CN105772022B - Superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst and preparation method thereof - Google Patents

Superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst and preparation method thereof Download PDF

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CN105772022B
CN105772022B CN201610172162.2A CN201610172162A CN105772022B CN 105772022 B CN105772022 B CN 105772022B CN 201610172162 A CN201610172162 A CN 201610172162A CN 105772022 B CN105772022 B CN 105772022B
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platinum
cobalt
fischer
dispersiveness
superelevation
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海国良
宋德臣
刘倩倩
郑申棵
詹晓东
张岩丰
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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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
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • 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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Abstract

The object of the present invention is to provide a kind of superelevation dispersiveness cobalt platinum base fischer-tropsch synthetic catalyst and preparation method thereof.The superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst, including alumina support, active constituent cobalt and coagent platinum, the percentage by weight of each component is alumina support 53~84.5%, active constituent cobalt 15~45%, coagent platinum 0.5~2.0% in the catalyst；Also, the particle diameter of the alumina support is 0.6~2.4mm, specific surface area is 140~300m2/g；The particle diameter of the active constituent cobalt and coagent platinum is 3~20nm, they are loaded on the alumina support in the form of finely dispersed nanocluster.The catalyst activity is high, moreover, its preparation method process conditions are simple, cobalt keeps highly uniform high degree of dispersion state in obtained product catalyst.

Description

Superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst and preparation method thereof
Technical field
The invention belongs to F- T synthesis technical field, in particular to a kind of superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst and Its preparation method.
Background technology
F- T synthesis (Fischer-Tropsch synthesis) refers to that carbon monoxide is hydrogenated under catalyst action The process of hydro carbons and oxygenatedchemicals, the reaction are to be invented by German Franz Fischer and Hans Tropsch nineteen twenty-five , it is mainly used in and produces chemical products with high added-value, such as gasoline, diesel oil, paraffin by raw material of synthesis gas.Its product is free of Sulphur, nitrogen, no aromatic hydrocarbons, without metallic pollution is a kind of very clean energy.The progress of the F- T synthesis valency with oil always Lattice are closely related, with increasingly deficient and environmental requirement increasingly harsh, the F- T synthesis in past 20 years of petroleum resources The great interest of people is caused again, and using carbonaceous materials such as coal, natural gas, biomass as raw material, carbon monoxide is first made And hydrogen, then clear gusoline is obtained through Fischer-Tropsch synthesis, become a more feasible energy substitution route.
The metals such as iron, cobalt, nickel, ruthenium all have a F- T synthesis catalytic activity, wherein supported cobalt catalysts with its high activity, The advantages such as high stability, relatively low water-gas activity of conversion, become most potential research object.Supported cobalt catalysts are commonly used Carrier have：Titanium oxide, silica, aluminium oxide, molecular sieve, activated carbon etc., are also related to de- with carbon nanotubes, zirconium oxide, illiteracy Research of the porous materials such as soil as carrier.Influence of the carrier to fischer-tropsch synthetic catalyst performance is more complicated, the surface of carrier Acidity, pore passage structure, peptizaiton etc. may all influence whether the reactivity and selectivity of product of catalyst.It is documented By influencing catalyst performance to Vehicle element, but usually, grain size on active specy and the influence such as scattered be not Greatly；Also have to certain references disclose and promote the scattered of cobalt by adding oxides additive, strengthen the reduction of cobalt, improve catalyst Stability etc., but these auxiliary agents are often expensive, are additionally, since active specy and difficult reduzate is formd with carrier Kind, the reduction effect and unobvious of oxides additive.
Research shows, controls dispersion degree, reduction degree and load capacity of cobalt active specy etc. to realize that catalytic action is expected Property and effect.One of key problem of Co catalysts research is how to suppress the generation of methane under the premise of high activity. The dispersion degree of methane selectively and cobalt active specy has much relations, catalyst prepared by traditional infusion process, active component point Scattered uneven, with the rise of load capacity, especially when load capacity is more than 20wt%, cobalt active specy is easily reunited, point Dissipate uneven so as to have impact on the overall performance of catalyst.It is one that the dispersion degree of cobalt active component how is improved in high load amount A important research topic.United States Patent (USP) US5545674 by spraying process inorganic oxide carrier surface spraying cobalt metal Active surface, while the auxiliary agents such as zirconium, rhenium, hafnium, cerium, uranium, thorium are added, to improve the activity of catalyst, power of regeneration and liquid hydrocarbon Selectivity, catalyst inactivation is slow, high containing the cut oil yield of linear alkanes and alkene, but catalyst prepared by this method Active specy skewness, catalyst activity selectively improve limited.The Chinese invention of Application No. 200810055104.7 Patent discloses a kind of Fischer-Tropsch synthesis cobalt-based catalyst i.e. preparation method and application, which is prepared for cobalt using infusion process Be supported on the catalyst of different carriers, CO conversion can reach 82%, methane selectively between 7~13.4%, but It is that activation of catalyst prepared by this method is difficult, it is necessary to very long recovery time.As it can be seen that use infusion process or improvement above Catalyst prepared by infusion process, can not all avoid active component from disperseing non-uniform drawback, activation of catalyst is difficult, in activearm Catalyst performance is bad when dividing load capacity higher.Li Zezhuan etc. exists《Chemistry of fuel journal》2011,39 (1), what 54-58 was delivered 《Co/SiO prepared by thermal decomposition method2Fischer-Tropsch synthesis performance on catalyst》In one text, prepared by heat resolve cobalt nitrate Finely dispersed Co based Fischer-Tropsch synthesis catalyst, but the cobalt nitrate disclosed in this article decompose after metal oxide and carrier Interaction Force is stronger, is unfavorable for the reduction of metal, so as to have impact on the performance of catalyst.
