CN103785392A - Fischer-Tropsch synthesis catalyst and preparation method and application thereof - Google Patents
Fischer-Tropsch synthesis catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Fischer-Tropsch synthesis catalyst and a preparation method and application thereof. The catalyst is a composite metal catalyst with a perovskite structure, and the catalyst has a general formula AB'xB1-xO3, wherein A represents rare earth metal lanthanum and B' represents transition metal, and B represents transition metal cobalt. The preparation method of the cobalt based Fischer-Tropsch synthesis catalyst comprises the following steps: preparing a solution by using cobalt nitrate, copper nitrate and lanthanum nitrate as precursors, and citric acid or ethylene glycol as a complexing agent, and mixing evenly by stirring; then carrying out water evaporation to convert the solution from a transparent sol into a viscous gel; and finally drying and roasting to obtain a sample of the cobalt based Fischer-Tropsch synthesis catalyst with perovskite structure. The invention discloses the application of the catalyst to Fischer-Tropsch synthesis reaction. The catalyst can improve the conversion rate of CO and the selectivity of C5<+> and reduce methane selectivity.
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 the synthetic field of Fischer-Tropsch.
Background technology
Fischer-Tropsch is synthetic refers to that synthesis gas (carbon monoxide and hydrogen) catalyzes and synthesizes the reaction of liquid hydrocarbon fuel on catalyst.Fischer-Tropsch is synthetic to be had and not to rely on the advantages such as oil, product be clean.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, Fischer-Tropsch synthetic technology will be developed rapidly.
Co-based fischer-tropsch catalyst is one of key technology in Fischer-Tropsch synthetic technology efficiently, and each major oil companies have successively developed with amorphous Si O
2, TiO
2and Al
2o
3for the Co based Fischer-Tropsch synthesis catalyst of main carriers.
US6765026B2 discloses a kind of Fischer-Tropsch synthesis method of applying special catalyst and carrying out catalysis.The catalyst precursor that the method adopts is the soluble compounds of a kind of iron group (especially cobalt) metal or soluble compounds or the salt of salt and platinum.Presoma is contacted with the solution of hydroxyhy-drocarbyl amines or ammonium hydroxide, obtain a kind of special catalyst, make C
5 +hydrocarbon selective reaches 58% ~ 80%.But use the method to be worth low gaseous products CH
4selectively up to 10%.Thereby a kind of new Fischer-Tropsch synthesis method need to be proposed further to reduce CH
4selectively.
CN1417292A has reported a kind of preparation method take activated carbon as carrier Co based Fischer-Tropsch synthesis catalyst, mainly concentrates on the hydro carbons of diesel oil distillate section for prepare the linear paraffin of carbon number in 20 and carbon number take synthesis gas as raw material.Be 240 ℃ 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
4be selectively 8.5%, C
5 +be selectively 80.7%.
CN101224430A has reported 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 when Pt, catalyst system 15%Co0.8%Pt/SiO
2, organically-modified reagent adopts dimethyldiethoxysilane modification, and on pressurization static bed, reaction condition is 230 ℃, 1.0MPa, 1000h
-1(V/V), H
2/ CO=3/1, the conversion ratio of CO is 72.7%, methane be selectively 8.4%.The CH of above-mentioned technology
4selectively need further to reduce C
5 +selectively need further to improve.
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.Adopt this catalyst can improve CO conversion ratio and C
5 +selectively, reduce methane selectively.
A kind of fischer-tropsch synthetic catalyst, this catalyst is the composite metal catalyst with perovskite structure, general formula is AB '
xb
1-xo
3, wherein A is rare earth lanthanum, and B ' is transition metal copper, and B is transition metals cobalt, 0<x<1.
A kind of preparation method of fischer-tropsch synthetic catalyst, comprise following process: take cobalt nitrate, copper nitrate, lanthanum nitrate as presoma, take citric acid or ethylene glycol as complexing agent, wiring solution-forming mixing and stirring, then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, final drying, roasting, and the sample after roasting is the Co based Fischer-Tropsch synthesis catalyst with perovskite structure.
