CN104174398B - Autoreduction produces Fischer-Tropsch synthesis cobalt-based catalyst and application thereof - Google Patents
Autoreduction produces Fischer-Tropsch synthesis cobalt-based catalyst and application thereof Download PDFInfo
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Abstract
A kind of autoreduction produces Fischer-Tropsch synthesis cobalt-based catalyst and includes cobalt oxide, oxide carrier and surface passivation cobalt oxide: cobalt oxide is in metal, metallic cobalt 15-35wt%, and all the other are oxide carrier；Organic carbon source is introduced by preparing catalyst carrier process at deposition-precipitation method, organic carbon source is utilized to decompose the feature producing weak reduction components simple substance charcoal under an inert atmosphere, roasting after cobalt will be impregnated containing high-area carbon, realize the synchronization of cobalt-base catalyst roasting and autoreduction, obtain the catalyst after the autoreduction of surface passivation, be substantially reduced the online reduction temperature of cobalt-base catalyst。
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
It is the coal liquifaction technology realizing commercial applications at present that cobalt-based fixes bed, iron-based slurry bed system and fluid bed F-T synthesis technology。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, C5 +The advantage that selectivity is high and water gas shift reaction activity is low, thus co-based fischer-tropsch artificial oil has become as new technology commanding elevation, coal liquifaction field and competition spot。While it is true, cobalt-base catalyst also exists contradiction and the technology barrier of low temperature operating and high temperature reduction so that reactor material is required and the requirement of reaction process coupling greatly improves。Construct specific catalyst system and catalyzing, it is achieved the in-situ reducing of cobalt-base catalyst, it is possible to effectively solve the technology barrier of the operating of catalyst low temperature and high temperature reduction, significantly reduce reactor manufacture difficulty, effective Widening Technique application, through retrieval, not yet has Patents or article report at present。
Summary of the invention
It is an object of the invention to provide a kind of for fixed bed reactors and Co based Fischer-Tropsch synthesis catalyst and the application thereof reduced can be carried out at low temperatures。
The present invention introduces organic carbon source by preparing catalyst carrier process at deposition-precipitation method, organic carbon source is utilized to decompose the feature producing weak reduction components simple substance charcoal under an inert atmosphere, roasting after cobalt will be impregnated containing high-area carbon, realize the synchronization of cobalt-base catalyst roasting and autoreduction, obtain the catalyst after the autoreduction of surface passivation, being substantially reduced the online reduction temperature of cobalt-base catalyst, organic carbon source may also operate as the effect of catalyst reaming in the process of roasting carbonization and reduction cobalt simultaneously。
Catalyst of the present invention includes cobalt oxide, oxide carrier and surface passivation cobalt oxide: cobalt oxide is in metal, metallic cobalt 15-35 (wt) %, and all the other are oxide carrier；
Oxide carrier aluminium sesquioxide, 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, weigh soluble cobalt, add deionized water and be configured to solution；
(2) by carbon source: cobalt salt (w/w)=0.2-2:1, weigh carbon source powder body and be dissolved in distilled water, stirring, form suspension, gelatinizing 0.5-4h at 50-90 DEG C；
(3) gelatinization point is kept, stirring, form by final catalyst, the preparation aluminium salt of 0.1-2mol/L, zirconates or titanium salt solution, with 0.1-2mol/L alkaline precipitating agent co-precipitation, maintenance pH is 7.0-9.0；After precipitation terminates, aging 1-12h at 60-90 DEG C, after aging end, sucking filtration or centrifugation；
