CN104588022A - High-activity Fischer-Tropsch synthesis catalyst, and preparation method and application thereof - Google Patents
High-activity Fischer-Tropsch synthesis catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-activity Fischer-Tropsch synthesis catalyst, and a preparation method and an application thereof. The catalyst is a composite metal oxide with a perovskite structure, and the general formula of the catalyst is AB'<x>B<1-x>O<3>, wherein A is transition metal zirconium, B is transition metal cobalt, and x is greater than 0 and smaller than 0.2. The preparation method of the cobalt-based Fischer-Tropsch synthesis catalyst comprises the following steps: preparing a solution with cobalt nitrate, zirconium nitrate and lanthanum nitrate as precursors and citric acid or glycol as a complexing agent, uniformly stirring, carrying out water evaporation to make the solution become a viscous gel from a transparent sol, drying, and roasting to obtain the composite oxide Fischer-Tropsch synthesis catalyst with the perovskite structure. The catalyst can be applied to Fischer-Tropsch synthesis reactions. The catalyst has the advantages of CO conversation rate and C<5><+> selectivity improvement, methane selectivity reduction, and good long-cycle running stability.
Description
Technical field
The present invention relates to a kind of high activity fischer-tropsch synthetic catalyst and its preparation method and application, belong to the catalysis technique in F-T synthesis field.
Background technology
F-T synthesis refers to that synthesis gas (carbon monoxide and hydrogen) catalyzes and synthesizes the reaction of liquid hydrocarbon fuel on a catalyst.F-T synthesis has advantages such as not relying on oil, product cleans.Along with world energy sources structure from single oil dependent form to coal, oil and natural gas alliance type change and environmental requirement day by day improve, F-T synthesis technology will be developed rapidly.
Efficient co-based fischer-tropsch catalyst is one of key technology in F-T synthesis technology, and each major oil companies successively develop with amorphous Si O
2, TiO
2and Al
2o
3for the Co based Fischer-Tropsch synthesis catalyst of main carriers.
US6765026B2 discloses and a kind ofly applies the Fischer-Tropsch synthesis method that special catalyst carries out catalysis.The catalyst precursor that the method adopts is the soluble compounds of a kind of iron group (especially cobalt) metal or the soluble compounds of salt and platinum or salt.The solution of presoma with hydroxyhy-drocarbyl amines or ammonium hydroxide is contacted, obtains a kind of special catalyst, make C
5 +hydrocarbon selective reaches 58% ~ 80%.But use the method to be worth low gaseous products CH
4selective up to 10%.Thus need to propose a kind of new Fischer-Tropsch synthesis method to reduce CH further
4selective.
It take activated carbon as the preparation method of carrier Co based Fischer-Tropsch synthesis catalyst that CN1417292A reports a kind of, for synthesis gas being that the linear paraffin of carbon number within 20 prepared by raw material and carbon number mainly concentrates on the hydro carbons of diesel oil distillate section.Be 240 DEG C in reaction temperature, reaction pressure 2.5MPa, air speed 500h
-1under condition, the conversion ratio of fixed bed reaction system CO is 64.1%, CH
4selective be 8.5%, C
5 +selective is 80.7%.
CN101224430A reports a kind of hydrophobic organic modification of Co group Fischer-Tropsch synthesized catalyst, and noble metal and cobalt load on silica supports, then carries out organically-modified.Wherein when noble metal adopts Pt, catalyst system 15%Co0.8%Pt/SiO
2, organically-modified reagent adopts dimethyldiethoxysilane modification, and on pressurization static bed, reaction condition is 230 DEG C, 1.0MPa, 1000h
-1(V/V), H
2the conversion ratio of/CO=3/1, CO is 72.7%, and the selective of methane is 8.4%.The CH of above-mentioned technology
4selective need reduce further, C
5 +selective need improve further.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application.This catalyst is adopted to ensure high CO conversion ratio and C
5 +optionally reduce methane selectively simultaneously, and the good stability of long-term operation.