In the preparation method of fischer-tropsch synthetic catalyst of the present invention, complexing agent can be citric acid or ethylene glycol, and 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 ℃, are preferably at 50～70 ℃ and carry out.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 ℃, is preferably 80～150 ℃.Be 1～36 hour drying time, is preferably 8～24 hours.Sintering temperature is 400～1000 ℃, and roasting time is roasting 2 ~ 15 hours, is preferably at 700～900 ℃ roasting 3～8 hours.
The application of fischer-tropsch synthetic catalyst of the present invention: reaction temperature is 180 ~ 250 ℃, the volume space velocity of Fischer-Tropsch synthetic raw 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 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 copper, and B is transition metals cobalt, and 0<x<1 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 copper on B position, cobalt metal ion electric charge, radius are changed, thereby active component cobalt reduction degree is improved, and then be conducive to improve the activity of 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 application of the composite oxides that the present invention has a perovskite structure in Fischer-Tropsch synthesis.Experiment shows, under suitable process conditions, and C
5 +selectively can reach more than 90% (selectively calculating by the weight ratio of certain product and all product (except water)), and product methane selectively is less than 3%, greatly reduce investment and the operating cost of subsequent products separation equipment, the economy while being conducive to improve the application of Fischer-Tropsch synthetic technology.
Accompanying drawing explanation
Fig. 1 is the prepared Co based Fischer-Tropsch synthesis catalyst X-ray diffractogram of the embodiment of the present invention 1.
The specific embodiment
Further illustrate process and the effect of the inventive method below in conjunction with embodiment.
Embodiment 1
Get 20.7gCo (NO
3)
2﹒ 6H
2o and 1.9gCu (NO
3)
2﹒ 3H
2o puts into the beaker of 500mL, and making the mol ratio of Co and Cu is 0.9/0.1, adds the distilled water of 100mL, then beaker is placed in to the water-bath of 80 ℃, and mixing speed is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
3﹒ 6H
2o, puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the mixed solution of cobalt nitrate and copper nitrate, stir on dropping limit, limit.Get 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, now stir after 30 minutes until above-mentioned mixed solution, add slowly citric acid solution, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, heating rate with 3 ℃/min rises to 400 ℃ from room temperature, constant temperature calcining 3 hours, rise to 800 ℃ with the heating rate of 10 ℃/min again, constant temperature calcining 4 hours, obtains composite metal catalyst and is designated as C-1, and evaluation result is in table 1.
Embodiment 2
Get 16.1gCo (NO
3)
2﹒ 6H
2o and 5.7gCu (NO
3)
2﹒ 3H
2o puts into the beaker of 500mL, and making the mol ratio of Co and Cu is 0.7/0.3, is stirred to whole dissolvings.Add the distilled water of 100mL, then beaker is placed in to the water-bath of 80 ℃, mixing speed is 400rpm.Get 34.3g La (NO
3)
3﹒ 6H
2o, puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in cobalt nitrate and copper nitrate solution, stir on dropping limit, limit.Get 67g citric acid, citric acid and metal ion total amount mol ratio are 2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, stir after 30 minutes until above-mentioned mixed solution, add slowly citric acid solution, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, heating rate with 3 ℃/min rises to 400 ℃ from room temperature, constant temperature calcining 3 hours, rise to 800 ℃ with the heating rate of 10 ℃/min again, constant temperature calcining 4 hours, obtains composite metal catalyst and is designated as C-2, and evaluation result is in table 1.
Embodiment 3
Get 11.5g Co (NO
3)
2﹒ 6H
2o, 9.5gCu (NO
3)
2﹒ 3H
2o puts into the beaker of 500mL, and making the mol ratio of Co and Cu is 0.5/0.5, adds the distilled water of 100mL, then beaker is placed in to the water-bath of 80 ℃, and mixing speed is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
3﹒ 6H
2o, puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the mixed solution of cobalt nitrate and copper nitrate, stir on dropping limit, limit.Get 100g citric acid, citric acid and metal ion total amount mol ratio are 3:1, and the beaker of putting into 100mL is stirred to whole dissolvings, stir after 30 minutes until above-mentioned mixed solution, add slowly citric acid solution, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, heating rate with 3 ℃/min rises to 400 ℃ from room temperature, constant temperature calcining 2 hours, rise to 800 ℃ with the heating rate of 10 ℃/min again, constant temperature calcining 3 hours, obtains composite metal catalyst and is designated as C-3, and evaluation result is in table 1.
