CN105344356B - A kind of alumina load Co catalysts and preparation method and the application in F- T synthesis - Google Patents
A kind of alumina load Co catalysts and preparation method and the application in F- T synthesis Download PDFInfo
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Abstract
A kind of alumina load Co catalysts are made of cobaltosic oxide, metal promoter oxide and aluminium oxide, and weight group becomes cobaltosic oxide: metal promoter oxide: aluminium oxide=40-80:0.5-5:100.The present invention has the advantages that be used for slurry bed system and fixed bed Fischer-Tropsch synthesis with high activity and stability.
Description
Technical field
The present invention relates to a kind of fischer-tropsch synthetic catalyst and preparation method and applications, specifically a kind of aluminium oxide is negative
Carry Co based Fischer-Tropsch synthesis catalyst and preparation method and the application in F- T synthesis.
Background technique
With the development of world economy, the contradiction between the demand and reserves, distribution of petroleum resources becomes increasingly conspicuous, by new
It is China or even the significant problem that the whole world faces that method, which obtains liquid finished product oil fuel,.Fischer-Tropsch synthesis can be extensive
Produce the clean fuel and other high valuable chemicals of high-quality, and its unstripped gas in ground) it is from a wealth of sources, can by coal,
Natural gas, biomass are obtained by gasification, the Energy Situation for being suitble to China rich in coal and poor in oil.
Cobalt-base catalyst for F- T synthesis generallys use coprecipitation or infusion process is prepared.Wherein it is co-precipitated
For the catalyst that method is prepared since its active component is assembled, the activity for Fischer-Tropsch synthesis is high, while also causing to be catalyzed
Agent is easy to " temperature runaway " in reaction, affects its industrial application；And the catalyst that infusion process is prepared is due to active component
It is uniformly dispersed, carrier thermal conductivity and heat resistance are good, so catalyst reaction process is steady.Silica, aluminium oxide, titanium oxide,
Magnesia, zinc oxide, zirconium oxide, molecular sieve and active carbon etc. can be used as the carrier of impregnating metal cobalt, and wherein aluminium oxide is work
Industryization applies the most common carrier.The specific surface area of aluminium oxide, acid-base property, pore structure, intensity and mutual between metallic cobalt
Effect etc. is all an important factor for influencing the catalytic activity and stability of its load cobalt catalyst, and the influence of central hole structure is most
Greatly, obtaining has suitable pore size and the narrow aluminium oxide of pore size distribution range is the final mesh that this field researcher pursues
Mark.
Summary of the invention
Slurry bed system is used for high activity and stability to solve the above problems, the purpose of the present invention is to provide a kind of
With the alumina load Co catalysts and preparation method of fixed bed Fischer-Tropsch synthesis and in the application of F- T synthesis.
Present invention introduces organic carbon sources as aluminium oxide expanding agent, and guides aluminum precursor in organic carbon source under microwave radiation
In distribution, the final orderly pore size distribution for realizing porous aluminas after roasting, the mass transfer that load cobalt catalyst can be greatly improved passes
The thermal efficiency, and then improve F- T synthesis catalytic performance.
Catalyst of the present invention is made of cobaltosic oxide, metal promoter oxide and aluminium oxide, and weight group becomes four oxygen
Change three cobalts: metal promoter oxide: aluminium oxide=(40-80): (0.5-5): 100.
As described above, metal promoter oxide is strontium oxide strontia, yttrium oxide, niobium oxide, molybdenum oxide.
