CN114570412B - Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application - Google Patents

Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application Download PDF

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CN114570412B
CN114570412B CN202210153161.9A CN202210153161A CN114570412B CN 114570412 B CN114570412 B CN 114570412B CN 202210153161 A CN202210153161 A CN 202210153161A CN 114570412 B CN114570412 B CN 114570412B
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CN114570412A (en
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张玉兰
蔺锡柱
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Guizhou Institute of Technology
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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
    • 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
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B01J35/40—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a Fischer-Tropsch aromatic hydrocarbon catalyst, a preparation method and application thereof, which are characterized in that the catalyst is Fe 2 O 3 @SiO 2 Molecular sieve, fe 2 O 3 The morphology of the active metal oxide is dish-shaped, cage-shaped, polyhedral, cubic or spindle-shaped; siO (SiO) 2 The shell layer is of an amorphous structure; the molecular sieve is porous hierarchical structure. The catalyst prepared by the invention has low reaction temperature, simple preparation process and high yield, and can obtain the porous single-core double-shell catalyst with different morphologies and shell thicknesses by controlling reaction conditions, and Fe with different morphologies is obtained in the technical scheme of the invention 2 O 3 The shape of the nucleus is dish-shaped, cage-shaped, polyhedral, cubic or spindle-shaped. The selectivity of the aromatic hydrocarbon of the catalyst prepared by the invention can reach 70wt%; in addition, the catalyst prepared by the invention has controllable morphology and adjustable size, which provides different finite space for the Fischer-Tropsch reaction, thereby realizing high activity and high selectivity of the Fischer-Tropsch reaction.

Description

Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application
Technical Field
The invention relates to a Fischer-Tropsch aromatic hydrocarbon catalyst, a preparation method and application thereof, in particular to Fe with controllable morphology and shell thickness 2 O 3 @SiO 2 A molecular sieve Fischer-Tropsch catalyst and a preparation method thereof belong to the technical field of catalyst nano-confinement.
Background
The core-shell catalyst can effectively eliminate structural collapse caused by inconsistent pressure of the inner surface and the outer surface of the nano particles in the Fischer-Tropsch reaction process and nano particle growth caused by an Ostwald ripening mechanism, and can solve the problems of carbon deposition and sintering. Core-shell structures are favored by researchers due to their high catalytic activity and stability. Fischer-Tropsch is a process for synthesizing gas (H) 2 +co) catalyzes the conversion to liquid fuel, polymerization reaction that proceeds at the catalyst surface. The packing of the synthesis gas on the inner and outer surfaces of the active particles in the Fischer-Tropsch reaction can damage the structural integrity of the catalyst, reduce the nano-confinement effect, and further reduce the catalytic activity and the product selectivity. The preparation of the core-shell catalyst can inhibit structural collapse caused by inconsistent internal and external pressures of active particles in the Fischer-Tropsch reaction, so that the nano-domain effect of the holes is effectively improved, the active sites are prevented from being sintered, and the contact between synthesis gas and the active sites is not influenced. The selectivity of 100% to the target product can be realized while the catalytic activity and stability are maintained. In order to effectively improve the yield of aromatic hydrocarbon, the porosity, pore size and shell thickness of the shell layer can be regulated and controlled to regulate and control the diffusion speed of reactants and products to active sites; the morphology of the active particles is regulated and controlled, and the synergistic effect of the active metal and the shell material is maximized.
The method of preparing the core-shell structure is generally an impregnation method. The method comprises the steps of taking a template as a core layer or a shell layer, coating a required material on the template core or adsorbing the required material on the template shell through a vacuum suction filtration method, and removing impurities through calcination to form the catalyst with a core-shell structure. The literature "C Wu, L Dong, J Onwudii, PT Williams, J Huang [ J ]. Acs Sustainable Chemistry & Engineering,2013,1, 1083-1091", "the literature" X Zhang, CY Guo, ZC Zhang, JS Gao, CM Xu [ J ]. Journal of Catalysis,2012, 292, 213-226 "," all disclose methods of preparing core-shell catalysts, all methods being impregnation methods; the synthesized nano particles have strong interaction with the carrier, so that the contact between the synthesis gas and the active site is affected to a certain extent, and the catalytic activity and the selectivity of the target product are not improved. In addition, the impregnation method is suitable for preparing a core-shell structure, and is not suitable for synthesizing a single-core double-shell catalyst. Document "J Bao, J He, Y Zhang, Y Yoneyama, N Tsubaki [ J ]. Angewandte Chemie International Edition,2008, 120, 359-362", "document" S Sartrapi, JE van Dijk, J Gascon, F Kapteijn [ J ]. Applied Catalysis A: general,2013, 456, 11-22, "discloses a synthesis method of a dual-core-shell catalyst, in which a core-shell structure is synthesized by an impregnation method, an outermost shell layer is synthesized by a hydrothermal method, and then a soft template is removed by heating and calcining to obtain the core-shell catalyst.
