CN103831115B - Cobalt group catalyst synthesized and the method for making of syrup state bed Fischer Tropsch and application - Google Patents
Cobalt group catalyst synthesized and the method for making of syrup state bed Fischer Tropsch and application Download PDFInfo
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- CN103831115B CN103831115B CN201310646070.XA CN201310646070A CN103831115B CN 103831115 B CN103831115 B CN 103831115B CN 201310646070 A CN201310646070 A CN 201310646070A CN 103831115 B CN103831115 B CN 103831115B
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Abstract
Does the cobalt group catalyst synthesized weight of a kind of syrup state bed Fischer Tropsch consist of? Co
3o
4: 10-40%, transition metal oxide: 0.1-15%, all the other are carrier A l
2o
3.It is simple that the present invention has preparation technology, and be easy to realize industrialization, prepared catalyst is microspheroidal, and particle diameter is adjustable, and for good fluidity in slurry reactor, scuff resistance is high, the active advantage with having good stability of F-T synthesis.
Description
Technical field
The present invention relates to a kind of preparation method and application of fischer-tropsch synthetic catalyst, specifically a kind of cobalt-based syrup state bed Fischer Tropsch synthetic catalyst and preparation method and application.
Background technology
Coal produces fuel oil through F-T synthesis and chemicals is one of the important content in clean coal technology field.Now, fixed bed, fluid bed and paste state bed reactor are the main reactor of Fischer-Tropsch synthesis.Paste state bed reactor has that structure is simple, mass-and heat-transfer is functional, and reaction temperature is even, without the advantage of focus existence in reactor.The catalyst that slurry bed system uses mostly is ferrum-based catalyst, and Sasol company is the company of comparatively early exploitation precipitated iron-based catalyst, in paste state bed reactor, achieve industrialization.At present, domestic Zhongke Synthetic Oil Technology Co., Ltd. successfully develops complete slurry bed system ferrum-based catalyst F-T synthesis and products thereof process technology, and establishes 160kt/a artificial oil demonstration plant in Shenhua Group, the safe group of Inner Mongol gouy, Shanxi Lu An group.
Though cobalt-base catalyst technique has high C
5 +selective, low methane selectively, low water gas shift reaction, and in paste state bed reactor easily with the plurality of advantages such as product wax is separated, but the research and development of cobalt-based syrup state bed Fischer Tropsch synthetic catalyst and reaction process relatively lag behind.
Shell company develops with SiO
2for the Co based Fischer-Tropsch synthesis catalyst of carrier, at Malaysia operation diameter 5m natural gas liquefaction paste state bed reactor, but the production accident occurred afterwards slows process of industrialization.TiO mainly studies in Exxon company
2for the Co based Fischer-Tropsch synthesis catalyst of carrier, successively applied for that patent reaches a section up to a hundred, and to develop with slurry bed system be the AGC-21 new technology of core, complete demonstration plant experiment.The catalyst of Chevron company is with Al
2o
3do carrier, and add the exploitation cobalt-base catalysts such as ruthenium, oxides additive and rare earth metal, its most of catalyst application is in fixed bed and fluid bed, and a small amount of catalyst is applicable to slurry bed system.
The cobalt-base catalyst pattern that conventional method is prepared differs, and granularity is uneven, and rheological characteristic is bad, has a strong impact on the mass-and heat-transfer of course of reaction, and causes catalyst to wear and tear in the liquid phase greatly, and economic loss is large.
Summary of the invention
In order to solve the problem, the invention provides one and there is high activity, the cobalt-base catalyst for syrup state bed Fischer Tropsch synthetic reaction of good stability and preparation method and application.
The weight of catalyst of the present invention consists of:
Co
3o
4: 10-40%, transition metal oxide: 0.1-15%, all the other are carrier A l
2o
3.
Transition metal described above is the one of manganese, vanadium, titanium, copper, zinc, zirconium, rhenium, thorium, lanthanum, cerium, ruthenium, rhodium, palladium, iridium, platinum etc. or two kinds.
