CN105861024A - Application method of cobalt-based Fischer-Tropsch synthesis catalyst - Google Patents
Application method of cobalt-based Fischer-Tropsch synthesis catalyst Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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Abstract
The invention discloses an application method of a cobalt-based Fischer-Tropsch synthesis catalyst. The method comprises the following steps: filling a fixed bed or slurry bed reactor with a cobalt-based catalyst to perform one-time reduction; carbonizing at the end of the one-time reduction; performing secondary reduction; switching synthesis gas when the temperature drops below 120 DEG C to perform a Fischer-Tropsch synthesis reaction. The method has the advantage of greatly increasing the Fischer-Tropsch synthesis catalytic activity of the cobalt-based catalyst.
Description
Technical field
The present invention relates to the application process of a kind of Co based Fischer-Tropsch synthesis catalyst.
Background technology
Greatly develop and can change coal in China main body energy general layout with coal for Material synthesis oil (CTL) technology, can
Realize the optimization deep exploitation of coal clean utilization.CTL technique has Appropriate application coal resources, alleviates world's energy
Source demand and the contradiction of constructional aspect, produce the advantages such as ultra-clean liquid motor fuels and senior lubricant, oneself
Paid close attention to through widely.At present, countries in the world successfully develop artificial oil technology, such as South Africa Sasol
Fixed fluidized bed (SAS) and slurry bed system (SSPD) technique of company, fixing in addition with Shell company of Holland
Bed SMDS technique, the GTL technique of Syntrolem company, the AGC-21 technique of Exxon company,
The GasCat technique of EnergeInternational company and the iron-based slurry of Zhong Ke artificial oil company of China
Bed process etc..
The hydrogenation activity being mainly characterized by CO of cobalt-base catalyst is high, chain growing ability is strong, be difficult to carbon distribution is poisoned,
Generate low-carbon alkene and the selectivity that oxygenatedchemicals is few, methane generates is low, reaction condition is gentle.Cobalt-based
Catalyst is to H2/ CO ratio, temperature and pressure remolding sensitivity ferrum-based catalyst high, the narrow range of operation, device
Requirement high；Co catalysts must operate at low temperatures and could obtain suitable selectivity, thus causes reaction
Speed declines, and space-time yield is lower than ferrum-based catalyst, limits its production application.Therefore, must take effectively
Means improve catalytic performance so that cobalt-base catalyst is greatly improved its CO hydrogenation activity in operating temperature range,
The production efficiency of cobalt-base catalyst just can be greatly improved, thus realize commercial Application.
Summary of the invention
It is an object of the invention to provide a kind of cobalt-base catalyst F-T synthesis that can be greatly improved and be catalyzed answering of activity
Use method.
The present invention introduces " carbonization " mistake in the applying step " reduction-F-T synthesis " of conventional cobalt-base catalyst
Journey, is " reduction-carbonization-reduction-F-T synthesis " by applying step improvement.So, in reduction rear catalyst
The crystalline phase of simple substance cobalt became mainly by the close pile structure of six side (HCP) from main be made up of face-centred cubic structure (FCC)
Composition, as shown in XRD (X-ray Diffraction) Fig. 1.The simple substance cobalt of the six close pile structures of side compares the center of area
Cubic structure simple substance cobalt has higher F-T synthesis catalysis activity.
The present invention be directed to self-control or patent, literary composition that in final finished catalyst, cobalt exists with oxidation states
The improved application of the cobalt-base catalyst of the open report of other forms such as chapter.