The synthesis of the existing core-shell Fischer-Tropsch catalyst requires that the core-shell catalyst is obtained by adopting an impregnation method through vacuum suction filtration, and impurities are removed after calcination; the final core-shell structure can be obtained after the template substance is synthesized and calcined in the solution by a hydrothermal method. The process is relatively complicated, the morphology and the size of the prepared active particles are uncontrollable, and the required core-shell catalyst cannot be conveniently and rapidly prepared according to the needs.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the Fischer-Tropsch aromatic hydrocarbon catalyst which has the advantages of controllable morphology, adjustable shell thickness and adjustable size and is convenient to apply.
The invention also provides active metal oxide Fe with different morphologies 2 O 3 Fe with controllable core and shell thickness 2 O 3 @SiO 2 The preparation method of the core-shell structure and the hierarchical porous molecular sieve is simple, easy, convenient and quick, and the morphology and the size of the prepared core-shell catalyst with controllable morphology and size are easier to control.
The invention also provides application of the Fischer-Tropsch aromatic hydrocarbon catalyst in preparation of aromatic hydrocarbon.
The invention provides a simple and convenient method for preparing the Fischer-Tropsch aromatic hydrocarbon catalyst with controllable morphology and size and the obtained Fe 2 O 3 @SiO 2 The molecular sieve Fischer-Tropsch catalyst has the following specific technical scheme:
a Fischer-Tropsch aromatic hydrocarbon catalyst has the following performance parameters: is Fe 2 O 3 The shape of the nucleus is dish, cage, polyhedron, cube,Spindle shape.
Dishing Fe 2 O 3 The diameter of the polymer is 100-300 nanometers, and the thickness is 6-15 nanometers; cage Fe 2 O 3 The diameter of the catalyst is 1000-3000 nanometers; polyhedral Fe 2 O 3 The length of the polymer is 30-100 nanometers; cubic Fe 2 O 3 Length of 20-80 nm, spindle-shaped Fe 2 O 3 The length of the nano-meter is 500-3000 nanometers; siO (SiO) 2 The thickness of the shell layer is 5-40 nanometers, and the aperture is 3-4 nanometers; the Si/Al ratio of the porous molecular sieve is 15-30.
The invention relates to a preparation method of a Fischer-Tropsch aromatic hydrocarbon catalyst, which comprises the following steps:
(1) Fe with different morphology 2 O 3 Is prepared from the following steps: dissolving ferric salt in deionized water to prepare a solution; dissolving a hydrolysis accelerator and a protective agent in the solution, fully mixing the solution under stirring to obtain a mixed solution, and then transferring the mixed solution into a hydrothermal reaction kettle for heat preservation reaction at 180-200 ℃ for 8-10 h;
(2) Post-treatment: centrifugally separating and washing the product obtained in the step (1) to obtain disc-shaped, cage-shaped, polyhedral, cubic and spindle-shaped Fe 2 O 3 ；
(3) Core-shell Fe 2 O 3 @SiO 2 Is prepared from the following steps: fe with different morphologies synthesized in the step (1) 2 O 3 Dispersing tetraethyl orthosilicate in absolute ethyl alcohol, stirring and reacting for a certain time, introducing ammonia water and deionized water, and continuing stirring and reacting;
(4) Post-treatment: centrifugally separating and washing the product obtained in the step (3) to obtain core-shell Fe 2 O 3 @SiO 2 ；
(5) Preparation of molecular sieves: dissolving aluminum isopropoxide, tetraethyl orthosilicate and tetrapropylammonium hydroxide in deionized water, and carrying out reflux reaction; stirring and adding the triamino trimethoxysilane;
(6) Post-treatment: and (3) centrifugally separating, washing and calcining the product obtained in the step (5) to obtain the molecular sieve.