The content of the invention
The object of the present invention is to provide a kind of superelevation dispersiveness cobalt platinum base fischer-tropsch synthetic catalyst and preparation method thereof.This is urged Agent activity is high, moreover, its preparation method process conditions are simple, cobalt keeps highly uniform height in obtained product catalyst Dispersity.
To achieve the above object, superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst of the invention, including alumina support, work Property component cobalt and coagent platinum, it is characterized in that：The percentage by weight of each component is carrying alumina in the catalyst Body 53~84.5%, active constituent cobalt 15~45%, coagent platinum 0.5~2.0%；Also, the grain of the alumina support Footpath is 0.6~2.4mm, specific surface area is 140~300m2/g；The particle diameter of the active constituent cobalt and coagent platinum for 3~ 20nm, they load on the alumina support in the form of finely dispersed nanocluster.
Preferably, the particle diameter of the alumina support be 0.8~2.2mm, specific surface area be 160~280m2/g；The work The particle diameter of property component cobalt and coagent platinum is 5~18nm.
It is further preferred that the particle diameter of the alumina support is 1.0~2.0mm, specific surface area is 180~260m2/g； The particle diameter of the active constituent cobalt and coagent platinum is 8~15nm.
The preparation method of the superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst, it comprises the following steps：
1) alumina support is subjected to calcination process under conditions of 350~600 DEG C, acquisition particle diameter is 0.6~2.4mm, Specific surface area is 140~300m2The superfines of/g；
2) platinum salt is weighed for the 0.5~2.0% of whole finished catalyst weight by the load capacity of coagent platinum, and be dissolved in In acetonitrile solvent, the alumina support for accounting for whole finished catalyst weight 53~84.5% is then added, is sufficiently stirred, then be added dropwise Mole is the NaOH solution of 6~12 times of platinum salt, and 10~24h is reacted under conditions of 20~35 DEG C；
3) 45~70 DEG C and then by reactant are heated to, then enough formaldehyde is added dropwise and carries out reduction reaction, reaction time 10 ~24h, maintains pH=11~12 by the way that lye is added dropwise in reaction process, after completion of the reaction cleans reduzate, dries, obtain The alumina support of Supported Pt Nanoparticles；
4) cobalt salt is weighed for the 15~45% of whole finished catalyst weight put into high pressure by the load capacity of active constituent cobalt In reaction kettle, then the alumina support of gained Supported Pt Nanoparticles is put into, add organic solvent to autoclave and be filled with hydrogen and one The mixed gas of carbonoxide, is forced into 8~15Mpa, is warming up to 120~180 DEG C, 1~12h of stirring reaction；
5) room temperature, pressure release are then cooled to, the hydrogen and carbon monoxide being filled with nitrogen discharge autoclave；
6) nitrogen atmosphere is kept, autoclave is slowly heated to 100~200 DEG C, stirring 8~36h of reaction, makes activity Component cobalt and coagent platinum disperse load on the alumina support in the form of nanocluster, you can obtain superelevation dispersiveness cobalt platinum Fischer-tropsch synthetic catalyst.
Any of following scheme can be as the optimal technical scheme of preparation method of the present invention：
In the step 1), calcination process temperature is 400~500 DEG C, roasting time is 2~4h.
In the step 2), platinum salt is platinum acetate or platinum nitrate.
In the step 2), the mole that NaOH solution is added dropwise is 8~10 times of platinum salt.
In the step 2), the weight percent concentration that NaOH solution is added dropwise is 3~10%.
In the step 2), the weight percent concentration that NaOH solution is added dropwise is 5~8%.
In the step 3), reactant is heated to 55~65 DEG C.
In the step 3), the molar ratio that formaldehyde and platinum salt is added dropwise is 30~80 ︰ 1.
In the step 3), the molar ratio that formaldehyde and platinum salt is added dropwise is 40~50 ︰ 1.
In the step 3), it is the NaOH solution that weight percent concentration is 10~25% that lye, which is added dropwise,.
In the step 3), reduzate is cleaned by the way of deionized water and ethanol are alternately rinsed several times, so Reduzate is dried under conditions of 70~90 DEG C again afterwards.
In the step 4), used organic solvent is one kind or its combination in ethanol, n-octyl alcohol or isopropanol.
In the step 4), cobalt salt is cobalt carbonate.
In the step 4), in the mixed gas of hydrogen and carbon monoxide, the volume ratio of hydrogen and carbon monoxide for 1 ︰ 1~ 3。
In the preparation method of the Co based Fischer-Tropsch synthesis catalyst of the present invention in each step technological parameter effect and its restriction Principle is as follows：
By the way that alumina support is carried out the roasting pretreatment at 350~600 DEG C in step 1), useless catalysis can be effectively removed Moisture and remaining organic substance impurity in agent, obtain the aluminium oxide of high-purity.
Step 2) selects metal platinum salt according to coagent platinum load capacity for the ratio of whole catalyst weight 0.5~2%, Platinum salt adds pretreated alumina support and sodium hydroxide solution after being dissolved in acetonitrile solvent, and platinum salt is in alkaline environment Under react to obtain platinic hydroxide precipitation, reaction equation is：
2NaOH+Pt2+—Pt(OH)2+2Na+
In reaction, it is that 6~12 ︰ 1 are to be conducive to platinum salt fully to convert to control the molar ratio of added NaOH and platinum salt, and is had Enough sodium hydroxides maintain reaction environment into alkalescence.
Step 3) is at a certain temperature, to add reducing agent formaldehyde, react to obtain simple substance platinum, the list of generation with platinic hydroxide Matter platinum is attached to alumina carrier surface, and reaction equation is：
2Pt(OH)2+2HCHO+2OH-→2Pt+2HCOO-+4H2O
In this step, it is 30~80 ︰ 1 preferably to control the molar ratio of formaldehyde and platinum salt, is conducive to the abundant conversion of platinum salt.