The application process of the present invention is realized by following steps:
(1) cobalt-base catalyst is filled in fixed bed or paste state bed reactor；
(2) once being reduced in fixed bed or paste state bed reactor by cobalt-base catalyst, fixed bed is reduced
Condition is: 280～500 DEG C, 0.1～1.5MPa, GHSV=500～1500h-1, constant temperature 6～48h, use in nitrogen
Hydrogen is reducing gases, H2Volume content is 5%～100%；Slurry bed system reducing condition is: 250～380 DEG C,
0.1～1.0MPa, GHSV=500～1500h-1, constant temperature 6～48h, using hydrogen in nitrogen is reducing gases, H2Volume contains
Amount is 5%～100%, and rotating speed is 400～1500rpm；
(3) once reduction carries out carbonization after terminating, and fixed bed Carbonization Conditions is: 180～350 DEG C, and 0.1～2.0MPa,
GHSV=500～2000h-1, constant temperature 2～12h, use CO gas or CO and H2Gaseous mixture；Slurry bed system carbonization
Condition is: 180～350 DEG C, 0.1～2.0MPa, GHSV=500～2000h-1, constant temperature 2～12h, use CO gas
Or CO and H2Gaseous mixture, rotating speed is 400～1500rpm；
(4) carrying out secondary reduction after carbonization terminates, fixed bed reducing condition is: 250～450 DEG C, 0.1～1.0MPa,
GHSV=500～1500h-1, constant temperature 6～36h, using hydrogen in nitrogen is reducing gases, H2Volume content is 5%～100%；
Slurry bed system reducing condition is: 250～350 DEG C, 0.1～1.0MPa, GHSV=500～1500h-1, constant temperature 6～36h,
Using hydrogen in nitrogen is reducing gases, H2Volume content is 5%～100%, and rotating speed is 400～1500rpm.
(5), after secondary reduction terminates, treating temperature to be down to less than 120 DEG C switching and merging gas, to carry out F-T synthesis anti-
Should, fixed bed reaction condition is: 170～250 DEG C, 1.0～5.0Mpa, GHSV=500～3000h-1,
H2/ CO (v/v)=1.8～3.0；Slurry reactor condition is: 180～240 DEG C, 1.0～5.0MPa,
GHSV=500～3000h-1, H2/ CO (v/v)=2.0～3.0, rotating speed is 400～1500rpm.
Cobalt-base catalyst as above is self-control or reports according to other forms such as patent, article are open
Prepared by method.
Procedure described above (3) CO and H2Gaseous mixture be CO volume content be the gaseous mixture of 50%-95%.
The application process of catalyst of the present invention has the advantage that
(1) application process of the present invention can be greatly improved the F-T synthesis catalysis activity of cobalt-base catalyst；
(2) application process of the present invention is simple to operate, it is not necessary to increase equipment investment, is very easy to realize.
Accompanying drawing explanation
Fig. 1 is the XRD figure that the present invention improves before and after's catalyst.
Detailed description of the invention
Embodiment 1:
Cobalt-base catalyst is prepared: account for by aluminium oxide according to the method for patent ZL 201210160020.6 embodiment 7
89 (wt) % of final catalyst measures boehmite, prepares the Na of 4.5mol/L simultaneously2CO3Solution, two
It is 8.5 that person mixes regulation boehmite serosity pH.Account for 1.0 (wt) % of final catalyst by Barium monoxide, join
Ba (the NO of 1.0mol/L processed3)2Solution, is under agitation simultaneously added dropwise boehmite alkali liquor with above-mentioned alkali liquor
In, keeping 55 DEG C, control endpoint pH 8.5, precipitation terminates rear static burn in 5h, washs, filters to nothing
Impurity.Filter cake is dried at 80 DEG C 8h, then roasting 9h at 450 DEG C, prepares catalyst carrier.
9.9 (wt) % and 0.1 (wt) % that account for final catalyst by cobalt oxide and Palladium monoxide respectively weigh
Co(NO3)2·6H2O and PdCl2, measuring deionized water according to equi-volume impregnating, preparation mixing salt solution is also
Impregnated in above-mentioned carrier, dip time is 9h, is then dried 6h at 85 DEG C, finally 300 DEG C of roastings 10
H, prepares catalyst.Final catalyst quality percentage ratio is Co3O4: BaO:PdO2: Al2O3=9.9:1.0:
0.1:89.
Taking above-mentioned catalyst 20g to fill in fixed bed reactors and once reduce, reducing condition is:
400 DEG C, 1.5MPa, GHSV=1500h-1, constant temperature 6h, use hydrogen reduction gas in nitrogen, H2Content is 10% (v/v)；
Carrying out carbonization after once having reduced, Carbonization Conditions is: 350 DEG C, 0.1MPa, GHSV=500h-1, constant temperature 12h,
Use CO atmosphere；After carbonization terminates, carrying out secondary reduction, secondary reduction condition is: 450 DEG C, 0.1MPa,
GHSV=500h-1, constant temperature 36h, use hydrogen reduction gas in nitrogen, H2Content is 35% (v/v)；Secondary reduction terminates
After, treat that temperature is down to less than 120 DEG C, switching and merging gas carries out Fischer-Tropsch synthesis, and reaction condition is: 220 DEG C,
3.0Mpa, GHSV=800h-1, H2/ CO (v/v)=3.0.Reaction result is shown in Table 1, and with patent ZL
201210160020.6 the Comparative result of embodiment 7.
