CN105289613A - Alumina supported cobalt Fischer-Tropsch synthesis catalyst and preparation method and application thereof - Google Patents
Alumina supported cobalt Fischer-Tropsch synthesis catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an alumina supported cobalt Fischer-Tropsch synthesis catalyst. The alumina supported cobalt Fischer-Tropsch synthesis catalyst is prepared from cobaltosic oxide, silicon dioxide and aluminum oxide according to the molar ratio of 0.1-0.25:0.02-0.2:1. The catalyst has the advantages of being high in stability and capable of being applied to a slurry bed or fixed bed reactor.
Description
Technical field
The present invention relates to a kind of Co based Fischer-Tropsch synthesis catalyst and preparation method and application, specifically a kind of alumina load cobalt fischer-tropsch synthetic catalyst and its preparation method and application.
Background technology
Fischer-Tropsch synthesis is the process that CO catalytic hydrogenation generates hydrocarbon compound, and its product environmental friendliness, aromatic-free, sulfide and nitrogen compound etc., receive increasingly extensive concern.Cobalt-base catalyst for Fischer-Tropsch synthesis has higher chain growth ability, insensitive to water gas shift reaction, stable in course of reaction, not easily oxygenatedchemicals is few in carbon deposit and poisoning, product, and CO transforms can close to theoretical yield.Cobalt-base catalyst adopts cobalt to load to aluminium oxide to prepare usually, but the hydrothermal stability of aluminium oxide is poor, be easy to carry out hydration reaction under the hydrothermal condition of Fischer-Tropsch synthesis, form Al-O-Al bridged bond and generate boehmite, cause that alumina ratio surface area declines to a great extent, pore structure destroys, the metal of load on it easily comes off, and finally causes catalysqt deactivation.
Therefore, need to take measures to carry out modification to alumina support, to improve its catalytic stability as carrier.In aluminium oxide structure, introduce some ion, effectively can remove hydroxyl and the anions and canons hole of alumina surface, and its intrinsic pore passage structure and specific area can be maintained, on hydrothermal stability, the suppression phase transformation improving aluminium oxide, there is remarkable impact.
Summary of the invention
The object of the invention is that providing a kind of can be used for Co based Fischer-Tropsch synthesis catalyst of the high stability of slurry bed system or fixed bed reactors and its preparation method and application.
The present invention introduces Si element in the preparation process of alumina precursor, Si can be combined with alumina precursor surface hydroxyl, generate glassy surface layer, Si-O-Si or Si-O-Al key can be formed in presoma roasting dehydroxylation process, eliminate surperficial anion vacancy, improve roasting rear oxidation aluminium hydrothermal stability, thus improve the F-T synthesis stability of load cobalt catalyst.
Catalyst of the present invention is made up of cobaltosic oxide, silica and aluminium oxide, and its mole consists of cobaltosic oxide: silica: aluminium oxide=(0.1-0.25): (0.02-0.2): 1.
The preparation method of catalyst of the present invention is as follows:
(1) form by final catalyst, take nitric acid and be mixed with water solution A, take sodium metaaluminate and be mixed with aqueous solution B, take silicon source again and be mixed with ethanolic solution C, solution A volume=B solution volume+C solution volume, wherein, nitric acid: (sodium metaaluminate+silicon source) amount of substance ratio=(0.95-1.1): 1;
(2) first solution A and solution B are carried out co-precipitation at water-bath 50-85 DEG C, A, B volume flow is identical, and after solution B precipitation, solution A is proceeded co-precipitation with solution C under the water-bath of identical temperature, and A, C volume flow is identical;
(3) after precipitation, aging 2-24h at 70-90 DEG C;
(4) after aging end, spend sodium ion in deionized water to filtrate and be less than 5ppm, then filter and obtain filter cake, filter cake is placed in 90-120 DEG C of drying 10 ~ 24h and obtains silicon-aluminum containing presoma, by the presoma that obtains in 400-800 DEG C of roasting 4-10h, obtain silicon-containing alumina carrier;
(5) form by final catalyst, take the water-soluble obtain solution of cobalt nitrate, incipient impregnation is in above-mentioned silicon-containing alumina carrier, and dry 10-24h, 300-400 DEG C of roasting 4-10h at 90-120 DEG C, obtains final catalyst.
