CN104368344B - Co based Fischer-Tropsch synthesis catalyst and its preparation method and application - Google Patents
Co based Fischer-Tropsch synthesis catalyst and its preparation method and application Download PDFInfo
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- CN104368344B CN104368344B CN201410532646.4A CN201410532646A CN104368344B CN 104368344 B CN104368344 B CN 104368344B CN 201410532646 A CN201410532646 A CN 201410532646A CN 104368344 B CN104368344 B CN 104368344B
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Abstract
The invention discloses a kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application, this catalyst includes mesoporous carbon carrier and active component cobalt, and active component cobalt confinement is in mesoporous carbon carrier；The specific surface area of catalyst is 220～400m2/ g, particle diameter is 50～150um；This preparation method uses phenol resin solution to make organic precursor, and active component Co is embedded on mesoporous carbon carrier by recycling sol-gal process；Only need to be passed through noble gas at a certain temperature i.e. can obtain the catalyst containing metallic cobalt to catalyst prepared by the present invention before the use, it is not necessary to hydrogen reducing.The catalyst of the present invention has high reduction degree and high degree of dispersion, good stability concurrently, and active component size is uniform, and carrier aperture is controlled, and diesel oil selectivity is high, meets the paste state bed reactor requirement to catalyst anti-wear performance.
Description
Technical field
The present invention relates to Industrial Catalysis F-T synthesis field, in particular to a kind of co-based fischer-tropsch synthesis
Catalyst and its preparation method and application.
Background technology
F-T synthesis refers to be mainly composed of H by what coal or natural gas prepared2Synthesis with CO
Gas is the course of reaction of synthetic hydrocarbon liquid fuel under catalyst, is to realize ICL for Indirect Coal Liquefaction
One of important step of technology.Fischer-Tropsch synthetic has without sulfur, nitrogen-free, low arene content etc.
Advantage, in more development potentiality today that environmental pollution is the most serious.And develop high activity,
The catalyst of high product selectivity and high stability is one of key technology of F-T synthesis.Fischer-Tropsch
Catalyst used by synthesis has multiple, has the predominantly cobalt-based of essential industry using value at present
Catalyst and ferrum-based catalyst.Research shows, cobalt-base catalyst is because having high conversion per pass
Water gas shift reaction activity with insensitive, is more suited to natural gas base synthesis gas
(H2/ CO=1.6～2.2) conversion；Ferrum-based catalyst is lived because having higher water gas shift reaction
Property, it is more suitable for the coal based synthetic gas (H of low hydrogen-carbon ratio2/ CO=0.5～0.7) conversion.
Co catalysts is high due to heavy hydrocarbon selectivity, and product is prone to be hydrocracked and oxygen-containing chemical combination
The advantages such as thing is less and extensively studied by Chinese scholars.As: CN1084153A discloses one
Planting the preparation method being used for preparing the cobalt-base catalyst of higher hydrocarbon, this catalyst includes Co/Al2O3
The metal insensitive to load capacity with the second, although the catalyst of this patent report has higher
Catalysis activity, but its products distribution still conforms to ASF (Anderson-Shulz-Flory)
Distribution, this makes the selectivity of the gasoline in product and diesel component the lowest, to a certain extent
Constrain Non oil-based route and prepare the extensive application of clean fuel liquid technology；CN1785515A
Disclose the preparation method and application of a kind of catalyst for synthesis gas synthetic mesophase fraction oil,
The method is first by the nitrate aqueous solution containing non-noble metal oxide or Organic Alcohol acid esters
Alcoholic solution is impregnated on mesoporous zircite, then by the nitrate of noble metal or muriatic water-soluble
Liquid and zirconium nitrate are impregnated on the mesoporous zircite carrier having loaded metal-oxide, prepare cobalt-based
Catalyst, the metallic cobalt content of this catalyst is 5.0～35.0wt%, bullion content be 0～
2.0wt%, non-noble metal oxide content is 0～10wt%, and the zirconic content of carrier is
53.0～93.0wt%, when carrier aperture is 12.6nm, C12～C18The choosing of intermediate oil
Selecting property reaches 32.32%, and the noble metal price comparison used by the method is high, uses equal-volume leaching
Stain method, metallic cobalt is easily in the reunion of the surface of molecular sieve, and major part can not enter in the duct of carrier,
Causing the DeGrain of selectivity synthesis, the hydrothermal stability of carrier is poor simultaneously；
Ohtmuka etc. use mesoporous silica molecular sieve in " Catalysis Today, 2004,89,419 "
Supported Co species carry out Fischer-Tropsch synthesis, find that the duct of mesoporous silicon is big and adjustable, and structure is advised
Whole, pore-size distribution is narrow, and this carrier structure is to controlling cobalt granule size and improving product
The diffusion of thing molecule is highly beneficial, and its selective activization can control the distribution of Fischer-Tropsch synthetic,
The selectivity of obtained intermediate oil is higher, but owing to carrier is prone to and cobalt/cobalt oxide shape
Becoming the cobalt species of difficulty reduction, the reduction degree of cobalt is relatively low, and the activity causing catalyst is relatively low, methane
Selectivity > 15%, further, since carrier is different from the interaction strength of cobalt/cobalt oxide,
Cobalt granule can be grown up being dried and reuniting during roasting, limits cobalt species at carrier surface
Dispersibility and the uniformity of granular size, cause end product selectivity synthesis effect fail to understand
Aobvious；CN1297343C discloses a kind of iron/manganese catalyst for F-T synthesis and preparation thereof
Methods and applications, the weight ratio of this catalyst consists of Fe: Mn: Ni: alkaline-earth metal: alkali
Metal: carrier=100: 2～100: 0.01～50: 1～40: 0.1～10: 1～45, this is urged
Agent uses continuous coprecipitation and spray drying technology to prepare, and this catalyst is alive by adding
Property metallic nickel element also adds multiple auxiliary agent to improve the activity of catalyst, selectivity and stability
, although prepared catalyst has certain wear resistance, but what the method was added
Auxiliary agent kind is more, it addition, utilize spray drying technology to improve catalytic mechanical intensity, though
So the improvement of preparation technology can improve catalyst strength to a certain extent, but due to catalyst
The main determining factor of intensity is that catalyst forms, and therefore this route can not be fully solved and ask
Topic.
