CN104174398A - Fischer-Tropsch synthesis cobalt-based catalyst produced by self-reduction and application thereof - Google Patents
Fischer-Tropsch synthesis cobalt-based catalyst produced by self-reduction and application thereof Download PDFInfo
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Abstract
The invention discloses a Fischer-Tropsch synthesis cobalt-based catalyst produced by self-reduction. The Fischer-Tropsch synthesis cobalt-based catalyst produced by self-reduction comprises an oxide carrier and surface-passivated cobalt oxide, wherein the cobalt oxide comprises 15-35wt% of metal cobalt and the rest of the oxide carrier. A production method of the Fischer-Tropsch synthesis cobalt-based catalyst comprises the following steps: introducing an organic carbon source during preparing of a catalyst carrier by using a deposition-precipitation method, dipping a carbon-containing carrier with cobalt and then roasting by utilizing the characteristic that the organic carbon source is decomposed under an inert atmosphere to produce weak reduction component elemental carbon, and synchronizing the roasting and self-reduction of the cobalt-based catalyst to obtain a surface-passivated catalyst after being subjected to self-reduction. The online reduction temperature of the cobalt-based catalyst is greatly reduced.
Description
Technical field
The present invention relates to a kind of fischer-tropsch synthetic catalyst, specifically a kind of Co based Fischer-Tropsch synthesis catalyst and application thereof.
Technical background
Cobalt-based fixed bed, iron-based slurry state bed and fluid bed Fischer-Tropsch synthetic technology are to realize at present the coal liquefaction technology of commercial applications.Wherein cobalt-base catalyst has advantages of that adaptability to raw material is strong, catalyst stability good and reproducible utilization, and product has that methane selectively is low, C
5 +the selective high and active low advantage of water gas shift reaction, thereby co-based fischer-tropsch artificial oil has become coal liquefaction field new technology commanding elevation and competition spot.However, cobalt-base catalyst exists contradiction and the technology barrier of low temperature running and high temperature reduction, makes the requirement of reactor material requirement and reaction process coupling greatly improve.Construct specific catalyst system and catalyzing, realize the in-situ reducing of cobalt-base catalyst, can effectively solve the technology barrier of the running of catalyst low temperature and high temperature reduction, significantly reduce reactor manufacture difficulty, effectively Widening Technique application, through retrieval, not yet has Patents or article report at present.
Summary of the invention
The object of the present invention is to provide a kind of Co based Fischer-Tropsch synthesis catalyst and the application thereof that also can reduce at low temperatures for fixed bed reactors.
The present invention is by introducing organic carbon source in deposition-precipitation method Kaolinite Preparation of Catalyst carrier process, utilize organic carbon source under inert atmosphere, to decompose the feature that produces weak reduction components simple substance charcoal, will be containing roasting after charcoal carrier impregnation cobalt, realize the synchronous of cobalt-base catalyst roasting and autoreduction, obtain the catalyst after the autoreduction of surface passivation, greatly reduce the online reduction temperature of cobalt-base catalyst, organic carbon source can also play the effect of catalyst reaming in the process of roasting carbonization and reduction cobalt simultaneously.
Catalyst of the present invention comprises cobalt oxide, oxide carrier and surface passivation cobalt oxide: cobalt oxide is in metal, metallic cobalt 15-35 (wt) %, and all the other are oxide carrier;
Oxide carrier alundum (Al2O3), zirconium dioxide or titanium dioxide.
The concrete preparation method of catalyst of the present invention is as follows:
(1) by the composition of final catalyst, take solubility cobalt salt, add deionized water and be mixed with solution;
(2) by carbon source: cobalt salt (w/w)=0.2-2:1, take carbon source powder and be dissolved in distilled water, stir, form suspension, gelatinization 0.5-4h at 50-90 ℃;
(3) keep gelatinization point, stir, by final catalyst, form, aluminium salt, zirconates or the titanium salt solution of preparation 0.1-2mol/L, with 0.1-2mol/L alkaline precipitating agent co-precipitation, maintenance pH is 7.0-9.0; After precipitation finishes, aging 1-12h at 60-90 ℃, after aging end, suction filtration or centrifugation;
(4) filter cake is put in drying box and at 60-120 ℃, is dried 6-24h, be then placed in tube furnace, under inert atmosphere, roasting 2-8h at 350-800 ℃, makes containing charcoal carrier;
(5) cobalt salt solution of step (1) be impregnated in to above-mentioned carrier by equi-volume process;
(6) step (5) gained is placed in to drying box, dry 6-24h at 60-120 ℃, after being dried, under inert atmosphere, roasting 2-10h at 200-400 ℃, room temperature passivation 2-12h to be down to, makes final catalyst.