A kind of fischer-tropsch synthetic catalyst, this catalyst is the composite metal oxide with perovskite structure, and general formula is AB '
xb
1-xo
3, wherein A is rare earth lanthanum, and B ' is transition metal zirconium, and B is transition metals cobalt, 0<x<0.2.
A kind of preparation method of fischer-tropsch synthetic catalyst, comprise following process: with cobalt nitrate, zirconium nitrate, lanthanum nitrate for presoma, with citric acid or ethylene glycol for complexing agent, wiring solution-forming mixing and stirring, then moisture evaporation is carried out, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, and the sample after roasting is the composite oxides fischer-tropsch synthetic catalyst with perovskite structure.
In the preparation method of fischer-tropsch synthetic catalyst of the present invention, complexing agent and metal ion mol ratio are 1:1 ~ 8:1, are preferably 1:1 ~ 4:1.Preparation and agitating solution, at 20 ~ 90 DEG C, carry out at being preferably 50 ~ 70 DEG C.Stir speed (S.S.) is 200 ~ 500rpm, is preferably 300 ~ 400rpm.Mixing time is 3 ~ 8 hours, is preferably 4 ~ 6 hours.Baking temperature is 60 ~ 200 DEG C, is preferably 80 ~ 150 DEG C.Drying time is 1 ~ 36 hour, is preferably 8 ~ 24 hours.Sintering temperature is 600 ~ 1000 DEG C, and roasting time is roasting 2 ~ 15 hours, is preferably roasting 3 ~ 8 hours at 700 ~ 900 DEG C.
The method of reducing of fischer-tropsch synthetic catalyst of the present invention, adopts conventional method of reducing or segmentation reduction mode, preferred the latter.Described segmentation reduction mode first reduction 4 ~ 24h under the atmosphere of hydrogen, reduction temperature is 300-400 DEG C, reduction pressure 0.5 ~ 1.5MPa, then reduction 6 ~ 12h under the atmosphere of hydrogen and methane mixed gas, reduction temperature is 200 ~ 240 DEG C, reduction pressure is 0.5 ~ 3MPa, and the volumetric mixture ratio of hydrogen and methane gas is 10:1 ~ 2:1.Adopt segmentation reduction mode can improve the activity stability of catalyst further and reduce the selective of methane.
The application of fischer-tropsch synthetic catalyst of the present invention: reaction temperature is 180 ~ 250 DEG C, the volume space velocity of F-T synthesis unstripped gas (being made up of hydrogen and carbon monoxide) is 400 ~ 1000h
-1, reaction pressure is 1.0 ~ 5.0MPa, H in unstripped gas
2/ CO=1 ~ 3(mol ratio).
The present invention prepares a kind of composite metal oxide with perovskite structure as fischer-tropsch synthetic catalyst, and its general formula is AB '
xb
1-xo
3, wherein A is rare earth lanthanum, and B ' is transition metal zirconium, and B is transition metals cobalt, and 0<x<0.2 has special duct and surface nature.Rare earth lanthanum on A position can improve the structural stability of perovskite and thermally-stabilised, the doping of zirconium on B position, make cobalt metal ion electric charge, radius changes, thus active component cobalt reduction degree is improved, and then be conducive to the activity stability improving catalyst, and greatly reduce the selective of its methane production.
The composite oxides fischer-tropsch synthetic catalyst that the present invention has perovskite structure adopts the preparation of citric acid complex one-step method, and operating process is simple, and technical maturity, is suitable for industrial production.
The present invention has the application of composite oxides in Fischer-Tropsch synthesis of perovskite structure.Experiment shows, under appropriate process conditions, and C
5 +selectively can reach more than 90% (the selective weight ratio by certain product and all product (except water) calculates), and product methane is selective less than 4%, greatly reduce investment and the operating cost of subsequent products separation equipment, be conducive to economy when improving the application of F-T synthesis technology.
Detailed description of the invention
Process and the effect of the inventive method is further illustrated below in conjunction with embodiment.