Step 4), cobalt is selected according to the load capacity of active component cobalt for the ratio of whole finished catalyst weight 15~45% Salt, adds the alumina support and organic solvent for being attached to simple substance platinum, cobalt salt is fully dissolved, under hydrogen and heating condition Cobalt salt and reaction of carbon monoxide generation hydroxyl cobalt, are supported on alumina carrier surface.Reaction equation is：
2CoCO3+8CO+2H2→Co2(CO)8+CO2+2H2O
In step 6), the carbonyl cobalt of alumina carrier surface is supported at 100~200 DEG C, fully reacts 8~36h, is decomposed Cobalt simple substance is generated, attachment is on the alumina support.Reaction equation is：
Co2(CO)8→2Co+8CO。
For the present invention by selecting suitable aluminium oxide to be used as carrier, first supporting Pt salt, is made Pt/Al2O3Catalyst, this is urged Agent can reduce the reaction pressure of carbonyl cobalt synthesis, while improve carbonyl cobalt yield；Then, then using cobalt salt as cobalt source, in Pt/ Al2O3Under the conditions of existing, cobalt carbonate generates carbonyl cobalt with reaction of carbon monoxide at high temperature under high pressure；Carbonyl cobalt is in certain condition Under oxidation aluminium surface gradually resolve into metallic cobalt, metallic cobalt is tightly combined with carrier, and be in homogeneously dispersed state can obtain To the Co based Fischer-Tropsch synthesis catalyst of high dispersive.In the present invention, Pt plays dual effect, you can as carbonyl cobalt synthesis Catalyst, also can be as the auxiliary agent of fischer-tropsch synthetic catalyst, and after carbonyl cobalt is synthesized, Pt is not required to separate with carbonyl cobalt, directly Heat resolve in situ is connected in reaction kettle, makes metallic cobalt uniform load in Pt/Al2O3On.Meanwhile the presence of platinum is also beneficial to cobalt Metal disperses, and can promote the catalytic activity of cobalt.
Catalyst prepared by method using the present invention, active component high degree of dispersion, cobalt are formed on carrier and are uniformly dispersed Nanocluster, be not easy to reunite in high load amount, active sites are more, can more give full play to the catalysis effectiveness of cobalt metal, While keeping high activity of catalyst, the selectivity of methane can be effectively reduced.
The advantageous effects of the present invention are：
1) i.e. decomposition in situ when heated after carbonyl cobalt synthesizes on the alumina support, carrier is slowly deposited on metallic state On, finely dispersed nanocluster is formed, even if can still keep highly uniform high degree of dispersion state when cobalt loading is very high, Avoid the crystal grain agglomeration of high load amount；
2) in preparation process, first in supported on carriers platinum, platinum is both the catalyst of synthesizing carbonyl cobalt, can also be used as Fischer-Tropsch to close Into the auxiliary agent of catalyst, it is i.e. usable that separation is not required to after carbonyl cobalt synthesis；
3) the Co catalysts active sites of obtained high degree of dispersion are more, can more give full play to the catalysis effectiveness of metallic cobalt, While high activity of catalyst is kept, the selectivity of methane can be effectively reduced.
4) catalyst, since active specy is directly supported on carrier with metallic state, reduces using aluminium oxide as carrier Catalyst reduction step, greatly improves the activity of catalyst, and can effectively reduce methane selectively.
Embodiment
The preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention is made further specifically with reference to specific embodiment It is bright.
Embodiment 1
A kind of superelevation dispersiveness cobalt platinum base fischer-tropsch synthetic catalyst A, including alumina support, active constituent cobalt and activity help Agent platinum, in catalyst A the percentage by weight of each component be alumina support 84%, active constituent cobalt 15%, coagent platinum 1%；Also, the particle diameter of the alumina support is 0.6~2.4mm, specific surface area 196m2/g；The active constituent cobalt and The particle diameter of coagent platinum is 3~20nm, they are loaded on the alumina support in the form of finely dispersed nanocluster.
Synthesize the Co based Fischer-Tropsch synthesis catalyst A of high dispersive：
1) alumina support 20g is placed in Muffle furnace at 450 DEG C and roasts 4h, acquisition particle diameter is 0.6~2.4mm, ratio Surface area is 196m2The superfines of/g；
2) on the basis of 10g carriers, acetic acid is weighed for the 1% of whole catalyst weight by coagent metal platinum load capacity Platinum 0.191g, and be dissolved in 30ml acetonitrile solvents, stirring adds the oxygen for accounting for whole finished catalyst weight 84% to being completely dissolved Change alumina supporter 10g, stir 5h, then be added dropwise weight percent concentration 5% the common 3.12g of NaOH solution (mole be platinum acetate 6 Times), 12h is reacted at 30 DEG C；
3) under 45 DEG C of water bath conditions, 2ml formaldehyde reduction reaction 12h are added dropwise, platinic hydroxide is reduced to obtain simple substance platinum, instead Should during by the way that NaOH solution maintenance system pH that weight percent concentration is 15% is added dropwise 11~12, with warm deionization Water and ethanol alternately punching 5 times, and obtain the alumina support of load simple substance platinum in 80 DEG C of drying；
4) cobalt carbonate 3.602g is weighed for the 15% of whole catalyst weight put into high pressure by active component cobalt loading In reaction kettle, the alumina support of load simple substance platinum obtained by step 3) is added, it is molten to add 150ml n-octyl alcohols in autoclave Solution, the oxygen in kettle is excluded with hydrogen inflation three times, then hydrogen and Co mixed gas (hydrogen are filled with into autoclave The volume ratio of gas and carbon monoxide is 1 ︰ 1) 8Mpa is forced into, 180 DEG C are warming up to, stirring reaction 8h；
5) it is cooled to room temperature, pressure release and the hydrogen and carbon monoxide that are filled with nitrogen discharge reaction kettle；
6) 200 DEG C are slowly heated to after keeping nitrogen atmosphere, stirring reaction 24h carbonyl cobalts decompose to obtain simple substance cobalt, so Active constituent cobalt and coagent platinum disperse load on the alumina support in the form of nanocluster, you can obtain superelevation dispersiveness Cobalt platinum fischer-tropsch synthetic catalyst A.