As described in step (1), cobalt salt is a kind of of cobalt nitrate, cobalt acetate, cobaltous sulfate etc.
As described in step (2), carbon source is a kind of of starch, methylcellulose, sesbania powder etc.
As described in step (3), aluminium salt is a kind of of aluminum nitrate, aluminum sulfate etc., and zirconates is a kind of of zirconium oxychloride, zirconium nitrate, zirconyl nitrate etc., and titanium salt is a kind of of Titanium Nitrate, titanium tetrachloride etc.; Alkaline precipitating agent is a kind of of ammoniacal liquor, ammonium carbonate, carbonic hydroammonium etc.
As described in step (4) and step (6), inert atmosphere is a kind of of nitrogen, argon gas, helium etc.
As described in step (6), passivation passivating gas used is nitrogen and oxygen gas mixture, and oxygen content is 1.0-20% (v/v).
The catalyst that the present invention makes is applied to fixed bed reactors.Reducing condition is: 180-250 ℃, 0.2-1.0MPa, hydrogen volume air speed 500-1500h
-1, constant temperature 6-24h; Reaction condition is: reaction temperature is 180-240 ℃, H
2/ CO (mol) is between 1.5-3.0, and pressure is 1.0-3.0MPa, and air speed is 500-5000h
-1.
Catalyst tool of the present invention has the following advantages:
(1) catalyst is realized drastic reduction at roasting process, only needs the cobalt oxide of lower temperature reduction surface oxidation during reaction, has reduced reduction temperature, has reduced the requirement to reactor material, has expanded the application of fischer-tropsch reaction in reactor transformation.
(2) catalyst of preparing has flourishing pore passage structure and larger specific area.
The specific embodiment
Embodiment 1
35 (wt) % that accounts for final catalyst by Co, takes Co (NO
3)
26H
2o, adds deionized water and is mixed with solution; Required by cobalt in the final catalyst of reduction, take a certain amount of methylcellulose powder and be dissolved in distilled water, wherein methylcellulose: cobalt nitrate (w/w)=0.2:1, stir, form suspension, gelatinization 0.5h at 90 ℃; Keep gelatinization point, by ZrO
2account for 65 (wt) % of final catalyst, the Al (NO of preparation 0.2mol/L
3)
39H
2o solution, with 0.4mol/LNH
3h
2o co-precipitation is in above-mentioned dextrin, and keeping pH is 7.5; After precipitation finishes, aging 1h at 90 ℃, after aging end, suction filtration, is put in filter cake in drying box and at 90 ℃, is dried 10h, is then placed in tube furnace, and under argon gas atmosphere, roasting 2h at 800 ℃, makes containing charcoal carrier.
By the cobalt nitrate solution incipient impregnation preparing in above-mentioned carrier, then be placed in baking oven, dry 24h at 65 ℃, after being dried, under nitrogen atmosphere, roasting 8h at 300 ℃, under room temperature to be down to, switch to nitrogen and oxygen gas mixture, oxygen content is 15% (v/v), passivation 5h, make final catalyst, catalyst weight consists of Co:Al
2o
3=35:65.
Get above-mentioned catalyst 10g and reduce in fixed bed reactors, reducing condition is: 180 ℃, and 0.5MPa, 500h
-1(V/V), hydrogen, constant temperature 12h.Reaction condition is: 180 ℃, and 1.0Mpa, 500h
-1(V/V), H
2/ CO (mol)=1.Reaction result is in Table 1.
Embodiment 2
25 (wt) % that accounts for final catalyst by Co, takes a certain amount of Co (CH
3cOO)
24H
2o, adds deionized water and is mixed with solution; Required by cobalt in the final catalyst of reduction, take a certain amount of starch and be dissolved in distilled water, wherein starch: cobalt acetate (w/w)=0.5:1, stir, form suspension, gelatinization 2.5h at 80 ℃, keeps gelatinization point, by TiO
2account for 75 (wt) % of final catalyst, prepare the Ti (NO of a certain amount of 1.0mol/L
3)
4solution, with 2.0mol/L (NH
4)
2cO
3co-precipitation is in above-mentioned dextrin, and keeping pH is 8.5; After precipitation finishes, aging 12h at 60 ℃, after aging end, suction filtration, is put in filter cake in drying box and at 110 ℃, is dried 6h, is then placed in tube furnace, under helium atmosphere, at 650 ℃, burns 2h, makes containing charcoal carrier.
