CN104174399B - A kind of autoreduction prepares Fischer-Tropsch synthesis cobalt-based catalyst and application - Google Patents
A kind of autoreduction prepares Fischer-Tropsch synthesis cobalt-based catalyst and application Download PDFInfo
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- CN104174399B CN104174399B CN201410409449.3A CN201410409449A CN104174399B CN 104174399 B CN104174399 B CN 104174399B CN 201410409449 A CN201410409449 A CN 201410409449A CN 104174399 B CN104174399 B CN 104174399B
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Abstract
A kind of autoreduction is prepared Fischer-Tropsch synthesis cobalt-based catalyst composition and is comprised cobalt oxide, oxide carrier and surface passivation cobalt oxide, and cobalt oxide is in metal, and metallic cobalt is 5-40wt%, and all the other are oxide carrier; Introduce organic carbon source in the preparation process of catalyst carrier, utilize organic carbon source to decompose the feature producing weak reduction components simple substance charcoal under an inert atmosphere, roasting after cobalt will be flooded containing high-area carbon, realize the synchronous of cobalt-base catalyst roasting and autoreduction.The present invention has the advantage of reducing for fixed bed reactors carrying out at low temperatures.
Description
Technical field
The present invention relates to a kind of fischer-tropsch synthetic catalyst, specifically a kind of Co based Fischer-Tropsch synthesis catalyst and application thereof.
Technical background
Cobalt-based fixed bed, iron-based slurry bed system and fluid bed F-T synthesis technology are the coal liquifaction technology realizing commercial applications at present.Wherein cobalt-base catalyst has that adaptability to raw material is strong, catalyst stability good and the advantage of reproducible utilization, and product has that methane selectively is low, C
5 +selective height and the active low advantage of water gas shift reaction, thus co-based fischer-tropsch artificial oil has become new technology commanding elevation, coal liquifaction field and competition spot.However, cobalt-base catalyst also exists contradiction and the technology barrier of low temperature running and high temperature reduction, makes greatly to improve the requirement of reactor material requirement and reaction process coupling.Construct specific catalyst system and catalyzing, realize the in-situ reducing of cobalt-base catalyst, effectively can solve the technology barrier of the running of catalyst low temperature and high temperature reduction, significantly reduce reactor manufacture difficulty, effective Widening Technique application, not yet has Patents or article report at present through retrieving.
Summary of the invention
The object of the present invention is to provide a kind of Co based Fischer-Tropsch synthesis catalyst of reducing for fixed bed reactors carrying out at low temperatures and application thereof.
The present invention introduces organic carbon source in the preparation process of catalyst carrier, organic carbon source is utilized to decompose the feature producing weak reduction components simple substance charcoal under an inert atmosphere, will containing roasting after high-area carbon dipping cobalt, realize the synchronous of cobalt-base catalyst roasting and autoreduction, obtain the catalyst after the autoreduction of surface passivation, greatly reduce the online reduction temperature of cobalt-base catalyst, simultaneously organic carbon source can also play the effect of catalyst reaming in the process of Roasting Decomposition and reduction cobalt.
Catalyst composition of the present invention comprises cobalt oxide, oxide carrier and surface passivation cobalt oxide, and cobalt oxide is in metal, and metallic cobalt is 5-40 (wt) %, and all the other are oxide carrier;
Oxide carrier is alundum (Al2O3), silica, zirconium dioxide or titanium dioxide
The concrete preparation method of catalyst of the present invention is as follows:
(1) by the composition of final catalyst, take soluble cobalt, add deionized water and be mixed with solution;
(2) by carbon source: cobalt salt weight ratio is 0.2-2:1, take carbon source powder and be dissolved in distilled water, stir, form suspension, gelatinization 0.5-4h at 50-90 DEG C;
(3) keep gelatinization point, form by final catalyst, be the carrier colloidal sol of 10%-40% by weight content, under agitation join in the dextrin of step (2), keep 1-4h;
(4) by step (3) gained suction filtration or centrifugation, by filter cake dry 6-24h at 60-120 DEG C, support precursor is obtained;
(5) by presoma under inert atmosphere, roasting 2-8h at 350-800 DEG C, obtained containing high-area carbon;
(6) step (1) gained cobalt salt solution be impregnated in containing high-area carbon by equi-volume process;
(7) step (6) gained is placed in drying box, dry 6-24h at 60-120 DEG C, after drying, under inert atmosphere, roasting 2-10h at 200-400 DEG C, room temperature passivation 2-2h to be down to, obtained final catalyst.