Silicon source as above is the one of methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate.
Fischer-Tropsch synthesis cobalt-based catalyst as above, can carry out reducing, reacting in fixed bed reactors; Reducing condition is: 350-450 DEG C, 0.3-1.5MPa, GHSV=300-1000h
-1, constant temperature 12-24h, adopts hydrogen reduction gas in nitrogen, H
2content is 15%-85% (v/v); Reaction condition is: 170-230 DEG C, 2.0-5.0Mpa, volume space velocity GHSV=700-2500h
-1, H
2/ CO (v/v)=2.0-2.5.
Fischer-Tropsch synthesis cobalt-based catalyst as above, can carry out reducing, reacting in paste state bed reactor; Reducing condition is: 270-320 DEG C, 0.2-1.2MPa, GHSV=500-800h
-1, constant temperature 12-36h, adopts hydrogen reduction gas in nitrogen, H
2content is 15%-85% (v/v), and rotating speed is 400-800rpm; Reaction condition is: 170-230 DEG C, 2.0-3.0MPa, volume space velocity GHSV=700-2000h
-1, H
2/ CO (v/v)=2.0-3.0, rotating speed is 400-800rpm.
The present invention mixes silicon aluminium oxide load cobalt catalyst compared with existing Fischer-Tropsch synthesis cobalt-based catalyst, under hydrothermal reaction condition, roasting rear oxidation aluminium can maintain intrinsic pore passage structure and high-specific surface area, improve hydrothermal stability, prevent aluminium oxide phase transformation, thus improve load cobalt catalyst F-T synthesis stability.
Detailed description of the invention
The present invention will be further described for embodiment below, and protection scope of the present invention is not by the restriction of these embodiments.
Embodiment 1:
Form according to final catalyst, the red fuming nitric acid (RFNA) taking 1909g66 (wt.) % is mixed with 40L water solution A, takes 1640g sodium metaaluminate and is mixed with 32L aqueous solution B, then takes 304g methyl silicate and be mixed with 8L ethanolic solution C; First solution A and solution B are carried out co-precipitation at water-bath 60 DEG C, A, B volume flow is identical; After treating solution B precipitation, continue solution A and solution C to carry out co-precipitation at 60 DEG C, A, C volume flow is identical; After treating solution A, C precipitation, aging 4h at 80 DEG C; After aging end, spend sodium ion in deionized water to filtrate and be less than 5ppm, filter and obtain filter cake, filter cake is placed in baking oven and obtains silicon-containing alumina presoma in 100 DEG C of dry 10h; The presoma obtained is placed in Muffle furnace, in 550 DEG C of roasting 6h, obtains silicon-containing alumina; Form by final catalyst, take 1746g cabaltous nitrate hexahydrate obtained aqueous solution, incipient impregnation is in above-mentioned carrier, dry 24h at 65 DEG C, 300 DEG C of roasting 8h, obtained final catalyst, its mole consists of cobaltosic oxide: silica: aluminium oxide=0.2:0.2:1.
Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 370 DEG C, 0.5MPa, constant temperature 12h, 1000h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 25% (v/v).Reaction condition is: 230 DEG C, 3.0MPa, 2000h
-1(v/v), H
2/ CO (mol)=2.3.Evaluation result: CO conversion ratio 41.5%, CH
4in selective 12.3%, the 720h of being, inactivation rate is 0.22%.
Get above-mentioned catalyst 20ml to evaluate in 1L paste state bed reactor, reducing condition is, 320 DEG C, 0.1MPa, 500h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 15% (v/v), constant temperature 12h, 600rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 225 DEG C, 2.0MPa, 1800h
-1(v/v), H
2/ CO (v/v)=2.2,600rpm.Evaluation result: CO conversion ratio 46.5%, CH
4in selective 11.2%, the 720h of being, inactivation rate is 1.13%.