Preparation method of the present invention is as follows:
(1) form by final catalyst, aluminum soluble salt, soluble cobalt and soluble transition metal salt be mixed with the mixed solution of 0.2-2mol/L, and with bases precipitant solution parallel-flow precipitation at 40-80 DEG C of 0.2-2mol/L; Or the first parallel-flow precipitation at 40-80 DEG C by the soluble aluminum salting liquid of 0.2-2mol/L and 0.2-2mol/L bases precipitant solution, be precipitated slurries, again soluble cobalt and soluble transition metal salt are mixed with the mixed solution of 0.2-2mol/L, and with the bases precipitant solution of 0.2-2mol/L at 40-80 DEG C parallel-flow precipitation in these slurries.
(2) step (1) precipitation is again through 60-90 DEG C of aging 0.5-4.0h, filtration, washing, making beating, obtains slurry, finally by mist projection granulating, roasting, obtains the micro-spherical catalyst of specified particle diameter.
Cobalt salt as above is the one of cobalt nitrate, cobalt acetate, cobalt carbonate, cobaltous sulfate etc.
Aluminium salt as above is the one of aluminum nitrate, sodium metaaluminate, sodium aluminate, aluminum sulfate, aluminium chloride etc.
Soluble transition metal salt as above is Mn (NO
3)
24H
2o, TiCl
4, NH
4reO
4, Zn (NO
3)
26H
2o, Th (NO
3)
4, La (NO
3)
36H
2o, Ce (NO
3)
36H
2o, Cu (NO
3)
23H
2o, ZrOCl
28H
2o, Mn (NO
3)
24H
2o, RuCl
33 (H
2o), Rh (NO
3)
32H
2o, Pd (NO
3)
22H
2o, IrCl
33H
2o, Pt (NO
3)
2deng.
Precipitating reagent as above is the one of sodium carbonate, NaOH, ammoniacal liquor, ammonium carbonate, carbonic hydroammonium etc.
The condition of mist projection granulating as above: EAT is 180-350 DEG C, aspiration pressure is 0.1-2.0MPa, leaving air temp is 90-150 DEG C, and spraying slurry therewith is dilution of being pulled an oar by filter cake is the suspension of 5 (wt) %-40 (wt) %.
Sintering temperature as above is 300-500 DEG C, and roasting time is 2-10h.
The particle diameter of Kaolinite Preparation of Catalyst of the present invention is 40-180 μm, and specific area (BET) is 105-330m
2/ g.
The catalyst that the present invention obtains carries out Fischer-Tropsch synthesis application in paste state bed reactor, and reducing condition is: H
2: N
2(v/v)=1:1 ~ 50,300 ~ 400 DEG C, 0.2 ~ 1.2MPa, volume space velocity 500 ~ 1500h
-1, constant temperature 6 ~ 12h; Reaction condition is: 190 ~ 250 DEG C, 1.5 ~ 3.0MPa, volume space velocity 500 ~ 5000h
-1, H
2: CO (v/v)=1 ~ 3:1, rotating speed 400 ~ 1200rpm.
The present invention compared with prior art tool has the following advantages:
1. catalyst preparation process is simple and practical, is easy to realize industrialization.
2. prepared catalyst is microspheroidal, and particle diameter is adjustable, and for good fluidity in slurry reactor, scuff resistance is high, and F-T synthesis is active and have good stability.