Embodiment 2:
Cobalt-base catalyst is prepared: by Co:W according to the method for patent ZL 201010539363.4 embodiment 5:
The ratio of Zn=16:43:39 prepares modified zinc oxide-loaded cobalt catalyst.Preparation 1.0M nitric acid zinc salt ethanol
Solution, preparation 1.2M ammonia spirit is as precipitant, at pH=7.5, precipitates zinc salt under the conditions of 50 DEG C, will
Cake Wash, to after neutrality, is dried at 110 DEG C, and roasting 5 hours at 400 DEG C, gained sample broke becomes 200
After powder below mesh stand-by.In setting ratio, prepare ammonium paratungstate aqueous solution, use equi-volume process to institute
Sample load tungsten, through 115 DEG C be dried, roasting 2 hours at 480 DEG C, gained sample broke become 200 mesh with
Under powder after stand-by.Account for 7wt%, Cr by Ni in final catalyst and account for amount and the cobalt of 8%, preparation nickel nitrate,
Chromic nitrate and the mixed solution of cobalt nitrate, use equi-volume process Supported Co, and sample is dried through 100 DEG C, 360 DEG C
Lower roasting i.e. obtains final catalyst in 5 hours.Catalyst consists of
13.88wt%Co/37.30wt%W/33.83wt%Zn/7.0wt%Ni/8.0wt%Cr.
Taking above-mentioned catalyst 20g to fill in fixed bed reactors and once reduce, reducing condition is:
450 DEG C, 1.2MPa, GHSV=1200h-1, constant temperature 12h, use hydrogen reduction gas in nitrogen, H2Content is 30% (v/v)；
Carrying out carbonization after once having reduced, Carbonization Conditions is: 330 DEG C, 0.2MPa, GHSV=700h-1, constant temperature 10h,
Use CO atmosphere；After carbonization terminates, carrying out secondary reduction, secondary reduction condition is: 400 DEG C, 0.3MPa,
GHSV=700h-1, constant temperature 30h, use hydrogen reduction gas in nitrogen, H2Content is 50% (v/v)；Secondary reduction terminates
After, treat that temperature is down to less than 120 DEG C, switching and merging gas carries out Fischer-Tropsch synthesis, and reaction condition is: 230 DEG C,
2.0Mpa, GHSV=1000h-1, H2/ CO (v/v)=2.0.Reaction result is shown in Table 1, and with patent ZL
201010539363.4 the Comparative result of embodiment 5.
Embodiment 3:
Cobalt-base catalyst is prepared: in reactor A according to the method for patent ZL 201210050261.5 embodiment 1
Add 4500g deionized water, after opening stirring motor, add 500g γ-Al2O3Powder stirs, and adds hydrochloric acid and continues
Continuous mixing is until slurry pH value is 5.0.In reactor B, add 5500g deionized water, and add 500g
γ-Al2O3Powder, after being uniformly mixed, by the slurry mix homogeneously of AB two still, stands after being heated to 80 DEG C
1 hour, continuing stirring, add alkaline silica sol, making sial mass ratio is SiO2: Al2O3=20:80, continues
Continue and be uniformly mixed.The zirconyl chloride solution of the 0.1mol/L prepared is slowly added in above-mentioned slurry,
Slurry temperature controls, at 25 DEG C, to use spray drying device spray shaping, the addition of zirconium oxychloride after mix homogeneously
Amount is SiO in slurry2、Al2O3And the 0.5% of zirconium oxychloride gross mass.The granular powder material obtained is existed
650 DEG C of roastings 6 hours, standby after cooling.The configuration cobalt nitrate solution of 1mol/L, 0.5mol/L
Lanthanum nitrate hexahydrate, the nitric acid ruthenium solution of 0.1mol/L and 0.1mol/L rhodium nitrate solution, use infusion process leaching
Carrier prepared by stain, will dipping after catalyst under conditions of 150 DEG C be dried 4 hours, after at 500 DEG C of bars
Under part, roasting obtains catalyst for 5 hours.In catalyst, the quality of cobalt is the 20% of catalyst gross mass, lanthanum
Quality is catalyst gross mass 0.91%, the quality of ruthenium is the 0.05% of catalyst gross mass, the quality of rhodium
For the 0.04% of catalyst gross mass, the quality of zirconium is the 0.2% of catalyst gross mass.
