste cobalt-base catalyst and heavy hydrocarbons. The method comprises: firstly, a mixture of the waste cobalt-base catalyst and the heavy hydrocarbons is extracted and separated with liquid paraffin with the initial boiling point of 210DEG C for three to four times while being heated and stirred; secondly, the mixture is extracted and separated with a dimethylbenzene solvent for two to three times, and a mixture of the liquid paraffin and the heavy hydrocarbons, which is recovered through extraction and separation, can be directly used for processing an oil product or be returned to a fluid bed reactor and recycled as a reaction medium. The treated waste cobalt-base catalyst in the present invention can be directly used for recovering noble metallic cobalt. The present invention has the advantages of simple method, short process flow and environmental pollution reduction. The recovery rate of the heavy hydrocarbons of the present invention is from 95 to 98%, the content of the catalyst in the recovered mixture of the liquid paraffin and the heavy hydrocarbons is lower than 0.5%, and the content of hydrocarbons in the waste cobalt-base catalyst is lower than 0.85%.
Description
Technical field
The present invention relates to the separation and recovery method of a kind of catalyzer and heavy hydrocarbon, relate in particular to behind a kind of industrial syrup state bed Fischer Tropsch building-up reactions end of run the useless cobalt-base catalyst that goes out from reactor unloading and the separation and recovery method of heavy hydrocarbon.
Background technology
By synthetic gas (CO+H
2) process of generation hydro carbons is called Fischer-Tropsch synthesis under catalyst action.Iron-based and cobalt-base catalyst are the catalyzer of present most widely used two kinds of Fischer-Tropsch synthesizes industrializations.Coal based synthetic gas (mol ratio 0.5～1.2) Fischer-Tropsch that ferrum-based catalyst is suitable for low hydrogen-carbon ratio synthesizes, and the Fischer-Tropsch that cobalt-base catalyst is suitable for the synthetic gas (mol ratio 2) of Sweet natural gas base synthesizes.
Fischer-Tropsch is synthetic can to carry out in reactors such as fixed bed, fluidized-bed, circulating fluidized bed or slurry attitude bed.Fischer-Tropsch synthesis is a strong exothermal reaction, so it is very important in time removing reaction heat in the Fischer-Tropsch synthesis process, not only can avoid the too high catalyst deactivation that causes sintering of catalyst and cause of temperature, but also can avoid the generation of aromatic hydroxy compound to make the catalyst surface pollution and produce more non-purpose product C H
4For improving the thermo-efficiency of Fischer-Tropsch building-up process, slurry attitude bed technique is widely used.The syrup state bed Fischer Tropsch synthetic technology that gas upwards reacts by the liquid phase inert media that contains powdered catalyst in the bubbling mode, start from people's such as German H.K bel in 1938 and P Alkermann research, this technology is all studied and has been used in the U.S., Britain and South Africa in succession subsequently.Paste state bed reactor not only has reactant and mixes; Pressure drop is little; Heat-transfer effect is good, but temperature of reaction is controlled characteristics such as isothermal operation easily, and has catalyzer and can onlinely load and unload; Can directly use low H
2The advantages such as coal based synthetic gas of/CO ratio are starched the attitude phase reactor simultaneously and are had few relatively investment, have demonstrated bigger technology, economic advantages, are the synthetic liquid fuel technology of giving priority in the world at present.
