CN104588033A - Slurry bed Fischer-Tropsch synthesis catalyst, and preparation method and application thereof - Google Patents
Slurry bed Fischer-Tropsch synthesis catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a slurry bed cobalt-based Fischer-Tropsch synthesis catalyst, and a preparation method and an application thereof. The catalyst adopts a composite metal oxide with a perovskite structure ABO3 as a carrier, wherein A is rare earth metal lanthanum, B is transition metal nickel; and the catalyst adopts cobalt as an active component and Pt as an assistant, and comprises 5-30wt% of cobalt and 0.1-2wt% of Pt. The preparation method of the Fischer-Tropsch synthesis catalyst comprises a preparation process of the composite metal oxide with the perovskite structure ABO3, and an active component and assistant supporting process. The catalyst has the advantages of high catalytic activity, low methane selectivity, good stability and long life cycle in slurry bed cobalt-based Fischer-Tropsch synthesis reactions.
Description
Technical field
The present invention relates to a kind of 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 slurry bed system Co based Fischer-Tropsch synthesis catalyst and its preparation method and application.It is high that this catalyst application has catalytic activity in syrup state bed Fischer Tropsch synthetic reaction, the advantages such as methane selectively is low, catalyst stability good, life cycle is long.
A kind of fischer-tropsch synthetic catalyst, to have perovskite structure ABO
3composite metal oxide be carrier, wherein A is rare earth lanthanum, and B is transiting metal nickel, take cobalt as active component, and Pt is auxiliary agent, in final catalyst the weight content of active component cobalt be 5% ~ 30%, the weight content 0.1% ~ 2% of auxiliary agent Pt.
A preparation method for fischer-tropsch synthetic catalyst, comprises and has perovskite structure ABO
3the preparation process of composite metal oxide carrier and the loading process of active component and auxiliary agent.
In the preparation method of above-mentioned fischer-tropsch synthetic catalyst, described has perovskite structure ABO
3the preparation process of composite metal oxide carrier as follows: with nickel nitrate and 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, the sample after roasting is the composite oxides F-T synthesis carrier with perovskite structure.Wherein, 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 400 ~ 1000 DEG C, and roasting time is roasting 2 ~ 15 hours, is preferably roasting 3 ~ 8 hours at 700 ~ 900 DEG C.What basic ammonium salts solution impregnation can be adopted to prepare has perovskite structure ABO
3composite metal oxide carrier it is further processed.Basic ammonium salts solution comprises ammoniacal liquor, ammonium carbonate and carbonic hydroammonium, preferred carbonic hydroammonium.Basic ammonium salts concentration of polymer solution is 5-15%, and dipping temperature is 60 ~ 90 DEG C, and dip time is 2 ~ 6h.The impregnation process of basic ammonium salts solution can significantly improve the performance of catalyst.
In the preparation method of above-mentioned fischer-tropsch synthetic catalyst, the loading process of described active component and auxiliary agent adopts infusion process, cross volume impregnation or incipient impregnation, total immersion stain or step impregnation, the impregnated activated component cobalt of preferred elder generation then impregnation aids Pt, more preferably the pH controlling cobalt salt dipping solution in the process of impregnated activated component Co is 3 ~ 5, is preferably 3.5 ~ 4.5; In the process of impregnation aids Pt, the pH controlled containing Pt solution is less than 3, is preferably 0.1 ~ 3.Cobalt salt dipping solution is generally cobalt nitrate solution, is generally platinum acid chloride solution containing Pt solution.The pH value of dipping solution adopts various appropriate substances to regulate, and regulates as adopted nitric acid, ammonium nitrate, ammoniacal liquor etc.Comprise drying and roasting after dipping terminates, also only can carry out drying, dry and roasting adopts method and the condition of this area routine.
The application of fischer-tropsch synthetic catalyst of the present invention, reaction temperature is 180 ~ 250 DEG C, and the volume space velocity of F-T synthesis unstripped gas (being made up of hydrogen and carbon monoxide) is 200 ~ 1000h
-1, reaction pressure is 1.0 ~ 4.0MPa, H in unstripped gas
2/ CO=1 ~ 3(mol ratio).
The present invention adopts the perovskite with suitable composition as carrier, and the synergy of itself and active component and auxiliary agent, significantly improves the performance of catalyst.Especially in the dipping process of active component and auxiliary agent, regulation and control certain pH value, thus the decentralization of active component cobalt reduction degree and auxiliary agent Pt is improved, more difficult generation causes the cobalt carbonyl compound of catalysqt deactivation in the reaction, and then be conducive to the activity improving catalyst, and greatly reduce the selective of its methane production.
The application of fischer-tropsch synthetic catalyst of the present invention in syrup state bed Fischer Tropsch synthetic reaction.Experiment shows, under appropriate process conditions, and C while CO conversion ratio reaches more than 85%
5 +selectively can reach more than 85% (the selective weight ratio by certain product and all product (except water) calculates), and product methane is selective less than 5%, greatly reduce investment and the operating cost of subsequent products separation equipment, and can stable operation, 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.