As described in step (1), cobalt salt is the one of cobalt nitrate, cobalt acetate, cobaltous sulfate etc.
As described in step (2), carbon source is the one of starch, methylcellulose or sesbania powder etc.
As described in step (5) and step (7), inert atmosphere is the one of nitrogen, argon gas, helium etc.
As described in step (7), passivation passivating gas used is nitrogen and oxygen gas mixture, and wherein oxygen content is 1.0-20% (v/v).
The catalyst application that the present invention obtains carries out F-T synthesis in fixed bed reactors.Reducing condition is: 180-250 DEG C, 0.2-1.0MPa, hydrogen volume air speed 500-1500h
-1, constant temperature 6-24h; Reaction condition is: H
2/ CO (mol) is between 1.5-3.0, and reaction temperature is 180-240 DEG C, and pressure is 1.0-3.0MPa, and air speed is 500-5000h
-1.
Catalyst tool of the present invention has the following advantages:
(1) catalyst realizes drastic reduction at roasting process, only needs the cobalt oxide of lower temperature reduction surface oxidation, reduce reduction temperature, reduce the requirement to reactor material, expand the application that fischer-tropsch reaction is transformed at reactor during reaction.
(2) catalyst prepared has flourishing pore passage structure and larger specific area.
Detailed description of the invention
Embodiment 1
Account for 30 (wt) % of final catalyst by Co, take Co (NO
3)
26H
2o, adds deionized water and is mixed with solution; By in the final catalyst of reduction needed for cobalt, take starch and be dissolved in distilled water, wherein starch: cobalt nitrate (w/w)=2:1, stir, form suspension, gelatinization 4h at 50 DEG C; Keep gelatinization point, by Al
2o
3account for 70 (wt) % of final catalyst, the Alumina gel of 20 (wt) % is under agitation joined in gelatinized corn starch, continue to stir 2h; Suction filtration is separated, and filter cake is placed in baking oven dry 6h at 120 DEG C, obtains support precursor; Presoma is placed in tube furnace, under nitrogen atmosphere, roasting 2h at 800 DEG C, obtained containing high-area carbon;
By the cobalt nitrate solution incipient impregnation for preparing in above-mentioned carrier, be then placed in baking oven, dry 24h at 60 DEG C, after drying, under argon gas atmosphere, roasting 10h at 250 DEG C.Switch to nitrogen and oxygen gas mixture under room temperature to be down to, oxygen content is 1% (v/v), passivation 12h, and obtained final catalyst, weight consists of Co:Al
2o
3=30:70.
Get above-mentioned catalyst 10g to reduce in fixed bed reactors, reducing condition is: 180 DEG C, 0.5MPa, 500h-1 (V/V), hydrogen, constant temperature 12h.Reaction condition is: 180 DEG C, 1.0Mpa, 500h
-1(V/V), H
2/ CO (mol)=1.Reaction result is in table 1.
Embodiment 2
Account for 5 (wt) % of final catalyst by Co, take a certain amount of Co (CH
3cOO)
24H
2o, adds deionized water and is mixed with solution; By in the final catalyst of reduction needed for cobalt, take a certain amount of sesbania powder and be dissolved in distilled water, wherein sesbania powder: cobalt acetate (w/w)=0.5:1, stir, form suspension, gelatinization 3h at 60 DEG C; Keep gelatinization point, by SiO
2account for 95 (wt) % of final catalyst, the Ludox of a certain amount of 30 (wt) % is under agitation joined in gelatinized corn starch, continue to stir 3h; Suction filtration is separated, and filter cake is placed in baking oven dry 8h at 110 DEG C, obtains support precursor; Presoma is placed in tube furnace, under nitrogen atmosphere, roasting 3h at 700 DEG C, obtained containing high-area carbon.
By the cobalt acetate solution incipient impregnation for preparing in above-mentioned carrier, be then placed in baking oven, dry 18h at 80 DEG C, after drying, under nitrogen atmosphere, roasting 10h at 300 DEG C.Switch to nitrogen and oxygen gas mixture under room temperature to be down to, oxygen content is 3% (v/v), passivation 10h, and obtained final catalyst, catalyst weight consists of Co:SiO
2=5:95.