(7) Fe is added to 2 O 3 @SiO 2 Mixing with molecular sieve physically, tabletting and granulating to obtain Fe 2 O 3 @SiO 2 Molecular sieve core shell fischer-tropsch catalysts.
The ferric salt in the step (1) is ferrous oxalate dihydrate, ferric chloride hexahydrate, ferric nitrate, ferric ammonium citrate or ferrous ammonium sulfate; the anhydrous acetate is anhydrous potassium acetate, anhydrous sodium acetate and anhydrous ammonium acetate; the protective agent is polyvinylpyrrolidone, N-methyl pyrrolidone, vinyl pyrrolidone, 2-pyrrolidone or cetyl trimethyl ammonium bromide.
In the step (1), the concentration ratio of ferric salt to hydrolysis promoter to protective agent in the step (1) is 0.06-0.69:0.02-0.66:0.02-0.7, and the concentration of the reactant can be controlled to adjust Fe 2 O 3 Is a performance parameter of (a).
In the step (1), the reaction temperature is 150-200 ℃ and the reaction time is 6-15 h.
In the step (3) of the present invention, fe 2 O 3 The volume ratio of the absolute ethyl alcohol is 1:40-90.
In the step (3), the volume ratio of absolute ethyl alcohol to tetraethyl orthosilicate to ammonia water to water is 300:0.5-1.5:2-8:10-30, and the hydrolysis speed can be regulated and controlled by regulating the proportion relation among the absolute ethyl alcohol, the tetraethyl orthosilicate and the ammonia water to water so as to regulate and control SiO (silicon dioxide) 2 The thickness of the shell and the pore size.
In the step (3), the stirring reaction time is sequentially 2-5 h and 3-6 h, and the SiO can be regulated by regulating the reaction time 2 The thickness of the shell layer.
In the step (5), the mass ratio of the aluminum isopropoxide to the tetraethyl orthosilicate to the tetrapropylammonium hydroxide to the triamino trimethoxysilane is 1:10-40:10-30:0.5-2.
In the step (5), the reflux time is 15-30 h, the hydrothermal reaction temperature is 150-200 ℃, and the hydrothermal reaction time is 100-150 h.
In the step (6), the calcining temperature is 400-650 ℃ and the calcining time is 4-8h.
In the step (7) of the present invention, fe 2 O 3 @SiO 2 The mass ratio of the catalyst to the molecular sieve is 1.0:0.3 to 1.0.
Fischer-Tropsch aromatic hydrocarbon catalyst, which is used for Fischer-Tropsch reaction, and has reaction conditions of 300-350 ℃ and 2MPa, and flow rate of 2000-3000 mlh -1 g cat -1 Synthesis gas (H) 2 The ratio of/CO) is 1:1, and the Fischer-Tropsch product is aromatic hydrocarbon.
The invention has the beneficial effects that: the invention adopts a hydrothermal method to synthesize a Fischer-Tropsch aromatic hydrocarbon catalyst, firstly, ferric salt, a hydrolysis promoter and a protective agent are dissolved in deionized water, and then the solution is placed in a hydrothermal reaction kettle to react for a certain time to obtain Fe with different morphologies 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Next, a certain amount of Fe 2 O 3 Dispersing core and tetraethyl orthosilicate in a certain amount of absolute ethyl alcohol, stirring and reacting for a certain time at room temperature, then respectively adding a certain amount of ammonia water and deionized water, continuing stirring and reacting for a certain time at room temperature, and obtaining porous core-shell Fe 2 O 3 @SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Thirdly, dissolving aluminum isopropoxide, tetraethyl orthosilicate and tetrapropylammonium hydroxide in deionized water for reflux reaction; stirring and adding a molecular sieve with the mass of triamino trimethoxysilane and performing hydrothermal reaction; finally, fe is 2 O 3 @SiO 2 Mixing with molecular sieve physically, tabletting and granulating to obtain Fe 2 O 3 @SiO 2 Molecular sieve core shell fischer-tropsch catalysts. The invention synthesizes Fe with controllable morphology and size by utilizing simple hydrothermal reaction 2 O 3 @SiO 2 Molecular sieve Fischer-Tropsch catalysts due to SiO 2 The presence of the shell layer can avoid the active metal oxide (Fe 2 O 3 ) The collapse of the structure during the fischer-tropsch reaction is caused by inconsistent pressures on the inner and outer surfaces of the active particles. The method is also other kinds of SiO 2 The preparation of a stable catalyst provides technical support. Fe (Fe) 2 O 3 The morphology and size of the core are determined by the concentration of the starting reactants, the types of hydrolysis promoters and protectants, the reaction temperature and the reaction time, and the core-shell Fe 2 O 3 @SiO 2 SiO of (B) 2 The shell thickness is related to the volume ratio of absolute ethyl alcohol, tetraethyl orthosilicate, ammonia water, water and reaction time, and the Si/Al ratio of the molecular sieve is determined by the concentration of the initial reactant. Thus, can be communicated withOverregulating the relation of the reaction conditions to obtain Fe with required size and shell thickness 2 O 3 @SiO 2 Molecular sieve fischer-tropsch catalysts. Compared with the existing impregnation method and coprecipitation method, the preparation method is simple, the repeatability of preparation is good, the morphology, the size and the shell thickness are easier to control, and the granularity and pore size distribution are narrow.