The preparation method of fischer-tropsch synthetic catalyst carrier of the present invention: get 23gNi (NO
3)
2﹒ 6H
2o puts into the beaker of 500mL, 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 nickel 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.Now continue stirring after 5 hours until above-mentioned mixed solution, 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 400 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, obtain composite metal catalyst carrier.
Embodiment 1
(1) get the impregnated activated component of above-mentioned carrier 30 as one kind g and auxiliary agent, by catalyst cobalt content 10wt%, take cobalt nitrate 10.49g and be dissolved in 34ml, and equal 4 by ammonium nitrate adjust ph, and add in above-mentioned carrier, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.
(2) by catalyst platinum content 1wt%, take after chloroplatinic acid 1.04g is dissolved in 34ml water, and equal 0.5 by nitric acid adjust ph, add in above-mentioned carrier and flood, aging 2 hours, 80 DEG C of dryings 6 hours, roasting 4 hours in 350 DEG C.Obtained catalyst is designated as C-1, and evaluation result is in table 1.
Embodiment 2
Be the pH value not regulating dipping solution in the dipping process of cobalt and Pt with embodiment 1, obtained catalyst is designated as C-2, and evaluation result is in table 1.
Embodiment 3
Be that to be prepended to mass concentration in impregnated activated component be in the ammonium bicarbonate soln of 10% to carrier with embodiment 1, dipping temperature is 80 DEG C, and dip time is 4h.Obtained catalyst is designated as C-3, and evaluation result is in table 1.
Embodiment 4
(1) get the impregnated activated component of above-mentioned carrier 30 as one kind g and auxiliary agent, by catalyst cobalt content 15wt%, take cobalt nitrate 15.74g and be dissolved in 34ml, and equal 3.5 by ammonium nitrate adjust ph, and add in above-mentioned carrier, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.
(2) by catalyst platinum content 1.5wt%, take after chloroplatinic acid 1.56g is dissolved in 34ml water, and equal 0.2 by nitric acid adjust ph, add in above-mentioned carrier and flood, aging 2 hours, 80 DEG C of dryings 6 hours, roasting 4 hours in 350 DEG C.Obtained catalyst is designated as C-4, and evaluation result is in table 1.
Embodiment 5
(1) get the impregnated activated component of above-mentioned carrier 30 as one kind g and auxiliary agent, by catalyst cobalt content 20wt%, take cobalt nitrate 20.99g and be dissolved in 34ml, and equal 4 by ammonium nitrate adjust ph, and add in above-mentioned carrier, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.
(2) by catalyst platinum content 0.2wt%, take after chloroplatinic acid 0.21g is dissolved in 34ml water, and equal 1.5 by nitric acid adjust ph, add in above-mentioned carrier and flood, aging 2 hours, 80 DEG C of dryings 6 hours, roasting 4 hours in 350 DEG C.Obtained catalyst is designated as C-5, and evaluation result is in table 1.
Embodiment 6
(1) get the impregnated activated component of above-mentioned carrier 30 as one kind g and auxiliary agent, by catalyst cobalt content 10wt%, take cobalt nitrate 10.49g and be dissolved in 34ml, and equal 4.5 by ammonium nitrate adjust ph, and add in above-mentioned carrier, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.
(2) by catalyst platinum content 1wt%, take after chloroplatinic acid 1.04g is dissolved in 34ml water, and equal 0.3 by nitric acid adjust ph, add in above-mentioned carrier and flood, aging 3 hours, 80 DEG C of dryings 6 hours, roasting 6 hours in 350 DEG C.Obtained catalyst is designated as C-6, and evaluation result is in table 1.
Comparative example 1
Adopt coprecipitation preparation containing the composite metal oxide (without perovskite structure) of lanthanum, nickel, cobalt, then dip loading Pt, the content of each metal component is with embodiment 1.Obtained catalyst is designated as B-1, and evaluation result is in table 1.
Comparative example 2
Be that carrier adopts infusion process Supported Co, lanthanum, nickel with silica, platinum, the addition of cobalt, lanthanum, nickel, platinum is with embodiment 1.Obtained catalyst is designated as B-2, and evaluation result is in table 1.
Carry out activity rating to the catalyst prepared by above-described embodiment and comparative example, evaluation test is in high pressure CSTR, and using paraffin as solvent, to reduce 12 hours at pure hydrogen 350 DEG C, pressure is 1.0MPa.After cooling, switching and merging gas reacts.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 200 DEG C, 500h
-1, 2.0MPa, H
2/ CO=2(mol ratio).300h evaluation result is in table 1.