Embodiment 1
Get 20.7gCo (NO
3)
2﹒ 6H
2o and 2.7gZr (NO
3)
4﹒ 5H
2o puts into the beaker of 500mL, makes the mol ratio of its Co and Zr be 0.9/0.1, adds the distilled water of 100mL, and then beaker is placed in the water-bath of 80 DEG C, mixing speed is 400rpm, is stirred to whole dissolving.Get 34.3g La (NO
3)
3﹒ 6H
2o, is placed with in the beaker of 100mL distilled water, is stirred to whole dissolving.Then lanthanum nitrate hexahydrate is added drop-wise in cobalt nitrate and zirconium nitrate solution, dropping limit, limit is stirred, get 40g citric acid, citric acid and metal ion total amount mol ratio are 1:1, be placed with in the beaker of 100mL and be stirred to whole dissolving, now after above-mentioned mixed solution stirs 30 minutes, add citric acid solution slowly, dropping limit, limit is stirred.After above-mentioned mixed solution stirs 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, rise to 600 DEG C with the heating rate of 3 DEG C/min from room temperature, constant temperature calcining 3 hours, rise to 800 DEG C with the heating rate of 10 DEG C/min again, constant temperature calcining 4 hours, obtains fischer-tropsch synthetic catalyst.Obtained catalyst is designated as C-1, and evaluation result is in table 1.
Embodiment 2
Get 21.85gCo (NO
3)
2﹒ 6H
2o and 1.35gZr (NO
3)
4﹒ 5H
2o puts into the beaker of 500mL, makes the mol ratio of its Co and Zr be 0.95/0.05, adds the distilled water of 100mL, and then beaker is placed in the water-bath of 80 DEG C, mixing speed is 400rpm, is stirred to whole dissolving.Get 34.3g La (NO
3)
3﹒ 6H
2o, is placed with in the beaker of 100mL distilled water, is stirred to whole dissolving.Then lanthanum nitrate hexahydrate is added drop-wise in cobalt nitrate and zirconium nitrate solution, dropping limit, limit is stirred.Get 40g citric acid, citric acid and metal ion total amount mol ratio are 1:1, are placed with in the beaker of 100mL and are stirred to whole dissolving, now after above-mentioned mixed solution stirs 30 minutes, add citric acid solution slowly, and dropping limit, limit is stirred.After above-mentioned mixed solution stirs 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, rise to 600 DEG C with the heating rate of 3 DEG C/min from room temperature, constant temperature calcining 3 hours, rise to 800 DEG C with the heating rate of 10 DEG C/min again, constant temperature calcining 4 hours, obtains fischer-tropsch synthetic catalyst.Obtained catalyst is designated as C-2, and evaluation result is in table 1.
Embodiment 3
Get 18.4gCo (NO
3)
2﹒ 6H
2o and 5.4gZr (NO
3)
4﹒ 5H
2o ﹒ 6H
2o puts into the beaker of 500mL, makes the mol ratio of its Co and Zr be 0.8/0.2, adds the distilled water of 100mL, and then beaker is placed in the water-bath of 80 DEG C, mixing speed is 400rpm, is stirred to whole dissolving.Get 34.3g La (NO
3)
3﹒ 6H
2o, is placed with in the beaker of 100mL distilled water, is stirred to whole dissolving.Then lanthanum nitrate hexahydrate is added drop-wise in cobalt nitrate and zirconium nitrate solution, dropping limit, limit is stirred.Get 40g citric acid, citric acid and metal ion total amount mol ratio are 1:1, are placed with in the beaker of 100mL and are stirred to whole dissolving, now after above-mentioned mixed solution stirs 30 minutes, add citric acid solution slowly, and dropping limit, limit is stirred.After above-mentioned mixed solution stirs 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, rise to 600 DEG C with the heating rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 800 DEG C with the heating rate of 10 DEG C/min again, constant temperature calcining 2 hours, obtains fischer-tropsch synthetic catalyst.Obtained catalyst is designated as C-3, and evaluation result is in table 1.