(4) filter cake is put in drying baker at 60-120 DEG C and dries 6-24h, be subsequently placed in tube furnace, under inert atmosphere, roasting 2-8h at 350-800 DEG C, prepare containing high-area carbon；
(5) cobalt salt solution of step (1) be impregnated in above-mentioned carrier by equi-volume process；
(6) step (5) gained is placed in drying baker, dry 6-24h at 60-120 DEG C, after drying, under inert atmosphere, roasting 2-10h at 200-400 DEG C, room temperature to be down to passivation 2-12h, prepare final catalyst。
As described in step (1), cobalt salt is the one of cobalt nitrate, cobaltous acetate, cobaltous sulfate etc.。
As described in step (2), carbon source is the one of starch, methylcellulose, sesbania powder etc.。
As described in step (3), aluminium salt is the one of aluminum nitrate, aluminum sulfate etc., and zirconates is the one of zirconium oxychloride, zirconium nitrate, zirconyl nitrate etc., and titanium salt is the one of Titanium Nitrate, titanium tetrachloride etc.；Alkaline precipitating agent is the one of ammonia, ammonium carbonate, ammonium hydrogen carbonate etc.。
As described in step (4) and step (6), inert atmosphere is the one of nitrogen, argon, helium etc.。
As described in step (6), the passivating gas used by passivation is nitrogen and oxygen gas mixture, and oxygen content is 1.0-20% (v/v)。
The catalyst that the present invention prepares is applied to 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: reaction temperature is 180-240 DEG C, H2/ CO (mol) is between 1.5-3.0, and pressure is 1.0-3.0MPa, and air speed is 500-5000h-1。
Catalyst of the present invention has the advantage that
(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 the pore passage structure of prosperity and bigger specific surface area。
Detailed description of the invention
Embodiment 1
Account for 35 (wt) % of final catalyst by Co, weigh Co (NO3)2·6H2O, adds deionized water and is configured to solution；Needed for cobalt in the final catalyst of reduction, weigh a certain amount of methylcellulose powder body and be dissolved in distilled water, wherein methylcellulose: cobalt nitrate (w/w)=0.2:1, stirring, form suspension, gelatinizing 0.5h at 90 DEG C；Keep gelatinization point, by ZrO2Account for 65 (wt) % of final catalyst, the Al (NO of preparation 0.2mol/L3)3·9H2O solution, with 0.4mol/LNH3·H2O co-precipitation is in above-mentioned dextrin, and keeping pH is 7.5；After precipitation terminates, aging 1h at 90 DEG C, after aging end, sucking filtration, filter cake is put in drying baker at 90 DEG C and dries 10h, be subsequently placed in tube furnace, under argon gas atmosphere, roasting 2h at 800 DEG C, prepare containing high-area carbon。
By the cobalt nitrate solution incipient impregnation for preparing in above-mentioned carrier, it is subsequently placed in baking oven, dry 24h at 65 DEG C, after drying, under nitrogen atmosphere, roasting 8h at 300 DEG C, switching to nitrogen and oxygen gas mixture under room temperature to be down to, oxygen content is 15% (v/v), is passivated 5h, preparing final catalyst, catalyst weight consists of Co:Al2O3=35:65。
Taking 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), H2/ CO (mol)=1。Reaction result is in Table 1。
Embodiment 2
Account for 25 (wt) % of final catalyst by Co, weigh a certain amount of Co (CH3COO)2·4H2O, adds deionized water and is configured to solution；Needed for cobalt in the final catalyst of reduction, weigh a certain amount of starch and be dissolved in distilled water, wherein starch: cobaltous acetate (w/w)=0.5:1, stirring, form suspension, gelatinizing 2.5h at 80 DEG C, keep gelatinization point, by TiO2Account for 75 (wt) % of final catalyst, prepare the Ti (NO of a certain amount of 1.0mol/L3)4Solution, with 2.0mol/L (NH4)2CO3Co-precipitation is in above-mentioned dextrin, and keeping pH is 8.5；After precipitation terminates, aging 12h at 60 DEG C, after aging end, sucking filtration, filter cake is put in drying baker at 110 DEG C and dries 6h, be subsequently placed in tube furnace, under helium atmosphere, burn 2h at 650 DEG C, prepare containing high-area carbon。