Specific calculating process is as follows in the present embodiment：
If the quality of platinum is x, the quality of cobalt is y, on the basis of 10g carriers, then：
1)2)
Two formula simultaneous can obtain：X=0.119, y=1.785
According to the molal weight 313.13g/mol of platinum acetate, the molal weight 118.93g/mol of cobalt carbonate, can calculate Go out, it is necessary to platinum acetate 0.191g, cobalt carbonate 3.602g.
Embodiment 2
A kind of superelevation dispersiveness cobalt platinum base fischer-tropsch synthetic catalyst B, including alumina support, active constituent cobalt and activity help Agent platinum, in catalyst B the percentage by weight of each component be alumina support 69%, active constituent cobalt 30%, coagent platinum 1%；Also, the particle diameter of the alumina support is 0.6~2.4mm, specific surface area 213m2/g；The active constituent cobalt and The particle diameter of coagent platinum is 3~20nm, they are loaded on the alumina support in the form of finely dispersed nanocluster.
Synthesize the Co based Fischer-Tropsch synthesis catalyst B of high dispersive：
1) commercial alumina carrier 30 as one kind g is placed in Muffle furnace at 500 DEG C and roasts 3h, obtain particle diameter for 0.6~ 1.8mm, specific surface area 196m2The superfines of/g；
2) on the basis of 20g carriers, platinum acetate is weighed for 1% by metal platinum load capacity in final catalyst weight 0.466g, and be dissolved in 30ml acetonitrile solvents, stirring adds the oxidation for accounting for whole finished catalyst weight 69% to being completely dissolved Alumina supporter 20g, stirs 5h, and the common 6.24g of NaOH solution that weight percent concentration is 5% is added dropwise, and (mole is the 6 of platinum acetate Times), 12h is reacted at room temperature；
3) under 45 DEG C of water bath conditions, 4ml formaldehyde reduction reactions are added dropwise, are 15% by the way that weight percent concentration is added dropwise NaOH solution maintenance system pH is 11~12；One night of aging at room temperature, with warm deionized water and ethanol alternately punching 5 times, 80 DEG C Dry 12h, obtains the carrier of load simple substance platinum；
4) cobalt carbonate 17.548g is weighed by cobalt loading for whole catalyst weight 30% to add in autoclave, then Add the load obtained by step 3) platinum aluminium oxide, the dissolving of 150ml n-octyl alcohols is added in autoclave, three are inflated with hydrogen Oxygen in secondary exclusion kettle, hydrogen and carbon monoxide are by 1 ︰, 1 volume ratio punching presses to 12Mpa, 160 DEG C of reaction 8h；
5) it is cooled to room temperature, the hydrogen and carbon monoxide being filled with nitrogen discharge reaction kettle；
6) 200 DEG C are slowly heated to after keeping nitrogen atmosphere, stirring reaction 24h, carbonyl cobalt decomposes to obtain simple substance cobalt, so Active constituent cobalt and coagent platinum disperse load on the alumina support in the form of nanocluster, you can obtain the cobalt of high dispersive Base fischer-tropsch synthetic catalyst B.
Embodiment 3
A kind of superelevation dispersiveness cobalt platinum base fischer-tropsch synthetic catalyst C, including alumina support, active constituent cobalt and activity help Agent platinum, in catalyst C the percentage by weight of each component be alumina support 54%, active constituent cobalt 45%, coagent platinum 1%；Also, the particle diameter of the alumina support is 1.3~2.1mm, specific surface area 157m2/g；The active constituent cobalt and The particle diameter of coagent platinum is 3~20nm, they are loaded on the alumina support in the form of finely dispersed nanocluster.
Synthesize the Co based Fischer-Tropsch synthesis catalyst C of high dispersive：
1) alumina support 20g is placed in Muffle furnace at 550 DEG C and roasts 2.5h, acquisition particle diameter for 1.3~2.1mm, Specific surface area is 157m2The superfines of/g；
2) on the basis of 5g carriers, platinum acetate 0.149g is weighed for 1% by metal platinum load capacity in whole catalyst weight, And be dissolved in 30ml acetonitrile solvents, stirring adds the alumina support for accounting for whole finished catalyst weight 54% to being completely dissolved 5g, stirs 6h, and the common 1.56g of NaOH solution (mole is 6 times of platinum acetate) that weight percent concentration is 5%, room temperature is added dropwise Lower one night of aging；
3) under 65 DEG C of water bath conditions, 1ml formaldehyde reduction reaction 20h are added dropwise, by the way that weight percent concentration is added dropwise as 15% NaOH solution maintenance system pH 11~12, one night of aging at room temperature, with warm deionized water and ethanol alternately punching 5 times, 80 DEG C dry 12h, obtains the carrier of Supported Pt Nanoparticles；
4) cobalt carbonate 8.408g is weighed for whole catalyst weight 45% to add in autoclave, then add by cobalt loading Enter the aluminium oxide that platinum was loaded obtained by step 3), the dissolving of 150ml isopropanols is added in autoclave, arranged three times with hydrogen inflation Except the oxygen in kettle, hydrogen and carbon monoxide are re-filled with, hydrogen and carbon monoxide are by 1 ︰, 2 volume ratio punching presses to 15Mpa, 120 DEG C React 8h；
5) it is cooled to room temperature, discharges hydrogen and carbon monoxide in reaction kettle, be filled with nitrogen；
6) 180 DEG C are heated to after keeping nitrogen atmosphere, stirring reaction 12h carbonyl cobalts decompose to obtain simple substance cobalt, So active constituent cobalt and coagent platinum disperse load on the alumina support in the form of nanocluster, you can obtain high dispersive Co based Fischer-Tropsch synthesis catalyst C.