When Fischer-Tropsch synthesis carries out in slurry attitude phase reactor, to add the light liquid hydrocarbon compound in the reactor in advance as reaction medium, in entire reaction course, granules of catalyst is suspended in the liquid medium, and the solid content of slurries will maintain in the scope of 5～35wt%.Fischer-Tropsch synthesis can generate the product of gas, liquid and solid three-phase mixture, and solid phase heavy hydrocarbon product is collected by wax trap (180 ℃), but through underpressure distillation production food grade hard wax, lubricant base and detergent raw material; Oil phase and water liquid product are collected by hot trap (105 ℃) and cold-trap (0 ℃), produce gasoline, diesel oil, petroleum naphtha, aviation kerosene through the normal pressure distillation; Gas-phase product that can't condensation is that tail gas returns vapourizing furnace and generates the synthetic gas recycle after low temperature reclaims low-carbon alkene.Along with the carrying out of Fischer-Tropsch synthesis, the heavy hydrocarbon that reaction generates finishes the displacement of light liquid phase hydrocarbon compound medium gradually, and this moment, solid catalyst was suspended in the heavy hydrocarbon mixture of the high boiling point (150-300 ℃) that is in liquid phase under reaction conditions fully.When reaction finished, with liquid-phase mixing together, unloading back Yin Wendu reduction (being lower than 120 ℃) catalyzer was solid-state with the mixture that reacts the heavy hydrocarbon that generates very quick setting to the heavy hydrocarbon of catalyzer and reaction generation under temperature of reaction (250～280 ℃).The mixture of this catalyzer and solid-state heavy hydrocarbon can only be used as waste it is abandoned if be left intact, contaminate environment not only, and, be undoubtedly a kind of great waste for the cobalt-base catalyst that contains than the noble metal cobalt.Cobalt-base catalyst separates with heavy hydrocarbon so will give up, reclaim heavy hydrocarbon and be used for oil product processing or Returning reactor, simultaneously useless cobalt-base catalyst is reclaimed wherein more valuable cobalt metal, not only turn waste into wealth again as reaction medium, economic benefit is considerable, and can reduce the pollution to environment.But through the document investigation, the separation and recovery method about synthetic spent catalyst of industrial syrup state bed Fischer Tropsch and heavy hydrocarbon does not still have bibliographical information at present.
Summary of the invention
The object of the present invention is to provide a kind of industrial syrup state bed Fischer Tropsch building-up reactions to finish the useless cobalt-base catalyst that the back goes out from reactor unloading and the separation and recovery method of heavy hydrocarbon.
Separation and recovery method of the present invention comprises the steps:
1. analyze the content of useless cobalt-base catalyst of the mixture of the useless cobalt-base catalyst from paste state bed reactor, unload out and heavy hydrocarbon;
2. the mixture of cobalt-base catalyst and heavy hydrocarbon of will giving up adds in the reactor, be that 210 ℃ liquid paraffin,light is made solvent to the initial boiling point that wherein adds 2～5 times of useless cobalt-base catalyst and heavy hydrocarbon mixture weight then, begin when being heated to 70～100 ℃ to stir, continue to be heated to 120～180 ℃ then, and under this temperature, stirred 60～120 minutes;
3. when settling temperature is 80～120 ℃, standing sedimentation 30～90 minutes, solid-liquid separation, and in the time of 80～120 ℃, discharge the liquid paraffin,light on upper strata and the mixed solution of heavy hydrocarbon;
4. the initial boiling point that adds 2～6 times of useless cobalt-base catalyst weight once more in reactor is 210 ℃ a liquid paraffin,light, is heated to 120～180 ℃, stirs 30～90 minutes; When settling temperature is 80～120 ℃, standing sedimentation 30～90 minutes, solid-liquid separation, and in the time of 80～120 ℃, discharge the liquid paraffin,light on upper strata and the mixed solution of heavy hydrocarbon;
5. repeating step 4 one is to secondary;
6. the liquid paraffin,light that can't discharge with the standing sedimentation solid-liquid separation in the reactor is distilled 210～320 ℃ temperature range;
7. in reactor, add the dimethylbenzene of 2～6 times of useless cobalt-base catalyst weight, the useless cobalt-base catalyst that separated through the liquid paraffin,light extracting is heated to 80～100 ℃, stir extracting 20～60 minutes;
8. standing sedimentation is 30～60 minutes, and solid-liquid separation is discharged the xylene solution that the upper strata is dissolved with hydrocarbon;
9. 7,8 orders repeat one successively to secondary set by step;
10. the xylene solution that can't discharge with the standing sedimentation solid-liquid separation in the reactor is distilled 136～144 ℃ temperature range.
Aforesaid (2) step is in the mixture adding reactor with useless cobalt-base catalyst and heavy hydrocarbon, be that 210 ℃ liquid paraffin,light is made solvent to wherein adding best 2～3 times initial boiling point of useless cobalt-base catalyst and heavy hydrocarbon mixture weight then, begin when being heated to best 80～90 ℃ to stir, continue to be heated to best 140～150 ℃ then, and under this temperature, stirred best 60～90 minutes;
Aforesaid (3) step is when settling temperature is best 100～120 ℃, best 60～90 minutes of standing sedimentation, and solid-liquid separation, and in the time of best 80～120 ℃, discharge the liquid paraffin,light on upper strata and the mixed solution of heavy hydrocarbon.