Embodiment 2:
Form according to final catalyst, the fuming nitric aicd taking 1286g98 (wt.) % is mixed with 20L water solution A, takes 1640g sodium metaaluminate and is mixed with 19L aqueous solution B, then takes 208g ethyl orthosilicate and be mixed with 1L ethanolic solution C; First solution A and solution B are carried out co-precipitation at water-bath 70 DEG C, A, B volume flow is identical; After treating solution B precipitation, continue solution A and solution C to carry out co-precipitation at 70 DEG C, A, C volume flow is identical; After treating solution A, C precipitation, aging 2h at 90 DEG C; After aging end, spend sodium ion in deionized water to filtrate and be less than 5ppm, filter and obtain filter cake, filter cake is placed in baking oven and obtains silicon-containing alumina presoma in 90 DEG C of dry 24h; The presoma obtained is placed in Muffle furnace, in 400 DEG C of roasting 10h, obtains silicon-containing alumina; Form by final catalyst, take 2182.5g cabaltous nitrate hexahydrate obtained aqueous solution, incipient impregnation is in above-mentioned carrier, dry 24h at 90 DEG C, 300 DEG C of roasting 10h, obtained final catalyst, its mole consists of cobaltosic oxide: silica: aluminium oxide=0.25:0.1:1.Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 450 DEG C, 1.5MPa, constant temperature 15h, 300h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 70% (v/v).Reaction condition is: 220 DEG C, 2.0MPa, 1000h
-1(v/v), H
2/ CO (mol)=2.5.Evaluation result: CO conversion ratio 52.6%, CH
4in selective 6.9%, the 720h of being, inactivation rate is 0.03%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 300 DEG C, 1.2MPa, 700h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 80% (v/v), constant temperature 12h, 750rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 210 DEG C, 2.2MPa, 1500h
-1(v/v), H
2/ CO (v/v)=2.2,700rpm.Evaluation result: CO conversion ratio 60.5%, CH
4in selective 6.4%, the 720h of being, inactivation rate is 0.92%.
Embodiment 3:
Form according to final catalyst, the red fuming nitric acid (RFNA) taking 926.5g68 (wt.) % is mixed with 20L water solution A, takes 620g sodium metaaluminate and is mixed with 19.5L aqueous solution B, then takes the positive silicic acid propyl ester of 26.4g and be mixed with 0.5L ethanolic solution C; First solution A and solution B are carried out co-precipitation at water-bath 50 DEG C, A, B volume flow is identical; After treating solution B precipitation, continue solution A and solution C to carry out co-precipitation at 50 DEG C, A, C volume flow is identical; After treating solution A, C precipitation, aging 24h at 70 DEG C; After aging end, spend sodium ion in deionized water to filtrate and be less than 5ppm, filter and obtain filter cake, filter cake is placed in baking oven and obtains silicon-containing alumina presoma in 100 DEG C of dry 8h; The presoma obtained is placed in Muffle furnace, in 500 DEG C of roasting 8h, obtains silicon-containing alumina; Form by final catalyst, take 873g cabaltous nitrate hexahydrate obtained aqueous solution, incipient impregnation is in above-mentioned carrier, dry 20h at 10 DEG C, 320 DEG C of roasting 8h, obtained final catalyst, its mole consists of cobaltosic oxide: silica: aluminium oxide=0.2:0.02:1.Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 360 DEG C, 0.5MPa, constant temperature 24h, 600h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 25% (v/v).Reaction condition is: 225 DEG C, 2.5MPa, 800h
-1(v/v), H
2/ CO (mol)=2.2.Evaluation result: CO conversion ratio 75.3%, CH
4in selective 7.7%, the 720h of being, inactivation rate is 0.05%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 340 DEG C, 0.5MPa, 900h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 70% (v/v), constant temperature 18h, 720rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 225 DEG C, 2.8MPa, 2500h
-1(v/v), H
2/ CO (v/v)=3.0,850rpm.Evaluation result: CO conversion ratio 49.5%, CH
4in selective 5.0%, the 720h of being, inactivation rate is 0.34%.