Detailed description of the invention
Embodiment 1:
Account for 15 (wt) %, 4.9 (wt) % of final catalyst respectively by cobaltosic oxide, vanadic anhydride, ruthenium-oxide and alundum (Al2O3), 0.1 (wt) % and 80 (wt) % takes Co (NO
3)
26H
2o, NH
4vO
3, RuCl
33H
2o and Al (NO
3)
39H
2o, is mixed with the salting liquid of 0.2mol/L, with 0.5mol/L ammonia spirit parallel-flow precipitation, controlling precipitation temperature is 60 DEG C, precipitation pH=7.5, after precipitation at 90 DEG C aging 2h, washing, filter, be the suspension of 40% again by filter cake dilution through making beating, then mist projection granulating (EAT 250 DEG C, pressure 0.5MPa, leaving air temp 100 DEG C), finally at 300 DEG C, roasting 10h obtains micro-spherical catalyst.The particle diameter of final catalyst is 202 μm, and specific area is 110m
2/ g, weight consists of Co
3o
4: V
2o
5: RuO
2: Al
2o
3=15:4.9:0.1:80.
Get above-mentioned catalyst pulp 10g, apply in paste state bed reactor, reducing condition is: 300 DEG C, 1.2MPa, H
2: N
2(v/v)=1:50,1500h
-1(v/v), constant temperature 8h; Reaction condition is: 200 DEG C, 2.4MPa, 1200h
-1(v/v), H
2/ CO (v/v)=1.0, rotating speed 1200rpm.Catalyst reaction the results are shown in Table 1.
Embodiment 2:
40 (wt) %, 5% and 55% accounting for final catalyst by cobaltosic oxide, cerium oxide and alundum (Al2O3) respectively takes Co (NO
3)
26H
2o, Ce (NO
3)
36H
2o and Al
2(SO
4)
3, be mixed with the salting liquid of 2.0mol/L, with the sal volatile parallel-flow precipitation of 0.5mol/L, controlling precipitation temperature is 40 DEG C, precipitation pH=6.0, after precipitation at 50 DEG C aging 4h, washing, filter, be the suspension of 5% again by filter cake dilution, then mist projection granulating (EAT 150 DEG C, pressure 1.5MPa, leaving air temp 100 DEG C), finally at 500 DEG C, roasting 2h obtains micro-spherical catalyst.The particle diameter of final catalyst is 330 μm, and specific area is 40m
2/ g, weight consists of Co
3o
4: CeO
2: Al
2o
3=40:5:55.
Get above-mentioned catalyst pulp 10g, apply in paste state bed reactor, reducing condition is: 350 DEG C, 0.2MPa, H
2: N
2(v/v)=1:1,500h
-1(v/v), constant temperature 10h; Reaction condition is: 235 DEG C, 1.5Mpa, 1000h
-1(v/v), H
2/ CO (v/v)=1.5, rotating speed 1000rpm.Catalyst reaction the results are shown in Table 1.
Embodiment 3:
Account for 75% of final catalyst by alundum (Al2O3) and take sodium metaaluminate, be mixed with the aluminum salt solution of 1.5mol/L, with the sal volatile parallel-flow precipitation of 2.0mol/L.Precipitate complete, then take CoCO by 22 (wt) %, 2.5 (wt) % and 0.5% that cobaltosic oxide, lanthana and iridium dioxide account for final catalyst respectively
3, La (NO
3)
36H
2o and IrCl
33H
2o, is mixed with the mixing salt solution of 0.5mol/L, with 0.2mol/L ammonium bicarbonate soln parallel-flow precipitation in these slurries, controlling precipitation temperature is 80 DEG C, precipitation pH=8.5, after precipitation at 90 DEG C aging 0.5h, washing, filter, be the suspension of 25% again by filter cake dilution through making beating, then mist projection granulating (EAT 270 DEG C, pressure 0.2MPa, leaving air temp 120 DEG C), finally at 350 DEG C, roasting 6h obtains micro-spherical catalyst.Final particle diameter is 272 μm, and specific area is 120m
2/ g, catalyst weight consists of Co
3o
4: LaO
2: IrO
2: Al
2o
3=22:2.5:0.5:75.