Aforesaid (4) step is that to add useless best 2～3 times initial boiling point of cobalt-base catalyst weight once more in reactor be 210 ℃ liquid paraffin,light, is heated to best 140～150 ℃, stirs best 45～60 minutes; When settling temperature is best 100～120 ℃, best 45～60 minutes of standing sedimentation, solid-liquid separation, and in the time of best 80～120 ℃, discharge the liquid paraffin,light on upper strata and the mixed solution of heavy hydrocarbon.
Aforesaid (7) step is to add useless best 2～3 times dimethylbenzene of cobalt-base catalyst weight in reactor, and the useless cobalt-base catalyst that separated through the liquid paraffin,light extracting is heated to best 80～90 ℃, stirs best 40～60 minutes of extracting.
Aforesaid (8) step is best 40～60 minutes of standing sedimentation, and solid-liquid separation is discharged the xylene solution that the upper strata is dissolved with hydrocarbon;
The heavy hydrocarbon that the present invention obtains and the mixture of whiteruss are directly used in oil product processing or return slurry bed ft synthetic reactor again as reaction medium.
The useless cobalt-base catalyst that the present invention obtains can be directly used in the wherein more valuable cobalt metal of recovery.
The rate of recovery of heavy hydrocarbon of the present invention is 95～98%, and the content of catalyzer is less than 0.5% in the liquid paraffin,light that recovery obtains and the mixture of heavy hydrocarbon, and the content of hydrocarbon is less than 0.85% in the useless cobalt-base catalyst.
The invention has the advantages that:
1. method is simple, and technical process is short.
2. it is cheap and easy to get to separate the solvent liquid paraffin,light, separates the back and mixes with heavy hydrocarbon, and such mixture does not need any processing directly to utilize.
3. the separation solvent xylene that price is more expensive because of its boiling point far below heavy hydrocarbon, available distillatory method reclaims, recycle is with low cost.
4. useless cobalt-base catalyst can directly be used for reclaiming wherein more valuable cobalt metal after separating, kill two birds with one stone.
5. minimizing environmental pollution has favorable economic benefit.
Embodiment:
Describe several specific embodiments of the present invention below in detail, protection scope of the present invention is not subjected to the restriction of these embodiment.
The analysis test method that the present invention is used:
1. the mensuration of solid content: adopt gravimetric determination.
2. spent catalyst assay in the mixture of liquid paraffin,light of Hui Shouing and heavy hydrocarbon: adopt atomic spectroscopy to measure.
3. the mensuration of catalyst surface residual hydrocarbons (carbon containing, hydrogen): adopt organic element analyzer to measure, its principle is that measured matter decomposes through high-temp combustion, the gaseous mixture that reaction generates is separated after getting rid of chaff interference effectively, and the each component after the separation is examined and determine by thermal conductivity detector.
Embodiment 1:
1. the useless Co/SiO under unloading is carried
2The mixture of catalyzer and heavy hydrocarbon, solid content analytical results: spent catalyst 20.0%, heavy hydrocarbon 80.0%.
2. with 100 kilograms of useless Co/SiO
2The mixture of catalyzer and heavy hydrocarbon adds and has in the reactor of heated and stirred reflux, be that 210 ℃ liquid paraffin,light is made solvent to the initial boiling point that wherein adds 200 kilograms then, open stirring when being heated to 80 ℃, continue to be heated to 140 ℃ then, and under this temperature, stirred 100 minutes, making heavy hydrocarbon and initial boiling point is that 210 ℃ liquid paraffin,light is fully miscible.
3. 120 ℃ of following standing sedimentations 60 minutes, solid-liquid separation is discharged 225 kilograms of the mixed solutions of the liquid paraffin,light on upper strata and heavy hydrocarbon.
4. the initial boiling point that adds 80 kilograms once more in reactor is 210 ℃ a liquid paraffin,light, is heated to 140 ℃, stirs 60 minutes.
5. repeating step 3, discharge 92 kilograms of mixed solutions.
6. the initial boiling point that adds 80 kilograms for the third time in reactor is 210 ℃ a liquid paraffin,light, is heated to 140 ℃, stirs 60 minutes.