Taking above-mentioned catalyst 20g to fill in paste state bed reactor and once reduce, reducing condition is: 350 DEG C,
1.0MPa, GHSV=1000h-1, constant temperature 18h, 400rpm, use hydrogen reduction gas in nitrogen, H2Content is 40% (v/v)；
Carrying out carbonization after once having reduced, Carbonization Conditions is: 300 DEG C, 0.5MPa, GHSV=800h-1, constant temperature 8h,
600rpm, uses CO atmosphere；After carbonization terminates, carrying out secondary reduction, secondary reduction condition is: 350 DEG C,
0.5MPa, GHSV=800h-1, constant temperature 24h, 800rpm, use hydrogen reduction gas in nitrogen, H2Content is 60% (v/v)；
After secondary reduction terminates, treating that temperature is down to less than 120 DEG C, switching and merging gas carries out Fischer-Tropsch synthesis, reaction
Condition: reaction condition: 215 DEG C, 2.5Mpa, GHSV=2500h-1, H2/ CO (v/v)=2.0,1000rpm.
Reaction result is shown in Table 1, and with the Comparative result of patent ZL201210050261.5 embodiment 1.
Embodiment 4:
Cobalt-base catalyst is prepared: weigh commercially available silicon according to the method for patent ZL 201110184014.X embodiment 4
Glue 30g, dropping distilled water is to just profit, and the volume consuming water is 48ml.Silica gel is put in tube furnace, logical
Enter nitrogen to replace, then pass to ethylene and the gaseous mixture of helium, the volume of ethylene that volume ratio is 3:1
Air speed is 800h-1, it being passed through the time 10 hours, tube furnace temperature is 800 DEG C, and cooling prepares by final catalysis
Agent Nano carbon fibers dimension hplc is the modified silica gel carrier of 10.3%.Based on final catalyst zirconium content 2wt%,
Weigh nitrate trihydrate zirconium 2.82g, add distilled water to 48g, wait to be completely dissolved, add above-mentioned modified carrier
Impregnating in silica gel, aging 3 hours, 80 DEG C are dried 12 hours, roasting 4 hours in 350 DEG C.Press
Whole catalyst molybdenum content 1wt%, weighs ammonium molybdate 0.55g, adds distilled water to 48g, waits to be completely dissolved, add
In sample after above-mentioned load zirconium, aging 3 hours, 80 DEG C were dried 12 hours, under vacuum or
350 DEG C of roastings 4 hours in inert atmosphere.By final catalyst cobalt content 20wt%, cobalt nitrate hexahydrate 29.64g,
Add distilled water to 48g, wait to be completely dissolved, add in the sample after above-mentioned dipping zirconium and molybdenum, aging 3 hours,
80 DEG C are dried 12 hours, and 350 DEG C of roastings 4 hours under vacuum or in inert atmosphere, sieve takes 60-80
Mesh scope, prepares required catalyst.
Taking above-mentioned catalyst 20g to fill in fixed bed reactors and once reduce, reducing condition is: 500 DEG C,
1.0MPa, GHSV=1000h-1, constant temperature 24h, use hydrogen reduction gas in nitrogen, H2Content is 50% (v/v)；One
Secondary reduction carries out carbonization after completing, and Carbonization Conditions is: 270 DEG C, 0.7MPa, GHSV=1000h-1, constant temperature 6h,
Use CO atmosphere；After carbonization terminates, carrying out secondary reduction, secondary reduction condition is: 350 DEG C, 0.7MPa,
GHSV=800h-1, constant temperature 16h, use hydrogen reduction gas in nitrogen, H2Content is 90% (v/v)；Secondary reduction terminates
After, treat that temperature is down to less than 120 DEG C, switching and merging gas carries out Fischer-Tropsch synthesis, reaction condition: 215 DEG C,
2.0Mpa, GHSV=2500h-1, H2/ CO (v/v)=2.0.Reaction result is shown in Table 1, and with patent ZL
201110184014.X the Comparative result of embodiment 4.
