CN103785392B - A kind of fischer-tropsch synthetic catalyst and its preparation method and application - Google Patents
A kind of fischer-tropsch synthetic catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of fischer-tropsch synthetic catalyst and its preparation method and application.This catalyst is the composite metal catalyst 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 & lt; X & lt; 1.A kind of preparation method of Co based Fischer-Tropsch synthesis catalyst, comprise following process: with cobalt nitrate, copper 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 Co based Fischer-Tropsch synthesis catalyst with perovskite structure.The application of above-mentioned catalyst in Fischer-Tropsch synthesis.Adopt this catalyst can improve CO conversion ratio and C
5 +selective, reduce methane selectively.
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 Co based Fischer-Tropsch synthesis catalyst and its preparation method and application.Adopt this catalyst can improve CO conversion ratio and C
5 +selective, reduce methane selectively.
A kind of fischer-tropsch synthetic catalyst, this catalyst is the composite metal catalyst 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.
A kind of preparation method of fischer-tropsch synthetic catalyst, comprise following process: with cobalt nitrate, copper 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 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, is 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.
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 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, make cobalt metal ion electric charge, radius changes, thus active component cobalt reduction degree is improved, and then be conducive to the activity 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 3%, 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.
Accompanying drawing explanation
The Co based Fischer-Tropsch synthesis catalyst X-ray diffractogram of Fig. 1 prepared by the embodiment of the present invention 1.
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 1.9gCu (NO
3)
2﹒ 3H
2o puts into the beaker of 500mL, and the mol ratio making Co and Cu is 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 34.3gLa (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 the mixed solution of cobalt nitrate and copper nitrate, dropping limit, limit is stirred.Get 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, 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.Stir after 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 dried perovskite predecessor is taken out, be placed in Muffle furnace, 400 DEG C are risen to from room temperature with the heating rate of 3 DEG C/min, constant temperature calcining 3 hours, 800 DEG C are risen to again with the heating rate of 10 DEG C/min, constant temperature calcining 4 hours, obtain composite metal catalyst and be designated as C-1, 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 the mol ratio making Co and Cu is 0.7/0.3, is stirred to whole dissolving.Add the distilled water of 100mL, then beaker is placed in the water-bath of 80 DEG C, mixing speed is 400rpm.Get 34.3gLa (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 copper nitrate solution, dropping limit, limit is stirred.Get 67g citric acid, citric acid and metal ion total amount mol ratio are 2:1, are placed with in the beaker of 100mL and are stirred to whole dissolving, after above-mentioned mixed solution stirs 30 minutes, add citric acid solution slowly, and dropping limit, limit is stirred.Stir after 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 dried perovskite predecessor is taken out, be placed in Muffle furnace, 400 DEG C are risen to from room temperature with the heating rate of 3 DEG C/min, constant temperature calcining 3 hours, 800 DEG C are risen to again with the heating rate of 10 DEG C/min, constant temperature calcining 4 hours, obtain composite metal catalyst and be designated as C-2, evaluation result is in table 1.
Embodiment 3
Get 11.5gCo (NO
3)
2﹒ 6H
2o, 9.5gCu (NO
3)
2﹒ 3H
2o puts into the beaker of 500mL, and the mol ratio making Co and Cu is 0.5/0.5, 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 34.3gLa (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 the mixed solution of cobalt nitrate and copper nitrate, dropping limit, limit is stirred.Get 100g citric acid, citric acid and metal ion total amount mol ratio are 3:1, are placed with in the beaker of 100mL and are stirred to whole dissolving, after above-mentioned mixed solution stirs 30 minutes, add citric acid solution slowly, and dropping limit, limit is stirred.Stir after 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 dried perovskite predecessor is taken out, be placed in Muffle furnace, 400 DEG C are risen to from room temperature with the heating rate of 3 DEG C/min, constant temperature calcining 2 hours, 800 DEG C are risen to again with the heating rate of 10 DEG C/min, constant temperature calcining 3 hours, obtain composite metal catalyst and be designated as C-3, evaluation result is in table 1.
Embodiment 4
Get 4.6gCo (NO
3)
2﹒ 6H
2o and 15.2gCu (NO
3)
2﹒ 3H
2o puts into the beaker of 500mL, and the mol ratio making Co and Cu is 0.2/0.8, 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 34.3gLa (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 the mixed solution of cobalt nitrate and copper nitrate, dropping limit, limit is stirred.Get 134g citric acid, citric acid and metal ion total amount mol ratio are 4:1, are placed with in the beaker of 100mL and are stirred to whole dissolving, after above-mentioned mixed solution stirs 30 minutes, add citric acid solution slowly, and dropping limit, limit is stirred.Stir after 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 dried perovskite predecessor is taken out, be placed in Muffle furnace, 400 DEG C are risen to from room temperature with the heating rate of 3 DEG C/min, constant temperature calcining 2 hours, 800 DEG C are risen to again with the heating rate of 10 DEG C/min, constant temperature calcining 3 hours, obtain composite metal catalyst and be designated as C-4, evaluation result is in table 1.
Evaluating catalyst:
Comparative example 1
Adopt coprecipitation preparation containing the composite metal oxide (without perovskite structure) of lanthanum, copper, cobalt, in oxide, the content of lanthanum, copper, cobalt is with embodiment 1.
Comparative example 2
Be that carrier adopts infusion process Supported Co, lanthanum, copper with silica, the mol ratio of cobalt, lanthanum, copper is with embodiment 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).Evaluation result is in table 1.
Table 1 embodiment and comparative example fischer-tropsch synthetic catalyst evaluation result
| Catalyst | CO conversion ratio (%) | C 5 +Selective (wt%) | CH 4Selective (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 (7)
1. have the application of O composite metallic oxide catalyst in Fischer-Tropsch synthesis for perovskite structure, it is characterized in that: reaction temperature is 180 ~ 250 DEG C, the volume space velocity of F-T synthesis unstripped gas is 200 ~ 1000h
-1, reaction pressure is 1.0 ~ 4.0MPa, H in unstripped gas
2be 1 ~ 3 with the mol ratio of CO, described in there is the composite metal oxide of perovskite structure, general formula is AB '
xb
1-xo
3, wherein A is rare earth lanthanum, and B ' is transition metal copper, B is transition metals cobalt, 0<x<1, and preparation method is: with cobalt nitrate, lanthanum nitrate, copper nitrate for presoma, 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, and final drying, roasting obtain the composite metal oxide with perovskite structure.
2. according to application according to claim 1, it is characterized in that: complexing agent and metal ion mol ratio are 1:1 ~ 8:1.
3. according to application according to claim 2, it is characterized in that: complexing agent and metal ion mol ratio are 1:1 ~ 4:1.
4. according to application according to claim 1, 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.
5. according to application according to claim 4, 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.
6. according to application according to claim 1, 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.
7. according to application according to claim 6, 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.
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