CN105879899B - Nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst and preparation method thereof - Google Patents

Nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst and preparation method thereof Download PDF

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CN105879899B
CN105879899B CN201610266635.5A CN201610266635A CN105879899B CN 105879899 B CN105879899 B CN 105879899B CN 201610266635 A CN201610266635 A CN 201610266635A CN 105879899 B CN105879899 B CN 105879899B
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nucleocapsid
catalyst
pore canal
tropsch synthesis
multistage pore
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CN105879899A (en
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海国良
宋德臣
李昌元
刘倩倩
饶莎莎
詹晓东
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • C10G2/334—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 molecular sieve catalysts
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/60—Synthesis on support
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

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Abstract

The invention discloses a kind of nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalysts and preparation method thereof.It is SiO that the catalyst, which includes catalyst carrier S, the metal active component C o that is supported on catalyst carrier S and is wrapped in shell the molecular screen membrane M, catalyst carrier S on catalyst carrier S surfaces,2And Al2O3In one or two kinds of arbitrary proportion mixture, SiO2And Al2O3Traffic micro-simulation in spherical, its specific surface area be 160~290m2/ g, mean particle size range are between 10~50 mesh；Shell molecular screen membrane M is the finely dispersed clusters body of 5 nano particles of H ZSM, and the particle size ranges of 5 nano particles of H ZSM is between 10~30nm, its own micropore size is less than or equal to the gap between 2.0nm, adjacent 5 nano particles of H ZSM and is less than or equal to 100nm；The load capacity of metal active component C o accounts for the 10~30% of the sum of catalyst carrier S and metal active component C o weight.The shell of the fischer-tropsch synthetic catalyst has multistage pore canal, high catalytic efficiency, while the preparation method is simple for process, and low energy consumption.

Description

Nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst and preparation method thereof
Technical field
The invention belongs to F- T synthesis technical fields, in particular to a kind of nucleocapsid multistage pore canal formula co-based fischer-tropsch to synthesize Catalyst and preparation method thereof.
Background technology
Fischer-Tropsch synthesis refers to that the resources such as coal, natural gas, biomass pass through synthesis gas (CO and H2) it is catalytically conveted to carbon The process of hydrogen compound.The product of F- T synthesis has the characteristics that no sulphur, nitrogen-free and without aromatic hydrocarbons, thus by F- T synthesis generation Liquid fuel can meet increasingly strict ecological requirements, while the product of F- T synthesis is also comprising existing chemical industry rows such as low-carbon alkenes The critical materials of industry.Therefore, Fischer-Tropsch synthesis is non-oil base resource indirect reformer high-quality liquid fuel and industrial chemicals One of important channel.Low-carbon alkene is important Organic Chemicals, and production capacity is to weigh the chemical industrial level of a country Major criterion.Low-carbon alkene generation at present mainly uses the petrochemical industry route of light hydrocarbon cracking, and synthesis gas is anti-by F- T synthesis Direct preparing low-carbon olefins are answered, there are the advantages such as technological process is short, low energy consumption, be one of current hot research direction.However Traditional Fischer-Tropsch synthesis product obeys ASF distributions, and heavy hydrocarbon content is higher, and the strongly exothermic property of reaction easily causes the life of methane Into, and promote the low-carbon alkene of production that secondary response occurs, thus the selectivity for improving low-carbon alkene product becomes low-carbon alkene The difficult point of contract technical.
Molecular sieve passes through diffusion rate of the restriction molecule in duct, shape-selective selection because it is with unique pore passage structure Property and acid duct make its be widely used and it is a kind of it is important be hydrocracked, hydroisomerization catalyst.It is closed in Fischer-Tropsch Into after one layer of molecular screen membrane of catalyst outer wrapping, the product of F- T synthesis is diffused into molecular sieve layer and enters in duct, in hole Cracking or isomerization under the action of road acidity active sites, long chain hydrocarbon residence time in duct is longer, more has Possible cracking and isomerization reaction, and the presence of molecular screen membrane can limit and generate adsorbing again for alkene, so as to limit chain Growth.Before one layer of molecular screen membrane of fischer-tropsch synthetic catalyst outer wrapping prepares complex function catalyst with good application Scape.Before making the present invention,《Chemical Reaction Engineering and technique》, 2013,29 (1), 7-12 published what Zhang Yonghua etc. was delivered 《CoZr/AC@ZSM-5 catalyst with core-casing structure Fischer-Tropsch synthesis characteristics》One text, this article describe, and cobalt is loaded to work first Property high-area carbon on, then prepare ZSM-5 molecular sieve film on the catalyst by hydrothermal synthesis method, form nucleocapsid catalysis Agent, which be improved the selectivity of lower carbon number hydrocarbons, and the generation of heavy hydrocarbon is inhibited.But ZSM- prepared by the method 5 be Na types, acid weaker, and since the limitation of micropore causes CO conversion ratios to reduce, methane selectively increases.
In addition, Yang etc. is in Confinement effect and synergistic function of H-ZSM-5/ Cu-ZnO-Al2O3Capsule catalyst for one-step controlled synthesis, Journal of the American chemical society, 2010,132 (23):8129-8136 is disclosed through hydrothermal synthesis method in Cu- ZnO-Al2O3Catalyst surface is prepared for one layer of molecular screen membrane, and prepares dimethyl ether for one-step method from syngas, almost inhibits The production of by-product.But in this method molecular screen membrane micropore limitation, cause CO conversion ratios it is extremely low only 40% or so.And And aforementioned two methods can not solve molecular sieve bore diameter distribution and excessively concentrate on micropore, and conversion ratio is led to problems such as to decline.
Invention content
The object of the present invention is to provide a kind of nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst and its preparation sides Method, the shell of the fischer-tropsch synthetic catalyst have multistage pore canal, high catalytic efficiency, while the preparation method is simple for process, energy It consumes low.
To achieve the above object, the nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst designed by the present invention, packet The metal active component C o that include catalyst carrier S, is supported on catalyst carrier S and it is wrapped in catalyst carrier S surfaces Shell molecular screen membrane M, is characterized in that：
The catalyst carrier S is SiO2And Al2O3In one or two kinds of arbitrary proportion mixture, the SiO2 And Al2O3Traffic micro-simulation in spherical, its specific surface area be 160~290m2/ g, mean particle size range 10~50 mesh it Between；
The shell molecular screen membrane M is the finely dispersed clusters body of H-ZSM-5 nano particles, and the H-ZSM-5 receives The particle size range of rice grain is between 10~30nm, its own micropore size is less than or equal to 2.0nm, H-ZSM-5 nanometers adjacent Gap between particle is less than or equal to 100nm；
The load capacity of the metal active component C o account for the sum of catalyst carrier S and metal active component C o weight 10~ 30%.