Embodiment 5:
Cobalt-base catalyst is prepared: 1g CTAB is dissolved according to the method for patent ZL201110393919.8 embodiment 2
In 30ml 0.05mol/L NaOH aqueous solution, then add 6.74mlTEOS with the speed of 2ml/min, continue
After stirring 60min, stand 8h, then 100 DEG C of aging 72h.After filtering with deionized water and ethanol purge,
Dry 30h at 90 DEG C, with 3 DEG C/min at 650 DEG C of roasting 10h, obtain mesopore-macropore diplopore distribution carrier.Join
Put a certain amount of zeolite precursor liquid solution.By 0.8g sodium aluminate (NaAlO2) and 1g sodium hydroxide (NaOH) be dissolved in
In 50mL tetraethyl ammonium hydroxide (TEAOH 25% aqueous solution), add 10g White Carbon black and be stirred at room temperature
6h, in homogeneously, obtains the precursor solution of zeolite nano-cluster.The zeolite precursor liquid solution configured is taken 3ml
Join in 3g mesopore-macropore carrier obtained above, be subsequently adding 20ml glycerol, then at 200 DEG C
Proceed to from pressing crystallization 12 days in still.Last baking 30h at 90 DEG C, with 3 DEG C/min at 650 DEG C of roasting 10h,
Obtain micropore-mesopore-macropore multi-stage porous silicon carrier.3g carrier is contained the molten of 2.91g cobalt nitrate with being dissolved in 9ml
Liquid carries out incipient impregnation.The catalyst of non-drying after incipient impregnation 20h is put in autoclave,
Again the ammonia spirit of 10% is placed in the middle of the outer and inner lining of beaker, seals and be placed in 60 DEG C of baking ovens reaction
0.5h, naturally cools to room temperature, and 60 DEG C are dried 12h, finally 650 DEG C of roastings in Muffle furnace the most in an oven
10h, obtains required catalyst.
Take in the slurry stirred tank that the above-mentioned catalyst 15ml of more than 100 mesh puts into 1L, be subsequently adding 1000ml
Liquid paraffin, the most once reduces, and reducing condition is: 280 DEG C, 0.7MPa, GHSV=800h-1,
1000rpm, constant temperature 30h, use hydrogen reduction gas in nitrogen, H2Content is 70% (v/v)；After once having reduced
Carrying out carbonization, Carbonization Conditions is: 250 DEG C, 1.0MPa, GHSV=1200h-1, 1000rpm, constant temperature 5h, adopt
Use CO atmosphere；After carbonization terminates, carrying out secondary reduction, secondary reduction condition is: 320 DEG C, 0.7MPa,
GHSV=1000h-1, 1200rpm, constant temperature 18h, use hydrogen reduction gas in nitrogen, H2Content is 10% (v/v)；Two
After secondary reduction terminates, treating that temperature is down to less than 120 DEG C, switching and merging gas carries out Fischer-Tropsch synthesis, reacts bar
Part: 210 DEG C, 1.2Mpa, GHSV=2000h-1, H2/ CO (v/v)=3.0,1400rpm.Reaction result is shown in Table
1, and with the Comparative result of patent ZL 201110393919.8 embodiment 2.
Embodiment 6:
Cobalt-base catalyst is prepared: prepare a certain amount of according to the method for patent ZL 201210486283.6 embodiment 2
The aluminum isopropylate. aqueous solution of 0.1mol/L, and hydrolytic reagent HCl is joined in this solution by 0.01mol/L,
Microwave power is that under 20W, holding temperature is 75 DEG C, and then retention time 90min rubs with aluminum source by sol
You add peptizer HNO than for 0.05:13, microwave power is to be stirred at reflux under 200W to transparent colloidal sol,
Keeping 3h, then aged at room temperature 12h prepares gel.Gel is put in drying baker in 100 DEG C of dry 6h,
Again xerogel is placed in temperature programming stove, 1 DEG C/min of heating rate, roasting 10h at 350 DEG C, prepares and urge
Agent carrier.By Cobalto-cobaltic oxide, copper oxide and ruthenium-oxide account for respectively final catalyst 18 (wt) %,
10 (wt) % and 2% weigh Co (NO3)2·6H2O、Cu(NO3)2·3H2O and RuCl3·3H2O, according to equal-volume
Infusion process measures deionized water, is configured to mixing salt solution and impregnated in above-mentioned carrier, and dip time is 5h,
Then at 100 DEG C, it is dried 6h, finally at 340 DEG C of roasting 5h, 3.5 DEG C/min of heating rate, prepares catalysis
Agent.Final catalyst weight is Co3O4: CuO:RuO2: Al2O3=18:10:2:70.
