CN104588022B - Reduction method of Fischer-Tropsch synthesis catalyst - Google Patents
Reduction method of Fischer-Tropsch synthesis catalyst 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 F- T synthesis field
In catalysis technique.
Background technology
F- T synthesis refer to that synthesis gas (carbon monoxide and hydrogen) catalyzes and synthesizes the anti-of liquid hydrocarbon fuel on a catalyst
Should.F- T synthesis have the advantages that to be independent of oil, product cleans.With world energy sources structure from single oil dependent form to
Coal, oil and natural gas alliance type change and environmental requirement increasingly improves, and 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 priority is opened
Send out with amorphous sio2、tio2And al2o3Co based Fischer-Tropsch synthesis catalyst for main carriers.
Us6765026b2 discloses the Fischer-Tropsch synthesis method that a kind of application special catalyst is catalyzed.The method adopts
Catalyst precursor be a kind of soluble compounds of iron group (especially cobalt) metal or salt and platinum soluble compounds or salt.Will
Presoma is contacted with the solution of hydroxyhy-drocarbyl amines or ammonium hydroxide, obtains a kind of special catalyst, makes c5 +Hydrocarbon selective reaches
To 58% ~ 80%.But it is worth low gaseous products ch using the method4Selectivity be up to 10%.So that proposing a kind of new
Fischer-Tropsch synthesis method is to reduce ch further4Selectivity.
Cn1417292a reports a kind of preparation method with activated carbon for carrier Co based Fischer-Tropsch synthesis catalyst, for
Synthesis gas prepares linear paraffin within 20 for the carbon number for raw material and carbon number is concentrated mainly on the hydro carbons of diesel oil distillate section.In reaction
Temperature is 240 DEG C, reaction pressure 2.5mpa, air speed 500h-1Under the conditions of, the conversion ratio of fixed bed reaction system co is 64.1%,
ch4Selectivity be 8.5%, c5 +Selectivity is 80.7%.
Cn101224430a reports a kind of hydrophobic organic modification of Co group Fischer-Tropsch synthesized catalyst, and noble metal and cobalt are negative
It is downloaded on silica supports, then carry out organically-modified.Wherein when noble metal adopts pt, catalyst system 15%co0.8%
pt/sio2, organically-modified reagent adopts dimethyldiethoxysilane modified, and on pressurization static bed, reaction condition is 230
DEG C, 1.0mpa, 1000h-1(v/v), h2The conversion ratio of/co=3/1, co is 72.7%, and the selectivity of methane is 8.4%.Above-mentioned technology
Ch4Selectivity need to reduce further, c5 +Selectivity need to improve further.
Content of the invention
For the deficiencies in the prior art, the present invention provides a kind of Co based Fischer-Tropsch synthesis catalyst and preparation method thereof and answers
With.High co conversion ratio and c can ensured using this catalyst5 +Selective reduction methane selectively simultaneously, and long period
The good stability of operating.
A kind of fischer-tropsch synthetic catalyst, this catalyst is the metal composite oxide with perovskite structure, and formula is
ab’xb1-xo3, 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, including following process: be front with cobalt nitrate, zirconium nitrate, Lanthanum (III) nitrate
Drive body, with citric acid or ethylene glycol as chelating agent, wiring solution-forming mixing and stirring, then carry out moisture evaporation, solution by
Transparent colloidal sol is transformed into sticky gel, finally dry, roasting, and the sample after roasting is the composite oxygen with perovskite structure
Compound fischer-tropsch synthetic catalyst.
In the preparation method of fischer-tropsch synthetic catalyst of the present invention, chelating agent and metal ion mol ratio are 1:1～8:1, excellent
Elect 1:1～4:1 as.Prepare and agitating solution is at 20～90 DEG C, carry out at preferably 50～70 DEG C.Stir speed (S.S.) be 200～
500rpm, preferably 300～400rpm.Mixing time is 3～8 hours, preferably 4～6 hours.Baking temperature is 60～200
DEG C, preferably 80～150 DEG C.Drying time is 1～36 hour, preferably 8～24 hours.Sintering temperature is 600～1000 DEG C,
Roasting time is roasting 2 ~ 15 hours, roasting 3～8 hours preferably at 700～900 DEG C.