Embodiment 4
A kind of superelevation dispersiveness cobalt platinum base fischer-tropsch synthetic catalyst D, including alumina support, active constituent cobalt and activity help Agent platinum, in catalyst D the percentage by weight of each component be alumina support 68%, active constituent cobalt 30%, coagent platinum 2%；Also, the particle diameter of the alumina support is 0.6~2.3mm, specific surface area 195m2/g；The active constituent cobalt and The particle diameter of coagent platinum is 3~20nm, they are loaded on the alumina support in the form of finely dispersed nanocluster.
Synthesize the Co based Fischer-Tropsch synthesis catalyst D of high dispersive：
1) alumina support 30g is placed in Muffle furnace at 450 DEG C and roasts 3h, acquisition particle diameter is 0.6~2.3mm, ratio Surface area is 195m2The superfines of/g；
2) on the basis of 20g carriers, platinum acetate is weighed for 2% by metal platinum load capacity in whole catalyst weight 0.944g, and be dissolved in 30ml acetonitrile solvents, stirring adds the oxidation for accounting for whole finished catalyst weight 68% to being completely dissolved Alumina supporter 20g, stirs 5h, and the common 21g of NaOH solution (mole is 10 times of platinum acetate) of weight percent concentration 5% is added dropwise, One night of aging at room temperature；
3) under 65 DEG C of water bath conditions, the reduction of 5ml formaldehyde is added dropwise, is tieed up by the NaOH solution that weight percent concentration is 15% System pH is held 11~12, at room temperature one night of aging；With alternately punching 5 times of warm deionized water and ethanol, 80 DEG C of dry 12h, obtain To the carrier of Supported Pt Nanoparticles；
4) by active component cobalt loading for whole catalyst weight 30% weigh cobalt carbonate 17.804g add high pressure it is anti- Answer in kettle, add the aluminium oxide that platinum was loaded obtained by step 3), the dissolving of 150ml ethanol is added in autoclave, uses hydrogen Inflation excludes the oxygen in kettle, hydrogen and carbon monoxide by same ratio punching press to 12Mpa, 160 DEG C of reaction 8h three times；
5) it is cooled to room temperature, discharges hydrogen and carbon monoxide in reaction kettle, be filled with nitrogen；
6) 150 DEG C are slowly heated to after keeping nitrogen atmosphere, stirring reaction 12h carbonyl cobalts decompose to obtain simple substance cobalt, so Active constituent cobalt and coagent platinum disperse load on the alumina support in the form of nanocluster, you can obtain the cobalt of high dispersive Base fischer-tropsch synthetic catalyst D.
Embodiment 5
A kind of superelevation dispersiveness cobalt platinum base fischer-tropsch synthetic catalyst E, including alumina support, active constituent cobalt and activity help Agent platinum, in catalyst E the percentage by weight of each component be alumina support 68%, active constituent cobalt 30%, coagent platinum 2%；Also, the particle diameter of the alumina support is 0.8~2.1mm, specific surface area 277m2/g；The active constituent cobalt and The particle diameter of coagent platinum is 3~20nm, they are loaded on the alumina support in the form of finely dispersed nanocluster.
Synthesize the Co based Fischer-Tropsch synthesis catalyst E of high dispersive：
1) alumina support 20g is placed in Muffle furnace at 450 DEG C and roasts 3h, acquisition particle diameter is 0.8~2.1mm, ratio Surface area is 277m2The superfines of/g；
2) on the basis of 10g carriers, platinum acetate is weighed for 2% by metal platinum load capacity in whole catalyst weight 0.472g, and be dissolved in 30ml acetonitrile solvents, stirring adds the oxidation for accounting for whole finished catalyst weight 68% to being completely dissolved Alumina supporter 10g, stirs 5h, and the common 10.5g of NaOH solution that weight percent concentration is 5% is added dropwise, and (mole is the 10 of platinum acetate Times), one night of aging at room temperature；
3) under 65 DEG C of water bath conditions, the reduction of 2.5ml formaldehyde is added dropwise, platinic hydroxide is reduced to obtain simple substance platinum, reaction process It is middle that NaOH solution maintenance system pH that weight percent concentration is 15% is added dropwise 11~12, one night of aging at room temperature, with warm Deionized water and ethanol alternately punching 5 times, 80 DEG C of dry 12h, obtain the alumina support of Supported Pt Nanoparticles；
4) cobalt carbonate 8.903g is weighed for the 30% of whole catalyst weight by active component cobalt loading, it is anti-adds high pressure Answer in kettle, add the aluminium oxide that platinum was loaded obtained by step 3), the dissolving of 150ml n-octyl alcohols is added in autoclave, uses hydrogen Gas inflation excludes the oxygen in kettle three times, by hydrogen and carbon monoxide by same ratio punching press to 12Mpa, 160 DEG C of reaction 8h；
5) it is cooled to room temperature, discharges hydrogen and carbon monoxide in reaction kettle, be filled with nitrogen；
6) 200 DEG C are slowly heated to after keeping nitrogen atmosphere, stirring reaction 12h carbonyl cobalts decompose to obtain simple substance cobalt, so Active constituent cobalt and coagent platinum disperse load on the alumina support in the form of nanocluster, you can obtain superelevation dispersiveness Cobalt platinum fischer-tropsch synthetic catalyst E.
Embodiment 6
A kind of superelevation dispersiveness cobalt platinum base fischer-tropsch synthetic catalyst F, including alumina support, active constituent cobalt and activity help Agent platinum, in catalyst F the percentage by weight of each component be alumina support 83%, active constituent cobalt 15%, coagent platinum 2%；Also, the particle diameter of the alumina support is 0.7~2.3mm, specific surface area 175m2/g；The active constituent cobalt and The particle diameter of coagent platinum is 3~20nm, they are loaded on the alumina support in the form of finely dispersed nanocluster.