In sum, existing Co based Fischer-Tropsch synthesis catalyst is primarily present following shortcoming: 1)
Existing artificial oil process route typically must be through heavy hydrocarbon, and then repeated hydrogenation is refined obtains bavin
Oil, technique is tediously long and energy consumption is higher, and product is ASF distribution so that the gasoline in product
The lowest with the selectivity of diesel component；2) dispersion of active phase is the highest, catalysis
Activity also can be improved accordingly, and the least dispersion of cobalt oxide particles is the highest, but granule is more
Little the strongest with the interaction of carrier, more it is not easy to be reduced, therefore, existing co-based fischer-tropsch
Synthetic catalyst is difficult to have high reduction degree and high degree of dispersion concurrently；3) close along with paste state bed reactor
Become the development of oil tech, Co based Fischer-Tropsch synthesis catalyst wear resistance is proposed higher wanting
Asking, the wear resistance of existing Co based Fischer-Tropsch synthesis catalyst is the most preferable, causes catalysis
The loss of agent active component or rupture, makes catalytic performance and service life reduce, and product quality is received
Rate declines, and the catalyst meeting pollution products worn and torn, increase the difficulty that downstream product is refined.
Summary of the invention
Present invention aim to provide a kind of Co based Fischer-Tropsch synthesis catalyst and preparation side thereof
Method and application, this catalyst performance is excellent, it is not necessary to reduce under hydrogen atmosphere, and diesel oil selects
Property high.
For achieving the above object, the technical solution used in the present invention is: a kind of co-based fischer-tropsch synthesis
Catalyst, including mesoporous carbon carrier and active component cobalt, described active component cobalt confinement is in described
In mesoporous carbon carrier；The specific surface area of described catalyst is 220～400m2/ g, particle diameter is
50～150um.
Further, the average pore size of described catalyst is 3～6nm.
Further, the pore volume of described catalyst is 0.2～0.6mL/g.
Further, the content of described active component cobalt accounts for the 1～7% of total catalyst weight, institute
The content giving an account of hole carbon carrier accounts for the 83～98% of total catalyst weight.
Further, outside described active component cobalt, it is coated with mesoporous material shell, described mesoporous
The thickness of material shell is 1～15um.
Further, the content of described mesoporous material shell account for total catalyst weight 1～
10%.
A kind of preparation method of above-mentioned Co based Fischer-Tropsch synthesis catalyst, it comprises the following steps:
1) preparation of organic precursor: the mass content made is the phenolic aldehyde tree of 18～22%
Lipoprotein solution；
2) preparation of catalyst: take surfactant and ethanol, by surfactant for the first time
Add in ethanol solution, and stirring makes surfactant dissolve at a temperature of 35～45 DEG C, then
Be added thereto to cobalt salt solution and step 1) prepare phenol resin solution, obtain mixed solution,
After continuing stirring 30～90min, described mixed solution is at room temperature placed 24～30h, then
At a temperature of 100～120 DEG C, it is dried 20～26h, finally dried mixed solution is transferred to
In carbide furnace, carbonization 5～10h at a temperature of 750～900 DEG C, it is thus achieved that co-based fischer-tropsch synthesis is urged
Agent.
Further, it also includes step 3), second time takes surfactant and ethanol, will
Surfactant is dissolved in ethanol, and adds sym-trimethylbenzene., stirs 5～8h, then adds wherein
Enter inorganic precursor, nitric acid and citric acid, after stirring 12～18h, be then added thereto to step
Rapid 2) Co based Fischer-Tropsch synthesis catalyst prepared by, after continuing stirring 30～60min, by institute
Obtain solution at 50～85 DEG C, be dried 18～26h, obtain solid product；Then by gained solid
Product grind into powder, and by described powder in 450～600 DEG C of roasting temperatures 4～6h, i.e.
The Co based Fischer-Tropsch synthesis catalyst of mesoporous material cladding can be obtained.
Further, described step 2) in, the surfactant taken for the first time and ethanol and phenol
The mass ratio of urea formaldehyde is 1: 8～20: 1～1.8；Cobalt salt solution accounts for catalysis by final cobalt content
The 1 of agent gross weight～7% adds.
Further, described step 3) in, the surfactant taken for the second time and ethanol, all
The mass ratio of trimethylbenzene, inorganic precursor, nitric acid, citric acid and Co based Fischer-Tropsch synthesis catalyst
It is 1: 20～40: 0～3: 2～3: 0.6～1: 0.4～1: 5～10.
Further, described step 3) in, inorganic precursor is sodium metaaluminate or aluminum isopropylate..
Further, described step 2) and step 3) in, the surfactant that takes for the first time and
The surfactant that second time takes is one or more in P123, F127 or F108.P123
For poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer, its molecular formula is
EO20PO70EO20；F127 is the triblock polymer of epoxy ethane-epoxy propane-oxirane,
Its molecular formula is EO106PO70EO106；F108 is epoxy ethane-epoxy propane-oxirane
Triblock polymer, its molecular formula is EO132-PO50-EO132。
Further, described step 2) in, cobalt salt solution be cobalt nitrate solution or cobaltous acetate molten
Liquid.
Further, described step 1) in, the compound method of phenol resin solution is: will
Phenol adds sodium hydroxide after being heated to 40～45 DEG C of dissolvings, after stirring 8～15min, keeps pressure
Power is constant, drips formalin the most wherein, is warming up to 70～95 DEG C of reactions 50～75min,
Wherein, phenol, the mol ratio of sodium hydroxide and formaldehyde is 1: 0.1～0.3: 2～5；Then will
Gained solution regulates solution PH after being cooled to room temperature to neutral and dry at a temperature of 40～60 DEG C
Dry 12～24h, finally it is added thereto to dehydrated alcohol constant volume, prepared mass content is 18～22%
Phenol resin solution.