Catalyst of the present invention is specific to weigh alumina precursor the preparation method is as follows: according to final catalyst composition, prepares
The molten slurry of alumina precursor for being 10-30wt% at solid content, the agitating and heating 0.5-2h at 40-70 DEG C obtain slurries A；It presses
The 10-200wt% that alumina precursor is accounted for according to organic carbon source, weighs organic carbon source, and being configured to solid content is having for 10-30wt%
The molten slurry of machine carbon source, is gelatinized 1-6h at 50-90 DEG C, obtains slurries B；Slurries A and slurries B is mixed, with ultrasonic oscillation 0.5-
3.0h is subsequently placed in micro-wave oven, is taken out after microwave radiation 5-60min in the case where power is 200-800W, true at 60-90 DEG C
Carbon containing alumina precursor is obtained after the dry 12-36h of sky, obtains alumina support after then roasting 4-12h at 450-800 DEG C；
Soluble cobalt and soluble promoter metal salt are dissolved in water incipient impregnation on above-mentioned alumina support, in 60-90 DEG C again
Lower dry 12-24h roasts 2-6h at 300-400 DEG C, obtains final catalyst.
As described above, alumina precursor is one kind of aluminium carbonate ammonia, aluminium hydroxide or boehmite.
As described above, organic carbon source is one kind of starch, cellulose, hemicellulose, plant glycogen, agar-agar or pectin etc..
As described above, soluble cobalt is cobalt nitrate or cobalt acetate.
As described above, soluble promoter metal salt is strontium nitrate, yttrium nitrate, niobium oxalate or ammonium dimolybdate.
Fischer-Tropsch synthesis cobalt-based catalyst as described above can be restored in fixed bed reactors, be reacted；Restore item
Part are as follows: 350-450 DEG C, 0.3-1.5MPa, GHSV=500-1000h-1, constant temperature 12-36h, using hydrogen reduction gas, H in nitrogen2Content
For 15%-85% (v/v)；Reaction condition are as follows: 170-230 DEG C, 2.0-3.0Mpa, GHSV=700-2500h-1, H2/CO(v/v)
=2.0-2.5.
Fischer-Tropsch synthesis cobalt-based catalyst as described above can be restored in paste state bed reactor, be reacted；Restore item
Part are as follows: 270-320 DEG C, 0.2-1.2MPa, GHSV=500-800h-1, constant temperature 12-36h, using hydrogen reduction gas, H in nitrogen2Content
For 15%-85% (v/v), revolving speed 400-800rpm；Reaction condition are as follows: 170-230 DEG C, 2.0-3.0MPa, GHSV=700-
2500h-1, H2/ CO (v/v)=2.0-3.0, revolving speed 400-800rpm.
Catalyst of the present invention has the characteristics that large specific surface area, cellular structure are abundant, mass-and heat-transfer performance is good, is used for Fischer-Tropsch
Synthetic reaction can accelerate reaction rate, improve C5+ selectivity simultaneously reduces methane selectively.
Specific embodiment
Embodiment 1
It is formed according to final catalyst, weighs 117.65g boehmite, being configured to solid content is the quasi- of 10 (wt.) %
The molten slurry of boehmite, the agitating and heating 2.0h at 40 DEG C, obtains slurries A；The 100 of boehmite are accounted for according to plant glycogen
(wt.) % weighs 117.65g plant glycogen, is configured to the molten slurry of plant glycogen that solid content is 10 (wt.) %, pastes at 70 DEG C
Change 3h, obtains slurries B；Slurries A and slurries B is mixed, with ultrasonic oscillation 3.0h, is subsequently placed in micro-wave oven, is in power
It is taken out after microwave radiation 15min under 400W, carbon containing alumina precursor is obtained after being dried in vacuo 36h at 60 DEG C, then in horse
Alumina catalyst support is obtained after not roasting 4h at 800 DEG C in furnace；144.95g cobalt acetate and 2.02g niobium oxalate are dissolved in the bodies such as water again
Product is impregnated in above-mentioned alumina support, the dry 12h at 90 DEG C, roasts 6h at 300 DEG C, obtains final catalyst, final to be catalyzed
Agent weight group becomes Co3O4: Nb2O5: Al2O3=40:0.5:100.