By the cobalt acetate solution incipient impregnation preparing in above-mentioned carrier, then be placed in baking oven, dry 8h at 120 ℃, after dry, under helium atmosphere, at 200 ℃, under roasting 10h room temperature to be down to, switch to nitrogen and oxygen gas mixture, oxygen content is 5% (v/v), passivation 4h, makes final catalyst, and catalyst weight consists of Co:TiO
2=25:75.
Get above-mentioned catalyst 10g and reduce in fixed bed reactors, reducing condition is: 200 ℃, and 0.5MPa, 1000h
-1(V/V), hydrogen, constant temperature 24h.Reaction condition is: 190 ℃, and 1.5Mpa, 1000h
-1(V/V), H
2/ CO (mol)=1.5.Reaction result is in Table 1.
Embodiment 3
30 (wt) % that accounts for final catalyst by Co, takes a certain amount of CoSO
47H
2o, adds deionized water and is mixed with solution; Required by cobalt in the final catalyst of reduction, take a certain amount of sesbania powder and be dissolved in distilled water, wherein sesbania powder: cobaltous sulfate (w/w)=0.75:1, stir, form suspension, gelatinization 4h at 70 ℃, keeps gelatinization point, by ZrO
2account for 70 (wt) % of final catalyst, prepare the ZrOCl of a certain amount of 0.5mol/L
28H
2o solution, with 1.5mol/LNH
3h
2o co-precipitation is in above-mentioned dextrin, and keeping pH is 8.5; After precipitation finishes, aging 6h at 70 ℃, after aging end, suction filtration, is put in filter cake in drying box and at 120 ℃, is dried 12h, is then placed in tube furnace, and under argon gas atmosphere, roasting 6h at 500 ℃, makes containing charcoal carrier.
By the cobalt sulfate solution incipient impregnation preparing in above-mentioned carrier, then be placed in baking oven, dry 12h at 110 ℃, after dry, under helium atmosphere, at 350 ℃, under roasting 6h room temperature to be down to, switch to nitrogen and oxygen gas mixture, oxygen content is 15% (v/v), passivation 4h, makes final catalyst, and catalyst weight consists of Co:ZrO
2=30:70.
Get above-mentioned catalyst 10g and reduce in fixed bed reactors, reducing condition is: 190 ℃, and 0.3MPa, 1500h
-1(V/V), hydrogen, constant temperature 12h.Reaction condition is: 2000 ℃, and 1.8Mpa, 1500h
-1(V/V), H
2/ CO (mol)=1.8.Reaction result is in Table 1.
Embodiment 4
32 (wt) % that accounts for final catalyst by Co, takes a certain amount of Co (NO
3) 6H
2o, adds deionized water and is mixed with solution; Required by cobalt in the final catalyst of reduction, take a certain amount of methylcellulose powder and be dissolved in distilled water, wherein methylcellulose: cobalt nitrate (w/w)=1.0:1, stir, form suspension, at 60 ℃, stick with paste 3h, keep gelatinization point, by ZrO
2account for 68 (wt) % of final catalyst, prepare the Zr (NO of a certain amount of 0.2mol/L
3)
45H
2o solution, with 0.6mol/LNH
4hCO
3co-precipitation is in above-mentioned dextrin, and keeping pH is 7.0; After precipitation finishes, aging 12h at 60 ℃, after aging end, suction filtration, is put in filter cake in drying box and at 120 ℃, is dried 6h, is then placed in tube furnace, and under nitrogen atmosphere, roasting 8h at 500 ℃, makes containing charcoal carrier.
By the cobalt nitrate solution incipient impregnation preparing in above-mentioned carrier, then be placed in baking oven, dry 18h at 100 ℃, after dry, under nitrogen atmosphere, at 400 ℃, under roasting 2h room temperature to be down to, switch to nitrogen and oxygen gas mixture, oxygen content is 20% (v/v), passivation 2h, makes final catalyst, and catalyst weight consists of Co:ZrO
2=32:68.
Get above-mentioned catalyst 10g and reduce in fixed bed reactors, reducing condition is: 210 ℃, and 0.7MPa, 1200h
-1(V/V), hydrogen, constant temperature 18h.Reaction condition is: 210 ℃, and 2.1Mpa, 2000h
-1(V/V), H
2/ CO (mol)=2.Reaction result is in Table 1.