Embodiment 4
Get 19.55gCo (NO
3)
2﹒ 6H
2o and 4.05gNi (NO
3)
2﹒ 6H
2o puts into the beaker of 500mL, makes the mol ratio of its Co and Zr be 0.85/0.15, adds the distilled water of 100mL, and then beaker is placed in the water-bath of 80 DEG C, mixing speed is 400rpm, is stirred to whole dissolving.Get 34.3g La (NO
3)
3﹒ 6H
2o, is placed with in the beaker of 100mL distilled water, is stirred to whole dissolving.Then lanthanum nitrate hexahydrate is added drop-wise in cobalt nitrate and zirconium nitrate solution, dropping limit, limit is stirred.Get 40g citric acid, citric acid and metal ion total amount mol ratio are 1:1, are placed with in the beaker of 100mL and are stirred to whole dissolving, now after above-mentioned mixed solution stirs 30 minutes, add citric acid solution slowly, and dropping limit, limit is stirred.After above-mentioned mixed solution stirs 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, rise to 700 DEG C with the heating rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 800 DEG C with the heating rate of 10 DEG C/min again, constant temperature calcining 3 hours, obtains fischer-tropsch synthetic catalyst.Obtained catalyst is designated as C-4, and evaluation result is in table 1.
Comparative example 1
Adopt coprecipitation preparation containing the composite metal oxide (without perovskite structure) of lanthanum, zirconium, cobalt, in oxide, the content of lanthanum, zirconium, cobalt is with embodiment 1.
Comparative example 2
Be that carrier adopts infusion process Supported Co, lanthanum, zirconium with silica, the mol ratio of cobalt, lanthanum, zirconium is with embodiment 1.
Embodiment 5
Carry out activity rating to the catalyst prepared by embodiment and comparative example, evaluation test is in high pressure CSTR, and using paraffin as solvent, adopt conventional reduction method namely to reduce 18 hours at pure hydrogen 350 DEG C, pressure is 2MPa.After cooling, switching and merging gas reacts.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 220 DEG C, 500h
-1, 2.0MPa, H
2/ CO=2(mol ratio).200h operates evaluation result in table 1.
Table 1 catalyst reaction performance
| Catalyst | CO conversion ratio (%) | C 5 +Selective (wt%) | CH 4Selective (wt%) |
| C-1 | 92.1 | 91.4 | 3.75 |
| B-1 | 37.8 | 62.1 | 23.1 |
| B-2 | 62.7 | 75.7 | 14.7 |
| C-2 | 90.9 | 90.3 | 3.43 |
| C-3 | 91.1 | 90.7 | 3.77 |
| C-4 | 90.7 | 90.2 | 3.44 |
Embodiment 6
Activity rating is carried out to the catalyst of embodiment 1-4, evaluation test is in high pressure CSTR, using paraffin as solvent, adopt segmentation method of reducing, wherein the reducing condition of embodiment 1 is: reduce 8h first in a hydrogen atmosphere, reduction temperature 300 DEG C, reduction pressure 1MPa, then under volume ratio is the hydrogen of 5:1 and the mixed atmosphere of methane, 8h is reduced, reduction temperature 210, reduction pressure 1MPa; The reducing condition of embodiment 2 is: reduce 6h first in a hydrogen atmosphere, reduction temperature 350 DEG C, reduction pressure 0.5MPa, under volume ratio is the hydrogen of 3:1 and the mixed atmosphere of methane, then reduce 6h, reduction temperature 220, reduction pressure 1.5MPa; The reducing condition of embodiment 3 is: reduce 16h first in a hydrogen atmosphere, reduction temperature 350 DEG C, reduction pressure 1MPa, under volume ratio is the hydrogen of 8:1 and the mixed atmosphere of methane, then reduce 12h, reduction temperature 200 DEG C, reduction pressure 2MPa; The reducing condition of embodiment 4 is: reductase 12 0h first in a hydrogen atmosphere, reduction temperature 400 DEG C, reduction pressure 1MPa, under volume ratio is the hydrogen of 2:1 and the mixed atmosphere of methane, then reduce 6h, reduction temperature 230 DEG C, reduction pressure 2.5MPa.Reduction terminates rear cooling switching and merging gas and reacts.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 220 DEG C, 500h
-1, 2.0MPa, H
2/ CO=2(mol ratio).200h operates evaluation result in table 2.