The application of a kind of above-mentioned Co based Fischer-Tropsch synthesis catalyst, before the use, utilizes indifferent gas
Described Co based Fischer-Tropsch synthesis catalyst is reduced by body, wherein, and the volume of described noble gas
Air speed is 1000～3000h-1, heating rate is 1～3 DEG C/min, and temperature is 480～500 DEG C,
Recovery time is 6～10h, and reduction pressure is 0.1～1.0MPa；Then the cobalt after reduction is utilized
Base fischer-tropsch synthetic catalyst carries out Fischer-Tropsch with synthesis gas for reacting gas in paste state bed reactor
Synthetic reaction, wherein, reaction temperature is 200～250 DEG C, and reaction pressure is 1.0～3.0MPa,
H in synthesis gas2: the volume ratio of CO is 2: 1, and synthesis gas air speed is 1000～3000h-1。
The principle that the present invention prepares Co based Fischer-Tropsch synthesis catalyst is as follows: the present invention uses phenolic aldehyde tree
Active component Co is embedded into Jie as organic precursor, recycling sol-gal process by lipoprotein solution
On the carbon carrier of hole, sol-gal process before the spatial network of mesoporous carbon carrier is formed by active component
It is incorporated on mesoporous carbon carrier, it may be assumed that cobalt introduces during preparation mesoporous carbon, and it is real
Show the catalyst uniform mixing in molecular atoms size, the catalyst prepared in this way
Active component even size distribution, granule is relatively thin, and granule confinement is difficult to reunion, length in the carrier
Big or run off, the pore size of meso-porous carbon material can pass through Control architecture agent (surfactant)
Kind control；One layer of mechanical strength height optionally it is coated with the most again in the outside of catalyst
Mesoporous material shell, mesoporous material shell not only can strengthen the antiwear property of catalyst,
But also be CO and H2Provide Deng reactant and be available for reactant close to catalyst active center
And the good mass-transfer passage of product diffusion abjection, reduce the probability that catalyst is aoxidized by water,
Substantially increase catalysis activity and the stability of catalyst.Carry it addition, meso-porous carbon material is inertia
Body, it and active component will not form the cobalt species of difficult reduction, thus improve going back of metallic cobalt
Former degree.The prepared material with carbon element of the present invention is not general activated carbon, CNT, stone
Ink alkene or amorphous carbon material, but by the network structure cross-linked in a large number and stable SP3Type
C-C key forms so that the graphite flake layer formed after carbonization arranges pell-mell, folding even occurs
Folded, it is wound around and crimps, these untight graphite flake layers have more weak adsorption to oxygen, make
Under certain conditions, meso-porous carbon material can with cobalt oxide generation redox reaction, and
Have certain confinement effect to active component, such catalyst before the use only need to be certain
At a temperature of be passed through noble gas and i.e. can obtain the catalyst containing metallic cobalt, it is not necessary to hydrogen is carried out also
Former.
Compared with prior art, the invention have the advantages that
One, the active component cobalt of the present invention be confinement on carrier be not utilize traditional negative
Load method loads to carrier surface, and the active component particles of prepared catalyst is relatively thin, distribution of sizes
Uniformly, active particle confinement is difficult to reunite, grow up or run off in the carrier.
Its two, the least dispersion of active phase granule is the highest, and the active sites of exposure is also got over
Many, the dispersion of active phase is the highest, and the activity of catalysis also can be improved accordingly, but
It is that granule is the least the strongest with the interaction of carrier, is more not easy to be reduced, therefore, traditional
Co based Fischer-Tropsch synthesis catalyst is difficult to take into account reduction degree and dispersion, and the cobalt prepared by the present invention
Base fischer-tropsch synthetic catalyst has high reduction degree and high degree of dispersion, good stability concurrently, and active component is big
Little uniformly carrier aperture is controlled, and diesel oil selectivity is high.
Its three, the present invention first mesoporous carbon-loaded catalyst outer layer be coated with one layer of mechanical strength
Higher mesoporous material shell, add the abrasion strength resistance of catalyst, it is to avoid catalyst is lived
Property the loss of component or rupture, reduce in the catalytic performance and the service life that improve catalyst, also
Prevent the catalyst contamination product of abrasion, increase the difficulty that downstream product is refined, improve product
Product yield, meets the paste state bed reactor requirement to catalyst anti-wear performance；It addition, mesoporous material
Material shell not only can strengthen the antiwear property of catalyst, but also is CO and H2Deng reaction
Thing provides and is available for reactant and spreads the good of abjection close to catalyst active center and product
Mass transfer channel, reduces the probability that catalyst is aoxidized by water, substantially increases the catalysis of catalyst
Activity and stability.
Its four, the catalyst prepared by the present invention by mesoporous carbon carrier, active component cobalt and mesoporous
Material shell forms, it is not necessary to add auxiliary agent；Only need to be passed through at a certain temperature before the use
Noble gas i.e. can obtain the catalyst containing metallic cobalt, it is not necessary to hydrogen reducing.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, it is simple to becomes apparent from
The present invention is understood on ground, but they do not constitute restriction to the present invention.
Embodiment 1
Catalyst A: include active component Co of 2wt%, remaining is for mesoporous carbon carrier；Activity
The confinement of component Co is in mesoporous carbon carrier.
The preparation method process of catalyst A is as follows:
1) weigh 6g phenol and join in four-hole boiling flask, after dissolving at 40 DEG C, more wherein
After adding the sodium hydroxide stirring 15min that 3.2g mass fraction is 20%, by 15.53g37wt%'s
Formalin joins in constant pressure funnel, then is added dropwise in flask, is warming up to 90 DEG C,
Preferably it is warming up to 70～95 DEG C, is more preferably warming up to 80～90 DEG C, after reaction 50min, by molten
Liquid is transferred in beaker, after being cooled to room temperature, adds nitric acid regulation pH value of solution extremely neutrality, then
In the vacuum drying oven of 40 DEG C, it is dried 24h, removes moisture, obtain phenolic resin, then weigh
Appropriate ethanol solution is added thereto, and being made into mass fraction is 20% phenol resin solution；
2) weigh 8gF127 and join 65.16g (NO Han 1.16gCo3)2·6H2The ethanol solution of O
In, stir at 35 DEG C to F127 and all dissolve, then be added thereto to 12g step 1) phenol for preparing
Urea formaldehyde solution, continues aged at room temperature 30h after stirring 90min, dry in the baking oven of 100 DEG C
Dry 26h, is finally transferred in carbide furnace, 750 DEG C of lower carbonization 10h of nitrogen protection, to obtain final product
Co based Fischer-Tropsch synthesis catalyst catalyst A.
The specific surface area of gained catalyst A is 400m2/ g, average pore size is 3.0nm, and pore volume is
0.28mL/g, mean diameter is 50um.