Preferably, the SiO2And Al2O3Specific surface area be 180~270m2/ g, particle size range are between 20~40 mesh.
Further, the average particle size range of the H-ZSM-5 nano particles is between 15~25nm, its own micropore hole Gap of the diameter between 0.5~1.0nm, adjacent H-ZSM-5 nano particles is less than or equal to 80nm.
Still further, the load capacity of the metal active component C o accounts for catalyst carrier S and metal active component C o is total The 15~25% of weight.
The present invention also provides the preparation methods of the nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, it includes Following steps：
1) SiO is weighed2And Al2O3In one or two kinds of arbitrary proportion mixture carry out roasting removal of impurities processing, obtain Traffic micro-simulation is 160~290m in spherical, specific surface area2The superfine powder of/g, mean particle size range between 10~50 mesh End, as catalyst carrier S；
2) according to the load capacity of metal active component C o account for the sum of catalyst carrier S and metal active component C o weight 10~ 30% ratio weighs cobalt salt, is configured to cobalt salt solution, and cobalt salt solution is impregnated into catalyst carrier S using full hole infusion process On；
3) calcination process is dried to the catalyst carrier S for being impregnated with cobalt salt, obtains catalyst core portion Co/S, i.e. Co/ SiO2Or Co/Al2O3Or both mixture；
4) gained catalyst core portion Co/S is scattered in solvent, and under agitation add in polyvinylpyrrolidone and Ammonia spirit makes polyvinylpyrrolidone absorption on catalyst core portion Co/S；
5) ethyl orthosilicate, aluminium isopropoxide, tetrapropylammonium hydroxide and water are uniformly mixed, are configured to sol solutions；
6) gained sol solutions are added in the catalyst core portion Co/S dispersion solvents for being adsorbed with polyvinylpyrrolidone, after Continuous stirring promotes polyvinylpyrrolidone and tetrapropylammonium hydroxide shape up to ethyl orthosilicate and aluminium isopropoxide complete hydrolysis Into strong interaction, so as to complete molecular sieve self assembly on catalyst core portion Co/S surfaces；
7) heating evaporation processing is carried out to the catalyst core portion Co/S mixed sols liquid through over-molecular sieve self assembly, removes it In ethyl alcohol, isopropanol and part moisture content, obtain concentration sol solutions；
8) methylamine water solution is added in gained concentrates sol solutions, it is carried out quickly to stand Crystallizing treatment, is then carried out Centrifuging treatment obtains solid product；
9) obtained solid product is rinsed well, drying and roasting is handled again, and nucleocapsid multistage pore canal formula is finally made Co based Fischer-Tropsch synthesis catalyst, i.e. Co/SiO2@H-ZMS-5 or Co/Al2O3The mixture of@H-ZMS-5 or both.
The restriction of any one technical solution below, can be as the preferred embodiment of preparation method of the present invention：
In the step 1), the condition of roasting removal of impurities processing is：350~600 DEG C of calcination temperature, roasting time 2.0~ 5.0h；Preferred 400~500 DEG C of calcination temperature, 2.5~3.5h of roasting time.
In the step 2), cobalt salt selects cobalt nitrate and/or cobalt acetate, accounts for and urges according to the load capacity of metal active component C o The ratio of the sum of agent carrier S and metal active component C o weight 15~25% weighs.
In the step 3), the condition of drying and roasting processing is：Dry 3~8h first at a temperature of 60~120 DEG C, so 2~6h is roasted at a temperature of 300~550 DEG C afterwards.Further preferably, dry 5 first at a temperature of 80~100 DEG C~ Then 8h roasts 3~5h at a temperature of 350~450 DEG C.
In the step 4), solvent uses ethyl alcohol or deionized water, adds in polyvinylpyrrolidone and catalyst core portion The weight ratio of Co/S is 0.5~2.5 ︰ 1；More preferably, polyvinylpyrrolidone and catalyst core portion Co/S weight are added in Than for 1.0~2.0 ︰ 1.
In the step 4), for the control of the volume-fraction concentration of ammonia spirit 25~35%, dosage is every gram of polyethylene pyrrole Pyrrolidone adds in 90~120ml of ammonia spirit；Further preferably, the volume-fraction concentration control of ammonia spirit 30~ 35%, dosage adds in 100~120ml of ammonia spirit for every gram of polyvinylpyrrolidone.
In the step 5), each component molar ratio of sol solutions meets following mathematical relationship：Zheng Gui Suan Yi Zhi ︰ isopropanols Lv ︰ tetra- propyl Qing oxidation An ︰ water=1 ︰ 0.2X ︰ 15X of X ︰, X=20~100；More preferably described X=25~50.
In the step 6), the weight ratio of ethyl orthosilicate and catalyst core portion Co/S in sol solutions is 2~5 ︰ 1, is stirred Time control is mixed in 4~8h.It is highly preferred that the weight ratio of the ethyl orthosilicate and catalyst core portion Co/S in sol solutions is 3.0 ~4.0 ︰ 1, mixing time are controlled in 5~7h.
In the step 7), the condition of heating evaporation processing is：100~120 DEG C of evaporating temperature, 2~4h of evaporation time.
In the step 8), the molar ratio for adding in methylamine and ethyl orthosilicate is 1 ︰ 0.2~2, stands Crystallizing treatment Condition is：80~120 DEG C of dwell temperature, 60~80h of return time.It is highly preferred that added in methylamine and ethyl orthosilicate rub Your ratio is 1 ︰ 0.5~1.5, and the condition for standing Crystallizing treatment is：95~105 DEG C of dwell temperature, 65~75h of return time.
In the step 9), the condition of drying and roasting processing is again：Dry 6 first at a temperature of 60~120 DEG C~ Then 15h roasts 3~8h at a temperature of 300~550 DEG C.It is highly preferred that the condition of drying and roasting processing is again：First Dry 8~12h, then roasts 4~6h at a temperature of 350~450 DEG C at a temperature of 80~100 DEG C.