Embodiment 5
15 (wt) % that accounts for final catalyst by Co, takes a certain amount of Co (CH
3cOO)
24H
2o, adds deionized water and is mixed with solution; Required by cobalt in the final catalyst of reduction, take a certain amount of starch and be dissolved in distilled water, wherein starch: cobalt acetate (w/w)=1.25:1, stir, form suspension, gelatinization 2.5h at 65 ℃, keeps gelatinization point, by Al
2o
3account for 85 (wt) % of final catalyst, prepare the Al of a certain amount of 1.2mol/L
2(SO
4)
318H
2o solution, with 2.0mol/L (NH
4)
2cO
3co-precipitation is in above-mentioned dextrin, and keeping pH is 9.0; After precipitation finishes, aging 10h at 750 ℃, after aging end, suction filtration, is put in filter cake in drying box and at 60 ℃, is dried 24h, is then placed in tube furnace, and under argon gas atmosphere, roasting 8h at 350 ℃, makes containing charcoal carrier.
By the cobalt acetate solution incipient impregnation preparing in above-mentioned carrier, then be placed in baking oven, dry 16h at 80 ℃, after dry, under nitrogen atmosphere, at 250 ℃, under roasting 8h room temperature to be down to, switch to nitrogen and oxygen gas mixture, oxygen content is 2.5% (v/v), passivation 10h, makes final catalyst, and catalyst weight consists of Co:Al
2o
3=15:85.
Get above-mentioned catalyst 10g and reduce in fixed bed reactors, reducing condition is: 220 ℃, and 0.8MPa, 1300h
-1(V/V), hydrogen, constant temperature 10h.Reaction condition is: 220 ℃, and 2.5Mpa, 3000h
-1(V/V), H
2/ CO (mol)=2.2.Reaction result is in Table 1.
Embodiment 6
35 (wt) % that accounts for final catalyst by Co, takes a certain amount of Co (NO
3)
26H
2o, adds deionized water and is mixed with solution; Required by cobalt in the final catalyst of reduction, take a certain amount of sesbania powder and be dissolved in distilled water, wherein sesbania powder: cobalt nitrate (w/w)=1.5:1, stir, form suspension, gelatinization 1.5h at 85 ℃, keeps gelatinization point, by TiO
2account for 80 (wt) % of final catalyst, prepare the Ti (NO of a certain amount of 0.25mol/L
3)
4solution, with 0.8mol/LNH
4hCO
3co-precipitation is in above-mentioned dextrin, and keeping pH is 8.5; After precipitation finishes, aging 6h at 75 ℃, after aging end, suction filtration, is put in filter cake in drying box and at 100 ℃, is dried 5h, is then placed in tube furnace, and under nitrogen atmosphere, roasting 6h at 400 ℃, makes containing charcoal carrier.
By the cobalt nitrate solution incipient impregnation preparing in above-mentioned carrier, then be placed in baking oven, dry 24h at 60 ℃, after dry, under argon gas atmosphere, at 320 ℃, under roasting 5h room temperature to be down to, switch to nitrogen and oxygen gas mixture, oxygen content is 8% (v/v), passivation 14h, makes final catalyst, and catalyst weight consists of Co:TiO
2=20:80.
Get above-mentioned catalyst 10g and reduce in fixed bed reactors, reducing condition is: 230 ℃, and 0.9MPa, 800h
-1(V/V), hydrogen, constant temperature 6h.Reaction condition is: 230 ℃, and 2.8Mpa, 4000h
-1(V/V), H
2/ CO (mol)=2.5.Reaction result is in Table 1.
Embodiment 7
22 (wt) % that accounts for final catalyst by Co, takes a certain amount of CoSO
47H
2o, adds deionized water and is mixed with solution; Required by cobalt in the final catalyst of reduction, take a certain amount of starch and be dissolved in distilled water, wherein starch: cobaltous sulfate (w/w)=2.0:1, stir, form suspension, gelatinization 3.5h at 75 ℃, keeps gelatinization point, by Al
2o
3account for 78 (wt) % of final catalyst, prepare the Al (NO of a certain amount of 2.0mol/L
3)
39H
2o solution, with 4.0mol/LNH
3h
2o co-precipitation is in above-mentioned dextrin, and keeping pH is 7.5; After precipitation finishes, aging 4h at 80 ℃, after aging end, suction filtration, is put in filter cake in drying box and at 80 ℃, is dried 7h, is then placed in tube furnace, and under argon gas atmosphere, roasting 3h at 450 ℃, makes containing charcoal carrier.
By the cobalt sulfate solution incipient impregnation preparing in above-mentioned carrier, then be placed in baking oven, dry 18h at 70 ℃, after dry, under helium atmosphere, at 300 ℃, under roasting 8h room temperature to be down to, switch to nitrogen and oxygen gas mixture, oxygen content is 10% (v/v), passivation 6h, makes final catalyst, and catalyst weight consists of Co:Al
2o
3=22:78.