Get above-mentioned catalyst pulp 10g, apply in paste state bed reactor, reducing condition is, 320 DEG C, 1.0MPa, H
2: N
2(v/v)=1:40,1000h
-1(v/v), constant temperature 6h; Reaction condition is: 220 DEG C, 3.0MPa, 5000h
-1(v/v), H
2/ CO (v/v)=1.8, rotating speed 900rpm.Catalyst reaction the results are shown in Table 1.
Embodiment 4:
10 (wt) %, 15 (wt) % and 75 (wt) % that account for final catalyst by cobaltosic oxide, zirconia and alundum (Al2O3) respectively take C
4h
6o
4co4H
2o, Zr (NO
3)
45H
2o and Al (NO
3)
39H
2o, is mixed with the salting liquid of 1.0mol/L, with the sodium carbonate liquor parallel-flow precipitation of 1.0mol/L, controlling precipitation temperature is 80 DEG C, precipitation pH=8.0, after precipitation at 80 DEG C aging 1h, washing, filter, be the suspension of 15% again by filter cake dilution, then mist projection granulating (EAT 310 DEG C, pressure 1.2MPa, leaving air temp 130 DEG C), finally at 400 DEG C, roasting 5h obtains micro-spherical catalyst.The particle diameter of final catalyst is 105 μm, and specific area is 180m
2/ g, weight consists of Co
3o
4: ZrO
2: Al
2o
3=10:15:75.
Get above-mentioned catalyst pulp 10g, apply in paste state bed reactor, reducing condition is, 370 DEG C, 0.5MPa, H
2: N
2(v/v)=1:30,750h
-1(v/v), constant temperature 12h; Reaction condition is: 220 DEG C, 2.0MPa, 1800h
-1(v/v), H
2/ CO (v/v)=2.0, rotating speed 800rpm.Catalyst reaction the results are shown in Table 1.
Embodiment 5:
35 (wt) %, 2 (wt) % and 63 (wt) % that account for final catalyst by cobaltosic oxide, rheium oxide and alundum (Al2O3) respectively take CoSO
47H
2o, NH
4vO
3and NH
4.ReO
4, be mixed with the aqueous solution of 0.8mol/L, with the ammonia spirit parallel-flow precipitation of 1.8mol/L, controlling precipitation temperature is 60 DEG C, precipitation pH=7.5, after precipitation at 90 DEG C aging 2h, washing, filter, be the suspension of 40% again by filter cake dilution through making beating, then mist projection granulating (EAT 260 DEG C, pressure 0.5MPa, leaving air temp 110 DEG C), finally at 450 DEG C, roasting 3h obtains micro-spherical catalyst.The particle diameter of final catalyst is 259 μm, and specific area is 100m
2/ g, weight consists of Co
3o
4: ReO
2: Al
2o
3=35:2:63.
Get above-mentioned catalyst pulp 10g, apply in paste state bed reactor, reducing condition is: 330 DEG C, 1.0MPa, H
2: N
2(v/v)=1:20,1200h
-1(v/v), constant temperature 10h; Reaction condition is: 190 DEG C, 2.0Mpa, 500h
-1(v/v), H
2/ CO (v/v)=2.2, rotating speed 600rpm.Catalyst reaction the results are shown in Table 1.
Embodiment 6:
Account for 68% of final catalyst by alundum (Al2O3) and take sodium aluminate, be mixed with the aluminum salt solution of 1.8mol/L, with the ammonium bicarbonate soln parallel-flow precipitation of 0.3mol/L.Precipitate complete, then take CoSO by 22 (wt) % and 10 (wt) % that cobaltosic oxide and manganese dioxide account for final catalyst respectively
47H
2o and Mn (NO
3)
24H
2o, is mixed with the mixing salt solution of 0.6mol/L, with the ammonium bicarbonate soln parallel-flow precipitation of 0.3mol/L in these these slurries, controlling precipitation temperature is 55 DEG C, precipitation pH=6.5, after precipitation at 85 DEG C aging 4.0h, washing, filter, be the suspension of 35% again by filter cake dilution, then mist projection granulating (EAT 350 DEG C, pressure 0.2MPa, leaving air temp 150 DEG C), finally at 350 DEG C, roasting 8h obtains micro-spherical catalyst.The particle diameter of final catalyst is 186 μm, and specific area is 150m
2/ g, weight consists of Co
3o
4: MnO
2: Al
2o
3=22:10:68.