Each step is anti-in nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst of the present invention and preparation method thereof Answer principle and process parameter control as follows：
In preparation process, active component Co is supported on catalyst carrier S, full hole infusion process is used to carry out load can be with Load capacity and dispersion degree is effectively ensured.The polyvinylpyrrolidone selected in step 4) is amphiphilic reagent, in the alkali that ammonium hydroxide is formed Under the conditions of property, for catalyst core portion Co/S when being scattered in solvent, oxygen on polyvinylpyrrolidonemolecules molecules chain pyridine ring can be with The hydroxyl of carrier forms hydrogen bond, makes polyvinylpyrrolidone absorption on catalyst core portion Co/S, is then added in step 6) molten After glue, polyvinylpyrrolidone occur ring-opening reaction and it is negatively charged, with the template tetrapropyl hydrogen in added in sol solutions Amine-oxides form stronger interaction, make molecular sieve in carrier surface self assembly, formation molecular sieve shell.Then pass through step 7) heating evaporation concentration sol solutions, step 8) add methylamine as mineralising reagent, can promote the generation of new core, and inhibit Core is grown up, then through subsequent crystallization, centrifugation, clean, drying process, you can obtains the conjunction of nucleocapsid multistage pore canal Fischer-Tropsch Into catalyst.
The fischer-tropsch synthetic catalyst being prepared by the method for the present invention is in Co/SiO2Or Co/Al2O3Upper package H-ZSM- 5 molecular screen membranes prepare catalyst with core-casing structure, i.e. Co/SiO2@H-ZMS-5 or Co/Al2O3The mixture of@H-ZMS-5 or both, H-ZSM-5 molecular sieves be it is a kind of it is excellent be hydrocracked and hydroisomerization catalyst, isomerized products and alkene can be effectively improved Selectivity.
Molecular sieve shell in catalyst of the present invention is the aggregation of molecular sieve nano particle, H-ZSM-5 nano particles Average particle size range is between 10~30nm, its own micropore size is less than or equal to 2.0nm, adjacent H-ZSM-5 nano particles Between gap be less than or equal to 100nm.So entire shell includes multistage pore canal, and the preparation method of the present invention can be with One step prepares nanometer acidic molecular sieve.The presence of molecular sieve shell can also effectively prevent active component to reunite in the present invention, make It keeps high activity under long period reaction condition, and the duct of molecular sieve has limit threshold effect, on the one hand can inhibit long-chain carbon On the other hand the generation of hydrogen compound also limits and has been desorbed adsorbing again for the activated product that diffuses out nucleocapsid reaction system, press down Make the growth of new chain.The presence of these multistage pore canals overcomes micro porous molecular sieve and is unfavorable for spreading in synthesis gas and water in molecular sieve The shortcomings that external diffusion.And multistage pore canal nano molecular sieve has stronger carbon accumulation resisting ability, so as to extend making for catalyst Use the service life.
Specific embodiment
With reference to specific embodiment to the present invention nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst and its Preparation method is described in further detail：
Embodiment 1
A kind of nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, including catalyst carrier S, is supported on catalyst Metal active component C o in the carrier S and shell molecular screen membrane M for being wrapped in catalyst carrier S surfaces, wherein, catalyst Carrier S is SiO2, SiO2Traffic micro-simulation in spherical, its specific surface area average value be 210m2/ g, particle size range 20~ 40 mesh；Shell molecular screen membrane M is the finely dispersed clusters body of H-ZSM-5 nano particles, and H-ZSM-5 nano particles are averaged Particle size range is 10~30nm, its own micropore size is less than or equal to the seam between 2.0nm, adjacent H-ZSM-5 nano particles Gap is less than or equal to 100nm；The load capacity of metal active component C o accounts for the sum of catalyst carrier S and metal active component C o weight 15%.
Preparation method includes the following steps：
1) appropriate SiO is weighed2It is placed in 350 DEG C of roasting 4h in Muffle furnace and carries out roasting removal of impurities processing, obtain microstructure shape State is 210m in spherical, specific surface area average value2The superfines of/g, particle size range between 10~50 mesh takes 10g to be used as and urges Agent carrier S is spare；
2) 8.72g cabaltous nitrate hexahydrates are weighed to be dissolved in deionized water, liquor capacity is diluted to 11ml with deionized water, Cobalt saline solution is impregnated on the catalyst carrier S of step 1 using full hole infusion process；
3) after placing 12h at room temperature, 8h is dried under the conditions of 60 DEG C to the catalyst carrier S for being impregnated with cobalt salt, with postposition 350 DEG C of roasting 5h, obtain catalyst core portion Co/S, i.e. Co/SiO in Muffle furnace2, catalyst core portion Co/S weight is 12.2g；
4) the core portion Co/S for weighing 5g catalyst is scattered in 500ml ethyl alcohol, forms ethanol solution, and under agitation The polyvinylpyrrolidone of 2.5g and 250ml ammonium hydroxide (volume-fraction concentration 30% of ammonium hydroxide), stirring are added in into ethanol solution 3h makes polyvinylpyrrolidone absorption on catalyst core portion Co/S；
5) 1.17g aluminium isopropoxides (AIP) are weighed to be dissolved in 20ml deionized waters, stirs to being completely dissolved, adds 11.7g Tetrapropylammonium hydroxide (TPAOH), 12g ethyl orthosilicates (TEOS) are Zheng Gui Suan Yi Zhi ︰ Yi propyl alcohol Lv ︰ tetra- in molar ratio Propyl Qing oxidation An ︰ water=10 ︰, 1 ︰, 2 ︰ 150, is made into sol solutions；
6) gained sol solutions are added in the catalyst core portion Co/S dispersion solvents for being adsorbed with polyvinylpyrrolidone, it is molten The weight ratio of ethyl orthosilicate and catalyst core portion Co/S in glue is 2.4 ︰ 1, continues to stir 5h, ethyl orthosilicate and isopropyl Aluminium alcoholates complete hydrolysis, and polyvinylpyrrolidone is promoted to form strong interaction with tetrapropylammonium hydroxide, so as in catalyst Complete molecular sieve self assembly in core portion Co/S surfaces；
7) the catalyst core portion Co/S mixed sols liquid through over-molecular sieve self assembly is carried out being heated to 100 DEG C, evaporates 3h, Ethyl alcohol therein, isopropanol and part moisture content are removed, obtains concentration sol solutions；
8) aqueous solution of the methylamine containing 8.93g is added in gained concentrates sol solutions, adds in methylamine and ethyl orthosilicate Molar ratio is 1 ︰ 0.5, it is carried out quickly to stand Crystallizing treatment, and reflux 72h is stood at 100 DEG C, place is then centrifuged Reason obtains solid product；
9) it is obtained solid product distilled water flushing is clean, the calcination process 12h at 60 DEG C is dried again, is subsequently placed in 500 DEG C of roasting 5h, are finally made nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, i.e. Co/SiO in Muffle furnace2@H- ZMS-5。
Embodiment 2
A kind of nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, including catalyst carrier S, is supported on catalyst Metal active component C o in the carrier S and shell molecular screen membrane M for being wrapped in catalyst carrier S surfaces, wherein, catalyst Carrier S is Al2O3, Al2O3Traffic micro-simulation in spherical, its specific surface area average value be 290m2/ g, particle size range for 10~ 50 mesh；Shell molecular screen membrane M is the finely dispersed clusters body of H-ZSM-5 nano particles, and H-ZSM-5 nano particles are averaged Particle size range is 10~30nm, its own micropore size is less than or equal to the seam between 2.0nm, adjacent H-ZSM-5 nano particles Gap is less than or equal to 100nm；The load capacity of metal active component C o accounts for the sum of catalyst carrier S and metal active component C o weight 20%.