Get above-mentioned catalyst 10g and reduce in fixed bed reactors, reducing condition is: 240 ℃, and 1.0MPa, 700h
-1(V/V), hydrogen, constant temperature 16h.Reaction condition is: 240 ℃, and 3.0Mpa, 5000h
-1(V/V), H
2/ CO (mol)=3.Reaction result is in Table 1.
Table 1 catalyst reaction result
Claims (9)
1. autoreduction is produced a Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that catalyst comprises cobalt oxide, oxide carrier and surface passivation cobalt oxide: cobalt oxide is in metal, metallic cobalt 15-35wt%, and all the other are oxide carrier;
And preparation by the following method:
(1) by the composition of final catalyst, take solubility cobalt salt, add deionized water and be mixed with solution;
(2) by carbon source: cobalt salt weight ratio is 0.2-2:1, take carbon source powder and be dissolved in distilled water, stir, form suspension, gelatinization 0.5-4h at 50-90 ℃;
(3) keep gelatinization point, stir, by final catalyst, form, aluminium salt, zirconates or the titanium salt solution of preparation 0.1-2 mol/L, with 0.1-2 mol/L alkaline precipitating agent co-precipitation, maintenance pH is 7.0-9.0; After precipitation finishes, aging 1-12h at 60-90 ℃, after aging end, suction filtration or centrifugation;
(4) filter cake is put in drying box and at 60-120 ℃, is dried 6-24h, be then placed in tube furnace, under inert atmosphere, roasting 2-8h at 350-800 ℃, makes containing charcoal carrier;
(5) cobalt salt solution of step (1) be impregnated in to above-mentioned carrier by equi-volume process;
(6) step (5) gained is placed in to drying box, dry 6-24h at 60-120 ℃, after being dried, under inert atmosphere, roasting 2-10 h at 200-400 ℃, room temperature passivation 2-12h to be down to, makes final catalyst.
2. a kind of autoreduction as claimed in claim 1 is produced Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that described oxide carrier is alundum (Al2O3), zirconium dioxide or titanium dioxide.
3. a kind of autoreduction as claimed in claim 1 is produced Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that the described cobalt salt of step (1) is a kind of in cobalt nitrate, cobalt acetate, cobaltous sulfate.
4. a kind of autoreduction as claimed in claim 1 is produced Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that the described carbon source of step (2) is a kind of in starch, methylcellulose, sesbania powder.
5. a kind of autoreduction as claimed in claim 1 is produced Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that the described aluminium salt of step (3) is a kind of in aluminum nitrate, aluminum sulfate, zirconates is a kind of in zirconium oxychloride, zirconium nitrate, zirconyl nitrate, and titanium salt is a kind of in Titanium Nitrate, titanium tetrachloride.
6. a kind of autoreduction as claimed in claim 1 is produced Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that the described alkaline precipitating agent of step (3) is a kind of in ammoniacal liquor, ammonium carbonate, carbonic hydroammonium.
7. a kind of autoreduction as claimed in claim 1 is produced Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that step (4) and the described inert atmosphere of step (6) are a kind of in nitrogen, argon gas, helium.
8. a kind of autoreduction as claimed in claim 1 is produced Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that the described passivation of step (6) passivating gas used is nitrogen and oxygen gas mixture, and wherein oxygen volume content is 1.0-20%.
9. the application that a kind of autoreduction as described in claim 1-8 any one is produced Fischer-Tropsch synthesis cobalt-based catalyst, is characterized in that catalyst is applied to fixed bed reactors, and reducing condition is: 180-250 ℃, 0.2-1.0 MPa, hydrogen volume air speed 500-1500h
-1, constant temperature 6-24 h; Reaction condition is: reaction temperature is 180-240 ℃, H
2/ CO mol ratio is between 1.5-3.0, and pressure is 1.0-3.0MPa, and air speed is 500-5000h
-1.
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| CN108654637A (en) * | 2017-03-29 | 2018-10-16 | 中国石油化工股份有限公司 | A kind of cobalt-base catalyst and preparation method and application and Fischer-Tropsch synthesis method |
| CN114929382A (en) * | 2020-01-10 | 2022-08-19 | 英国石油有限公司 | Process for producing a fischer-tropsch synthesis catalyst and fischer-tropsch start-up process |
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| CN108654637B (en) * | 2017-03-29 | 2021-10-08 | 中国石油化工股份有限公司 | Cobalt-based catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method |
| CN114929382A (en) * | 2020-01-10 | 2022-08-19 | 英国石油有限公司 | Process for producing a fischer-tropsch synthesis catalyst and fischer-tropsch start-up process |
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