Synthesize the Co based Fischer-Tropsch synthesis catalyst F of high dispersive：
1) alumina support 20g is placed in Muffle furnace at 450 DEG C and roasts 3h, acquisition particle diameter is 0.7~2.3mm, ratio Surface area is 175m2The superfines of/g；
2) on the basis of 5g carriers, platinum acetate 1.94g is weighed for 2% by metal platinum load capacity in whole catalyst weight, And be dissolved in 30ml acetonitrile solvents, stirring adds the alumina support for accounting for whole finished catalyst weight 83% to being completely dissolved 5g, stirs 5h, and the common 5.25g of NaOH solution (mole is 10 times of platinum acetate) that weight percent concentration is 5%, room temperature is added dropwise Lower one night of aging；
3) under 65 DEG C of water bath conditions, the reduction of 1.25ml formaldehyde is added dropwise, platinic hydroxide is reduced to obtain simple substance platinum, reaction process In by the way that NaOH solution maintenance system pH that weight percent concentration is 15% is added dropwise 11~12, one night of aging at room temperature；With Warm alternately punching 5 times of deionized water and ethanol, 80 DEG C of dry 12h；
4) cobalt carbonate 1.823g is weighed for the 15% of whole catalyst weight by active component cobalt loading, it is anti-adds high pressure Answer in kettle, add the aluminium oxide that platinum was loaded obtained by step 3), the dissolving of 150ml ethanol is added in autoclave, uses hydrogen Inflation excludes the oxygen in kettle three times, by hydrogen and carbon monoxide by same ratio punching press to 8Mpa, 180 DEG C of reaction 8h；
5) it is cooled to room temperature, discharges hydrogen and carbon monoxide in reaction kettle, be filled with nitrogen；
6) 150 DEG C are slowly heated to after keeping nitrogen atmosphere, stirring reaction 36h, carbonyl cobalt decomposes to obtain simple substance cobalt, so Active constituent cobalt and coagent platinum disperse load on the alumina support in the form of nanocluster, you can obtain superelevation dispersiveness Cobalt platinum fischer-tropsch synthetic catalyst F.
Embodiment 7
A kind of superelevation dispersiveness cobalt platinum base fischer-tropsch synthetic catalyst G, including alumina support, active constituent cobalt and activity help Agent platinum, in catalyst G the percentage by weight of each component be alumina support 69.5%, active constituent cobalt 30%, coagent platinum 0.5%；Also, the particle diameter of the alumina support is 0.8~1.7mm, specific surface area 295m2/g；The active constituent cobalt Particle diameter with coagent platinum is 3~20nm, they are loaded on the alumina support in the form of finely dispersed nanocluster.
Synthesize the Co based Fischer-Tropsch synthesis catalyst G of high dispersive：
1) alumina support 20g is placed in Muffle furnace at 450 DEG C and roasts 3h, acquisition particle diameter is 0.8~1.7mm, ratio Surface area is 295m2The superfines of/g；
2) on the basis of 10g carriers, platinum acetate is weighed for 0.5% by metal platinum load capacity in whole catalyst weight 0.116g, and be dissolved in 30ml acetonitrile solvents, stirring adds the oxygen for accounting for whole finished catalyst weight 69.5% to being completely dissolved Change alumina supporter 10g, stir 5h, the common 3.2g of NaOH solution that weight percent concentration is 5% is added dropwise, and (mole is the 12 of platinum acetate Times), one night of aging at room temperature；
3) under 55 DEG C of water bath conditions, the reduction of 1.6ml formaldehyde is added dropwise, passes through the NaOH solution that weight percent concentration is 15% Maintenance system pH is 11~12, one night of aging at room temperature, with warm deionized water and ethanol alternately punching 5 times, 80 DEG C of dry 12h；
4) cobalt carbonate 8.712g is weighed for the 30% of whole catalyst weight by active component cobalt loading, it is anti-adds high pressure Answer in kettle, add the aluminium oxide that 10g loaded platinum, the dissolving of 150ml ethanol is added in autoclave, with hydrogen inflation three times The oxygen in kettle is excluded, by hydrogen and carbon monoxide by same ratio punching press to 12Mpa, 160 DEG C of reaction 8h；
5) it is cooled to room temperature, discharges hydrogen and carbon monoxide in reaction kettle, be filled with nitrogen；
6) 150 DEG C are heated to, stirring reaction 36h carbonyl cobalts decompose to obtain simple substance cobalt, and such active constituent cobalt and activity help Agent platinum disperses load on the alumina support in the form of nanocluster, you can obtains the Co based Fischer-Tropsch synthesis catalyst G of high dispersive.
Embodiment 8
A kind of superelevation dispersiveness cobalt platinum base fischer-tropsch synthetic catalyst H, including alumina support, active constituent cobalt and activity help Agent platinum, in catalyst H the percentage by weight of each component be alumina support 54.5%, active constituent cobalt 45%, coagent platinum 0.5%；Also, the particle diameter of the alumina support is 1.1~2.4mm, specific surface area 187m2/g；The active constituent cobalt Particle diameter with coagent platinum is 3~20nm, they are loaded on the alumina support in the form of finely dispersed nanocluster.