Preparation method includes the following steps：
1) appropriate Al is weighed2O3It is placed in 550 DEG C of roasting 3h in Muffle furnace and carries out roasting removal of impurities processing, obtain microstructure shape State is 290m in spherical, specific surface area average value2The superfines of/g, particle size range between 10~50 mesh takes 10g to be used as and urges Agent carrier S is spare；
2) 5.05g cabaltous nitrate hexahydrates are weighed to be dissolved in deionized water, liquor capacity is diluted to 11ml with deionized water, Cobalt saline solution is impregnated on the 10g catalyst carriers S of step 1 using full hole infusion process；
3) after placing 12h at room temperature, 6h is dried under the conditions of 90 DEG C to the catalyst carrier S for being impregnated with cobalt salt, with postposition 500 DEG C of roasting 3h, obtain catalyst core portion Co/S, i.e. Co/Al in Muffle furnace2O3, catalyst core portion Co/S weight is 13.4g.
4) the core portion Co/S for weighing 5g catalyst is scattered in 500ml ethyl alcohol, forms ethanol solution, and under agitation The polyvinylpyrrolidone of 3.3g and 330ml ammonium hydroxide (ammonium hydroxide volume-fraction concentration 25%), stirring are added in into ethanol solution 3h makes polyvinylpyrrolidone absorption on catalyst core portion Co/S；
5) 0.98g aluminium isopropoxides (AIP) are weighed to be dissolved in 20ml deionized waters, stirs to being completely dissolved, adds 14.6g Tetrapropylammonium hydroxide (TPAOH), 15g ethyl orthosilicates (TEOS) are Zheng Gui Suan Yi Zhi ︰ Yi propyl alcohol Lv ︰ that is, according to molar ratio Si propyl Qing oxidation An ︰ water=15 ︰, 1 ︰, 3 ︰ 225 are made into sol solutions；
6) gained sol solutions are added in the catalyst core portion Co/S dispersion solvents for being adsorbed with polyvinylpyrrolidone, it is molten The weight ratio of ethyl orthosilicate and catalyst core portion Co/S in glue is 3 ︰ 1, continues to stir 5h, ethyl orthosilicate and isopropanol Aluminium complete hydrolysis, and polyvinylpyrrolidone is promoted to form strong interaction with tetrapropylammonium hydroxide, so as in catalyst core Complete molecular sieve self assembly in portion Co/S surfaces；
7) the catalyst core portion Co/S mixed sols liquid through over-molecular sieve self assembly is carried out being heated to 110 DEG C, evaporation 2.5h removes ethyl alcohol therein, isopropanol and part moisture content, obtains concentration sol solutions；
8) aqueous solution of the methylamine containing 5.5g is added in gained concentrates sol solutions, that is, added in methylamine and ethyl orthosilicate Molar ratio is 1 ︰ 1, it is carried out quickly to stand Crystallizing treatment, and reflux 70h is stood at 100 DEG C, processing is then centrifuged, Obtain solid product；
9) it is obtained solid product distilled water flushing is clean, the calcination process 10h at 90 DEG C is dried again, is subsequently placed in 450 DEG C of roasting 4h, are finally made nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, i.e. Co/Al in Muffle furnace2O3@H- ZMS-5。
Embodiment 3
A kind of nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, including catalyst carrier S, is supported on catalyst Metal active component C o in the carrier S and shell molecular screen membrane M for being wrapped in catalyst carrier S surfaces, wherein, catalyst Carrier S is SiO2, SiO2Traffic micro-simulation in spherical, its specific surface area average value be 170m2/ g, particle size range 10~ 50 mesh；Shell molecular screen membrane M is the finely dispersed clusters body of H-ZSM-5 nano particles, and H-ZSM-5 nano particles are averaged Particle size range is between 10~30nm, its own micropore size is less than or equal between 2.0nm, adjacent H-ZSM-5 nano particles Gap be less than or equal to 100nm；The load capacity of metal active component C o accounts for catalyst carrier S and metal active component C o weight The sum of 15%.