The reactivity worth of table 1 catalyst
| Catalyst | CO conversion ratio (%) | C 5 +Selective (wt%) | CH 4Selective (wt%) |
| C-1 | 88.3 | 87.2 | 4.74 |
| B-1 | 37.9 | 62.4 | 23.1 |
| B-2 | 74.7 | 75.7 | 10.7 |
| C-2 | 81.2 | 82.2 | 6.54 |
| C-3 | 89.0 | 88.1 | 3.17 |
| C-4 | 85.7 | 87.2 | 4.54 |
| C-5 | 86.0 | 85.1 | 4.97 |
| C-6 | 87.1 | 86.3 | 4.43 |
Claims (17)
1. a fischer-tropsch synthetic catalyst, is characterized in that: this catalyst is to have perovskite structure ABO
3composite metal oxide be carrier, wherein A is rare earth lanthanum, and B is transiting metal nickel, take cobalt as active component, and Pt is auxiliary agent, in final catalyst the weight content of active component cobalt be 5% ~ 30%, the weight content 0.1% ~ 2% of auxiliary agent Pt.
2. the preparation method of catalyst described in claim 1, is characterized in that: comprise and have perovskite structure ABO
3the preparation process of composite metal oxide carrier and the loading process of active component and auxiliary agent.
3. in accordance with the method for claim 2, it is characterized in that: with nickel nitrate and 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 oxide carrier with perovskite structure.
4. in accordance with the method for claim 3, it is characterized in that: complexing agent and metal ion mol ratio are 1:1 ~ 8:1.
5. in accordance with the method for claim 4, it is characterized in that: complexing agent and metal ion mol ratio are 1:1 ~ 4:1.
6. in accordance with the method for claim 3, 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.
7. in accordance with the method for claim 6, 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.
8. in accordance with the method for claim 3, 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.
9. in accordance with the method for claim 8, 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.
10. in accordance with the method for claim 2, it is characterized in that: what adopt basic ammonium salts solution impregnation to prepare has perovskite structure ABO
3composite metal oxide carrier it is further processed.
11. in accordance with the method for claim 10, it is characterized in that: basic ammonium salts solution comprises ammoniacal liquor, ammonium carbonate and carbonic hydroammonium, preferred carbonic hydroammonium, and basic ammonium salts concentration of polymer solution is 5-15%, and dipping temperature is 60 ~ 90 DEG C, and dip time is 2 ~ 6h.
12., according to the method described in claim 2 or 10, is characterized in that: the loading process of active component and auxiliary agent adopts infusion process, crosses volume impregnation or incipient impregnation, total immersion stain or step impregnation.
13. in accordance with the method for claim 12, it is characterized in that: first impregnated activated component cobalt then impregnation aids Pt.
14. in accordance with the method for claim 13, it is characterized in that: the pH controlling cobalt salt dipping solution in the process of impregnated activated component Co is 3 ~ 5, is preferably 3.5 ~ 4.5; In the process of impregnation aids Pt, the pH controlled containing Pt solution is less than 3, is preferably 0.1 ~ 3.
15. in accordance with the method for claim 14, it is characterized in that: cobalt salt dipping solution is cobalt nitrate solution, is platinum acid chloride solution containing Pt solution, and the pH value of dipping solution adopts nitric acid, ammonium nitrate, ammoniacal liquor to regulate.
16. in accordance with the method for claim 2, it is characterized in that: comprise drying and roasting after dipping terminates, and dry and roasting adopts method and the condition of this area routine.
The preparation method of catalyst described in 17. claims 1, is characterized in that: reaction temperature is 180 ~ 250 DEG C, and the volume space velocity of F-T synthesis unstripped gas (being made up of hydrogen and carbon monoxide) is 200 ~ 1000h
-1, reaction pressure is 1.0 ~ 4.0MPa, H in unstripped gas
2/ CO=1 ~ 3(mol ratio).
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Cited By (5)
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| CN106669821A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Cobalt-based Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
| CN106669729A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Slurry reactor Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
| CN110064421A (en) * | 2018-01-23 | 2019-07-30 | 中国石油天然气股份有限公司 | A kind of reforming catalyst and preparation method thereof |
| CN112403491A (en) * | 2020-11-26 | 2021-02-26 | 厦门大学 | Catalyst for preparing liquid fuel by high-selectivity conversion of synthesis gas and preparation method and application thereof |
| CN112808275A (en) * | 2019-11-18 | 2021-05-18 | 中国科学院大连化学物理研究所 | Preparation method of cobalt-based catalyst for preparing oil from synthetic gas |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669821A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Cobalt-based Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
| CN106669729A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Slurry reactor Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
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| CN110064421A (en) * | 2018-01-23 | 2019-07-30 | 中国石油天然气股份有限公司 | A kind of reforming catalyst and preparation method thereof |
| CN110064421B (en) * | 2018-01-23 | 2021-11-30 | 中国石油天然气股份有限公司 | Reforming catalyst and preparation method thereof |
| CN112808275A (en) * | 2019-11-18 | 2021-05-18 | 中国科学院大连化学物理研究所 | Preparation method of cobalt-based catalyst for preparing oil from synthetic gas |
| CN112403491A (en) * | 2020-11-26 | 2021-02-26 | 厦门大学 | Catalyst for preparing liquid fuel by high-selectivity conversion of synthesis gas and preparation method and application thereof |
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