Catalyst A first carries out pre-reduction before the use on a fixed bed, and reducing gas is pure
Argon, after reduction, transfers to paste state bed reactor under the conditions of anhydrous and oxygen-free by catalyst
In, carry out Fischer-Tropsch synthesis with synthesis gas for reacting gas.Catalyst A is on a fixed bed
Reducing condition is: the volume space velocity of argon is 1000h-1, heating rate is 1 DEG C/min, reduction
Temperature is 490 DEG C, and the recovery time is 8h, and reduction pressure is 1.0MPa；Catalyst A is in slurry
Reaction condition on bed reactor is: reaction temperature is 200 DEG C, and reaction pressure is 3.0MPa,
H in synthesis gas2: CO volume ratio is 2: 1, and synthesis gas air speed is 1000h-1。
Embodiment 2
Catalyst B: include active component Co of 7wt%, remaining is mesoporous carbon carrier and machinery
The mesoporous material shell that intensity is high；The confinement of active component Co is in mesoporous carbon carrier.
The preparation method process of catalyst B is as follows:
1) weigh 6g phenol and join in four-hole boiling flask, after dissolving at 43 DEG C, more wherein
Adding 6.4g mass fraction is the sodium hydroxide of 20%, after stirring 10min, by 25.87g37wt%
Formalin join in constant pressure funnel, then be added dropwise in flask, react at 80 DEG C
After 75min, transfer the solution in beaker, after being cooled to room temperature, add nitre acid-conditioning solution
PH, to neutral, be dried 18h in the vacuum drying oven of 50 DEG C, remove moisture, obtain phenolic aldehyde
Resin, then weigh appropriate ethanol solution and be added thereto, be made into mass fraction be 18～
22%, the phenol resin solution of preferably 20%, wherein, phenol: sodium hydroxide: rubbing of formaldehyde
That ratio preferably 1: 0.1～0.3: 2～5；
2) weigh 8g surfactant F127 and join 164.66g (NO Han 4.66gCo3)2·6H2O
Ethanol solution in, stir at 42 DEG C to F127 and all dissolve, then be added thereto to 14.4g step
Rapid 1) phenol resin solution prepared, continues aged at room temperature 28h after stirring 60min, then at 110
DEG C baking oven in be dried 24h, then be transferred in carbide furnace, 800 DEG C of lower carbonizations of nitrogen protection
8h, obtains primary catalyst, wherein, and surfactant: ethanol: the mass ratio of phenolic resin
It is preferably 1: 8～20: 1～1.8；The preferred cobalt nitrate solution of cobalt salt solution, it is also possible to be acetic acid
Cobalt liquor；
3) weigh 2g surfactant P123 stirring and dissolving in the ethanol of 40g, add 4g
Organic additive sym-trimethylbenzene., stirs 6h, then is added thereto to 4g aluminum isopropylate., 0.6g under room temperature
The nitric acid of 35wt% and the citric acid of 2g, stir 15h under room temperature, then by step 2) prepared
Primary catalyst weigh 10g and join in solution, continue stirring 30min, then solution shifted
In culture dish, in baking oven, at 70 DEG C, it is dried 20h, then gained solid abrasive is become powder,
Roasting 4h at 600 DEG C in Muffle furnace, the co-based fischer-tropsch synthesis obtaining mesoporous material cladding is urged
Agent B, mesoporous material shell is actually meso-porous alumina, wherein, the surface in this step
Activating agent: ethanol: sym-trimethylbenzene.: aluminum isopropylate.: nitric acid: citric acid: primary catalyst
Mass ratio is preferably 1: 20～40: 0～3: 2～3: 0.6～1: 0.4～1: 5～10；Remove
Outside aluminum isopropylate. in the present embodiment, the sodium metaaluminate also can be used as inorganic precursor.
The specific surface area of gained catalyst B is 338m2/ g, average pore size are 4.7nm, pore volume is
0.46mL/g, the thickness of mesoporous material are 15um, mean diameter is 150um.
Catalyst B first carries out pre-reduction before the use on a fixed bed, and reducing gas is pure
N2, after reduction, catalyst is transferred in paste state bed reactor under the conditions of anhydrous and oxygen-free,
Fischer-Tropsch synthesis is carried out for reacting gas with synthesis gas.Catalyst B reduction on a fixed bed
Condition is: N2The volume space velocity of gas is 3000h-1, heating rate is 2 DEG C/min, reduction temperature
Being 500 DEG C, the recovery time is 6h, and reduction pressure is 0.5MPa；Catalyst B is anti-at slurry bed system
The reaction condition on device is answered to be: reaction temperature is 250 DEG C, and reaction pressure is 2.0MPa, synthesis
H in gas2: CO volume ratio is 2:1, and synthesis gas air speed is 3000h-1。
Embodiment 3
Catalyst C: include active component Co of 7wt%, remaining is mesoporous carbon carrier and machinery
The mesoporous material shell that intensity is high；The confinement of active component Co is in mesoporous carbon carrier.
During the preparation method of catalyst C, simply by the step 2 of embodiment 2) in surface
Activating agent F127 changes the mixture of P123 Yu F127 into, and wherein P123 accounts for the matter of surfactant
Amount mark be 25% (surfactant can use one or more in P123, F127 or F108,
Preferably employ P123 and F127), other steps are the most same as in Example 2.
The specific surface area of gained catalyst C is 349m2/ g, average pore size is 5.0nm, and pore volume is
0.51mL/g, the thickness of mesoporous material is 15um, mean diameter is 150um.
Catalyst C first carries out pre-reduction before the use on a fixed bed, and reducing gas is pure
N2, after reduction, catalyst is transferred in paste state bed reactor under the conditions of anhydrous and oxygen-free,
Fischer-Tropsch synthesis is carried out for reacting gas with synthesis gas.Catalyst C reduction on a fixed bed
Condition is: N2The volume space velocity of gas is 3000h-1, heating rate is 2 DEG C/min, reduction temperature
Being 500 DEG C, the recovery time is 6h, and reduction pressure is 0.5MPa；Catalyst C is anti-at slurry bed system
The reaction condition on device is answered to be: reaction temperature is 250 DEG C, and reaction pressure is 2.0MPa, synthesis
H in gas2: CO volume ratio is 2: 1, and synthesis gas air speed is 3000h-1。
Embodiment 4
Catalyst D: include active component Co of 7wt%, remaining is mesoporous carbon carrier and machinery
The mesoporous material shell that intensity is high；The confinement of active component Co is in mesoporous carbon carrier.
The preparation method process of catalyst D is simply by the step 2 of embodiment 2) in surface activity
Agent F127 changes the mixture of P123 with F127 into, and (wherein P123 accounts for the quality of surfactant and divides
Number is 40%), other steps are the most same as in Example 2.