Preparation method includes the following steps：
1) appropriate SiO is weighed2It is placed in 400 DEG C of roasting 4h in Muffle furnace and carries out roasting removal of impurities processing, obtain microstructure shape State is 170m in spherical, specific surface area average value2The superfines of/g, particle size range between 10~50 mesh takes 10g to be used as and urges Agent carrier S is spare；
2) 7.46g cobalt acetates are weighed to be dissolved in deionized water, liquor capacity is diluted to 11ml with deionized water, using full Cobalt saline solution is impregnated on the 10g catalyst carriers S of step 1 by hole infusion process；
3) after placing 12h at room temperature, 7h is dried under the conditions of 100 DEG C to the catalyst carrier S for being impregnated with cobalt salt, with postposition 550 DEG C of roasting 4h, obtain catalyst core portion Co/S, i.e. Co/SiO in Muffle furnace2；Catalyst core portion Co/S weight is 12.3g；
4) the core portion Co/S for weighing 5g catalyst is scattered in 500ml ethyl alcohol, forms ethanol solution, and under agitation 5g polyvinylpyrrolidones and 500ml ammonium hydroxide (volume-fraction concentration 35%) are added in into ethanol solution, 3h is stirred, makes poly- second Alkene pyrrolidone is adsorbed on catalyst core portion Co/S；
5) 0.44g aluminium isopropoxides are weighed to be dissolved in 20ml deionized waters, stirs to being completely dissolved, adds 21.96g 4 third Base ammonium hydroxide, 22.5g ethyl orthosilicates aoxidize An ︰ according to molar ratio for Zheng Gui Suan Yi Zhi ︰ Yi propyl alcohol Lv ︰ tetra- propyl Qing Water=50 ︰, 1 ︰, 10 ︰ 750 are made into sol solutions；
6) gained sol solutions are added in the catalyst core portion Co/S dispersion solvents for being adsorbed with polyvinylpyrrolidone, it is molten The weight ratio of ethyl orthosilicate and catalyst core portion Co/S in glue is 4.5 ︰ 1, continues to stir 5h, ethyl orthosilicate and isopropyl Aluminium alcoholates complete hydrolysis, and polyvinylpyrrolidone is promoted to form strong interaction with tetrapropylammonium hydroxide, so as in catalyst Complete molecular sieve self assembly in core portion Co/S surfaces；
7) the catalyst core portion Co/S mixed sols liquid through over-molecular sieve self assembly is carried out being heated to 100 DEG C, evaporates 4h, Ethyl alcohol therein, isopropanol and part moisture content are removed, obtains concentration sol solutions；
8) aqueous solution of the methylamine containing 5.58g is added in gained concentrates sol solutions, adds in methylamine and ethyl orthosilicate Molar ratio is 1 ︰ 1.4, it is carried out quickly to stand Crystallizing treatment, and reflux 60h is stood at 100 DEG C, place is then centrifuged Reason obtains solid product；
9) it is obtained solid product distilled water flushing is clean, the calcination process 12h at 100 DEG C is dried again, is then put 550 DEG C of roasting 5h, are finally made nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, i.e. Co/SiO in Muffle furnace2@ H-ZMS-5。
Embodiment 4
A kind of nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, including catalyst carrier S, is supported on catalyst Metal active component C o in the carrier S and shell molecular screen membrane M for being wrapped in catalyst carrier S surfaces, wherein, catalyst Carrier S is Al2O3, Al2O3Traffic micro-simulation in spherical, its specific surface area average value be 180m2/ g, particle size range 10~ Between 50 mesh；Shell molecular screen membrane M is the finely dispersed clusters body of H-ZSM-5 nano particles, H-ZSM-5 nano particles Average particle size range is between 10~30nm, its own micropore size is less than or equal to 2.0nm, adjacent H-ZSM-5 nano particles Between gap be less than or equal to 100nm；The load capacity of metal active component C o accounts for catalyst carrier S and metal active component C o The 25% of the sum of weight.
Preparation method includes the following steps：
1) appropriate Al is weighed2O3It is placed in 600 DEG C of roasting 3h in Muffle furnace and carries out roasting removal of impurities processing, obtain microstructure shape State is 180m in spherical, specific surface area average value2The superfines of/g, particle size range between 10~50 mesh takes 10g to be used as and urges Agent carrier S is spare；
2) 16.46g cabaltous nitrate hexahydrates are weighed to be dissolved in deionized water, are diluted to liquor capacity with deionized water Cobalt saline solution is impregnated on the 10g catalyst carriers S of step 1 by 11ml using full hole infusion process；
3) after placing 12h at room temperature, 8h is dried under the conditions of 110 DEG C to the catalyst carrier S for being impregnated with cobalt salt, with postposition 450 DEG C of roasting 5h, obtain catalyst core portion Co/S, i.e. Co/Al in Muffle furnace2O3；Catalyst core portion Co/S weight is 14.5g；
4) the core portion Co/S for weighing 5g catalyst is scattered in 500ml ethyl alcohol, forms ethanol solution, and under agitation The polyvinylpyrrolidone of 1.5g and 150ml ammonium hydroxide (volume-fraction concentration 25%) are added in into ethanol solution, 3h is stirred, makes Polyvinylpyrrolidone is adsorbed on catalyst core portion Co/S；
5) 0.42g aluminium isopropoxides (AIP) are weighed to be dissolved in 20ml deionized waters, stirs to being completely dissolved, adds 1.46g Tetrapropylammonium hydroxide (TPAOH), 15g ethyl orthosilicates (TEOS), i.e., according to Zheng Gui Suan Yi Zhi ︰ Yi propyl alcohol Lv ︰ tetrapropyl hydrogen Oxidation An ︰ water=35 ︰, 1 ︰, 7 ︰ 525 are made into sol solutions；
6) gained sol solutions are added in the catalyst core portion Co/S dispersion solvents for being adsorbed with polyvinylpyrrolidone, it is molten The molar ratio of ethyl orthosilicate and catalyst core portion Co/S in glue is 3 ︰ 1, continues to stir 5h, ethyl orthosilicate and isopropanol Aluminium complete hydrolysis, and polyvinylpyrrolidone is promoted to form strong interaction with tetrapropylammonium hydroxide, so as in catalyst core Complete molecular sieve self assembly in portion Co/S surfaces；
7) the catalyst core portion Co/S mixed sols liquid through over-molecular sieve self assembly is carried out being heated to 110 DEG C, evaporation 2.5h removes ethyl alcohol therein, isopropanol and part moisture content, obtains concentration sol solutions；
8) aqueous solution of the methylamine containing 2.79g is added in gained concentrates sol solutions, methylamine is added in and rubs with ethyl orthosilicate You carry out it quickly to stand Crystallizing treatment, reflux 72h are stood at 100 DEG C, processing is then centrifuged, obtains than being 1 ︰ 2 Obtain solid product；
9) it is obtained solid product distilled water flushing is clean, the calcination process 12h at 110 DEG C is dried again, is then put 450 DEG C of roasting 5h, are finally made nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, i.e. Co/Al in Muffle furnace2O3@ H-ZMS-5。
Embodiment 5
A kind of nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, including catalyst carrier S, is supported on catalyst Metal active component C o in the carrier S and shell molecular screen membrane M for being wrapped in catalyst carrier S surfaces, wherein, catalyst Carrier S is SiO2, SiO2Traffic micro-simulation in spherical, its specific surface area average value be 180m2/ g, particle size range 10~ Between 50 mesh；Shell molecular screen membrane M is the finely dispersed clusters body of H-ZSM-5 nano particles, H-ZSM-5 nano particles Average particle size range is between 10~30nm, its own micropore size is less than or equal to 2.0nm, adjacent H-ZSM-5 nano particles Between gap be less than or equal to 100nm；The load capacity of metal active component C o accounts for catalyst carrier S and metal active component C o The 20% of the sum of weight.