The method of reducing of fischer-tropsch synthetic catalyst of the present invention, reduces mode using conventional method of reducing or segmentation, preferably
The latter.Described segmentation reduction mode reduces 4 ~ 24h first under the atmosphere of hydrogen, and reduction temperature is 300-400 DEG C, reduces pressure
0.5 ~ 1.5mpa, then reduces 6 ~ 12h under the atmosphere of hydrogen and methane mixed gas, and reduction temperature is 200 ~ 240 DEG C, reduction pressure
Power is 0.5 ~ 3mpa, and the volumetric mixture ratio of hydrogen and methane gas is 10:1 ~ 2:1.Can be carried further using segmentation reduction mode
The activity stability of high catalyst and the selectivity reducing methane.
The application of fischer-tropsch synthetic catalyst of the present invention: reaction temperature is 180 ~ 250 DEG C, and F- T synthesis unstripped gas is (by hydrogen
With carbon monoxide composition) volume space velocity be 400 ~ 1000h-1, reaction pressure is 1.0 ~ 5.0mpa, h in unstripped gas2/ co=1～3
(mol ratio).
The present invention prepares a kind of metal composite oxide with perovskite structure as fischer-tropsch synthetic catalyst, and it leads to
Formula is ab 'xb1-xo3, wherein a is rare earth lanthanum, and b ' is transition metal zirconium, and b is transition metals cobalt, 0 < x < 0.2, it is special to have
Duct and surface nature.Rare earth lanthanum on a position can improve the structural stability of perovskite and thermally-stabilised, zirconium on b position
Doping, so that cobalt metal ion electric charge, radius is changed, so that active component cobalt reduction degree improves, and then be conducive to carrying
The activity stability of high catalyst, and greatly reduce the selectivity of its methane production.
The composite oxides fischer-tropsch synthetic catalyst that the present invention has perovskite structure adopts citric acid complex one-step method system
Standby, operating process is simple, and technical maturity is suitable to commercial production.
The present invention has the application in Fischer-Tropsch synthesis of the composite oxides of perovskite structure.Experiment shows, suitable
Preferably under process conditions, c5 +Selectivity can reach more than 90% (selectivity is by certain product and all product (except water)
Weight ratio meter calculate), and product methane selectivity, less than 4%, greatly reduces investment and the operating cost of subsequent products separation equipment
With being conducive to economy when improving F- T synthesis technology application.
Specific embodiment
Further illustrate process and the effect of the inventive method with reference to embodiment.
Embodiment 1
Take 20.7gco (no3)26h2O and 2.7gzr (no3)45h2O puts in the beaker of 500ml so as to co and zr's rubs
Your ratio is 0.9/0.1, adds the distilled water of 100ml, then beaker is placed in 80 DEG C of water-bath, and mixing speed is 400rpm,
Stir and dissolve to whole.Take 34.3g la (no3)36h2O, is placed with the beaker of 100ml distilled water, stirs and dissolves to whole.
Then lanthanum nitrate hexahydrate is added drop-wise in cobalt nitrate and zirconium nitrate solution, stirs in Deca, take 40g citric acid, citric acid with
Metal ion total amount mol ratio is 1:1, is placed with the beaker of 100ml to stir and dissolves to whole, now treats above-mentioned mixed solution
After stirring 30 minutes, slowly add citric acid solution, stir in Deca.Stir after 5 hours after above-mentioned mixed solution, palm fibre
Color solution has been dehydrated the gel becoming thick, gel is taken out in the drying baker putting into 110 DEG C, is 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
3 hours of roasting, then rise to 800 DEG C with the heating rate of 10 DEG C/min, 4 hours of constant temperature calcining, obtain F- T synthesis catalysis
Agent.Prepared catalyst is designated as c-1, and evaluation result is shown in Table 1.
Embodiment 2
Take 21.85gco (no3)26h2O and 1.35gzr (no3)45h2O puts in the beaker of 500ml so as to co and zr
Mol ratio is 0.95/0.05, adds the distilled water of 100ml, then beaker is placed in 80 DEG C of water-bath, mixing speed is
400rpm, stirs and dissolves to whole.Take 34.3g la (no3)36h2O, is placed with the beaker of 100ml distilled water, stir to
All dissolve.Then lanthanum nitrate hexahydrate is added drop-wise in cobalt nitrate and zirconium nitrate solution, stirs in Deca.Take 40g Fructus Citri Limoniae
Acid, citric acid is 1:1 with metal ion total amount mol ratio, is placed with the beaker of 100ml to stir and dissolves to whole, now treats
After stating mixed solution stirring 30 minutes, slowly add citric acid solution, stir in Deca.Treat above-mentioned mixed solution stirring 5
After individual hour, brown solution has been dehydrated the gel becoming thick, gel is taken out in the drying baker putting into 110 DEG C, does
Dry overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with the heating rate of 3 DEG C/min from room temperature liter
To 600 DEG C, 3 hours of constant temperature calcining, then rise to 800 DEG C with the heating rate of 10 DEG C/min, and 4 hours of constant temperature calcining, obtain
Fischer-tropsch synthetic catalyst.Prepared catalyst is designated as c-2, and evaluation result is shown in Table 1.