The specific surface area of gained catalyst D is 282m2/ g, average pore size is 4.5nm, and pore volume is
0.33mL/g, the thickness of mesoporous material is 15um, mean diameter is 150um.
Catalyst C first carries out pre-reduction before the use on a fixed bed, and reducing gas is pure
N2, after reduction, catalyst is transferred in paste state bed reactor under the conditions of anhydrous and oxygen-free,
Fischer-Tropsch synthesis is carried out for reacting gas with synthesis gas.Catalyst C reduction on a fixed bed
Condition is: N2The volume space velocity of gas is 3000h-1, heating rate is 2 DEG C/min, reduction temperature
Being 500 DEG C, the recovery time is 6h, and reduction pressure is 0.5MPa；Catalyst C is anti-at slurry bed system
The reaction condition on device is answered to be: reaction temperature is 250 DEG C, and reaction pressure is 2.0MPa, synthesis
H in gas2: CO volume ratio is 2: 1, and synthesis gas air speed is 3000h-1。
Embodiment 5
Catalyst E: include active component Co of 7wt%, remaining be mesoporous carbon carrier and machinery strong
Spend high mesoporous material shell；The confinement of active component Co is in mesoporous carbon carrier.
The preparation method process of catalyst E is simply by the step 2 of embodiment 2) in surface activity
Agent F127 changes the mixture of P123 with F127 into, and (wherein P123 accounts for the quality of surfactant and divides
Number is 50%), other steps are the most same as in Example 2.
The specific surface area of gained catalyst E is 220m2/ g, average pore size is 4.3nm, and pore volume is
0.2mL/g, the thickness of mesoporous material is 15um, mean diameter is 150um.
Catalyst E first carries out pre-reduction before the use on a fixed bed, and reducing gas is pure
N2, after reduction, catalyst is transferred in paste state bed reactor under the conditions of anhydrous and oxygen-free,
Fischer-Tropsch synthesis is carried out for reacting gas with synthesis gas.Catalyst E reduction on a fixed bed
Condition is: N2The volume space velocity of gas is 3000h-1, heating rate is 2 DEG C/min, reduction temperature
Being 500 DEG C, the recovery time is 6h, and reduction pressure is 0.5MPa；Catalyst E is anti-at slurry bed system
The reaction condition on device is answered to be: reaction temperature is 250 DEG C, and reaction pressure is 2.0MPa, synthesis
H in gas2: CO volume ratio is 2: 1, and synthesis gas air speed is 3000h-1。
Embodiment 6
Catalyst F: include active component Co of 5wt%, remaining be mesoporous carbon carrier and machinery strong
Spend high mesoporous material shell；The confinement of active component Co is in mesoporous carbon carrier.
The preparation method process of catalyst F is as follows:
1) weigh 6g phenol and join in four-hole boiling flask, after dissolving at 45 DEG C, more wherein
After adding 1.28g sodium hydroxide stirring 8min, the formalin of 10.35g37wt% is joined
In constant pressure funnel, then it is added dropwise in flask, after reacting 65min at 85 DEG C, solution is turned
Move on in beaker, after being cooled to room temperature, add nitric acid and make solution be neutral, true then at 60 DEG C
Empty drying baker is dried 12h, removes moisture, obtain phenolic resin, then weigh appropriate anhydrous
Ethanol solution is added thereto, and is made into the phenol resin solution that mass fraction is 20%；
2) (wherein P123 accounts for the quality of surfactant to weigh the mixture of 8g F127 Yu P123
Mark is 25%) join 123.21g (NO Han 3.21gCo3)2·6H2In the ethanol solution of O,
The mixture stirred at 45 DEG C to F127 with P123 all dissolves, then is added thereto to 8g step 1)
The phenol resin solution prepared, continues aged at room temperature 24h after stirring 30min, then at 120 DEG C
Baking oven is dried 26h, then is transferred in carbide furnace, 900 DEG C of lower carbonization 5h of nitrogen protection,
Obtain primary catalyst；
3) weigh 1g surfactant P123 stirring and dissolving in the ethanol of 40g, add 3g
Organic additive sym-trimethylbenzene., stirs 8h, then is added thereto to 3g aluminum isopropylate., 1g under room temperature
The nitric acid of 35wt% and the citric acid of 0.4g, stir 18h under room temperature, then by step 2) made
Standby primary catalyst weighs 10g and joins in solution, continues stirring 60min, then is turned by solution
Move on in culture dish, in baking oven, at 85 DEG C, be dried 18h, then gained solid abrasive become powder
End, roasting 5h at 500 DEG C in Muffle furnace, i.e. prepare the co-based fischer-tropsch of mesoporous material cladding
Synthetic catalyst F.
The specific surface area of gained catalyst F is 353m2/ g, average pore size are 6.0nm, pore volume is
0.6mL/g, the thickness of mesoporous material shell are 8.5um, mean diameter is 95um.
Catalyst F first carries out pre-reduction before the use on a fixed bed, and reducing gas is pure
N2, after reduction, catalyst is transferred in paste state bed reactor under the conditions of anhydrous and oxygen-free,
Fischer-Tropsch synthesis is carried out for reacting gas with synthesis gas.Catalyst F reduction on a fixed bed
Condition is: N2The volume space velocity of gas is 1500h-1, heating rate is 3 DEG C/min, reduction temperature
Being 480 DEG C, the recovery time is 10h, and reduction pressure is 0.1MPa；Catalyst F is anti-at slurry bed system
The reaction condition on device is answered to be: reaction temperature is 220 DEG C, and reaction pressure is 1.0MPa, synthesis
H in gas2: CO volume ratio is 2:1, and synthesis gas air speed is 1500h-1。
Embodiment 7
Catalyst G: include active component Co of 5wt%, remaining is mesoporous carbon carrier and machinery
The mesoporous material shell that intensity is high；The confinement of active component Co is in mesoporous carbon carrier.
The preparation method process of catalyst G is as follows:
1) weigh 6g phenol and join in four-hole boiling flask, after dissolving at 45 DEG C, more wherein
After adding 1.28g sodium hydroxide stirring 8min, the formalin of 10.35g37wt% is joined
In constant pressure funnel, then it is added dropwise in flask, after reacting 65min at 85 DEG C, solution is turned
Move on in beaker, after being cooled to room temperature, add nitric acid and make solution be neutral, true then at 60 DEG C
Empty drying baker is dried 12h, removes moisture, obtain phenolic resin, then weigh appropriate anhydrous
Ethanol solution is added thereto, and is made into the solution that mass fraction is 20%.