Preparation method includes the following steps：
1) appropriate SiO is weighed2It is placed in 500 DEG C of roasting 4h in Muffle furnace and carries out roasting removal of impurities processing, obtain microstructure shape State is 180m in spherical, specific surface area average value2The superfines of/g, particle size range between 10~50 mesh takes 10g to be used as and urges Agent carrier S is spare；
2) the sum of catalyst carrier S and metal active component C o weight 20% is accounted for according to the load capacity of metal active component C o Ratio weigh 10.57g cobalt acetates and be dissolved in deionized water, liquor capacity is diluted to 11ml with deionized water, using full hole Cobalt saline solution is impregnated on the 10g catalyst carriers S of step 1 by infusion process；
3) after placing 12h at room temperature, 8h is dried under the conditions of 120 DEG C to the catalyst carrier S for being impregnated with cobalt salt, with postposition 400 DEG C of roasting 5h, obtain catalyst core portion Co/S, i.e. Co/SiO in Muffle furnace2；The weight of catalyst core portion Co/S is 13.1g；
4) the core portion Co/S for weighing 5g catalyst is scattered in 500ml ethyl alcohol, forms ethanol solution, and under agitation 2g polyvinylpyrrolidones and 200ml ammonium hydroxide (volume-fraction concentration 25%) are added in into ethanol solution, 3h is stirred, makes poly- second Alkene pyrrolidone is adsorbed on catalyst core portion Co/S；
5) 0.98g aluminium isopropoxides are weighed to be dissolved in 20ml deionized waters, stirs to being completely dissolved, adds 1.46g 4 third Base ammonium hydroxide, 15g ethyl orthosilicates aoxidize An ︰ water according to molar ratio for Zheng Gui Suan Yi Zhi ︰ Yi propyl alcohol Lv ︰ tetra- propyl Qing 1 ︰ of=15 ︰, 3 ︰ 225 are made into sol solutions；
6) gained sol solutions are added in the catalyst core portion Co/S dispersion solvents for being adsorbed with polyvinylpyrrolidone, it is molten The weight ratio of ethyl orthosilicate and catalyst core portion Co/S in glue is 3 ︰ 1, continues to stir 5h, ethyl orthosilicate and isopropanol Aluminium complete hydrolysis, and polyvinylpyrrolidone is promoted to form strong interaction with tetrapropylammonium hydroxide, so as in catalyst core Complete molecular sieve self assembly in portion Co/S surfaces；
7) the catalyst core portion Co/S mixed sols liquid through over-molecular sieve self assembly is carried out being heated to 100 DEG C, evaporates 3h, Ethyl alcohol therein, isopropanol and part moisture content are removed, obtains concentration sol solutions；
8) aqueous solution of the methylamine containing 27.9g is added in gained concentrates sol solutions, adds in methylamine and ethyl orthosilicate Molar ratio is 1 ︰ 0.2, it is carried out quickly to stand Crystallizing treatment, and reflux 72h is stood at 100 DEG C, place is then centrifuged Reason obtains solid product；
9) it is obtained solid product distilled water flushing is clean, the calcination process 12h at 120 DEG C is dried again, is then put 400 DEG C of roasting 5h, are finally made nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, i.e. Co/SiO in Muffle furnace2@ H-ZMS-5。
Embodiment 6
A kind of nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, including catalyst carrier S, is supported on catalyst Metal active component C o in the carrier S and shell molecular screen membrane M for being wrapped in catalyst carrier S surfaces, wherein, catalyst Carrier S is SiO2, SiO2Traffic micro-simulation in spherical, its specific surface area average value be 285m2/ g, particle size range 10~ 50 mesh；Shell molecular screen membrane M is the finely dispersed clusters body of H-ZSM-5 nano particles, and H-ZSM-5 nano particles are averaged Particle size range is between 10~30nm, its own micropore size is less than or equal between 2.0nm, adjacent H-ZSM-5 nano particles Gap be less than or equal to 100nm；The load capacity of metal active component C o accounts for catalyst carrier S and metal active component C o weight The sum of 25%.
Preparation method includes the following steps：
1) appropriate SiO is weighed2It is placed in 450 DEG C of roasting 4h in Muffle furnace and carries out roasting removal of impurities processing, obtain microstructure shape State is 285m in spherical, specific surface area average value2The superfines of/g, particle size range between 10~50 mesh takes 10g to be used as and urges Agent carrier S is spare；
2) the sum of catalyst carrier S and metal active component C o weight 25% is accounted for according to the load capacity of metal active component C o Ratio weigh 14.1g cobalt acetates and be dissolved in deionized water, liquor capacity is diluted to 11ml with deionized water, is soaked using full hole Cobalt saline solution is impregnated on the 10g catalyst carriers S of step 1) by stain method；
3) after placing 12h at room temperature, 8h is dried under the conditions of 80 DEG C to the catalyst carrier S for being impregnated with cobalt salt, with postposition 350 DEG C of roasting 5h, obtain catalyst core portion Co/S, i.e. Co/SiO in Muffle furnace2；Catalyst core portion Co/S weight is 14.0g；
4) the core portion Co/S for weighing 5g catalyst is scattered in 500ml ethyl alcohol, forms ethanol solution, and under agitation 1g polyvinylpyrrolidones and 110ml ammonium hydroxide (volume-fraction concentration 25%) are added in into ethanol solution, 3h is stirred, makes poly- second Alkene pyrrolidone is adsorbed on catalyst core portion Co/S；
5) 0.59g aluminium isopropoxides are weighed to be dissolved in 20ml deionized waters, stirs to being completely dissolved, adds 1.46g 4 third Base ammonium hydroxide, 15g ethyl orthosilicates aoxidize An ︰ water according to molar ratio for Zheng Gui Suan Yi Zhi ︰ Yi propyl alcohol Lv ︰ tetra- propyl Qing 1 ︰ of=25 ︰, 5 ︰ 375, are made into sol solutions；
6) gained sol solutions are added in the catalyst core portion Co/S dispersion solvents for being adsorbed with polyvinylpyrrolidone, it is molten The weight ratio of ethyl orthosilicate and catalyst core portion Co/S in glue is 2 ︰ 1, continues to stir 5h, ethyl orthosilicate and isopropanol Aluminium complete hydrolysis, and polyvinylpyrrolidone is promoted to form strong interaction with tetrapropylammonium hydroxide, so as in catalyst core Complete molecular sieve self assembly in portion Co/S surfaces；
7) the catalyst core portion Co/S mixed sols liquid through over-molecular sieve self assembly is carried out being heated to 100 DEG C, evaporates 3h, Ethyl alcohol therein, isopropanol and part moisture content are removed, obtains concentration sol solutions；
8) aqueous solution of the methylamine containing 5.58g is added in gained concentrates sol solutions, adds in methylamine and catalyst core portion Co/ The molar ratio of S is 1 ︰ 1, it is carried out quickly to stand Crystallizing treatment, and reflux 72h is stood at 100 DEG C, place is then centrifuged Reason obtains solid product；
9) it is obtained solid product distilled water flushing is clean, the calcination process 12h at 100 DEG C is dried again, is then put 350 DEG C of roasting 5h, are finally made nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst, i.e. Co/SiO in Muffle furnace2@ H-ZMS-5。
The catalyst of comparative example 1~2 is conventionally prepared, side is so as follows：
Comparative example 1
1) appropriate SiO is weighed2Carrier, is placed in Muffle furnace after 350 DEG C of roasting 4h that take out 10g spare.