It takes above-mentioned catalyst 5ml not dilute and is loaded in fixed bed reactors (10 × 500mm of Ф), reducing condition are as follows: 450
DEG C, 0.3MPa, constant temperature 12h, 1000h-1(v/v), using hydrogen in nitrogen, H2Content is 15% (v/v),.Reaction condition are as follows: 180 DEG C,
3.0MPa, 700h-1(v/v), H2/ CO (mol)=2.0.Evaluation result: CO conversion ratio 90.6%, CH4Selectivity is 2.3%, C5 +
Selectivity is 93.3%.
Above-mentioned catalyst 10ml is taken to be evaluated in 1L paste state bed reactor, reducing condition is 320 DEG C, 0.2MPa,
700h-1(v/v), using hydrogen in nitrogen, H2Content is 15% (v/v), constant temperature 30h, 750rpm.Room temperature switching is down to after reduction
It is reacted at synthesis gas, reaction condition is 230 DEG C, 2.0MPa, 2500h-1(v/v), H2/ CO (v/v)=3.0,700rpm.It comments
Valence result: CO conversion ratio 41.2%, CH4Selectivity is 15.6%, C5 +Selectivity is 72.2%.
Embodiment 2
It is formed according to final catalyst, weighs 273.55g aluminium carbonate ammonia, be configured to the carbonic acid that solid content is 15 (wt.) %
The molten slurry of aluminium ammonia, the agitating and heating 1.8h at 50 DEG C, obtains slurries A；50 (wt.) % that aluminium carbonate ammonia is accounted for according to starch, weigh
136.78g starch is configured to the molten slurry of starch that solid content is 15 (wt.) %, is gelatinized 6h at 50 DEG C, obtains slurries B；By slurries
A and slurries B mixing, with ultrasonic oscillation 2.5h, is subsequently placed in micro-wave oven, in the case where power is 200W after microwave radiation 60min
It takes out, obtains carbon containing alumina precursor after being dried in vacuo 32h at 65 DEG C, after then roasting 6h at 700 DEG C in Muffle furnace
Obtain alumina catalyst support；155.04g cobalt nitrate and 2.32g ammonium dimolybdate are dissolved in water incipient impregnation in above-mentioned carrying alumina again
Body dries 14h at 85 DEG C, roasts 6h at 320 DEG C, obtains final catalyst, and final catalyst weight group becomes Co3O4:
MoO3: Al2O3=50:1:100.
It takes above-mentioned catalyst 5ml not dilute and is loaded in fixed bed reactors (10 × 500mm of Ф), reducing condition are as follows: 425
DEG C, 0.5MPa, constant temperature 16h, 900h-1(v/v), using hydrogen in nitrogen, H2Content is 25% (v/v),.Reaction condition are as follows: 190 DEG C,
2.8MPa, 1000h-1(v/v), H2/ CO (mol)=2.0.Evaluation result: CO conversion ratio 80.5%, CH4Selectivity is 3.8%, C5 +Selectivity is 88.9%.
Above-mentioned catalyst 10ml is taken to be evaluated in 1L paste state bed reactor, reducing condition is 310 DEG C, 0.4MPa,
500h-1(v/v), using hydrogen in nitrogen, H2Content is 85% (v/v), constant temperature 36h, 450rpm.Room temperature switching is down to after reduction
It is reacted at synthesis gas, reaction condition is 220 DEG C, 2.2MPa, 2200h-1(v/v), H2/ CO (v/v)=2.8,800rpm.It comments
Valence result: CO conversion ratio 54.4%, CH4Selectivity is 11.7%, C5 +Selectivity is 78.5%.