Embodiment 4:
Form according to final catalyst, the red fuming nitric acid (RFNA) taking 1894.7g66.5 (wt.) % is mixed with 30L water solution A, takes 1640g sodium metaaluminate and is mixed with 27.5L aqueous solution B, then takes 160g butyl silicate and be mixed with 2.5L ethanolic solution C; First solution A and solution B are carried out co-precipitation at water-bath 80 DEG C, A, B volume flow is identical; After treating solution B precipitation, continue solution A and solution C to carry out co-precipitation at 80 DEG C, A, C volume flow is identical; After treating solution A, C precipitation, aging 4h at 85 DEG C; After aging end, spend sodium ion in deionized water to filtrate and be less than 5ppm, filter and obtain filter cake, filter cake is placed in baking oven and obtains silicon-containing alumina presoma in 120 DEG C of dry 12h; The presoma obtained is placed in Muffle furnace, in 700 DEG C of roasting 5h, obtains silicon-containing alumina; Form by final catalyst, take 873g cabaltous nitrate hexahydrate obtained aqueous solution, incipient impregnation is in above-mentioned carrier, dry 18h at 95 DEG C, 340 DEG C of roasting 6h, obtained final catalyst, its mole consists of cobaltosic oxide: silica: aluminium oxide=0.1:0.05:1.Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 310 DEG C, 0.3MPa, constant temperature 18h, 600h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 30% (v/v).Reaction condition is: 215 DEG C, 5.0MPa, 2000h
-1(v/v), H
2/ CO (mol)=2.0.Evaluation result: CO conversion ratio 71.3%, CH
4in selective 9.6%, the 720h of being, inactivation rate is 0.21%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 350 DEG C, 0.1MPa, 1000h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 60% (v/v), constant temperature 36h, 600rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 190 DEG C, 3.0MPa, 1300h
-1(v/v), H
2/ CO (v/v)=2.0,700rpm.Evaluation result: CO conversion ratio 72.8%, CH
4in selective 5.8%, the 720h of being, inactivation rate is 0.22%.
Embodiment 5:
Form according to final catalyst, the fuming nitric aicd taking 1928.6g98 (wt.) % is mixed with 80L water solution A, takes 2460g sodium metaaluminate and is mixed with 75L aqueous solution B, then takes 342.5g methyl silicate and be mixed with 8L ethanolic solution C; First solution A and solution B are carried out co-precipitation at water-bath 80 DEG C, A, B volume flow is identical; After treating solution B precipitation, continue solution A and solution C to carry out co-precipitation at 80 DEG C, A, C volume flow is identical; After treating solution A, C precipitation, aging 6h at 85 DEG C; After aging end, spend sodium ion in deionized water to filtrate and be less than 5ppm, filter and obtain filter cake, filter cake is placed in baking oven and obtains silicon-containing alumina presoma in 120 DEG C of dry 10h; The presoma obtained is placed in Muffle furnace, in 750 DEG C of roasting 5h, obtains silicon-containing alumina; Form by final catalyst, take 3273.8g cabaltous nitrate hexahydrate obtained aqueous solution, incipient impregnation is in above-mentioned carrier, dry 16h at 100 DEG C, 380 DEG C of roasting 4h, obtained final catalyst, its mole consists of cobaltosic oxide: silica: aluminium oxide=0.25:0.15:1.
Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 400 DEG C, 0.5MPa, constant temperature 12h, 800h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 10% (v/v).Reaction condition is: 170 DEG C, 2.0MPa, 700h
-1(v/v), H
2/ CO (mol)=2.5.Evaluation result: CO conversion ratio 85.5%, CH
4in selective 7.5%, the 720h of being, inactivation rate is 0.02%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 270 DEG C, 01.2MPa, 500h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 85% (v/v), constant temperature 36h, 700rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 195 DEG C, 1.5MPa, 700h
-1(v/v), H
2/ CO (v/v)=2.2,600rpm.Evaluation result: CO conversion ratio 88.8%, CH
4in selective 6.7%, the 720h of being, inactivation rate is 0.11%.