By the cobalt acetate solution incipient impregnation for preparing in above-mentioned carrier, it is subsequently placed in baking oven, dry 8h at 120 DEG C, after drying, under helium atmosphere, at 200 DEG C, switch to nitrogen and oxygen gas mixture under roasting 10h room temperature to be down to, oxygen content is 5% (v/v), passivation 4h, prepares final catalyst, and catalyst weight consists of Co:TiO2=25:75。
Taking 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), H2/ CO (mol)=1.5。Reaction result is in Table 1。
Embodiment 3
Account for 30 (wt) % of final catalyst by Co, weigh a certain amount of CoSO4·7H2O, adds deionized water and is configured to solution；Needed for cobalt in the final catalyst of reduction, weigh a certain amount of sesbania powder and be dissolved in distilled water, wherein sesbania powder: cobaltous sulfate (w/w)=0.75:1, stirring, form suspension, gelatinizing 4h at 70 DEG C, keep gelatinization point, by ZrO2Account for 70 (wt) % of final catalyst, prepare the ZrOCl of a certain amount of 0.5mol/L2·8H2O solution, with 1.5mol/LNH3·H2O co-precipitation is in above-mentioned dextrin, and keeping pH is 8.5；After precipitation terminates, aging 6h at 70 DEG C, after aging end, sucking filtration, filter cake is put in drying baker at 120 DEG C and dries 12h, be subsequently placed in tube furnace, under argon gas atmosphere, roasting 6h at 500 DEG C, prepare containing high-area carbon。
By the cobalt sulfate solution incipient impregnation for preparing in above-mentioned carrier, it is subsequently placed in baking oven, dry 12h at 110 DEG C, after drying, under helium atmosphere, at 350 DEG C, switch to nitrogen and oxygen gas mixture under roasting 6h room temperature to be down to, oxygen content is 15% (v/v), passivation 4h, prepares final catalyst, and catalyst weight consists of Co:ZrO2=30:70。
Taking 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), H2/ CO (mol)=1.8。Reaction result is in Table 1。
Embodiment 4
Account for 32 (wt) % of final catalyst by Co, weigh a certain amount of Co (NO3)·6H2O, adds deionized water and is configured to solution；Needed for cobalt in the final catalyst of reduction, weigh a certain amount of methylcellulose powder body and be dissolved in distilled water, wherein methylcellulose: cobalt nitrate (w/w)=1.0:1, stirring, form suspension, at 60 DEG C, stick with paste 3h, keep gelatinization point, by ZrO2Account for 68 (wt) % of final catalyst, prepare the Zr (NO of a certain amount of 0.2mol/L3)4·5H2O solution, with 0.6mol/LNH4HCO3Co-precipitation is in above-mentioned dextrin, and keeping pH is 7.0；After precipitation terminates, aging 12h at 60 DEG C, after aging end, sucking filtration, filter cake is put in drying baker at 120 DEG C and dries 6h, be subsequently placed in tube furnace, under nitrogen atmosphere, roasting 8h at 500 DEG C, prepare containing high-area carbon。
By the cobalt nitrate solution incipient impregnation for preparing in above-mentioned carrier, it is subsequently placed in baking oven, dry 18h at 100 DEG C, after drying, under nitrogen atmosphere, at 400 DEG C, switch to nitrogen and oxygen gas mixture under roasting 2h room temperature to be down to, oxygen content is 20% (v/v), passivation 2h, prepares final catalyst, and catalyst weight consists of Co:ZrO2=32:68。
Taking 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), H2/ CO (mol)=2。Reaction result is in Table 1。
Embodiment 5