Take above-mentioned catalyst 20g to carry out in equipped with the 1L slurry bed system stirred tank of 500ml liquid paraffin once also
Former, reducing condition is: 300 DEG C, 0.5MPa, GHSV=700h-1, constant temperature 42h, 1000rpm, use in nitrogen
Hydrogen reduction gas, H2Content is 80% (v/v)；Carrying out carbonization after once having reduced, Carbonization Conditions is: 200 DEG C,
1.5MPa, GHSV=1500h-1, constant temperature 4h, 600rpm, use CO atmosphere；After carbonization terminates, carry out two
Secondary reduction, secondary reduction condition is: 300 DEG C, 0.8MPa, GHSV=1200h-1, constant temperature 12h, 800rpm,
Use hydrogen reduction gas in nitrogen, H2Content is 30% (v/v)；After secondary reduction terminates, treat temperature be down to 120 DEG C with
Under, switching and merging gas carries out Fischer-Tropsch synthesis, reaction condition: 220 DEG C, 3.0Mpa, GHSV=2000h-1,
H2/ CO (v/v)=3.0,1000rpm.Reaction result is shown in Table 1, and real with patent ZL 201210486283.6
Execute the Comparative result of example 2.
Embodiment 7:
Cobalt-base catalyst is prepared: prepare a certain amount of according to the method for patent ZL 201210486282.1 embodiment 1
The aluminum sulfate aqueous solution of lmol/L, and hydrolytic reagent NaOH is joined in this solution by 0.05mol/L,
Keeping bath temperature is 40 DEG C, retention time 180min, accounts for 0.1 (wt) % of final catalyst by oxidation nail
Weigh RuC13·3H2O joins in this solution, is then that 1:1 adds glue by sol and aluminum source mol ratio
Solvent H2SO4, microwave power is to be stirred at reflux under 50W to transparent colloidal sol, keeps 6h, then under room temperature
Aging 24h prepares gel.Gel is put in drying baker in 50 DEG C of dry 2h, then xerogel is placed in program
In intensification microwave oven, 2 DEG C/min of heating rate, roasting 12h at 550 DEG C, prepare catalyst carrier.By four
Oxidation three brill accounts for 16.8 (wt) % of final catalyst and weighs Co (NO3)2·6H2O, according to equi-volume impregnating amount
Removing ionized water, be configured to mixing salt solution and impregnated in above-mentioned carrier, dip time is 10h, then exists
It is dried 24h at 120 DEG C, finally at 450 DEG C of roasting l0h, prepares catalyst.Final catalyst weight is Co3O4:
RuO2: A12O3=16.8:0.2:83.
Take above-mentioned catalyst 20g to carry out in equipped with the 1L slurry bed system stirred tank of 500ml liquid paraffin once also
Former, reducing condition is: 330 DEG C, 0.1MPa, GHSV=500h-1, constant temperature 48h, 400rpm, use in nitrogen
Hydrogen reduction gas, H2Content is 90% (v/v)；Carrying out carbonization after once having reduced, Carbonization Conditions is: 180 DEG C,
2.0MPa, GHSV=2000h-1, constant temperature 2h, 1500rpm, use CO atmosphere；After carbonization terminates, carry out two
Secondary reduction, secondary reduction condition is: 250 DEG C, 1.0MPa, GHSV=1500h-1, constant temperature 6h, 600rpm,
Use hydrogen reduction gas in nitrogen, H2Content is 70% (v/v)；After secondary reduction terminates, treat temperature be down to 120 DEG C with
Under, switching and merging gas carries out Fischer-Tropsch synthesis, reaction condition: 220 DEG C, 3.0Mpa, GHSV=2000h-1,
H2/ CO (v/v)=2.0,800rpm.Reaction result is shown in Table 1, and implements with patent ZL 201210486282.1
The Comparative result of example 1.