The catalyst prepared by the invention has low reaction temperature, simple preparation process and high yield, and can obtain the porous single-core double-shell catalyst with different morphologies and shell thicknesses by controlling reaction conditions, and Fe with different morphologies is obtained in the technical scheme of the invention 2 O 3 The shape of the nucleus is dish-shaped, cage-shaped, polyhedral, cubic or spindle-shaped. Dishing Fe 2 O 3 The diameter of the polymer is 100-300 nanometers, and the thickness is 6-15 nanometers; cage Fe 2 O 3 The diameter of the catalyst is 1000-3000 nanometers; polyhedral Fe 2 O 3 The length of the polymer is 30-100 nanometers; cubic Fe 2 O 3 Length of 20-80 nm, spindle-shaped Fe 2 O 3 The length of the nano-meter is 500-3000 nanometers; siO (SiO) 2 The thickness of the shell layer is 5-40 nanometers, and the aperture is 3-4 nanometers; the Si/Al ratio of the porous molecular sieve is 15-30. Due to SiO 2 The stabilizing effect of the shell layer can effectively avoid active Fe 2 O 3 The deactivation and carbon deposition phenomena caused by the collapse of the core structure in the Fischer-Tropsch reaction process can greatly improve the catalytic activity and the product selectivity of the Fischer-Tropsch aromatic hydrocarbon catalyst, and compared with the existing shell-free protection iron-based catalyst (Wen CX, et al, fuel 2019, 244, 492-498; wen CX, et al, energy)&Fuel 2020, 34 (9), 11282-11289), the selectivity of the catalyst aromatic hydrocarbon prepared by the invention can reach 70wt%; in addition, the catalyst prepared by the invention has controllable morphology and adjustable size, which provides different finite space for the Fischer-Tropsch reaction, thereby realizing high activity and high selectivity of the Fischer-Tropsch reaction. In addition, the catalyst prepared by the invention has great application value in photocatalysis, biomass catalytic conversion and other aspects.
Drawings
FIG. 1 shows a disk-shaped Fe synthesized in example 1 of the present invention 2 O 3 Scanning electron microscope of (a)(SEM) pictures.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of a molecular sieve having a Si/Al ratio of 26 synthesized in example 1 of the present invention
FIG. 3 shows the synthesized cage Fe of example 2 of the present invention 2 O 3 Scanning Electron Microscope (SEM) pictures of (a).
FIG. 4 shows the synthesized cage Fe of example 2 of the present invention 2 O 3 @SiO 2 Transmission Electron Microscope (TEM) pictures of (a).
FIG. 5 is a Scanning Electron Microscope (SEM) photograph of a molecular sieve having a Si/Al ratio of 26 synthesized in example 3 of the present invention.
FIG. 6 shows a polyhedral Fe synthesized in example 5 of the present invention 2 O 3 Scanning Electron Microscope (SEM) pictures of (a).
FIG. 7 shows a cubical Fe synthesized in example 6 of the present invention 2 O 3 Scanning Electron Microscope (SEM) pictures of (a).
FIG. 8 shows spindle-shaped Fe synthesized in example 7 of the present invention 2 O 3 Scanning Electron Microscope (SEM) pictures of (a).
FIG. 9 shows a 22nm thick shell layer of spindle Fe synthesized in example 7 of the present invention 2 O 3 @SiO 2 Transmission Electron Microscope (TEM) pictures of (a).