Embodiment 3
It is formed according to final catalyst, weighs 152.94g aluminium hydroxide, be configured to the hydrogen-oxygen that solid content is 20 (wt.) %
Change the molten slurry of aluminium, the agitating and heating 1.5h at 55 DEG C obtains slurries A；10 (wt.) % that aluminium hydroxide is accounted for according to cellulose, weigh
15.29g cellulose is configured to the molten slurry of cellulose that solid content is 17.5 (wt.) %, is gelatinized 5h at 60 DEG C, obtains slurries B；
Slurries A and slurries B is mixed, with ultrasonic oscillation 2.0h, is subsequently placed in micro-wave oven, the microwave radiation in the case where power is 300W
It is taken out after 50min, obtains carbon containing alumina precursor after being dried in vacuo 28h at 70 DEG C, then roasted at 650 DEG C in Muffle furnace
Alumina catalyst support is obtained after burning 6h；199.3g cobalt acetate and 5.09g yttrium nitrate are dissolved in water incipient impregnation in above-mentioned oxidation again
Alumina supporter dries 16h at 80 DEG C, roasts 5h at 340 DEG C, obtains final catalyst, and final catalyst weight group becomes Co3O4:
Y2O3: Al2O3=55:1.5:100.
It takes above-mentioned catalyst 5ml not dilute and is loaded in fixed bed reactors (10 × 500mm of Ф), reducing condition are as follows: 400
DEG C, 0.7MPa, constant temperature 20h, 800h-1(v/v), using hydrogen in nitrogen, H2Content is 35% (v/v),.Reaction condition are as follows: 200 DEG C,
2.6MPa, 1500h-1(v/v), H2/ CO (mol)=2.2.Evaluation result: CO conversion ratio 70.7%, CH4Selectivity is 7.6%, C5 +Selectivity is 84.6%.
Above-mentioned catalyst 10ml is taken to be evaluated in 1L paste state bed reactor, reducing condition is 300 DEG C, 0.5MPa,
600h-1(v/v), using hydrogen in nitrogen, H2Content is 75% (v/v), constant temperature 32h, 550rpm.Room temperature switching is down to after reduction
It is reacted at synthesis gas, reaction condition is 210 DEG C, 2.2MPa, 2000h-1(v/v), H2/ CO (v/v)=2.6,600rpm.It comments
Valence result: CO conversion ratio 58.6%, CH4Selectivity is 7.9%, C5 +Selectivity is 85.5%.
Embodiment 4
It is formed according to final catalyst, weighs 117.65g boehmite, being configured to solid content is the quasi- of 25 (wt.) %
The molten slurry of boehmite, the agitating and heating 1.5h at 60 DEG C, obtains slurries A；The 20 of boehmite are accounted for according to hemicellulose
(wt.) % weighs 23.53g hemicellulose, is configured to the molten slurry of hemicellulose that solid content is 20 (wt.) %, is gelatinized at 65 DEG C
4h obtains slurries B；Slurries A and slurries B is mixed, with ultrasonic oscillation 1.5h, is subsequently placed in micro-wave oven, is in power
It is taken out after microwave radiation 40min under 400W, is dried in vacuo at 75 DEG C and obtains carbon containing alumina precursor afterwards for 24 hours, then in horse
Alumina catalyst support is obtained after not roasting 8h at 600 DEG C in furnace；186.05g cobalt nitrate and 4.08g strontium nitrate are dissolved in the bodies such as water again
Product is impregnated in above-mentioned alumina support, the dry 18h at 80 DEG C, roasts 4h at 350 DEG C, obtains final catalyst, final to be catalyzed
Agent weight group becomes Co3O4: SrO:Al2O3=60:2:100.
It takes above-mentioned catalyst 5ml not dilute and is loaded in fixed bed reactors (10 × 500mm of Ф), reducing condition are as follows: 375
DEG C, 0.8MPa, constant temperature for 24 hours, 750h-1(v/v), using hydrogen in nitrogen, H2Content is 45% (v/v),.Reaction condition are as follows: 210 DEG C,
2.5MPa, 1800h-1(v/v), H2/ CO (mol)=2.2.Evaluation result: CO conversion ratio 56.7%, CH4Selectivity is 9.4%, C5 +Selectivity is 84.7%.