Get above-mentioned catalyst 10g to reduce in fixed bed reactors, reducing condition is: 200 DEG C, 0.5MPa, 1000h
-1(V/V), hydrogen, constant temperature 24h.Reaction condition is: 190 DEG C, 1.5Mpa, 1000h
-1(V/V), H
2/ CO (mol)=1.5.Reaction result is in table 1.
Embodiment 3
Account for 40 (wt) % of final catalyst by Co, take a certain amount of CoSO
47H
2o, adds deionized water and is mixed with solution; By in the final catalyst of reduction needed for cobalt, take a certain amount of methylcellulose powder and be dissolved in distilled water, wherein methylcellulose: cobaltous sulfate (w/w)=1.0:1, stir, form suspension, gelatinization 2h at 70 DEG C; Keep gelatinization point, by ZrO
2account for 60 (wt) % of final catalyst, the zirconium colloidal sol of a certain amount of 40 (wt) % is under agitation joined in gelatinized corn starch, continue to stir 2.5h; Centrifugation, is placed in baking oven dry 8h at 110 DEG C, obtains support precursor by filter cake; Presoma is placed in tube furnace, under argon gas atmosphere, roasting 2.5h at 600 DEG C, obtained containing high-area carbon.
By the cobalt sulfate solution incipient impregnation for preparing in above-mentioned carrier, be then placed in baking oven, dry 12h at 60 DEG C, after drying, under argon gas atmosphere, roasting 6h at 350 DEG C.Switch to nitrogen and oxygen gas mixture under room temperature to be down to, oxygen content is 5% (v/v), passivation 8h, and obtained final catalyst, catalyst weight consists of Co:ZrO
2=40:60.
Get above-mentioned catalyst 10g to reduce in fixed bed reactors, reducing condition is: 190 DEG C, 0.3MPa, 1500h
-1(V/V), hydrogen, constant temperature 12h.Reaction condition is: 2000 DEG C, 1.8Mpa, 1500h
-1(V/V), H
2/ CO (mol)=1.8.Reaction result is in table 1.
Embodiment 4
Account for 25 (wt) % of final catalyst by Co, take a certain amount of Co (NO
3)
26H
2o, adds deionized water and is mixed with solution; By in the final catalyst of reduction needed for cobalt, take a certain amount of sesbania powder and be dissolved in distilled water, sesbania powder: cobalt nitrate (w/w)=0.75:1, stir, form suspension, gelatinization 2h at 80 DEG C; Keep gelatinization point, by TiO
2account for 80 (wt) % of final catalyst, the titanium colloidal sol of a certain amount of 20 (wt) % is under agitation joined in gelatinized corn starch, continue to stir 1.5h; Suction filtration is separated, and filter cake is placed in baking oven dry 16h at 90 DEG C, obtains support precursor; Presoma is placed in tube furnace, under helium atmosphere, roasting 3h at 700 DEG C, obtained containing high-area carbon.
By the cobalt nitrate solution incipient impregnation for preparing in above-mentioned carrier, be then placed in baking oven, dry 16h at 90 DEG C, after drying, under helium atmosphere, roasting 4h at 300 DEG C.Switch to nitrogen and oxygen gas mixture under room temperature to be down to, oxygen content is 10% (v/v), passivation 6h, and obtained final catalyst, catalyst weight consists of Co:TiO
2=20:80.
Get above-mentioned catalyst 10g to reduce in fixed bed reactors, reducing condition is: 210 DEG C, 0.7MPa, 1200h
-1(V/V), hydrogen, constant temperature 18h.Reaction condition is: 210 DEG C, 2.1Mpa, 2000h
-1(V/V), H
2/ CO (mol)=2.Reaction result is in table 1.