Embodiment 6:
Form according to final catalyst, the red fuming nitric acid (RFNA) taking 940.3 (wt.) % is mixed with 40L water solution A, takes 820g sodium metaaluminate and is mixed with 37.5L aqueous solution B, then takes 52.1g ethyl orthosilicate and be mixed with 2.5L ethanolic solution C; First solution A and solution B are carried out co-precipitation at water-bath 85 DEG C, A, B volume flow is identical; After treating solution B precipitation, continue solution A and solution C to carry out co-precipitation at 5 DEG C, A, C volume flow is identical; After treating solution A, C precipitation, aging 12h at 90 DEG C; After aging end, spend sodium ion in deionized water to filtrate and be less than 5ppm, filter and obtain filter cake, filter cake is placed in baking oven and obtains silicon-containing alumina presoma in 105 DEG C of dry 12h; The presoma obtained is placed in Muffle furnace, in 800 DEG C of roasting 4h, obtains silicon-containing alumina; Form by final catalyst, take 654.8g cabaltous nitrate hexahydrate obtained aqueous solution, incipient impregnation is in above-mentioned carrier, dry 10h at 120 DEG C, 400 DEG C of roasting 5h, obtained final catalyst, its mole consists of cobaltosic oxide: silica: aluminium oxide=0.15:0.05:1.
Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 450 DEG C, 0.3MPa, constant temperature 12h, 500h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 85% (v/v).Reaction condition is: 230 DEG C, 2.0MPa, 1500h
-1(v/v), H
2/ CO (mol)=2.0.Evaluation result: CO conversion ratio 52.3%, CH
4in selective 10.0%, the 720h of being, inactivation rate is 0.07%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 330 DEG C, 1.2MPa, 800h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 45% (v/v), constant temperature 20h, 700rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 180 DEG C, 2.5MPa, 1200h
-1(v/v), H
2/ CO (v/v)=3.0,750rpm.Evaluation result: CO conversion ratio 77.5%, CH
4in selective 2.5%, the 720h of being, inactivation rate is 0.09%.
Embodiment 7:
Form according to final catalyst, the fuming nitric aicd taking 128.6g98 (wt.) % is mixed with 2L water solution A, takes 164g sodium metaaluminate and is mixed with 1.8L aqueous solution B, then takes 14.6g ethyl orthosilicate and be mixed with 0.2L ethanolic solution C; First solution A and solution B are carried out co-precipitation at water-bath 60 DEG C, A, B volume flow is identical; After treating solution B precipitation, continue solution A and solution C to carry out co-precipitation at 60 DEG C, A, C volume flow is identical; After treating solution A, C precipitation, aging 10h at 70 DEG C; After aging end, spend sodium ion in deionized water to filtrate and be less than 5ppm, filter and obtain filter cake, filter cake is placed in baking oven and obtains silicon-containing alumina presoma in 95 DEG C of dry 20h; The presoma obtained is placed in Muffle furnace, in 500 DEG C of roasting 7h, obtains silicon-containing alumina; Form by final catalyst, take 1746g cabaltous nitrate hexahydrate obtained aqueous solution, incipient impregnation is in above-mentioned carrier, dry 24h at 110 DEG C, 400 DEG C of roasting 4h, obtained final catalyst, its mole consists of cobaltosic oxide: silica: aluminium oxide=0.15:0.07:1.
Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 390 DEG C, 1.5MPa, constant temperature 12h, 900h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 15% (v/v).Reaction condition is: 200 DEG C, 2.4MPa, 1000h
-1(v/v), H
2/ CO (mol)=2.4.Evaluation result: CO conversion ratio 76.8%, CH
4in selective 5.6%, the 720h of being, inactivation rate is 0.01%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 340 DEG C, 0.7MPa, 800h
-1(v/v), hydrogen in nitrogen is adopted, H
2content is 50% (v/v), constant temperature 24h, 700rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 205 DEG C, 2.0MPa, 800h
-1(v/v), H
2/ CO (v/v)=2.6,650rpm.Evaluation result: CO conversion ratio 92.3%, CH
4in selective 2.7%, the 720h of being, inactivation rate is 0.1%.