Above-mentioned catalyst 10ml is taken to be evaluated in 1L paste state bed reactor, reducing condition is 290 DEG C, 0.6MPa,
750h-1(v/v), using hydrogen in nitrogen, H2Content be 65% (v/v), constant temperature for 24 hours, 650rpm.Room temperature switching is down to after reduction
It is reacted at synthesis gas, reaction condition is 200 DEG C, 2.3MPa, 1000h-1(v/v), H2/ CO (v/v)=2.2,500rpm.It comments
Valence result: CO conversion ratio 70.0%, CH4Selectivity is 11.1%, C5 +Selectivity is 80.0%.
Embodiment 5
It is formed according to final catalyst, weighs 273.55g aluminium carbonate ammonia, be configured to the carbonic acid that solid content is 30 (wt.) %
The molten slurry of aluminium ammonia, the agitating and heating 1.2h at 60 DEG C, obtains slurries A；150 (wt.) % that aluminium carbonate ammonia is accounted for according to agar-agar, weigh
410.33g agar-agar is configured to the molten slurry of agar-agar that solid content is 22.5 (wt.) %, is gelatinized 3.5h at 70 DEG C, obtains slurries B；It will
Slurries A and slurries B mixing, with ultrasonic oscillation 1.5h, is subsequently placed in micro-wave oven, the microwave radiation in the case where power is 500W
It is taken out after 30min, obtains carbon containing alumina precursor after being dried in vacuo 20h at 80 DEG C, then roasted at 550 DEG C in Muffle furnace
Alumina catalyst support is obtained after burning 10h；235.54g cobalt acetate and 10.17g yttrium nitrate are dissolved in water incipient impregnation in above-mentioned oxygen again
Change alumina supporter, 20h is dried at 85 DEG C, 4h is roasted at 370 DEG C, obtains final catalyst, final catalyst weight group becomes
Co3O4: Y2O3: Al2O3=65:3:100.
It takes above-mentioned catalyst 5ml not dilute and is loaded in fixed bed reactors (10 × 500mm of Ф), reducing condition are as follows: 350
DEG C, 1.0MPa, constant temperature 28h, 600h-1(v/v), using hydrogen in nitrogen, H2Content is 55% (v/v),.Reaction condition are as follows: 220 DEG C,
2.4MPa, 2000h-1(v/v), H2/ CO (mol)=2.3.Evaluation result: CO conversion ratio 42.3%, CH4Selectivity is 12.9%,
C5 +Selectivity is 80.1%.
Above-mentioned catalyst 10ml is taken to be evaluated in 1L paste state bed reactor, reducing condition is 280 DEG C, 0.8MPa,
800h-1(v/v), using hydrogen in nitrogen, H2Content is 55% (v/v), constant temperature 12h, 750rpm.Room temperature switching is down to after reduction
It is reacted at synthesis gas, reaction condition is 200 DEG C, 2.5MPa, 1500h-1(v/v), H2/ CO (v/v)=2.5,400rpm.It comments
Valence result: CO conversion ratio 80.6%, CH4Selectivity is 15.6%, C5 +Selectivity is 72.6%.
Embodiment 6
It is formed according to final catalyst, weighs 152.94g aluminium hydroxide, be configured to the hydrogen that solid content is 17.5 (wt.) %
The molten slurry of aluminium oxide, the agitating and heating 1.0h at 65 DEG C, obtains slurries A；200 (wt.) % that aluminium hydroxide is accounted for according to pectin, weigh
305.88g pectin is configured to the molten slurry of pectin that solid content is 25 (wt.) %, is gelatinized 2h at 80 DEG C, obtains slurries B；By slurries
A and slurries B mixing, with ultrasonic oscillation 1.0h, is subsequently placed in micro-wave oven, in the case where power is 600W after microwave radiation 20min
It takes out, obtains carbon containing alumina precursor after being dried in vacuo 16h at 85 DEG C, after then roasting 10h at 500 DEG C in Muffle furnace
Obtain alumina catalyst support；217.06g cobalt nitrate and 13.56g yttrium nitrate are dissolved in water incipient impregnation in above-mentioned carrying alumina again
Body dries 22h at 85 DEG C, roasts 3h at 380 DEG C, obtains final catalyst, and final catalyst weight group becomes Co3O4:
Y2O3: Al2O3=70:4:100.