7. repeating step 3, discharge 62 kilograms of mixed solutions.
8. merge three extractings and separate the liquid paraffin,light of discharge and the mixed solution of heavy hydrocarbon, gross weight is 379 kilograms.
9. the liquid paraffin,light that can't discharge with the standing sedimentation solid-liquid separation in the reactor is distilled 210～320 ℃ temperature range, distillation receives 24 kilograms of liquid paraffin,lights, wherein the rate of recovery of heavy hydrocarbon is 95.7%, and the content of catalyzer is less than 0.5% in the liquid paraffin,light that recovery obtains and the mixed solution of heavy hydrocarbon.
10. the xylene solution that adds 100 kilograms in reactor is heated to 80 ℃, stirs extracting 20 minutes.
11. standing sedimentation 45 minutes, solid-liquid separation is discharged 95 kilograms of the xylene solutions that the upper strata is dissolved with small quantities of hydrocarbon.
12. in reactor, add 80 kilograms of xylene solutions once more, be heated to 80 ℃, stir extracting 20 minutes.
13. repeating step 11 is discharged 83 kilograms of upper strata xylene solutions.
14. merge the xylene solution that is dissolved with small quantities of hydrocarbon of twice discharge, gross weight is 178 kilograms.
15. to the xylene solution that can't discharge with the standing sedimentation solid-liquid separation in the reactor temperature at 136～144 ℃
Scope is distilled, and distillation receives 11 kilograms of xylene solutions.
16. distillation is dissolved with the xylene solution of small quantities of hydrocarbon, distillation receives 144 kilograms of xylene solutions, and the rate of recovery of xylene solution is 86.1%.The content of hydrocarbon is 0.81% in the spent catalyst.
Embodiment 2:
1. get from starching the useless Co/ZrO under the unloading of attitude bed
2/ SiO
2Catalyzer, solid content analytical results: spent catalyst 29.8%, heavy hydrocarbon 71.2%.
2. with 150 kilograms of useless Co/ZrO
2/ SiO
2The mixture of catalyzer and heavy hydrocarbon adds and has in the reactor of heated and stirred reflux, be that 210 ℃ liquid paraffin,light is made solvent to the initial boiling point that wherein adds 600 kilograms then, open stirring when being heated to 90 ℃, continue to be heated to 120 ℃ then, and under this temperature, stirred 75 minutes, making heavy hydrocarbon and initial boiling point is that 210 ℃ liquid paraffin,light is fully miscible.
3. 110 ℃ of following standing sedimentations 90 minutes, solid-liquid separation is discharged 645 kilograms of the mixed solutions of the liquid paraffin,light on upper strata and heavy hydrocarbon.
4. the initial boiling point that adds 120 kg once more in reactor is 210 ℃ a liquid paraffin,light, is heated to 120 ℃, stirs 30 minutes.
5. repeating step 3, discharge 126 kilograms of mixed solutions.
6. the initial boiling point that adds 120 kg for the third time in reactor is 210 ℃ a liquid paraffin,light, is heated to 120 ℃, stirs 30 minutes.
7. repeating step 3, discharge 123 kilograms of mixed solutions.
8. merge three extractings and separate the liquid paraffin,light of discharge and the mixed solution of heavy hydrocarbon, gross weight is 894 kilograms.
9. the liquid paraffin,light that can't discharge with the standing sedimentation solid-liquid separation in the reactor is distilled 210～320 ℃ temperature range, distillation receives 25.5 kilograms of liquid paraffin,lights, wherein the rate of recovery of heavy hydrocarbon is 97.1%, and the content of catalyzer is less than 0.5% in the liquid paraffin,light that recovery obtains and the mixed solution of heavy hydrocarbon.
10. the xylene solution that adds 100 kilograms in reactor is heated to 90 ℃, stirs extracting 60 minutes.
11. standing sedimentation 60 minutes, solid-liquid separation is discharged 90 kilograms of the xylene solutions that the upper strata is dissolved with small quantities of hydrocarbon.
12. in reactor, add 80 kilograms of xylene solutions once more, be heated to 90 ℃, stir extracting 60 minutes.
13. repeating step 11 is discharged 74 kilograms of upper strata xylene solutions.