Claims (5)
1. an alumina load cobalt fischer-tropsch synthetic catalyst, it is characterized in that catalyst is made up of cobaltosic oxide, silica and aluminium oxide, its mole consists of cobaltosic oxide: silica: aluminium oxide=0.1-0.25:0.02-0.2:1.
2. the preparation method of a kind of alumina load cobalt fischer-tropsch synthetic catalyst as claimed in claim 1, is characterized in that comprising the steps:
(1) form by final catalyst, take nitric acid and be mixed with water solution A, take sodium metaaluminate and be mixed with aqueous solution B, take silicon source again and be mixed with ethanolic solution C, solution A volume=B solution volume+C solution volume, wherein, nitric acid: (sodium metaaluminate+silicon source) amount of substance ratio=0.95-1.1:1;
(2) first solution A and solution B are carried out co-precipitation at water-bath 50-85 DEG C, A, B volume flow is identical, and after solution B precipitation, solution A is proceeded co-precipitation with solution C under the water-bath of identical temperature, and A, C volume flow is identical;
(3) after precipitation, aging 2-24h at 70-90 DEG C;
(4) after aging end, spend sodium ion in deionized water to filtrate and be less than 5ppm, then filter and obtain filter cake, filter cake is placed in 90-120 DEG C of dry 10-24h and obtains silicon-aluminum containing presoma, by the presoma that obtains in 400-800 DEG C of roasting 4-10h, obtain silicon-containing alumina carrier;
(5) form by final catalyst, take the water-soluble obtain solution of cobalt nitrate, incipient impregnation is in above-mentioned silicon-containing alumina carrier, and dry 10-24h, 300-400 DEG C of roasting 4-10h at 90-120 DEG C, obtains final catalyst.
3. the preparation method of a kind of alumina load cobalt fischer-tropsch synthetic catalyst as claimed in claim 1, is characterized in that described silicon source is the one of methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate.
4. the preparation method of a kind of alumina load cobalt fischer-tropsch synthetic catalyst as claimed in claim 1, is characterized in that described Fischer-Tropsch synthesis cobalt-based catalyst, carry out reducing, reacting in fixed bed reactors; Reducing condition is: 350-450 DEG C, 0.3-1.5MPa, GHSV=300-1000h
-1, constant temperature 12-24h, adopts hydrogen reduction gas in nitrogen, H
2volume content is 15%-85%; Reaction condition is: 170-230 DEG C, 2.0-5.0Mpa, volume space velocity GHSV=700-2500h
-1, H
2/ CO volume ratio=2.0-2.5.
5. the preparation method of a kind of alumina load cobalt fischer-tropsch synthetic catalyst as claimed in claim 1, is characterized in that described Fischer-Tropsch synthesis cobalt-based catalyst, carries out reducing, reacting in paste state bed reactor; Reducing condition is: 270-320 DEG C, 0.2-1.2MPa, GHSV=500-800h
-1, constant temperature 12-36h, adopts hydrogen reduction gas in nitrogen, H
2volume content is 15%-85%, and rotating speed is 400-800rpm; Reaction condition is: 170-230 DEG C, 2.0-3.0MPa, volume space velocity GHSV=700-2000h
-1, H
2/ CO volume ratio=2.0-3.0, rotating speed is 400-800rpm.
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| CN109289859A (en) * | 2018-10-09 | 2019-02-01 | 沈阳工业大学 | Co3O4/BiFeO3The preparation method of heterojunction photocatalyst and its application in reduction of hexavalent chromium |
| CN109304174A (en) * | 2017-07-26 | 2019-02-05 | 神华集团有限责任公司 | The method for preparing Fischer-Tropsch synthesis cobalt-based catalyst |
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