It takes above-mentioned catalyst 5ml not dilute and is loaded in fixed bed reactors (10 × 500mm of Ф), reducing condition are as follows: 325
DEG C, 1.2MPa, constant temperature 32h, 550h-1(v/v), using hydrogen in nitrogen, H2Content is 70% (v/v),.Reaction condition are as follows: 225 DEG C,
2.2MPa, 2200h-1(v/v), H2/ CO (mol)=2.4.Evaluation result: CO conversion ratio 51.0%, CH4Selectivity is 13.2%,
C5 +Selectivity is 77.7%.
Above-mentioned catalyst 10ml is taken to be evaluated in 1L paste state bed reactor, reducing condition is 280 DEG C, 1.0MPa,
650h-1(v/v), using hydrogen in nitrogen, H2Content is 45% (v/v), constant temperature 20h, 800rpm.Room temperature switching is down to after reduction
It is reacted at synthesis gas, reaction condition is 185 DEG C, 2.8MPa, 1000h-1(v/v), H2/ CO (v/v)=2.2,550rpm.It comments
Valence result: CO conversion ratio 83.0%, CH4Selectivity is 13.0%, C5 +Selectivity is 75.9%.
Embodiment 7
It is formed according to final catalyst, weighs 117.65g boehmite, being configured to solid content is 22.5 (wt.) %'s
The molten slurry of boehmite, the agitating and heating 0.5h at 70 DEG C, obtains slurries A；The 30 of boehmite are accounted for according to starch
(wt.) % weighs 35.3g starch, is configured to the molten slurry of starch that solid content is 30 (wt.) %, is gelatinized 1h at 90 DEG C, is starched
Liquid B；Slurries A and slurries B is mixed, with ultrasonic oscillation 0.5h, is subsequently placed in micro-wave oven, the microwave spoke in the case where power is 800W
It is taken out after penetrating 10min, carbon containing alumina precursor is obtained after being dried in vacuo 12h at 90 DEG C, then in Muffle furnace at 450 DEG C
Alumina catalyst support is obtained after roasting 12h；248.07g cobalt nitrate and 11.6g ammonium dimolybdate are dissolved in water incipient impregnation in upper again
Alumina support is stated, it is dry at 90 DEG C to roast 2h at 400 DEG C for 24 hours, obtain final catalyst, final catalyst weight composition
For Co3O4: Mo3O:Al2O3=80:5:100.
It takes above-mentioned catalyst 5ml not dilute and is loaded in fixed bed reactors (10 × 500mm of Ф), reducing condition are as follows: 300
DEG C, 1.5MPa, constant temperature 36h, 500h-1(v/v), using hydrogen in nitrogen, H2Content is 85% (v/v),.Reaction condition are as follows: 230 DEG C,
2.0MPa, 2500h-1(v/v), H2/ CO (mol)=2.5.Evaluation result: CO conversion ratio 41.5%, CH4Selectivity is 14.8%,
C5 +Selectivity is 71.2%.
Above-mentioned catalyst 10ml is taken to be evaluated in 1L paste state bed reactor, reducing condition is 270 DEG C, 1.2MPa,
550h-1(v/v), using hydrogen in nitrogen, H2Content is 30% (v/v), constant temperature 16h, 700rpm.Room temperature switching is down to after reduction
It is reacted at synthesis gas, reaction condition is 170 DEG C, 3.0MPa, 700h-1(v/v), H2/ CO (v/v)=2.0,650rpm.It comments
Valence result: CO conversion ratio 88.8%, CH4Selectivity is 3.2%, C5 +Selectivity is 91.1%.