14. merge the xylene solution that is dissolved with small quantities of hydrocarbon of twice discharge, gross weight is 164 kilograms.
15. to the xylene solution that can't discharge with the standing sedimentation solid-liquid separation in the reactor temperature at 136～144 ℃
Scope is distilled, and distillation receives 12.5 kilograms of xylene solutions.
16. distillation is dissolved with the xylene solution of small quantities of hydrocarbon, distillation receives 141 kilograms of xylene solutions, and the rate of recovery of xylene solution is 84.2%.The content of hydrocarbon is 0.74% in the spent catalyst.
Embodiment 3:
1. get from starching the useless Co/Al under the unloading of attitude bed
2O
3Catalyzer, solid content analytical results: spent catalyst 19.6%, heavy hydrocarbon 80.4%.
2. with 180 kilograms of useless Co/Al
2O
3The mixture of catalyzer and heavy hydrocarbon adds and has in the reactor of heated and stirred reflux, be that 210 ℃ liquid paraffin,light is made solvent to the initial boiling point that wherein adds 540 kilograms then, open stirring when being heated to 70 ℃, continue to be heated to 170 ℃ then, and under this temperature, stirred 120 minutes, making heavy hydrocarbon and initial boiling point is that 210 ℃ liquid paraffin,light is fully miscible.
3. 100 ℃ of following standing sedimentations 30 minutes, solid-liquid separation is discharged 580 kilograms of the mixed solutions of the liquid paraffin,light on upper strata and heavy hydrocarbon.
4. the initial boiling point that adds 100 kilograms once more in reactor is 210 ℃ a liquid paraffin,light, is heated to 170 ℃, stirs 90 minutes.
5. repeating step 3, discharge 130 kilograms of mixed solutions.
6. the initial boiling point that adds 100 kilograms for the third time in reactor is 210 ℃ a liquid paraffin,light, is heated to 170 ℃, stirs 90 minutes.
7. repeating step 3, discharge 116 kilograms of mixed solutions.
8. merge three extractings and separate the liquid paraffin,light of discharge and the mixed solution of heavy hydrocarbon, gross weight is 826 kilograms.
9. the liquid paraffin,light that can't discharge with the standing sedimentation solid-liquid separation in the reactor is distilled 210～320 ℃ temperature range, distillation receives 33 kilograms of liquid paraffin,lights, wherein the rate of recovery of heavy hydrocarbon is 97.1%, and the content of catalyzer is less than 0.5% in the liquid paraffin,light that recovery obtains and the mixed solution of heavy hydrocarbon.
10. the xylene solution that adds 210 kilograms in reactor is heated to 85 ℃, stirs extracting 30 minutes.
11. standing sedimentation 40 minutes, solid-liquid separation is discharged 195 kilograms of the xylene solutions that the upper strata is dissolved with small quantities of hydrocarbon.
12. in reactor, add 100 kilograms of xylene solutions once more, be heated to 85 ℃, stir extracting 30 minutes.
13. repeating step 11 is discharged 108 kilograms of upper strata xylene solutions.
14. merge the xylene solution that is dissolved with small quantities of hydrocarbon of twice discharge, gross weight is 303 kilograms.
15. to the xylene solution that can't discharge with the standing sedimentation solid-liquid separation in the reactor temperature at 136～144 ℃
Scope is distilled, and distillation receives 15.8 kilograms of xylene solutions.
16. distillation is dissolved with the xylene solution of small quantities of hydrocarbon, distillation receives 261 kilograms of xylene solutions, and the rate of recovery of xylene solution is 89.3%.The content of hydrocarbon is 0.84% in the spent catalyst.
Embodiment 4:
1. get from starching the useless Co/TiO under the unloading of attitude bed
2Catalyzer, solid content analytical results: spent catalyst 25.2%, heavy hydrocarbon 74.8%.
2. with the useless Co/TiO of 120 kg
2The mixture of catalyzer and heavy hydrocarbon adds and has in the reactor of heated and stirred reflux, be that 210 ℃ liquid paraffin,light is made solvent to the initial boiling point that wherein adds 480 kilograms then, open stirring when being heated to 100 ℃, continue to be heated to 150 ℃ then, and under this temperature, stirred 60 minutes, making heavy hydrocarbon and initial boiling point is that 210 ℃ liquid paraffin,light is fully miscible.