Embodiment 3
Take 18.4gco (no3)26h2O and 5.4gzr (no3)45h2O 6h2O put in the beaker of 500ml so as to co with
The mol ratio of zr is 0.8/0.2, adds the distilled water of 100ml, then beaker is placed in 80 DEG C of water-bath, mixing speed is
400rpm, stirs and dissolves to whole.Take 34.3g la (no3)36h2O, is placed with the beaker of 100ml distilled water, stir to
All dissolve.Then lanthanum nitrate hexahydrate is added drop-wise in cobalt nitrate and zirconium nitrate solution, stirs in Deca.Take 40g Fructus Citri Limoniae
Acid, citric acid is 1:1 with metal ion total amount mol ratio, is placed with the beaker of 100ml to stir and dissolves to whole, now treats
After stating mixed solution stirring 30 minutes, slowly add citric acid solution, stir in Deca.Treat above-mentioned mixed solution stirring 5
After individual hour, brown solution has been dehydrated the gel becoming thick, gel is taken out in the drying baker putting into 110 DEG C, does
Dry overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with the heating rate of 3 DEG C/min from room temperature liter
To 600 DEG C, 2 hours of constant temperature calcining, then rise to 800 DEG C with the heating rate of 10 DEG C/min, and 2 hours of constant temperature calcining, obtain
Fischer-tropsch synthetic catalyst.Prepared catalyst is designated as c-3, and evaluation result is shown in Table 1.
Embodiment 4
Take 19.55gco (no3)26h2O and 4.05gni (no3)26h2O puts in the beaker of 500ml so as to co and zr
Mol ratio is 0.85/0.15, adds the distilled water of 100ml, then beaker is placed in 80 DEG C of water-bath, mixing speed is
400rpm, stirs and dissolves to whole.Take 34.3g la (no3)36h2O, is placed with the beaker of 100ml distilled water, stir to
All dissolve.Then lanthanum nitrate hexahydrate is added drop-wise in cobalt nitrate and zirconium nitrate solution, stirs in Deca.Take 40g Fructus Citri Limoniae
Acid, citric acid is 1:1 with metal ion total amount mol ratio, is placed with the beaker of 100ml to stir and dissolves to whole, now treats
After stating mixed solution stirring 30 minutes, slowly add citric acid solution, stir in Deca.Treat above-mentioned mixed solution stirring 5
After individual hour, brown solution has been dehydrated the gel becoming thick, gel is taken out in the drying baker putting into 110 DEG C, does
Dry overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with the heating rate of 3 DEG C/min from room temperature liter
To 700 DEG C, 2 hours of constant temperature calcining, then rise to 800 DEG C with the heating rate of 10 DEG C/min, and 3 hours of constant temperature calcining, obtain
Fischer-tropsch synthetic catalyst.Prepared catalyst is designated as c-4, and evaluation result is shown in Table 1.
Comparative example 1
Using coprecipitation preparation containing lanthanum, zirconium, cobalt metal composite oxide (no perovskite structure), lanthanum in oxide,
Zirconium, the content of cobalt are with embodiment 1.
Comparative example 2
Infusion process Supported Co, lanthanum, zirconium are adopted for carrier with silicon oxide, cobalt, lanthanum, the mol ratio of zirconium are with embodiment 1.
Embodiment 5
Activity rating is carried out to the catalyst prepared by embodiment and comparative example, evaluation test is in high pressure continuous stirring autoclave
In reactor, using paraffin as solvent, conventional reduction method is adopted to reduce 18 hours with 350 DEG C of pure hydrogen, pressure is 2mpa.
After cooling, switching and merging gas is reacted.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 220 DEG C, 500h-1,
2.0mpa, h2/ co=2(mol ratio).200h operating evaluation result is shown in Table 1.