Claims (6)
1. a kind of alumina load Co catalysts, it is characterised in that catalyst is by cobaltosic oxide, metal promoter oxide and oxygen
Change aluminium composition, weight group becomes cobaltosic oxide: metal promoter oxide: aluminium oxide=40-80:0.5-5:100；
The metal promoter oxide is yttrium oxide, niobium oxide or molybdenum oxide；
And it prepares by the following method:
It is formed according to final catalyst, weighs alumina precursor, be configured to the alumina precursor that solid content is 10-30wt%
Molten slurry, the agitating and heating 0.5-2h at 40-70 DEG C, obtains slurries A；The 10- of alumina precursor is accounted for according to organic carbon source
200wt% weighs organic carbon source, is configured to the molten slurry of organic carbon source that solid content is 10-30wt%, is gelatinized 1-6h at 50-90 DEG C,
Obtain slurries B；Slurries A and slurries B is mixed, with ultrasonic oscillation 0.5-3.0h, is subsequently placed in micro-wave oven, is in power
It is taken out after microwave radiation 5-60min under 200-800W, before obtaining carbon containing aluminium oxide after vacuum drying 12-36h at 60-90 DEG C
Body obtains alumina support after then roasting 4-12h at 450-800 DEG C；Again by soluble cobalt and soluble promoter metal
Salt is dissolved in water incipient impregnation on above-mentioned alumina support, drying 12-24h at 60-90 DEG C, roasts 2- at 300-400 DEG C
6h obtains final catalyst；
The alumina precursor is one kind of aluminium carbonate ammonia, aluminium hydroxide or boehmite.
2. a kind of alumina load Co catalysts as described in claim 1, it is characterised in that the organic carbon source is starch, fibre
Tie up one of element, hemicellulose, plant glycogen, agar-agar or pectin.
3. a kind of alumina load Co catalysts as described in claim 1, it is characterised in that the soluble cobalt is nitric acid
Cobalt or cobalt acetate.
4. a kind of alumina load Co catalysts as described in claim 1, it is characterised in that the solubility promoter metal salt
For yttrium nitrate, niobium oxalate or ammonium dimolybdate.
5. a kind of application in F- T synthesis of alumina load Co catalysts according to any one of claims 1-4, special
Sign is to be restored in fixed bed reactors, react；Reducing condition are as follows: 350-450 DEG C, 0.3-1.5MPa, GHSV=500-
1000h-1, constant temperature 12-36h, using hydrogen reduction gas, H in nitrogen2Volume content is 15%-85%；Reaction condition are as follows: 170-230 DEG C,
2.0-3.0Mpa, GHSV=700-2500h-1, H2/ CO volume ratio=2.0-2.5.
6. a kind of application in F- T synthesis of alumina load Co catalysts according to any one of claims 1-4, special
Sign is to be restored in paste state bed reactor, react；Reducing condition are as follows: 270-320 DEG C, 0.2-1.2MPa, GHSV=500-
800h-1, constant temperature 12-36h, using hydrogen reduction gas, H in nitrogen2Volume content is 15%-85%, revolving speed 400-800rpm；React item
Part are as follows: 170-230 DEG C, 2.0-3.0MPa, GHSV=700-2500h-1, H2/ CO volume ratio=2.0-3.0, revolving speed 400-
800rpm。
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| CN103071481B (en) * | 2012-12-29 | 2014-05-21 | 万华化学集团股份有限公司 | Fischer-Tropsch synthesis cobalt-based catalyst and preparation method thereof |
| CN103831115B (en) * | 2013-12-04 | 2016-04-20 | 中国科学院山西煤炭化学研究所 | Cobalt group catalyst synthesized and the method for making of syrup state bed Fischer Tropsch and application |
| CN104162429B (en) * | 2014-08-19 | 2016-04-20 | 中国科学院山西煤炭化学研究所 | A kind of Fischer-Tropsch synthesis cobalt-based catalyst and application thereof |
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