2) 8.72g cabaltous nitrate hexahydrates are weighed to be dissolved in deionized water, liquor capacity is diluted to 11ml with deionized water, Solution is impregnated on 10g carriers using full hole infusion process, 60 DEG C of dry 8h after 12h is placed at room temperature, is subsequently placed at Muffle furnace In 350 DEG C roasting 5h, obtain Co/SiO2。
Comparative example 2
1) appropriate SiO is weighed2Carrier, is placed in Muffle furnace after 350 DEG C of roasting 4h that take out 10g spare.
2) 8.72g cabaltous nitrate hexahydrates are weighed to be dissolved in deionized water, liquor capacity is diluted to 11ml with deionized water, Solution is impregnated on 10g carriers using full hole infusion process, 60 DEG C of dry 8h after 12h is placed at room temperature, is subsequently placed at Muffle furnace In 350 DEG C roasting 5h, obtain Co/SiO2。
3) by Co/SiO2With H-ZMS-5 with the ratio mechanical mixture of 9 ︰ 1.It is named as Co/SiO2+H-ZMS-5。
Performance detection is carried out to catalyst prod obtained by the various embodiments described above and comparative example on fixed bed reactors.Reaction It is preceding that first catalyst to be measured is activated, 3g catalyst is fitted into reactor, with H2(purity>99.999%) it is reproducibility gas 1.5Mpa, body activates 10h at 400 DEG C.Reaction condition is：H2/ CO=2, T=240 DEG C, P=2Mpa, GHSV=1000h-1, inspection The results are shown in Table 1 for survey.
Table 1：Catalyst Fischer-Tropsch synthesis results of property
As can be seen from the above table, the catalyst activity of various embodiments of the present invention is very high, supporting molecular sieve membrane it is with obvious effects. Compared with the catalyst of uncoated molecular sieve layer (comparative example 1), C is greatly improved while CO conversion ratios are kept2- C4Selectivity, and olefine selective also significantly improves, more than 45%, C5+ selectivity is substantially reduced, and is fallen below by 80% 40% or so.The catalyst (comparative example 2) prepared by mechanical mixture selects compared with catalyst with core-casing structure of the present invention Property have a notable difference, catalyst olefine selective prepared by mechanical mixture is only 18.6% to prevent the production prepared less than the present invention Product.

Claims (22)

1. a kind of nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst including catalyst carrier S, is supported on catalyst load Metal active component C o on the body S and shell molecular screen membrane M for being wrapped in catalyst carrier S surfaces, it is characterised in that：
The catalyst carrier S is SiO2And Al2O3In one or two kinds of arbitrary proportion mixture, the SiO2With Al2O3Traffic micro-simulation in spherical, its specific surface area be 160~290m2/ g, particle size range are between 10~50 mesh；
The shell molecular screen membrane M be the finely dispersed clusters body of H-ZSM-5 nano particles, described H-ZSM-5 nanometers The average particle size range of grain is between 10~30nm, its own micropore size is less than or equal to 2.0nm, H-ZSM-5 nanometers adjacent Gap between particle is less than or equal to 100nm；
The load capacity of the metal active component C o account for the sum of catalyst carrier S and metal active component C o weight 10~ 30%；
The nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst preparation method, includes the following steps：
1) SiO is weighed2And Al2O3In one or two kinds of arbitrary proportion mixture carry out roasting removal of impurities processing, obtain it is microcosmic Structural form is 160~290m in spherical, specific surface area2The superfines of/g, mean particle size range between 10~50 mesh is made For catalyst carrier S；
2) the sum of catalyst carrier S and metal active component C o weight 10~30% is accounted for according to the load capacity of metal active component C o Ratio weigh cobalt salt, be configured to cobalt salt solution, cobalt salt solution be impregnated on catalyst carrier S using full hole infusion process；
3) calcination process is dried to the catalyst carrier S for being impregnated with cobalt salt, obtains catalyst core portion Co/S, i.e. Co/SiO2Or Co/Al2O3Or both mixture；
4) gained catalyst core portion Co/S is scattered in solvent, and adds in polyvinylpyrrolidone and ammonium hydroxide under agitation Solution makes polyvinylpyrrolidone absorption on catalyst core portion Co/S；
5) ethyl orthosilicate, aluminium isopropoxide, tetrapropylammonium hydroxide and water are uniformly mixed, are configured to sol solutions；
6) gained sol solutions are added in the catalyst core portion Co/S dispersion solvents for being adsorbed with polyvinylpyrrolidone, continue to stir It mixes up to ethyl orthosilicate and aluminium isopropoxide complete hydrolysis, and polyvinylpyrrolidone is promoted to be formed by force with tetrapropylammonium hydroxide Interaction, so as to complete molecular sieve self assembly on catalyst core portion Co/S surfaces；
7) heating evaporation processing is carried out to the catalyst core portion Co/S mixed sols liquid through over-molecular sieve self assembly, removed therein Ethyl alcohol, isopropanol and part moisture content obtain concentration sol solutions；
8) methylamine water solution is added in gained concentrates sol solutions, it is carried out quickly to stand Crystallizing treatment, is then centrifuged Separating treatment obtains solid product；
9) obtained solid product is rinsed well, drying and roasting is handled again, and nucleocapsid multistage pore canal formula cobalt-based is finally made Fischer-tropsch synthetic catalyst, i.e. Co/SiO2@H-ZSM-5 or Co/Al2O3The mixture of@H-ZSM-5 or both.
2. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：It is described SiO2And Al2O3Specific surface area be 180~270m2/ g, particle size range are between 20~40 mesh.
3. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：It is described The average particle size range of H-ZSM-5 nano particles is between 15~25nm, its own micropore size is 0.5~1.0nm, adjacent H- Gap between ZSM-5 nano particles is less than or equal to 80nm.
4. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：It is described The load capacity of metal active component C o accounts for the 15~25% of catalyst carrier S and metal active component C o total weights.
5. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：It is described In step 1), the condition of roasting removal of impurities processing is：350~600 DEG C of calcination temperature, 2.0~5.0h of roasting time.
6. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：It is described In step 1), the condition of roasting removal of impurities processing is：400~500 DEG C of calcination temperature, 2.5~3.5h of roasting time.
7. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：It is described In step 2), cobalt salt selects cobalt nitrate and/or cobalt acetate, according to the load capacity of metal active component C o account for catalyst carrier S with The ratio of the sum of metal active component C o weight 15~25% weighs.
8. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：It is described In step 3), the condition of drying and roasting processing is：Dry 3~8h first at a temperature of 60~120 DEG C, then 300~550 2~6h is roasted at a temperature of DEG C.
9. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：It is described In step 3), the condition of drying and roasting processing is：Dry 5~8h first at a temperature of 80~100 DEG C, then 350~450 3~5h is roasted at a temperature of DEG C.
10. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 4), solvent uses ethyl alcohol or deionized water, adds in the weight of polyvinylpyrrolidone and catalyst core portion Co/S Than for 0.5~2.5 ︰ 1.
11. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 4), solvent uses ethyl alcohol or deionized water, adds in polyvinylpyrrolidone and catalyst core portion Co/S weight ratios For 1.0~2.0 ︰ 1.
12. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 4), 25~35%, dosage adds in the control of the volume-fraction concentration of ammonia spirit for every gram of polyvinylpyrrolidone 90~120ml of ammonia spirit.
13. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 4), 30~35%, dosage adds in the control of the volume-fraction concentration of ammonia spirit for every gram of polyvinylpyrrolidone 100~120ml of ammonia spirit.
14. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 5), each component molar ratio of sol solutions meets following mathematical relationship：Zheng Gui Suan Yi Zhi ︰ Yi propyl alcohol Lv ︰ tetrapropyl hydrogen Aoxidize An ︰ water=1 ︰ 0.2X ︰ 15X of X ︰, X=20~100.
15. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 5), each component molar ratio of sol solutions meets following mathematical relationship：Zheng Gui Suan Yi Zhi ︰ Yi propyl alcohol Lv ︰ tetrapropyl hydrogen Aoxidize An ︰ water=1 ︰ 0.2X ︰ 15X of X ︰, X=25~50.
16. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 6), the weight ratio of the ethyl orthosilicate in sol solutions and catalyst core portion Co/S are 2~5 ︰ 1, and mixing time controls In 4~8h.
17. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 6), the weight ratio of the ethyl orthosilicate in sol solutions and catalyst core portion Co/S is 3.0~4.0 ︰ 1, mixing time Control is in 5~7h.
18. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 7), the condition of heating evaporation processing is：100 DEG C~120 DEG C of evaporating temperature, 2~4h of evaporation time.
19. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 8), the molar ratio for adding in methylamine and ethyl orthosilicate is 1 ︰ 0.2~2, and the condition for standing Crystallizing treatment is：It stands 80~120 DEG C of temperature, 60~80h of return time.
20. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 8), the molar ratio for adding in methylamine and ethyl orthosilicate is 1 ︰ 0.5~1.5, and the condition for standing Crystallizing treatment is：It is quiet Put 95~105 DEG C of temperature, 65~75h of return time.
21. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 9), the condition of drying and roasting processing is again：Dry 6~15h, Ran Hou first at a temperature of 60~120 DEG C 3~8h is roasted at a temperature of 300~550 DEG C.
22. nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：Institute It states in step 9), the condition of drying and roasting processing is again：Dry 8~12h, Ran Hou first at a temperature of 80~100 DEG C 4~6h is roasted at a temperature of 350~450 DEG C.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104001514A (en) * 2014-06-10 2014-08-27 中国科学院山西煤炭化学研究所 Eggshell cobalt-based Fischer-Tropsch synthesis catalyst, and preparation method and application thereof
CN104874417A (en) * 2014-02-28 2015-09-02 中国科学院青岛生物能源与过程研究所 Composite carrier-supported cobalt-based Fischer-Tropsch synthesis catalyst, and preparation method and application thereof
WO2016060330A1 (en) * 2014-10-17 2016-04-21 한국에너지기술연구원 Method for preparing cobalt-silica egg-shell nanocatalyst for fischer-tropsch synthesis reaction, and the catalyst, and method for synthesizing liquid hydrocarbon using same, and the liquid hydrocarbon

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6548440B1 (en) * 1999-05-26 2003-04-15 Science & Technology Corporation @ Unm Synthesis of attrition-resistant heterogeneous catalysts using templated mesoporous silica
CN105080597B (en) * 2014-05-14 2017-09-15 中国石油化工股份有限公司 Synthesis gas alkene catalyst and preparation method thereof
CN105879899B (en) * 2016-04-27 2018-06-19 武汉凯迪工程技术研究总院有限公司 Nucleocapsid multistage pore canal formula Co based Fischer-Tropsch synthesis catalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104874417A (en) * 2014-02-28 2015-09-02 中国科学院青岛生物能源与过程研究所 Composite carrier-supported cobalt-based Fischer-Tropsch synthesis catalyst, and preparation method and application thereof
CN104001514A (en) * 2014-06-10 2014-08-27 中国科学院山西煤炭化学研究所 Eggshell cobalt-based Fischer-Tropsch synthesis catalyst, and preparation method and application thereof
WO2016060330A1 (en) * 2014-10-17 2016-04-21 한국에너지기술연구원 Method for preparing cobalt-silica egg-shell nanocatalyst for fischer-tropsch synthesis reaction, and the catalyst, and method for synthesizing liquid hydrocarbon using same, and the liquid hydrocarbon

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Designing a Capsule Catalyst and Its Application for Direct Synthesis of Middle Isoparaffins;Jingjiang He et al;《Langmuir》;20050201;第21卷;第1699-1702页 *
Preparation of zeolite MFI membranes on alumina hollow fibers with high flux;Lijun Shan et al;《Journal of Membrane Science》;20110513;第378卷;第319-329页 *

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