Account for 15 (wt) % of final catalyst by Co, weigh a certain amount of Co (CH3COO)2·4H2O, adds deionized water and is configured to solution；Needed for cobalt in the final catalyst of reduction, weigh a certain amount of starch and be dissolved in distilled water, wherein starch: cobaltous acetate (w/w)=1.25:1, stirring, form suspension, gelatinizing 2.5h at 65 DEG C, keep gelatinization point, by Al2O3Account for 85 (wt) % of final catalyst, prepare the Al of a certain amount of 1.2mol/L2·(SO4)3·18H2O solution, with 2.0mol/L (NH4)2CO3Co-precipitation is in above-mentioned dextrin, and keeping pH is 9.0；After precipitation terminates, aging 10h at 750 DEG C, after aging end, sucking filtration, filter cake is put in drying baker at 60 DEG C and dries 24h, be subsequently placed in tube furnace, under argon gas atmosphere, roasting 8h at 350 DEG C, prepare containing high-area carbon。
By the cobalt acetate solution incipient impregnation for preparing in above-mentioned carrier, it is subsequently placed in baking oven, dry 16h at 80 DEG C, after drying, under nitrogen atmosphere, at 250 DEG C, switch to nitrogen and oxygen gas mixture under roasting 8h room temperature to be down to, oxygen content is 2.5% (v/v), passivation 10h, prepares final catalyst, and catalyst weight consists of Co:Al2O3=15:85。
Taking 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), H2/ CO (mol)=2.2。Reaction result is in Table 1。
Embodiment 6
Account for 35 (wt) % of final catalyst by Co, weigh a certain amount of Co (NO3)2·6H2O, adds deionized water and is configured to solution；Needed for cobalt in the final catalyst of reduction, weigh a certain amount of sesbania powder and be dissolved in distilled water, wherein sesbania powder: cobalt nitrate (w/w)=1.5:1, stirring, form suspension, gelatinizing 1.5h at 85 DEG C, keep gelatinization point, by TiO2Account for 80 (wt) % of final catalyst, prepare the Ti (NO of a certain amount of 0.25mol/L3)4Solution, with 0.8mol/LNH4HCO3Co-precipitation is in above-mentioned dextrin, and keeping pH is 8.5；After precipitation terminates, aging 6h at 75 DEG C, after aging end, sucking filtration, filter cake is put in drying baker at 100 DEG C and dries 5h, be subsequently placed in tube furnace, under nitrogen atmosphere, roasting 6h at 400 DEG C, prepare containing high-area carbon。
By the cobalt nitrate solution incipient impregnation for preparing in above-mentioned carrier, it is subsequently placed in baking oven, dry 24h at 60 DEG C, after drying, under argon gas atmosphere, at 320 DEG C, switch to nitrogen and oxygen gas mixture under roasting 5h room temperature to be down to, oxygen content is 8% (v/v), passivation 14h, prepares final catalyst, and catalyst weight consists of Co:TiO2=20:80。
Taking 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), H2/ CO (mol)=2.5。Reaction result is in Table 1。
Embodiment 7
Account for 22 (wt) % of final catalyst by Co, weigh a certain amount of CoSO4·7H2O, adds deionized water and is configured to solution；Needed for cobalt in the final catalyst of reduction, weigh a certain amount of starch and be dissolved in distilled water, wherein starch: cobaltous sulfate (w/w)=2.0:1, stirring, form suspension, gelatinizing 3.5h at 75 DEG C, keep gelatinization point, by Al2O3Account for 78 (wt) % of final catalyst, prepare the Al (NO of a certain amount of 2.0mol/L3)3·9H2O solution, with 4.0mol/LNH3·H2O co-precipitation is in above-mentioned dextrin, and keeping pH is 7.5；After precipitation terminates, aging 4h at 80 DEG C, after aging end, sucking filtration, filter cake is put in drying baker at 80 DEG C and dries 7h, be subsequently placed in tube furnace, under argon gas atmosphere, roasting 3h at 450 DEG C, prepare containing high-area carbon。
By the cobalt sulfate solution incipient impregnation for preparing in above-mentioned carrier, it is subsequently placed in baking oven, dry 18h at 70 DEG C, after drying, under helium atmosphere, at 300 DEG C, switch to nitrogen and oxygen gas mixture under roasting 8h room temperature to be down to, oxygen content is 10% (v/v), passivation 6h, prepares final catalyst, and catalyst weight consists of Co:Al2O3=22:78。
Taking 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), H2/ CO (mol)=3。Reaction result is in Table 1。
Table 1 catalyst reaction result
Claims (9)