3. 80 ℃ of following standing sedimentations 45 minutes, solid-liquid separation is discharged 495 kilograms of the mixed solutions of the liquid paraffin,light on upper strata and heavy hydrocarbon.
4. the initial boiling point that adds 120 kg once more in reactor is 210 ℃ a liquid paraffin,light, is heated to 150 ℃, stirs 45 minutes.
5. repeating step 3, discharge 132 kilograms of mixed solutions.
6. the initial boiling point that adds 120 kg for the third time in reactor is 210 ℃ a liquid paraffin,light, is heated to 150 ℃, stirs 45 minutes.
7. repeating step 3, discharge 128 kilograms of mixed solutions.
8. merge three extractings and separate the liquid paraffin,light of discharge and the mixed solution of heavy hydrocarbon, gross weight is 755 kilograms.
9. the liquid paraffin,light that can't discharge with the standing sedimentation solid-liquid separation in the reactor is distilled 210～320 ℃ temperature range, distillation receives 41 kilograms of liquid paraffin,lights, wherein the rate of recovery of heavy hydrocarbon is 97.7%, and the content of catalyzer is less than 0.5% in the liquid paraffin,light that recovery obtains and the mixed solution of heavy hydrocarbon.
10. the xylene solution that adds 90 kilograms in reactor is heated to 100 ℃, stirs extracting 40 minutes.
11. standing sedimentation 50 minutes, solid-liquid separation is discharged 85 kilograms of the xylene solutions that the upper strata is dissolved with small quantities of hydrocarbon.
12. in reactor, add 90 kilograms of xylene solutions once more, be heated to 100 ℃, stir extracting 40 minutes.
13. repeating step 11 is discharged 92 kilograms of upper strata xylene solutions.
14. merge the xylene solution that is dissolved with small quantities of hydrocarbon of twice discharge, gross weight is 177 kilograms.
15. to the xylene solution that can't discharge with the standing sedimentation solid-liquid separation in the reactor temperature at 136～144 ℃
Scope is distilled, and distillation receives 12 kilograms of xylene solutions.
16. distillation is dissolved with the xylene solution of small quantities of hydrocarbon, distillation receives 141 kilograms of xylene solutions, and the rate of recovery of xylene solution is 85%.The content of hydrocarbon is 0.79% in the spent catalyst.
Claims (6)
1, the separation and recovery method of synthetic useless cobalt-base catalyst of a kind of syrup state bed Fischer Tropsch and heavy hydrocarbon is characterized in that comprising the steps:
(1) analyzes the content of useless cobalt-base catalyst of the mixture of the useless cobalt-base catalyst from paste state bed reactor, unload out and heavy hydrocarbon;
(2) will the give up mixture of cobalt-base catalyst and heavy hydrocarbon adds in the reactor, be that 210 ℃ liquid paraffin,light is made solvent to the initial boiling point that wherein adds 2～5 times of useless cobalt-base catalyst and heavy hydrocarbon mixture weight then, begin when being heated to 70～100 ℃ to stir, continue to be heated to 120～180 ℃ then, and under this temperature, stirred 60～120 minutes;
(3) when settling temperature is 80～120 ℃, standing sedimentation 30～90 minutes, solid-liquid separation, and in the time of 80～120 ℃, discharge the liquid paraffin,light on upper strata and the mixed solution of heavy hydrocarbon;
(4) initial boiling point that adds 2～6 times of useless cobalt-base catalyst weight once more in reactor is 210 ℃ a liquid paraffin,light, is heated to 120～180 ℃, stirs 30～90 minutes; When settling temperature is 80～120 ℃, standing sedimentation 30～90 minutes, solid-liquid separation, and in the time of 80～120 ℃, discharge the liquid paraffin,light on upper strata and the mixed solution of heavy hydrocarbon;
(5) repeating step 4 one is to secondary;
(6) liquid paraffin,light that can't discharge with the standing sedimentation solid-liquid separation in the reactor is distilled 210～320 ℃ temperature range;
(7) in reactor, add the dimethylbenzene of 2～6 times of useless cobalt-base catalyst weight, the useless cobalt-base catalyst that separated through the liquid paraffin,light extracting is heated to 80～100 ℃, stirring extracting 20～60 minutes;
(8) standing sedimentation is 30～60 minutes, and solid-liquid separation is discharged the xylene solution that the upper strata is dissolved with hydrocarbon;
(9) set by step (7), (8) order repeat one successively to secondary;
(10) xylene solution that can't discharge with the standing sedimentation solid-liquid separation in the reactor is distilled 136～144 ℃ temperature range.