Embodiment 4
Get 4.6g Co (NO
3)
2﹒ 6H
2o and 15.2gCu (NO
3)
2﹒ 3H
2o puts into the beaker of 500mL, and making the mol ratio of Co and Cu is 0.2/0.8, adds the distilled water of 100mL, then beaker is placed in to the water-bath of 80 ℃, and mixing speed is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
3﹒ 6H
2o, puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the mixed solution of cobalt nitrate and copper nitrate, stir on dropping limit, limit.Get 134g citric acid, citric acid and metal ion total amount mol ratio are 4:1, and the beaker of putting into 100mL is stirred to whole dissolvings, stir after 30 minutes until above-mentioned mixed solution, add slowly citric acid solution, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, heating rate with 3 ℃/min rises to 400 ℃ from room temperature, constant temperature calcining 2 hours, rise to 800 ℃ with the heating rate of 10 ℃/min again, constant temperature calcining 3 hours, obtains composite metal catalyst and is designated as C-4, and evaluation result is in table 1.
Evaluating catalyst:
Comparative example 1
Adopt the composite metal oxide (without perovskite structure) of coprecipitation preparation containing lanthanum, copper, cobalt, in oxide, the content of lanthanum, copper, cobalt is with embodiment 1.
Comparative example 2
Adopt infusion process Supported Co, lanthanum, copper take silica as carrier, the mol ratio of cobalt, lanthanum, copper is with embodiment 1.
Above-described embodiment and the prepared catalyst of comparative example are carried out to activity rating, and evaluation test, in high pressure CSTR, using paraffin as solvent, is reduced 12 hours with at 350 ℃ of pure hydrogen, and pressure is 1.0MPa.After cooling, switching synthesis gas reacts.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 200 ℃, 500h
-1, 2.0MPa, H
2/ CO=2(mol ratio).Evaluation result is in table 1.
Table 1 embodiment and comparative example fischer-tropsch synthetic catalyst evaluation result
| Catalyst | CO conversion ratio (%) | C 5 +Selectively (wt%) | CH 4Selectively (wt%) |
| C-1 | 87.1 | 91.8 | 2.78 |
| B-1 | 37.9 | 62.4 | 23.1 |
| B-2 | 82.7 | 75.7 | 10.7 |
| C-2 | 88.9 | 90.3 | 2.91 |
| C-3 | 84.1 | 91.7 | 2.82 |
| C-4 | 84.7 | 90.1 | 2.79 |
Claims (9)
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 copper, and B is transition metals cobalt, 0<x<1.
2. the preparation method of catalyst claimed in claim 1, is characterized in that: take cobalt nitrate, lanthanum nitrate, copper nitrate as presoma, citric acid or ethylene glycol are complexing agent, wiring solution-forming mixing and stirring; Then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, and final drying, roasting obtain having the fischer-tropsch synthetic catalyst of perovskite structure.
3. it is characterized in that in accordance with the method for claim 2: complexing agent and metal ion mol ratio are 1:1～8:1.
4. it is characterized in that in accordance with the method for claim 3: 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 ℃, 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 ℃, 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 ℃, be 1～36 hour drying time, and roasting is roasting 2-15 hour at 400～1000 ℃.
8. in accordance with the method for claim 7, it is characterized in that: baking temperature is 80～150 ℃, be 8～24 hours drying time, roasting roasting 3～8 hours at 700～900 ℃.
9. the application of catalyst in Fischer-Tropsch synthesis described in claim 1: reaction temperature is 180 ~ 250 ℃, the volume space velocity of Fischer-Tropsch synthetic raw gas 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104071845A (en) * | 2014-07-15 | 2014-10-01 | 渤海大学 | Preparation method for SLTON perovskite NOx powder |
| CN104085927A (en) * | 2014-07-18 | 2014-10-08 | 渤海大学 | Preparation method of LSTON (La, Sc, Ta, O and N) perovskite-type nitrogen oxide solid solution powder |
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| CN104085927A (en) * | 2014-07-18 | 2014-10-08 | 渤海大学 | Preparation method of LSTON (La, Sc, Ta, O and N) perovskite-type nitrogen oxide solid solution powder |
| CN104085927B (en) * | 2014-07-18 | 2016-03-09 | 渤海大学 | The preparation method of LSTON perovskite typed oxynitride solid-solution powder |
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