Table 1 catalyst reaction performance
| Catalyst | Co conversion ratio (%) | c5 +Selectivity (wt%) | ch4Selectivity (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 in high pressure CSTR, with
As solvent, using segmentation method of reducing, the reducing condition of wherein embodiment 1 is paraffin: reduce 8h in a hydrogen atmosphere first,
300 DEG C of reduction temperature, reduces pressure 1mpa, then reduces 8h under the mixed atmosphere of the hydrogen for 5:1 for the volume ratio and methane, also
Former temperature 210, reduces pressure 1mpa；The reducing condition of embodiment 2 is: reduces 6h, reduction temperature 350 first in a hydrogen atmosphere
DEG C, reduce pressure 0.5mpa, under the mixed atmosphere of the hydrogen for 3:1 for the volume ratio and methane, then reduce 6h, reduction temperature
220, reduce pressure 1.5mpa；The reducing condition of embodiment 3 is: first in a hydrogen atmosphere reduce 16h, 350 DEG C of reduction temperature,
Reduction pressure 1mpa, then reduces 12h under the mixed atmosphere of the hydrogen for 8:1 for the volume ratio and methane, 200 DEG C of reduction temperature,
Reduction pressure 2mpa；The reducing condition of embodiment 4 is: reductase 12 0h in a hydrogen atmosphere first, 400 DEG C of reduction temperature, reduction pressure
Power 1mpa, then reduces 6h, 230 DEG C of reduction temperature under the mixed atmosphere of the hydrogen for 2:1 for the volume ratio and methane, reduces pressure
2.5mpa.After reduction terminates, cooling switching and merging gas is reacted.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction bar
Part is 220 DEG C, 500h-1, 2.0mpa, h2/ co=2(mol ratio).200h operating evaluation result is shown in Table 2.
Table 2 catalyst reaction performance
| Catalyst | Co conversion ratio (%) | c5 +Selectivity (wt%) | ch4Selectivity (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 (8)
1. a kind of method of reducing of fischer-tropsch synthetic catalyst it is characterised in that: described catalyst is to have answering of perovskite structure
Close metal-oxide, formula is ab 'xb1-xo3, wherein a is rare earth lanthanum, and b ' is transition metal zirconium, and b is transition metals cobalt, 0 <
X < 0.2, described method of reducing reduces 4 ~ 24h first under the atmosphere of hydrogen, and reduction temperature is 300-400 DEG C, reduces pressure 0.5
~ 1.5mpa, then reduces 6 ~ 12h under the atmosphere of hydrogen and methane mixed gas, and reduction temperature is 200 ~ 240 DEG C, reduces pressure
For 0.5 ~ 3mpa, the volumetric mixture ratio of hydrogen and methane gas is 10:1 ~ 2:1.
2. according to catalyst described in claim 1 method of reducing it is characterised in that: be front with cobalt nitrate, Lanthanum (III) nitrate, zirconium nitrate
Drive body, citric acid or ethylene glycol are chelating agent, wiring solution-forming mixing and stirring；Then carry out moisture evaporation, solution is by saturating
Bright colloidal sol is transformed into sticky gel, finally dry, roasting, obtains the composite oxides F- T synthesis with perovskite structure
Catalyst.
3. according to catalyst described in claim 2 method of reducing it is characterised in that: chelating agent and metal ion mol ratio are 1:
1～8:1.
4. according to catalyst described in claim 3 method of reducing it is characterised in that: chelating agent and metal ion mol ratio are 1:
1～4:1.
5. according to catalyst described in claim 2 method of reducing it is characterised in that: prepare and agitating solution at 20～90 DEG C
Carry out, mixing time is 3～8 hours, mixing speed is 200～500rpm.
6. according to catalyst described in claim 5 method of reducing it is characterised in that: prepare and agitating solution at 50～70 DEG C
Carry out, mixing time is 4～6 hours, stir speed (S.S.) is 300～400rpm.
7. according to catalyst described in claim 2 method of reducing it is characterised in that: baking temperature be 60～200 DEG C, when being dried
Between be 1～36 hour, roasting roasting 2-15 hour at 400～1000 DEG C.
8. according to catalyst described in claim 7 method of reducing it is characterised in that: baking temperature be 80～150 DEG C, when being dried
Between be 8～24 hours, roasting roasting 3～8 hours at 700～900 DEG C.
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| US20040024071A1 (en) * | 2002-08-01 | 2004-02-05 | Meier Paul F. | Perovskite compositions and method of making and process of using such compositions |
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