Embodiment 5
Account for 15 (wt) % of final catalyst by Co, take a certain amount of Co (CH
3cOO)
24H
2o, adds deionized water and is mixed with solution; By in the final catalyst of reduction needed for cobalt, take a certain amount of methylcellulose powder and be dissolved in distilled water, methylcellulose: cobalt acetate (w/w)=0.2:1, stir, form suspension, gelatinization 4h at 50 DEG C; Keep gelatinization point, by Al
2o
3account for 85 (wt) % of final catalyst, the Alumina gel of a certain amount of 15 (wt) % is under agitation joined in gelatinized corn starch, continue to stir 1.5h; Centrifugation, is placed in baking oven dry 18h at 80 DEG C, obtains support precursor by filter cake; Presoma is placed in tube furnace, under nitrogen atmosphere, roasting 6h at 400 DEG C, obtained containing high-area carbon.
By the cobalt acetate solution incipient impregnation for preparing in above-mentioned carrier, be then placed in baking oven, dry 12h at 120 DEG C, after drying, under helium atmosphere, roasting 4h at 350 DEG C.Switch to nitrogen and oxygen gas mixture under room temperature to be down to, oxygen content is 15% (v/v), passivation 4h, and obtained final catalyst, catalyst weight consists of Co:Al
2o
3=15:85.
Get above-mentioned catalyst 10g to reduce in fixed bed reactors, reducing condition is: 220 DEG C, 0.8MPa, 1300h
-1(V/V), hydrogen, constant temperature 10h.Reaction condition is: 220 DEG C, 2.5Mpa, 3000h
-1(V/V), H
2/ CO (mol)=2.2.Reaction result is in table 1.
Embodiment 6
Account for 25 (wt) % of final catalyst by Co, take a certain amount of Co (NO
3)
26H
2o, adds deionized water and is mixed with solution; By in the final catalyst of reduction needed for cobalt, take a certain amount of sesbania powder and be dissolved in distilled water, sesbania powder: cobalt nitrate (w/w)=1.25:1, stir, form suspension, gelatinization 3.5h at 60 DEG C; Keep gelatinization point, by SiO
2account for 75 (wt) % of final catalyst, the Ludox of a certain amount of 30 (wt) % is under agitation joined in gelatinized corn starch, continue to stir 1h; Centrifugation, is placed in baking oven dry 24h at 60 DEG C, obtains support precursor by filter cake; Presoma is placed in tube furnace, under helium atmosphere, roasting 8h at 350 DEG C, obtained containing high-area carbon.
By the cobalt nitrate solution incipient impregnation for preparing in above-mentioned carrier, be then placed in baking oven, dry 10h at 100 DEG C, after drying, under argon gas atmosphere, roasting 2h at 400 DEG C.Switch to nitrogen and oxygen gas mixture under room temperature to be down to, oxygen content is 12% (v/v), passivation 6h, and obtained final catalyst, catalyst weight consists of Co:SiO
2=25:75.
Get above-mentioned catalyst 10g to reduce in fixed bed reactors, reducing condition is: 230 DEG C, 0.9MPa, 800h
-1(V/V), hydrogen, constant temperature 6h.Reaction condition is: 230 DEG C, 2.8Mpa, 4000h
-1(V/V), H
2/ CO (mol)=2.5.Reaction result is in table 1.
Embodiment 7
Account for 35 (wt) % of final catalyst by Co, take a certain amount of CoSO
47H
2o, adds deionized water and is mixed with solution; By in the final catalyst of reduction needed for cobalt, take a certain amount of starch and be dissolved in distilled water, starch: cobaltous sulfate (w/w)=1.0:1, stir, form suspension, gelatinization 3h at 85 DEG C; Keep gelatinization point, by ZrO
2account for 65 (wt) % of final catalyst, the zirconium colloidal sol of a certain amount of 28 (wt) % is under agitation joined in gelatinized corn starch, continue to stir 3.5h; Suction filtration is separated, and filter cake is placed in baking oven dry 12h at 100 DEG C, obtains support precursor; Presoma is placed in tube furnace, under nitrogen atmosphere, roasting 2.5h at 450 DEG C, obtained containing high-area carbon.
By the cobalt sulfate solution incipient impregnation for preparing in above-mentioned carrier, be then placed in baking oven, dry 8h at 80 DEG C, after drying, under argon gas atmosphere, roasting 4h at 280 DEG C.Switch to nitrogen and oxygen gas mixture under room temperature to be down to, oxygen content is 20% (v/v), passivation 2h, and obtained final catalyst, catalyst weight consists of Co:ZrO
2=35:65.