Synthesize the Co based Fischer-Tropsch synthesis catalyst H of high dispersive：
1) alumina support 20g is placed in Muffle furnace at 450 DEG C and roasts 3h, acquisition particle diameter is 1.1~2.4mm, ratio Surface area is 187m2The superfines of/g；
2) on the basis of 10g carriers, platinum acetate is weighed for 0.5% by metal platinum load capacity in whole catalyst weight 0.147g, and be dissolved in 30ml acetonitrile solvents, stirring adds the oxygen for accounting for whole finished catalyst weight 54.5% to being completely dissolved Change alumina supporter 10g, stir 5h, the common 3.2g of NaOH solution that weight percent concentration is 5% is added dropwise, and (mole is the 12 of platinum acetate Times), one night of aging at room temperature；
3) under 55 DEG C of water bath conditions, the reduction of 1.6ml formaldehyde is added dropwise, passes through the NaOH solution that weight percent concentration is 15% Maintenance system pH is 11~12, one night of aging at room temperature, with warm deionized water and ethanol alternately punching 5 times, 80 DEG C of dry 12h, Obtain the carrier of load simple substance platinum；
4) cobalt carbonate 16.709g is weighed for whole catalyst weight 45% by cobalt loading, added in autoclave, then The aluminium oxide that 10g loaded platinum is added, the dissolving of 150ml isopropanols is added in autoclave, kettle is excluded three times with hydrogen inflation In oxygen, by hydrogen and carbon monoxide by same ratio punching press to 12Mpa, 160 DEG C of reaction 8h；
5) it is cooled to room temperature, discharges hydrogen and carbon monoxide in reaction kettle, be filled with nitrogen；
6) 180 DEG C are heated to, stirring reaction 24h carbonyl cobalts decompose to obtain simple substance cobalt, and such active constituent cobalt and activity help Agent platinum disperses load on the alumina support in the form of nanocluster, you can obtains the Co based Fischer-Tropsch synthesis catalyst H of high dispersive.
Embodiment 9
A kind of superelevation dispersiveness cobalt platinum base fischer-tropsch synthetic catalyst I, including alumina support, active constituent cobalt and activity help Agent platinum, in catalyst I the percentage by weight of each component be alumina support 69.5%, active constituent cobalt 30%, coagent platinum 0.5%；Also, the particle diameter of the alumina support is 0.7~2.1mm, specific surface area 275m2/g；The active constituent cobalt Particle diameter with coagent platinum is 3~20nm, they are loaded on the alumina support in the form of finely dispersed nanocluster.
Synthesize the Co based Fischer-Tropsch synthesis catalyst I of high dispersive：
1) alumina support 30g is placed in Muffle furnace at 450 DEG C and roasts 3h, acquisition particle diameter is 0.7~2.1mm, ratio Surface area is 275m2The superfines of/g；
2) on the basis of 20g carriers, platinum acetate is weighed for 0.5% by metal platinum load capacity in whole catalyst weight 0.232g, and be dissolved in 30ml acetonitrile solvents, stirring adds the oxygen for accounting for whole finished catalyst weight 69.5% to being completely dissolved Change alumina supporter 20g, stir 5h, the common 3.2g of NaOH solution that weight percent concentration is 5% is added dropwise, and (mole is the 12 of platinum acetate Times), one night of aging at room temperature；
3) under 55 DEG C of water bath conditions, the reduction of 3.2ml formaldehyde is added dropwise, passes through the NaOH solution that weight percent concentration is 15% Maintenance system pH is 11~12, one night of aging at room temperature, with warm deionized water and ethanol alternately punching 5 times, 80 DEG C of dry 12h, Obtain the carrier of load simple substance platinum；
4) cobalt carbonate 17.424g is weighed for whole catalyst weight 30% by cobalt loading, added in autoclave, then Add the load obtained by step 3) platinum alumina support, the dissolving of 150ml isopropanols is added in autoclave, is filled with hydrogen Gas excludes the oxygen in kettle three times, by hydrogen and carbon monoxide by same ratio punching press to 15Mpa, reacts 8h；
5) it is cooled to room temperature, discharges hydrogen and carbon monoxide in reaction kettle, be filled with nitrogen；
6) 100 DEG C are heated to, stirring reaction 36h carbonyl cobalts decompose to obtain simple substance cobalt, and such active constituent cobalt and activity help Agent platinum disperses load on the alumina support in the form of nanocluster, you can obtains the Co based Fischer-Tropsch synthesis catalyst I of high dispersive.
Reactant obtained by above-described embodiment is all transferred in the glove box of deoxygenation, is filtered under nitrogen atmosphere, incited somebody to action Catalyst after filter pours into starvation in the container equipped with wax oil and preserves, spare.
Comparative example 1
The catalyst J prepared with typical impregnation method：
10g alumina supports are taken, deionized water are added dropwise to first profit, the quality for consuming water is 11g.
Platinum acetate 0.191g is weighed for 1wt% by metal platinum load capacity in whole catalyst, and is dissolved in 20ml acetonitriles, is stirred Mix to being completely dissolved, add the baked carriers of 10g, stir 8h, 5h is dried at 150 DEG C.
Content by cobalt in whole catalyst is that the quality that 15wt% calculates cabaltous nitrate hexahydrate is 6.935g, required to go Ionized water is 8.5g, and cabaltous nitrate hexahydrate is dissolved in 8.5g deionized waters, is slowly added dropwise to 10g alumina supports, quiet Only 8h, 150 DEG C of dryings roast 5h after 450 DEG C, weigh 3g catalyst and be fitted into fixed bed reactors, in the hydrogen gas stream, 450 DEG C 4h is reduced up to catalyst J.
Comparative example 2
The catalyst K prepared with typical impregnation method：
10g alumina supports are taken, deionized water are added dropwise to first profit, the quality for consuming water is 11g.
Platinum acetate 0.233g is weighed for 1wt% by metal platinum load capacity, and is dissolved in 20ml acetonitriles, is stirred to completely molten Solution, adds the baked carriers of 10g, stirs 8h, 5h is dried at 150 DEG C.
It is that the quality that 30wt% calculates cabaltous nitrate hexahydrate is 16.89g by the content of cobalt, required deionized water is 5g, Cabaltous nitrate hexahydrate is dissolved in 5g deionized waters, is slowly added dropwise to 10g alumina supports, static 8h, after 150 DEG C of dryings 5h is roasted in 450 DEG C, 3g catalyst is weighed and is fitted into fixed bed reactors.In the hydrogen gas stream, 450 DEG C of reduction 4h are up to catalyst Obtain catalyst K.