2) (wherein P123 accounts for the mass fraction of template to weigh the mixture of 8gF127 Yu P123
It is 25%) join 123.21g (NO Han 3.21gCo3)2·6H2In the ethanol solution of O, 45 DEG C
Lower stirring is all dissolved to the mixture of F127 with P123, then is added thereto to 8g step 1) institute
The solution of preparation, continues aged at room temperature 24h after stirring 30min, dry in the baking oven of 120 DEG C
Dry 26h, then be transferred in carbide furnace, 900 DEG C of lower carbonization 5h of nitrogen protection, obtain containing cobalt
Catalyst.
3) weigh 1.5g surfactant P123 stirring and dissolving in the ethanol of 45g, stir under room temperature
Mix 5h, then be added thereto to 3.75g sodium metaaluminate, the nitric acid of 1.05g35wt% and the lemon of 1.2g
Lemon acid, under room temperature stir 12h, then by step 2) prepared by catalyst weigh 12g join
In solution, continue stirring 40min, then transfer the solution in culture dish, in baking oven 50 DEG C
Under be dried 26h, then gained solid abrasive is become powder, roasting at 450 DEG C in Muffle furnace
6h, obtains catalyst G.
The specific surface area of gained catalyst G is 345m2/ g, average pore size are 4.2nm, pore volume is
0.47mL/g, the thickness of mesoporous material shell are 11.1um, mean diameter is 120um.
Catalyst G first carries out pre-reduction before the use on a fixed bed, and reducing gas is pure
N2, after reduction, transfers to catalyst in paste state bed reactor under the conditions of anhydrous and oxygen-free,
Fischer-Tropsch synthesis is carried out for reacting gas with synthesis gas.
Catalyst G reducing condition on a fixed bed is: N2The volume space velocity of gas be 1000～
3000h-1, preferably 1500h-1, heating rate is 1～3 DEG C/min, preferably 3 DEG C/min, reduction
Temperature is 480～500 DEG C, preferably 480 DEG C, and the recovery time is 6～10h, preferably 10h, reduction
Pressure is 0.1～1.0MPa, preferably 0.1MPa；Then the co-based fischer-tropsch synthesis after reduction is utilized
Catalyst carries out Fischer-Tropsch synthesis with synthesis gas for reacting gas in paste state bed reactor, urges
Agent G reaction condition on paste state bed reactor be reaction temperature be 200～250 DEG C, preferably
220 DEG C, reaction pressure is 1.0～3.0MPa, preferably 1.0MPa, H in synthesis gas2: CO body
Long-pending ratio is 2: 1, and synthesis gas air speed is for for 1000～3000h-1, preferably 1500h-1。
Comparative example 1
Catalyst H: include active component Co of 5wt%, remaining is mesoporous carbon carrier and machinery
The mesoporous material shell that intensity is high；Active component Co is supported on mesoporous carbon carrier surface.
The preparation method process of catalyst H is as follows:
1) weigh 6g phenol and join in four-hole boiling flask, after dissolving at 45 DEG C, more wherein
After adding 1.28g sodium hydroxide stirring 8min, the formalin of 10.35g37wt% is joined
In constant pressure funnel, then it is added dropwise in flask, after reacting 65min at 85 DEG C, solution is turned
Move on in beaker, after being cooled to room temperature, add nitric acid regulation pH value of solution the most neutral, then at 60
DEG C vacuum drying oven in be dried 12h, remove moisture, obtain phenolic resin, then weigh appropriate
Ethanol solution be added thereto, be made into the phenol resin solution that mass fraction is 20%；
2) (wherein P123 accounts for the quality of surfactant to weigh the mixture of 8g F127 Yu P123
Mark is 25%) join in 95mL ethanol solution, stir to F127's Yu P123 at 45 DEG C
Mixture all dissolves, then is added thereto to 60g step 1) prepared by phenol resin solution,
Continue aged at room temperature 24h after stirring 30min, in the baking oven of 120 DEG C, be dried 26h, then by it
Transfer in carbide furnace, 900 DEG C of lower carbonization 5h of nitrogen protection, obtain mesoporous carbon carrier；
3) 3.21gCo (NO is weighed3)2·6H2O is dissolved in appropriate distilled water, by obtained
Cobalt nitrate solution incipient impregnation is to step 2) on the mesoporous carbon carrier of gained, aged at room temperature
24h, is dried 20h, roasting 6h at 450 DEG C, obtains the catalyst H containing cobalt at 100 DEG C.
Catalyst H first carries out pre-reduction before the use on a fixed bed, and reducing gas is pure
H2, after reduction, transfers to catalyst in paste state bed reactor under the conditions of anhydrous and oxygen-free,
Fischer-Tropsch synthesis is carried out for reacting gas with synthesis gas.Catalyst H reduction on a fixed bed
Condition is: H2The volume space velocity of gas is 1500h-1, heating rate is 3 DEG C/min, reduction temperature
Being 480 DEG C, the recovery time is 10h, and reduction pressure is 0.1MPa；Catalyst H is anti-at slurry bed system
The reaction condition on device is answered to be: reaction temperature is 220 DEG C, and reaction pressure is 1.0MPa, synthesis
H in gas2: CO volume ratio is 2: 1, and synthesis gas air speed is 1500h-1。
Above-described embodiment 1～7 and comparative example 1 prepared by the reaction-ure conversion-age of catalyst and product
Thing selectivity comparative evaluation's result see table 1:
Table 1
As can be seen from Table 1, catalyst A～G is by active component confinement on carrier, cobalt salt
With carrier generation redox reaction, the least defect may be formed at metal with carrier interface
Position, causes hydrogen benefit stream, so the selectivity of methane is higher；And catalyst H is to utilize tradition
Infusion process active component is loaded on carrier, so the selectivity of methane is relatively low, but
Being that the active force between the catalyst metals and carrier prepared due to infusion process is the most weak, metal holds very much
Easily reuniting at carrier surface, major part can not enter the duct of carrier, and catalyst H is to utilize
Traditional H2Reduce, the Co that the obvious Billy of metal Co particle diameter reduces with noble gas
Particle diameter is big, and dispersion is relatively low, and the selection synthetic effect causing diesel oil is inconspicuous, and, although
The resistance to mass tranfer of catalyst H is less, but in the case of active metallic content is the lowest, urges
The CO conversion ratio of agent H is much lower；Catalyst A is the catalysis of uncoated mesoporous material shell
Agent, resistance to mass tranfer is less, and the conversion ratio of CO is higher, but its wear resistance relatively catalyst B～
G is poor；From catalyst B～E it can be seen that change kind and the content of P123 of template, can
To change the specific surface area of catalyst, pore volume and aperture, when the quality shared by P123 is 25%,
The catalyst C i.e. prepared, the selectivity of its diesel oil is better than catalyst B, D and E；Catalyst
The shell thickness of F is thinner than catalyst C and G, and its resistance to mass tranfer is less, so the conversion ratio of CO
Higher, owing to the aperture of catalyst F is relatively big, the selectivity of its diesel oil the most relatively catalyst C and G is high.