2, the separation and recovery method of synthetic useless cobalt-base catalyst of a kind of syrup state bed Fischer Tropsch as claimed in claim 1 and heavy hydrocarbon, it is characterized in that described (2) step is in the mixture adding reactor with useless cobalt-base catalyst and heavy hydrocarbon, be that 210 ℃ liquid paraffin,light is made solvent to the initial boiling point that wherein adds 2～3 times of useless cobalt-base catalyst and heavy hydrocarbon mixture weight then, begin when being heated to 80～90 ℃ to stir, continue to be heated to 140～150 ℃ then, and under this temperature, stirred 60～90 minutes;
3, the separation and recovery method of synthetic useless cobalt-base catalyst of a kind of syrup state bed Fischer Tropsch as claimed in claim 1 and heavy hydrocarbon, it is characterized in that described (3) step is when settling temperature is 100～120 ℃, standing sedimentation 60～90 minutes, solid-liquid separation, and in the time of 80～120 ℃, discharge the liquid paraffin,light on upper strata and the mixed solution of heavy hydrocarbon.
4, the separation and recovery method of synthetic useless cobalt-base catalyst of a kind of syrup state bed Fischer Tropsch as claimed in claim 1 and heavy hydrocarbon, it is characterized in that described (4) step is that the initial boiling point that adds 2～3 times of useless cobalt-base catalyst weight once more in reactor is 210 ℃ a liquid paraffin,light, be heated to 140～150 ℃, stirred 45～60 minutes; When settling temperature is 100～120 ℃, standing sedimentation 45～60 minutes, solid-liquid separation, and in the time of 80～120 ℃, discharge the liquid paraffin,light on upper strata and the mixed solution of heavy hydrocarbon.
5, the separation and recovery method of synthetic useless cobalt-base catalyst of a kind of syrup state bed Fischer Tropsch as claimed in claim 1 and heavy hydrocarbon, it is characterized in that described (7) step is the dimethylbenzene that adds 2～3 times of useless cobalt-base catalyst weight in reactor, the useless cobalt-base catalyst that separated through the liquid paraffin,light extracting is heated to 80～90 ℃, stirs extracting 40～60 minutes.
6, the separation and recovery method of synthetic useless cobalt-base catalyst of a kind of syrup state bed Fischer Tropsch as claimed in claim 1 and heavy hydrocarbon is characterized in that described (8) step is standing sedimentation 40～60 minutes, and solid-liquid separation is discharged the xylene solution that the upper strata is dissolved with hydrocarbon.
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| CN 200410012201 CN1219569C (en) | 2004-03-19 | 2004-03-19 | Method of separating and reclaiming spent cobalt based catalyst and heavy hydrocarbon throuth Fishcher-Tropsch synthesis in slurry bed |
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| CN 200410012201 CN1219569C (en) | 2004-03-19 | 2004-03-19 | Method of separating and reclaiming spent cobalt based catalyst and heavy hydrocarbon throuth Fishcher-Tropsch synthesis in slurry bed |
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| CN1319635C (en) * | 2005-09-12 | 2007-06-06 | 南京工业大学 | Separation process of synthetic oil catalyst prepared in slurry bed reactor |
| FI120527B (en) | 2007-06-18 | 2009-11-30 | Crisolteq Oy | Method of recovery |
| CN102585885B (en) * | 2012-01-08 | 2014-05-21 | 辽宁地质工程职业学院 | Method for re-purifying and recovering liquid paraffin obtained after solvent extraction |
| CN110368983A (en) * | 2018-04-13 | 2019-10-25 | 株式会社模范 | A kind of preparation method of synthesis gas synthesis aviation kerosine catalyst and thus obtained catalyst and its application |
| CN111282574B (en) * | 2020-02-03 | 2020-12-15 | 中国矿业大学(北京) | Recovery method of Fischer-Tropsch synthesis iron catalyst |
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