Table 2 catalyst reaction performance
| Catalyst | CO conversion ratio (%) | C 5 +Selective (wt%) | CH 4Selective (wt%) |
| C-1 | 94.4 | 93.4 | 2.85 |
| C-2 | 93.9 | 92.3 | 2.63 |
| C-3 | 93.1 | 92.7 | 2.87 |
| C-4 | 92.7 | 91.4 | 2.94 |
Claims (11)
1. a fischer-tropsch synthetic catalyst, is characterized in that: this catalyst is the composite metal oxide with perovskite structure, and general formula is AB '
xb
1-xo
3, wherein A is rare earth lanthanum, and B ' is transition metal zirconium, and B is transition metals cobalt, 0<x<0.2.
2. the preparation method of fischer-tropsch synthetic catalyst described in claim 1, is characterized in that: with cobalt nitrate, lanthanum nitrate, zirconium nitrate for presoma, and citric acid or ethylene glycol are complexing agent, wiring solution-forming mixing and stirring; Then carry out moisture evaporation, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, obtains the composite oxides fischer-tropsch synthetic catalyst with perovskite structure.
3. in accordance with the method for claim 2, it is characterized in that: complexing agent and metal ion mol ratio are 1:1 ~ 8:1.
4. in accordance with the method for claim 3, it is characterized in that: complexing agent and metal ion mol ratio are 1:1 ~ 4:1.
5. in accordance with the method for claim 2, it is characterized in that: preparation and agitating solution carry out at 20 ~ 90 DEG C, and mixing time is 3 ~ 8 hours, and mixing speed is 200 ~ 500rpm.
6. in accordance with the method for claim 5, it is characterized in that: preparation and agitating solution carry out at 50 ~ 70 DEG C, and mixing time is 4 ~ 6 hours, and stir speed (S.S.) is 300 ~ 400rpm.
7. in accordance with the method for claim 2, it is characterized in that: baking temperature is 60 ~ 200 DEG C, drying time is 1 ~ 36 hour, and roasting is roasting 2-15 hour at 400 ~ 1000 DEG C.
8. in accordance with the method for claim 7, it is characterized in that: baking temperature is 80 ~ 150 DEG C, drying time is 8 ~ 24 hours, roasting roasting 3 ~ 8 hours at 700 ~ 900 DEG C.
9. the method for reducing of fischer-tropsch synthetic catalyst described in claim 1, is characterized in that: adopt conventional method of reducing or segmentation reduction mode.
10. method of reducing according to claim 9, it is characterized in that: described segmentation reduction mode first reduction 4 ~ 24h under the atmosphere of hydrogen, reduction temperature is 300-400 DEG C, reduction pressure 0.5 ~ 1.5MPa, then reduction 6 ~ 12h under the atmosphere of hydrogen and methane mixed gas, reduction temperature is 200 ~ 240 DEG C, and reduction pressure is 0.5 ~ 3MPa, and the volumetric mixture ratio of hydrogen and methane gas is 10:1 ~ 2:1.
The application of catalyst in Fischer-Tropsch synthesis described in 11. claims 1: it is characterized in that: reaction temperature is 180 ~ 250 DEG C, the volume space velocity of F-T synthesis unstripped gas is 400 ~ 1000h
-1, reaction pressure is 1.0 ~ 5.0MPa, H in unstripped gas
2/ CO=1 ~ 3(mol ratio).
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| CN113231078A (en) * | 2021-05-25 | 2021-08-10 | 厦门大学 | Catalyst for preparing ethanol by carbon monoxide hydrogenation, preparation method thereof and reaction for preparing ethanol by carbon monoxide hydrogenation |
| CN114477299A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Oxygen carrier and preparation method and application thereof |
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