1. an autoreduction produces Fischer-Tropsch synthesis cobalt-based catalyst, it is characterised in that catalyst includes cobalt oxide, oxide carrier and surface passivation cobalt oxide, element cobalt 15-35wt%, and all the other are oxide carrier；
And prepare by the following method:
(1) by the composition of final catalyst, weigh soluble cobalt, add deionized water and be configured to solution；
(2) by carbon source: cobalt salt weight ratio is 0.2-2:1, weigh carbon source powder body and be dissolved in distilled water, stirring, form suspension, gelatinizing 0.5-4h at 50-90 DEG C；
(3) gelatinization point is kept, stirring, form by final catalyst, the preparation aluminium salt of 0.1-2mol/L, zirconates or titanium salt solution, with 0.1-2mol/L alkaline precipitating agent co-precipitation, maintenance pH is 7.0-9.0；After precipitation terminates, aging 1-12h at 60-90 DEG C, after aging end, sucking filtration or centrifugation；
(4) filter cake is put in drying baker at 60-120 DEG C and dries 6-24h, be subsequently placed in tube furnace, under inert atmosphere, roasting 2-8h at 350-800 DEG C, prepare containing high-area carbon；
(5) cobalt salt solution of step (1) be impregnated in above-mentioned carrier by equi-volume process；
(6) step (5) gained is placed in drying baker, dry 6-24h at 60-120 DEG C, after drying, under inert atmosphere, roasting 2-10h at 200-400 DEG C, room temperature to be down to passivation 2-12h, prepare final catalyst。
2. a kind of autoreduction as claimed in claim 1 produces Fischer-Tropsch synthesis cobalt-based catalyst, it is characterised in that described oxide carrier is aluminium sesquioxide, zirconium dioxide or titanium dioxide。
3. a kind of autoreduction as claimed in claim 1 produces Fischer-Tropsch synthesis cobalt-based catalyst, it is characterised in that step (1) described cobalt salt is the one in cobalt nitrate, cobaltous acetate, cobaltous sulfate。
4. a kind of autoreduction as claimed in claim 1 produces Fischer-Tropsch synthesis cobalt-based catalyst, it is characterised in that step (2) described carbon source is the one in starch, methylcellulose, sesbania powder。
5. a kind of autoreduction as claimed in claim 1 produces Fischer-Tropsch synthesis cobalt-based catalyst, it is characterized in that step (3) described aluminium salt is the one in aluminum nitrate, aluminum sulfate, zirconates is the one in zirconium oxychloride, zirconium nitrate, zirconyl nitrate, and titanium salt is the one in Titanium Nitrate, titanium tetrachloride。
6. a kind of autoreduction as claimed in claim 1 produces Fischer-Tropsch synthesis cobalt-based catalyst, it is characterised in that step (3) described alkaline precipitating agent is the one in ammonia, ammonium carbonate, ammonium hydrogen carbonate。
7. a kind of autoreduction as claimed in claim 1 produces Fischer-Tropsch synthesis cobalt-based catalyst, it is characterised in that step (4) and step (6) described inert atmosphere are the one in nitrogen, argon, helium。
8. a kind of autoreduction as claimed in claim 1 produces Fischer-Tropsch synthesis cobalt-based catalyst, it is characterised in that the passivating gas used by step (6) described passivation is nitrogen and oxygen gas mixture, and wherein oxygen volume content is 1.0-20%。
9. a kind of autoreduction as described in any one of claim 1-8 produces the application of Fischer-Tropsch synthesis cobalt-based catalyst, it is characterised in that catalyst is applied to fixed bed reactors, and 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: reaction temperature is 180-240 DEG C, H2/ CO mol ratio is between 1.5-3.0, and pressure is 1.0-3.0MPa, and air speed is 500-5000h-1。
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| CN108654637B (en) * | 2017-03-29 | 2021-10-08 | 中国石油化工股份有限公司 | Cobalt-based catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method |
| WO2021139898A1 (en) * | 2020-01-10 | 2021-07-15 | Bp P.L.C. | Process for producing a fischer-tropsch synthesis catalyst and fischer-tropsch start-up process |
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