FIG. 10 shows a spindle Fe with a shell thickness of 66nm synthesized in example 8 of the present invention 2 O 3 @SiO 2 Transmission Electron Microscope (TEM) pictures of (a).
FIG. 11 shows a spindle Fe with a shell thickness of 48nm synthesized in example 9 of the present invention 2 O 3 @SiO 2 Transmission Electron Microscope (TEM) pictures of (a).
Detailed Description
The invention is further illustrated by the following specific examples. The following examples focus on the technical part of the present invention, it being understood that the following description is only illustrative and not limiting.
Example 1
1.1 dissolving 0.5g of ferric chloride hexahydrate in 30mL of ethanol, stirring and adding 1g of polyvinylpyrrolidone, then adding 0.3. 0.3 mL ammonia water, and then placing in a hydrothermal reaction kettle at 180 ℃ for reaction for 8 hours;
1.2 after the reaction, the reaction solution is respectively centrifugally washed by distilled water for 3 to 4 times (the centrifugal speed is 6000 rpm) to obtain dish-shaped Fe 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the FIG. 1 shows Fe synthesized in this example 2 O 3 From the SEM pictures of (C), it can be seen that Fe is obtained 2 O 3 Is dish-shaped, has an average diameter of 250 nm and an average thickness of 13 nm;
1.3 to 0.5g Fe 2 O 3 Dispersing in 300mL absolute ethyl alcohol, adding 1.0 mL tetraethyl orthosilicate into absolute ethyl alcohol solution, stirring at normal temperature for 3h, adding 5mL ammonia water and 20mL water into the solution, and continuously stirring for 4h;
1.4 after the reaction, the reaction solution is centrifugally washed with distilled water and absolute ethyl alcohol for 3 to 4 times (centrifugal speed is 12000 rpm) to obtain Fe 2 O 3 @SiO 2 ，SiO 2 The average thickness of the shell layer was 6nm.
1.5 dissolving 0.5g aluminum isopropoxide, 15g tetraethyl orthosilicate, 10g tetrapropylammonium hydroxide in 30ml deionized water, placing the mixed solution in a 90 ℃ device for reflux for 20h; stirring and adding 0.6g of triamino trimethoxysilane; stirring for 6h, and then placing the mixed solution into a hydrothermal reaction kettle with the temperature of 170 ℃ to react for 120h;
after the reaction is completed, the reaction solution is centrifugally washed by distilled water and absolute ethyl alcohol for 3 to 4 times (the centrifugal speed is 12000 rpm), dried and then placed at 550 ℃ for calcination for 5 hours, and the molecular sieve with Si/Al of 26 is obtained. Fig. 2 is an SEM image of the molecular sieve synthesized in this example, and it can be seen from the figure that the molecular sieve obtained has a hierarchical porous structure with an average size of 500nm.
1.7 0.4g of Fe 2 O 3 @SiO 2 Mixing with 0.4g molecular sieve, tabletting, granulating to obtain catalyst, placing into fixed bed reactor, and heating at 330 deg.C and 2MPa at flow rate of 3000ml h -1 g cat -1 1:1 synthesis gas (H) 2 and/CO) in the atmosphere to obtain aromatic hydrocarbon.
Example 2
2.1 1g of ferric chloride hexahydrate was dissolved in 30mL of deionized water, stirred and 1g of polyvinylpyrrolidone was added, followed by 0.3. 0.3 mL ammonia, and then placed in a hydrothermal reaction vessel at 200℃for reaction for 10 hours.
2.2 the washing procedure for the sample was as in example 1.2 above. FIG. 3 shows Fe synthesized in this example 2 O 3 From the SEM pictures of (C), it can be seen that Fe is obtained 2 O 3 In the form of a cage with an average size of 1000 a nm a.
2.3 preparation and washing procedure of sample were the same as in examples 1.3 and 1.4, FIG. 4 shows the synthesis of Fe in this example 2 O 3 @SiO 2 From the TEM image of (C), it can be seen that Fe is obtained 2 O 3 @SiO 2 Is of a core-shell structure, siO 2 The thickness of the shell layer is 160nm.
2.4 preparation and washing procedure of molecular sieves the catalyst was prepared as in examples 1.5 and 1.6 above and used in the Fischer-Tropsch reaction under the same conditions as in example 1.7 above.