The performance evaluation of catalyst carries out on fixed bed reactors, and reaction condition is：H2/ CO=2, T=230 DEG C, P= 2Mpa, GHSV=1000h-1.Obtained catalyst various performance parameters are as shown in table 1.
Table 1：Co/Al2O3The Fischer-Tropsch synthesis performance of catalyst
It can be seen that catalyst J, K of the traditional infusion process preparation of contrast by 1 data comparison of table, prepared by the method for the present invention Catalyst CO conversion ratios significantly improve, from the 75% of traditional catalyst lifting to more than 80%, and keeping high activity Meanwhile the selectivity of methane is effectively reduced, methane selectively is below 15%.Under identical load amount, using this hair The dispersion degree of the bright preparation-obtained catalyst A~I active metals of method is significantly greater than catalyst prepared by traditional infusion process, table Very excellent performance is revealed.Moreover, preparation method using the present invention, reduces reduction step, it will be apparent that improves anti- Should be active, performance is substantially better than catalyst prepared by traditional infusion process.

Claims (16)

1. a kind of superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst, including alumina support, active constituent cobalt and coagent platinum, It is characterized in that：The percentage by weight of each component is alumina support 53~84.5%, active constituent cobalt 15 in the catalyst ~45%, coagent platinum 0.5~2.0%；Also, the particle diameter of the alumina support is 0.6~2.4mm, specific surface area is 140~300m2/g；The particle diameter of the active constituent cobalt and coagent platinum is 3~20nm, they are with finely dispersed nanoclusters Cluster form loads on the alumina support, and its preparation method, comprises the following steps：
1) alumina support is subjected to calcination process under conditions of 350~600 DEG C, acquisition particle diameter is 0.6~2.4mm, compares table Area is 140~300m2The superfines of/g；
2) platinum salt is weighed for the 0.5~2.0% of whole finished catalyst weight by the load capacity of coagent platinum, and is dissolved in acetonitrile In solvent, then add and account for the alumina support of whole finished catalyst weight 53~84.5%, be sufficiently stirred, then be added dropwise mole The NaOH solution for 6~12 times of platinum salt is measured, 10~24h is reacted under conditions of 20~35 DEG C；
3) 45~70 DEG C and then by reactant are heated to, then enough formaldehyde progress reduction reactions are added dropwise, the reaction time 10~ 24h, maintains pH=11~12 by the way that lye is added dropwise in reaction process, after completion of the reaction cleans reduzate, dries, born Carry the alumina support of platinum；
4) cobalt salt is weighed for the 15~45% of whole finished catalyst weight put into reaction under high pressure by the load capacity of active constituent cobalt In kettle, then the alumina support of gained Supported Pt Nanoparticles is put into, add organic solvent to autoclave and be filled with hydrogen and an oxidation The mixed gas of carbon, is forced into 8~15Mpa, is warming up to 120~180 DEG C, 1~12h of stirring reaction；
5) room temperature, pressure release are then cooled to, the hydrogen and carbon monoxide being filled with nitrogen discharge autoclave；
6) nitrogen atmosphere is kept, autoclave is slowly heated to 100~200 DEG C, stirring 8~36h of reaction, makes active constituent Cobalt and coagent platinum disperse load on the alumina support in the form of nanocluster, you can obtain superelevation dispersiveness cobalt platinum Fischer-Tropsch Synthetic catalyst.
2. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 1, it is characterised in that：The carrying alumina The particle diameter of body is 0.8~2.2mm, specific surface area is 160~280m2/g；The particle diameter of the active constituent cobalt and coagent platinum For 5~18nm.
3. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 2, it is characterised in that：The carrying alumina The particle diameter of body is 1.0~2.0mm, specific surface area is 180~260m2/g；The particle diameter of the active constituent cobalt and coagent platinum For 8~15nm.
4. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 1, it is characterised in that：The preparation process Step 1) in, calcination process temperature is 400~500 DEG C, roasting time is 2~4h.
5. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 1, it is characterised in that：The preparation process Step 2) in, platinum salt is platinum acetate or platinum nitrate.
6. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 1, it is characterised in that：The preparation process Step 2) in, the mole that NaOH solution is added dropwise is 8~10 times of platinum salt.
7. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 1, it is characterised in that：The preparation process Step 2) in, be added dropwise NaOH solution weight percent concentration be 3~10%.
8. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 7, it is characterised in that：The preparation process Step 2) in, be added dropwise NaOH solution weight percent concentration be 5~8%.
9. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 1, it is characterised in that：The preparation process Step 3) in, reactant is heated to 55~65 DEG C.
10. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 1, it is characterised in that：It is described to prepare In the step 3) of journey, the molar ratio that formaldehyde and platinum salt is added dropwise is 30~80 ︰ 1.
11. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 10, it is characterised in that：It is described to prepare In the step 3) of journey, the molar ratio that formaldehyde and platinum salt is added dropwise is 40~50 ︰ 1.
12. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 1, it is characterised in that：It is described to prepare In the step 3) of journey, it is the NaOH solution that weight percent concentration is 10~25% that lye, which is added dropwise,.
13. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 1, it is characterised in that：It is described to prepare In the step 3) of journey, reduzate is cleaned by the way of deionized water and ethanol are alternately rinsed several times, then again 70 Reduzate is dried under conditions of~90 DEG C.
14. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 1, it is characterised in that：It is described to prepare In the step 4) of journey, used organic solvent is one kind or its combination in ethanol, n-octyl alcohol or isopropanol.
15. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 1, it is characterised in that：It is described to prepare In the step 4) of journey, cobalt salt is cobalt carbonate.
16. superelevation dispersiveness cobalt platinum fischer-tropsch synthetic catalyst according to claim 1, it is characterised in that：It is described to prepare In the step 4) of journey, in the mixed gas of hydrogen and carbon monoxide, the volume ratio of hydrogen and carbon monoxide is 1 ︰ 1~3.
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