In order to further illustrate the advantage of catalyst of the present invention, the present invention chooses representative
Catalyst A, F and H have carried out long period experiment, and catalyst A, F and H are under long time running
The conversion ratio contrast and experiment such as table 2 below of CO:
Table 2
| Catalyst | T=500h | T=800h | T=1000h | T=1500h | T=2000h |
| A | 60.5% | 58.7% | 54.9% | 50.4% | 46.3% |
| F | 59.6% | 58.1% | 59.1% | 57.8% | 54.7% |
| H | 30.1% | 27.8% | 23.1% | 19.2% | 18.7% |
It addition, catalyst A, F and H diesel oil (C under long time running10-C20) selectivity pair
Than experimental result such as table 3 below:
Table 3
| Catalyst | T=500h | T=800h | T=1000h | T=1500h | T=2000h |
| A | 47.1% | 47.0% | 44.7% | 40.6% | 36.4% |
| F | 57.0% | 56.5% | 55.3% | 54.9% | 53.1% |
| H | 45.7% | 39.3% | 33.1% | 28.7% | 21.9% |
From table 2 and table 3, the catalyst A of uncoated mesoporous lamella is through the most anti-
Should, although its reactivity decreases, but substantially ratio is with prepared by traditional infusion process
The activity of catalyst H is high, the life-span is long, is due to the confinement of active component Co in the carrier, instead
Active component Co difficult drop-off, movement during Ying, grow up and inactivate；Catalyst F is through machine
After the mesoporous material shell cladding that tool intensity is higher, its wear resistance is remarkably reinforced, mesoporous material
Material shell reduces the chance of active component and contact with moisture, and the long period through 2000h is tested
After, the active reduction amplitude of catalyst and be small, the wear resistance of catalyst H is the brightest
Aobvious not as catalyst F, it is when 2000h, and activity has fallen to less than half.
The thickness of the mesoporous material shell of the catalyst prepared by the present invention is preferably 1～15um, is situated between
The content of Porous materials shell preferably comprises the 1～10% of total catalyst weight, containing of active component cobalt
Amount preferably comprises the 1～7% of total catalyst weight, and it is total that the content of mesoporous carbon carrier preferably comprises catalyst
The 83～98% of weight, can be seen that the catalyst dispersion prepared by the present invention from above-described embodiment
Degree height, good stability, active component size is uniform, and catalyst antiwear property is good, uses the longevity
Long and diesel oil the selectivity of life is high, it is adaptable to bubble slurry bed or continuous stirring slurry bed system are anti-
Answer device.
Claims (13)
1. the Co based Fischer-Tropsch synthesis catalyst of a mesoporous material cladding, it is characterised in that: bag
Include mesoporous carbon carrier, active component cobalt, and mesoporous material shell, described active component cobalt confinement
In described mesoporous carbon carrier；The specific surface area of described catalyst is 220～400m2/ g, granule
A diameter of 50～150um；The thickness of described mesoporous material shell is 1～15um.
The Co based Fischer-Tropsch synthesis catalyst of mesoporous material cladding the most according to claim 1,
It is characterized in that: the average pore size of described catalyst is 3～6nm.
The Co based Fischer-Tropsch synthesis catalyst of mesoporous material cladding the most according to claim 1,
It is characterized in that: the pore volume of described catalyst is 0.2～0.6mL/g.
The Co based Fischer-Tropsch synthesis catalyst of mesoporous material cladding the most according to claim 1,
It is characterized in that: the content of described active component cobalt accounts for the 1～7% of total catalyst weight, described
The content of mesoporous carbon carrier accounts for the 83～98% of total catalyst weight.
The Co based Fischer-Tropsch synthesis catalyst of mesoporous material cladding the most according to claim 1,
It is characterized in that: the content of described mesoporous material shell accounts for the 1～10% of total catalyst weight.
6. the Co based Fischer-Tropsch synthesis catalyst of mesoporous material cladding described in a claim 1
Preparation method, it is characterised in that it comprises the following steps:
1) preparation of organic precursor: the mass content made is the phenolic aldehyde tree of 18～22%
Lipoprotein solution；
2) preparation of catalyst: take surfactant and ethanol, by surfactant for the first time
Add in ethanol solution, and stirring makes surfactant dissolve at a temperature of 35～45 DEG C, then
Be added thereto to cobalt salt solution and step 1) prepare phenol resin solution, obtain mixed solution,
After continuing stirring 30～90min, described mixed solution is at room temperature placed 24～30h, then
At a temperature of 100～120 DEG C, it is dried 20～26h, finally dried mixed solution is transferred to
In carbide furnace, carbonization 5～10h at a temperature of 750～900 DEG C, it is thus achieved that co-based fischer-tropsch synthesis is urged
Agent；
3) second time takes surfactant and ethanol, is dissolved in ethanol by surfactant, and
Add sym-trimethylbenzene., stir 5～8h, then be added thereto to inorganic precursor, nitric acid and Fructus Citri Limoniae
Acid, stirring 12～18h after, be then added thereto to step 2) prepared by co-based fischer-tropsch close
Become catalyst, after continuing stirring 30～60min, gained solution is dried at 50～85 DEG C
18～26h, obtain solid product；Then by gained solid product grind into powder, and by institute
State powder in 450～600 DEG C of roasting temperatures 4～6h, the cobalt of mesoporous material cladding can be obtained
Base fischer-tropsch synthetic catalyst.