Get above-mentioned catalyst 10g to reduce in fixed bed reactors, reducing condition is: 240 DEG C, 1.0MPa, 700h
-1(V/V), hydrogen, constant temperature 16h.Reaction condition is: 240 DEG C, 3.0Mpa, 5000h
-1(V/V), H
2/ CO (mol)=3.Reaction result is in table 1.
Table 1 catalyst reaction result
Claims (7)
1. autoreduction prepares a Fischer-Tropsch synthesis cobalt-based catalyst, and it is characterized in that catalyst composition comprises cobalt, oxide carrier and surface passivation cobalt oxide, cobalt oxide is in element, and cobalt element total content is 5-40wt%, and all the other are oxide carrier;
And prepare by the following method:
(1) by the composition of final catalyst, take soluble cobalt, add deionized water and be mixed with solution;
(2) by carbon source: cobalt salt weight ratio is 0.2-2:1, take carbon source powder and be dissolved in distilled water, stir, form suspension, gelatinization 0.5-4h at 50-90 DEG C;
(3) keep gelatinization point, form by final catalyst, be the carrier colloidal sol of 10%-40% by weight content, under agitation join in the dextrin of step (2), keep 1-4h;
(4) by step (3) gained suction filtration or centrifugation, by filter cake dry 6-24h at 60-120 DEG C, support precursor is obtained;
(5) by presoma under inert atmosphere, roasting 2-8h at 350-800 DEG C, obtained containing high-area carbon;
(6) step (1) gained cobalt salt solution be impregnated in containing high-area carbon by equi-volume process;
(7) step (6) gained is placed in drying box, dry 6-24h at 60-120 DEG C, after drying, under inert atmosphere, roasting 2-10h at 200-400 DEG C, room temperature passivation 2-2h to be down to, obtained final catalyst.
2. a kind of autoreduction as claimed in claim 1 prepares Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that described oxide carrier is alundum (Al2O3), silica, zirconium dioxide or titanium dioxide.
3. a kind of autoreduction as claimed in claim 1 prepares Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that described cobalt salt is the one in cobalt nitrate, cobalt acetate, cobaltous sulfate.
4. a kind of autoreduction as claimed in claim 1 prepares Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that step (2) described carbon source is the one in starch, methylcellulose or sesbania powder.
5. a kind of autoreduction as claimed in claim 1 prepares Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that step (5) and step (7) described inert atmosphere are the one in nitrogen, argon gas, helium.
6. a kind of autoreduction as claimed in claim 1 prepares Fischer-Tropsch synthesis cobalt-based catalyst, and it is characterized in that step (7) described passivation passivating gas used is nitrogen and oxygen gas mixture, wherein oxygen volume content is 1.0-20%.
7. a kind of autoreduction as described in any one of claim 1-6 prepares the application of Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that catalyst application carries out F-T synthesis in fixed bed reactors, reducing condition is: 180-250 DEG C, 0.2-1.0MPa, hydrogen volume air speed 500-1500h
-1, constant temperature 6-24h; Reaction condition is: H
2/ CO mol ratio between 1.5-3.0, reaction temperature is 180-240 DEG C, and pressure is 1.0-3.0MPa, and air speed is 500-5000h
-1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101269329A (en) * | 2008-05-19 | 2008-09-24 | 中国科学院山西煤炭化学研究所 | Cobalt group catalyst synthesized with fischer tropsch process, production method and application thereof |
| CN101269336A (en) * | 2008-05-19 | 2008-09-24 | 中国科学院山西煤炭化学研究所 | Multilevel hole material load cobalt catalyst, preparation method and application thereof |
| US20120165418A1 (en) * | 2009-06-17 | 2012-06-28 | Johnson Matthey Plc | Methanol synthesis process |
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| CN101269329A (en) * | 2008-05-19 | 2008-09-24 | 中国科学院山西煤炭化学研究所 | Cobalt group catalyst synthesized with fischer tropsch process, production method and application thereof |
| CN101269336A (en) * | 2008-05-19 | 2008-09-24 | 中国科学院山西煤炭化学研究所 | Multilevel hole material load cobalt catalyst, preparation method and application thereof |
| US20120165418A1 (en) * | 2009-06-17 | 2012-06-28 | Johnson Matthey Plc | Methanol synthesis process |
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