Table 1 catalyst reaction result
Claims (2)
1. the application process of a Co based Fischer-Tropsch synthesis catalyst, it is characterised in that comprise the following steps:
(1) cobalt-base catalyst is filled in fixed bed or paste state bed reactor；
(2) once being reduced in fixed bed or paste state bed reactor by cobalt-base catalyst, fixed bed reducing condition is: 280 ~ 500 DEG C, 0.1 ~ 1.5MPa, GHSV=500 ~ 1500h-1, constant temperature 6 ~ 48h, using hydrogen in nitrogen is reducing gases, H2Volume content is 5% ~ 100%；Slurry bed system reducing condition is: 250 ~ 380 DEG C, 0.1 ~ 1.0MPa, GHSV=500 ~ 1500h-1, constant temperature 6 ~ 48h, using hydrogen in nitrogen is reducing gases, H2Volume content is 5% ~ 100%, and rotating speed is 400 ~ 1500rpm；
(3) once reduction carries out carbonization after terminating, and fixed bed Carbonization Conditions is: 180 ~ 350 DEG C, 0.1 ~ 2.0MPa, GHSV=500 ~ 2000h-1, constant temperature 2 ~ 12h, use CO gas or CO and H2Gaseous mixture；Slurry bed system Carbonization Conditions is: 180 ~ 350 DEG C, 0.1 ~ 2.0MPa, GHSV=500 ~ 2000h-1, constant temperature 2 ~ 12h, use CO gas or CO and H2Gaseous mixture, rotating speed is 400 ~ 1500rpm；
(4) carrying out secondary reduction after carbonization terminates, fixed bed reducing condition is: 250 ~ 450 DEG C, 0.1 ~ 1.0MPa, GHSV=500 ~ 1500h-1, constant temperature 6 ~ 36h, using hydrogen in nitrogen is reducing gases, H2Volume content is 5% ~ 100%；Slurry bed system reducing condition is: 250 ~ 350 DEG C, 0.1 ~ 1.0MPa, GHSV=500 ~ 1500h-1, constant temperature 6 ~ 36h, using hydrogen in nitrogen is reducing gases, H2Volume content is 5% ~ 100%, and rotating speed is 400 ~ 1500rpm；
(5) after secondary reduction terminates, treating that temperature is down to less than 120 DEG C switching and merging gas and is carried out Fischer-Tropsch synthesis, fixed bed reaction condition is: 170 ~ 250 DEG C, 1.0 ~ 5.0Mpa, GHSV=500 ~ 3000h-1, H2/ CO volume=1.8 ~ 3.0；Slurry reactor condition is: 180 ~ 240 DEG C, 1.0 ~ 5.0MPa, GHSV=500 ~ 3000h-1, H2/ CO volume ratio=2.0 ~ 3.0, rotating speed is 400 ~ 1500rpm；
The application process of a kind of Co based Fischer-Tropsch synthesis catalyst the most as claimed in claim 1, it is characterised in that described step (3) CO and H2Gaseous mixture be CO volume content be the gaseous mixture of 50%-95%.
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| CN107020154A (en) * | 2017-05-02 | 2017-08-08 | 江南大学 | A kind of preprocess method of the cobalt-base catalyst activity of raising CO Hydrogenation alkene |
| CN108246313A (en) * | 2018-02-01 | 2018-07-06 | 中科合成油内蒙古有限公司 | A kind of high dispersive heavy hydrocarbon fischer-tropsch synthetic catalyst based on carbonization treatment method and preparation method thereof |
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| US20140087936A1 (en) * | 2011-05-30 | 2014-03-27 | Total Raffinage Chimie | Core-shell particles with catalytic activity |
| CN104815701A (en) * | 2015-04-10 | 2015-08-05 | 中国科学院上海高等研究院 | Cobalt-based catalyst reduction processing method used for Fischer-Tropsch synthesis |
| CN105344356A (en) * | 2015-11-19 | 2016-02-24 | 中国科学院山西煤炭化学研究所 | Alumina loaded cobalt catalyst and preparation method and uses in Fischer-Tropsch synthesis |
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| US20140087936A1 (en) * | 2011-05-30 | 2014-03-27 | Total Raffinage Chimie | Core-shell particles with catalytic activity |
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| CN108246313A (en) * | 2018-02-01 | 2018-07-06 | 中科合成油内蒙古有限公司 | A kind of high dispersive heavy hydrocarbon fischer-tropsch synthetic catalyst based on carbonization treatment method and preparation method thereof |
| CN108246313B (en) * | 2018-02-01 | 2021-03-02 | 中科合成油内蒙古有限公司 | High-dispersion heavy hydrocarbon Fischer-Tropsch synthesis catalyst based on carbonization treatment method and preparation method thereof |
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