The Co based Fischer-Tropsch synthesis catalyst that the most according to claim 6, mesoporous material is coated with
Preparation method, it is characterised in that: described step 2) in, the surfactant that takes for the first time and
The mass ratio of ethanol and phenolic resin is 1: 8～20: 1～1.8；Cobalt salt solution is contained by final cobalt
Amount account for total catalyst weight 1～7% add.
The system of the Co based Fischer-Tropsch synthesis catalyst of mesoporous material cladding the most according to claim 6
Preparation Method, it is characterised in that: described step 3) in, the surfactant taken for the second time and second
Alcohol, sym-trimethylbenzene., inorganic precursor, nitric acid, citric acid and Co based Fischer-Tropsch synthesis catalyst
Mass ratio is 1: 20～40: 0～3: 2～3: 0.6～1: 0.4～1: 5～10.
The system of the Co based Fischer-Tropsch synthesis catalyst of mesoporous material cladding the most according to claim 6
Preparation Method, it is characterised in that: described step 3) in, inorganic precursor is sodium metaaluminate or different
Aluminum tripropoxide.
The Co based Fischer-Tropsch synthesis catalyst that the most according to claim 6, mesoporous material is coated with
Preparation method, it is characterised in that: described step 2) and step 3) in, the surface taken for the first time
The surfactant that activating agent and second time take is the one in P123, F127 or F108 or several
Kind.
11. Co based Fischer-Tropsch synthesis catalysts that mesoporous material is coated with according to claim 6
Preparation method, it is characterised in that: described step 2) in, cobalt salt solution be cobalt nitrate solution or
Cobalt acetate solution.
12. Co based Fischer-Tropsch synthesis catalysts that mesoporous material is coated with according to claim 6
Preparation method, it is characterised in that: described step 1) in, the compound method of phenol resin solution
For: add sodium hydroxide after phenol is heated to 40～45 DEG C of dissolvings, after stirring 8～15min,
Keep pressure constant, drip formalin the most wherein, be warming up to 70～95 DEG C reaction 50～
75min, wherein, phenol, the mol ratio of sodium hydroxide and formaldehyde is 1: 0.1～0.3: 2～5；
Then pH value of solution is regulated after gained solution is cooled to room temperature the most neutral, and in 40～60 DEG C of temperature
Degree is lower is dried 12～24h, is finally added thereto to dehydrated alcohol constant volume, and prepared mass content is
18～the phenol resin solution of 22%.
The Co based Fischer-Tropsch synthesis catalyst of mesoporous material cladding described in 13. 1 kinds of claim 1
Application, it is characterised in that: before the use, utilize noble gas that described mesoporous material is coated with
Co based Fischer-Tropsch synthesis catalyst reduce, wherein, the volume space velocity of described noble gas is
1000～3000h-1, heating rate is 1～3 DEG C/min, and temperature is 480～500 DEG C, during reduction
Between be 6～10h, reduction pressure be 0.1～1.0MPa；Then the mesoporous material after reduction is utilized
Cladding Co based Fischer-Tropsch synthesis catalyst in paste state bed reactor with synthesis gas as reacting gas
Carrying out Fischer-Tropsch synthesis, wherein, reaction temperature is 200～250 DEG C, reaction pressure be 1.0～
3.0MPa, H in synthesis gas2: the volume ratio of CO is 2:1, synthesis gas air speed be 1000～
3000h-1。
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| CN107754793B (en) * | 2017-11-23 | 2020-04-17 | 中科合成油技术有限公司 | Porous carbon loaded Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
| CN110560069B (en) * | 2018-06-06 | 2023-01-31 | 国家能源投资集团有限责任公司 | Iron-based Fischer-Tropsch synthesis catalyst and preparation method thereof |
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| CN112892567B (en) * | 2019-12-03 | 2022-04-12 | 中国科学院大连化学物理研究所 | Cobalt-based Fischer-Tropsch synthesis catalyst, preparation and application |
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| CN113786851A (en) * | 2021-08-18 | 2021-12-14 | 中科博格(湖州)环保科技有限公司 | Hydrodeoxygenation catalyst and preparation method and application thereof |
| CN114100649B (en) * | 2021-12-01 | 2023-09-29 | 浙江工业大学 | High-heat-conductivity Fe-based catalyst, preparation method thereof and application thereof in Fischer-Tropsch synthesis reaction |
| CN115555023A (en) * | 2022-09-28 | 2023-01-03 | 西安工程大学 | Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas |
| CN115724420B (en) * | 2022-09-30 | 2024-04-16 | 深蓝汽车科技有限公司 | Bimetal doped porous carbon material, preparation method, application and coated anode material and preparation method thereof |
| CN115869956A (en) * | 2022-12-15 | 2023-03-31 | 西安交通大学 | FeCo with a domain-restricted structure 2 O 4 Photoelectrocatalysis thin film material, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013133651A1 (en) * | 2012-03-07 | 2013-09-12 | 한국화학연구원 | Catalyst activation method for fischer-tropsch synthesis |
| CN103506145A (en) * | 2012-06-25 | 2014-01-15 | 韩国energy技术研究院 | Preparation of iron/carbon nanocomposite catalysts for fischer-tropsch synthesis reaction and related production of liquid hydrocarbons |
| CN103920496A (en) * | 2014-04-22 | 2014-07-16 | 武汉凯迪工程技术研究总院有限公司 | Mesoporous material coated cobalt-based fischer-tropsch synthesis catalyst and preparation method thereof |
-
2014
- 2014-10-09 CN CN201410532646.4A patent/CN104368344B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013133651A1 (en) * | 2012-03-07 | 2013-09-12 | 한국화학연구원 | Catalyst activation method for fischer-tropsch synthesis |
| CN103506145A (en) * | 2012-06-25 | 2014-01-15 | 韩国energy技术研究院 | Preparation of iron/carbon nanocomposite catalysts for fischer-tropsch synthesis reaction and related production of liquid hydrocarbons |
| CN103920496A (en) * | 2014-04-22 | 2014-07-16 | 武汉凯迪工程技术研究总院有限公司 | Mesoporous material coated cobalt-based fischer-tropsch synthesis catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "A General Chelate-Assisted Co-Assembly to Metallic Nanoparticles-Incorporated Ordered Mesoporous Carbon Catalysts for Fischer-Tropsch Synthesis";Zhenkun Sun et al;《J. Am. Chem. Soc.》;20120928;第134卷;第2.2节，第17656页第3段，Table 1，Figure 4 * |
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