Get above-mentioned catalyst pulp 10g, apply in paste state bed reactor, reducing condition is, 360 DEG C, 0.8MPa, H
2: N
2(v/v)=1:10,800h
-1(v/v), constant temperature 8h; Reaction condition is: 250 DEG C, 2.5Mpa, 2000h
-1(v/v), H
2/ CO (v/v)=2.5, rotating speed 500rpm.Catalyst reaction the results are shown in Table 1.
Embodiment 7:
30.7 (wt) %, 0.3 (wt) % and 69% that account for final catalyst by cobaltosic oxide, palladium oxide and alundum (Al2O3) respectively take C
4h
6o
4co4H
2o, Pd (NO
3)
22H
2o and AlCl
3, be mixed with the salting liquid of 0.7mol/L, with the sodium hydroxide solution parallel-flow precipitation of 1.3mol/L, controlling precipitation temperature is 75 DEG C, precipitation pH=8.5, after precipitation at 75 DEG C aging 3h, washing, filter, be the suspension of 30% again by filter cake dilution through making beating, then mist projection granulating (EAT 200 DEG C, pressure 1.2MPa, leaving air temp 130 DEG C), finally at 280 DEG C, roasting 6h obtains micro-spherical catalyst.The particle diameter of final catalyst is 246 μm, and specific area is 90m
2/ g, weight consists of Co
3o
4: PdO:Al
2o
3=30.7:0.3:69.
Get above-mentioned catalyst pulp 10g, apply in paste state bed reactor, reducing condition is: 320 DEG C, 1.5MPa, H
2: N
2(v/v)=1:5,1000h
-1(v/v), constant temperature 6h; Reaction condition is: 210 DEG C, 2.6Mpa, 3000h
-1(v/v), H
2/ CO (v/v)=3.0, rotating speed 400rpm.Catalyst reaction the results are shown in Table 1.
Table 1: catalyst physical performance and reaction result
Claims (6)
1. a syrup state bed Fischer Tropsch is cobalt group catalyst synthesized, it is characterized in that the weight of catalyst consists of:
Co
3o
4: 10-40%, transition metal oxide: 0.1-15%, all the other are carrier A l
2o
3;
Described transition metal is one in manganese, copper, zinc, thorium, lanthanum or two kinds;
The particle diameter of described catalyst is 40-180 μm, and specific area is 105-330m
2/ g;
And prepared by following steps:
(1) form by final catalyst, aluminum soluble salt, soluble cobalt and soluble transition metal salt be mixed with the mixed solution of 0.2-2mol/L, and with bases precipitant solution parallel-flow precipitation at 40-80 DEG C of 0.2-2mol/L; Or the first parallel-flow precipitation at 40-80 DEG C by the soluble aluminum salting liquid of 0.2-2mol/L and 0.2-2mol/L bases precipitant solution, be precipitated slurries, again soluble cobalt and soluble transition metal salt are mixed with the mixed solution of 0.2-2mol/L, and with the bases precipitant solution of 0.2-2mol/L at 40-80 DEG C parallel-flow precipitation in these slurries;
(2) step (1) precipitation is again through 60-90 DEG C of aging 0.5-4.0h, filtration, washing, making beating, obtains slurry, finally by mist projection granulating, roasting, obtains the micro-spherical catalyst of specified particle diameter;
The condition of described mist projection granulating: EAT is 180-350 DEG C, aspiration pressure is 0.1-2.0MPa, and leaving air temp is 90-150 DEG C, and spraying slurry therewith is suspension filter cake making beating diluted for 5wt%-40wt%;
Described sintering temperature is 300-500 DEG C, and roasting time is 2-10h.
2. a kind of syrup state bed Fischer Tropsch as claimed in claim 1 is cobalt group catalyst synthesized, it is characterized in that described soluble cobalt is the one in cobalt nitrate, cobalt acetate, cobalt carbonate, cobaltous sulfate.
3. a kind of syrup state bed Fischer Tropsch as claimed in claim 1 is cobalt group catalyst synthesized, it is characterized in that described aluminum soluble salt is the one in aluminum nitrate, sodium metaaluminate, sodium aluminate, aluminum sulfate, aluminium chloride.
4. a kind of syrup state bed Fischer Tropsch as claimed in claim 1 is cobalt group catalyst synthesized, it is characterized in that described soluble transition metal salt is Mn (NO
3)
24H
2o, Zn (NO
3)
26H
2o, Th (NO
3)
4, La (NO
3)
36H
2o, Cu (NO
3)
23H
2o.
5. a kind of syrup state bed Fischer Tropsch as claimed in claim 1 is cobalt group catalyst synthesized, it is characterized in that described precipitating reagent is the one in sodium carbonate, NaOH, ammoniacal liquor, ammonium carbonate, carbonic hydroammonium.
6. the application that a kind of syrup state bed Fischer Tropsch as described in any one of claim 1-5 is cobalt group catalyst synthesized, it is characterized in that catalyst carries out Fischer-Tropsch synthesis in paste state bed reactor, reducing condition is: H
2: N
2volume ratio is 1:1 ~ 50,300 ~ 400 DEG C, 0.2 ~ 1.2MPa, volume space velocity 500 ~ 1500h
-1, constant temperature 6 ~ 12h; Reaction condition is: 190 ~ 250 DEG C, 1.5 ~ 3.0MPa, volume space velocity 500 ~ 5000h
-1, H
2: CO volume ratio is 1 ~ 3:1, rotating speed 400-1200rpm.
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| CN104162441A (en) * | 2014-08-19 | 2014-11-26 | 中国科学院山西煤炭化学研究所 | High-dispersion Fischer-Tropsch synthesis cobalt-based catalyst as well as preparation method and application thereof |
| CN105344356B (en) * | 2015-11-19 | 2019-01-04 | 中科潞安能源技术有限公司 | A kind of alumina load Co catalysts and preparation method and the application in F- T synthesis |
| CN105772107B (en) * | 2016-03-31 | 2018-06-19 | 中国科学院上海高等研究院 | A kind of carrier and preparation method thereof and cobalt-base catalyst and its preparation method and application |
| CN105771993A (en) * | 2016-05-03 | 2016-07-20 | 华东理工大学 | Fischer-Tropsch synthesis catalyst for preparing liquid hydrocarbon from syngas and preparation method of Fischer-Tropsch synthesis catalyst |
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| CN101530803A (en) * | 2009-04-08 | 2009-09-16 | 太原理工大学 | Method for preparing catalyst for methanol synthesis in slurry reactor and application thereof |
| CN101869840A (en) * | 2009-04-22 | 2010-10-27 | 中科合成油技术有限公司 | Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
| CN102000575A (en) * | 2010-09-20 | 2011-04-06 | 中国科学院山西煤炭化学研究所 | Cobalt-based Fischertropsch synthesis catalyst for slurry-bed reactor, and preparation method and application thereof |
| CN103272603A (en) * | 2013-05-21 | 2013-09-04 | 神华集团有限责任公司 | Fischer-Tropsch catalyst containing zinc-cobalt base and preparation method thereof |
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| CN101530803A (en) * | 2009-04-08 | 2009-09-16 | 太原理工大学 | Method for preparing catalyst for methanol synthesis in slurry reactor and application thereof |
| CN101869840A (en) * | 2009-04-22 | 2010-10-27 | 中科合成油技术有限公司 | Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
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