Example 3
3.1 The sample preparation and washing procedures were as in examples 2.1, 2.2 and 2.3 above.
3.2 dissolving 0.8g of aluminum isopropoxide, 15g of tetraethyl orthosilicate, 10g of tetrapropylammonium hydroxide in 30ml of deionized water, placing the mixed solution in a 90 ℃ device for reflux for 20h; stirring and adding 0.6g of triamino trimethoxysilane; stirring for 6h, and then placing the mixed solution into a hydrothermal reaction kettle with the temperature of 170 ℃ to react for 120h;
3.3 after the reaction, the reaction solution is centrifugally washed by distilled water and absolute ethyl alcohol for 3 to 4 times (the centrifugal speed is 12000 rpm), dried and then is calcined at 550 ℃ for 5 hours to obtain the molecular sieve with Si/Al of 18. Fig. 5 is an SEM image of the molecular sieve synthesized in this example, and it can be seen from the figure that the molecular sieve obtained has a hierarchical porous structure with an average size of 350nm.
3.4 0.4g of Fe 2 O 3 @SiO 2 Mixing with 0.4g molecular sieve, tabletting, granulating to obtain catalyst, placing into fixed bed reactor, and at 320 deg.C, 2MPa and flow rate of 3000ml h -1 g cat -1 1:1 synthesis gas (H) 2 and/CO) in the atmosphere to obtain aromatic hydrocarbon.
Example 4
4.1 preparation of samples and washing procedure were as in examples 3.1, 3.2 and 3.3 above.
4.2 0.5g Fe 2 O 3 @SiO 2 After being physically mixed with 0.3g molecular sieve, the mixture is pressed into tablets, granulated and then placed in a fixed bed reactor, and the mixture is subjected to 320 ℃ and 2MPa with the flow rate of 3000mlh -1 g cat -1 1:1 synthesis gas (H) 2 and/CO) in the atmosphere to obtain aromatic hydrocarbon.
Example 5
5.1 1g of ferric chloride hexahydrate and 2g of anhydrous sodium acetate were dissolved in 30mL of deionized water, stirred and 1g of cetyltrimethylammonium bromide was added, followed by 0.3. 0.3 mL ammonia, and then placed in a hydrothermal reaction vessel at 200℃for reaction for 10 hours.
5.2 the washing procedure for the sample was as in example 1.2 above. FIG. 6 shows the Fe synthesized in this example 2 O 3 From the SEM pictures of (C), it can be seen that Fe is obtained 2 O 3 Is polyhedral and has an average size of 55nm.
5.3 preparation of samples and washing procedure were as in examples 1.3, 1.4 above, siO was obtained 2 The thickness of the shell layer is 5nm.
5.4 molecular sieves were prepared and washed as in examples 1.5 and 1.6 above and the Fischer-Tropsch reaction conditions were as in example 1.7 above.
Example 6
6.1 1g of ferric chloride hexahydrate and 2g of anhydrous sodium acetate were dissolved in 30mL of deionized water, stirred and 1g of polyvinylpyrrolidone was added, followed by 0.3. 0.3 mL ammonia, and then placed in a hydrothermal reaction vessel at 200℃for reaction for 10 hours.
6.2 the washing procedure for the sample was as in example 1.2 above. FIG. 7 shows Fe synthesized in this example 2 O 3 From the SEM pictures of (C), it can be seen that Fe is obtained 2 O 3 Is cubic and has an average size of 45nm.
6.3 preparation of samples and washing procedure were as in examples 1.3, 1.4 above, siO was obtained 2 The thickness of the shell layer is 4.5nm.
6.4 molecular sieves were prepared and washed as in examples 1.5 and 1.6 above and the Fischer-Tropsch reaction conditions were as in example 4.2 above.
Example 7
7.1 1g of ferric chloride hexahydrate and 2g of anhydrous sodium acetate were dissolved in 30mL of deionized water, stirred and 1g of polyvinylpyrrolidone was added, followed by 1.0. 1.0 mL of ethylenediamine, and then placed in a hydrothermal reaction vessel at 200℃for reaction for 10 hours.
7.2 the washing procedure for the sample was as in example 1.2 above. FIG. 8 shows Fe synthesized in this example 2 O 3 From the SEM pictures of (C), it can be seen that Fe is obtained 2 O 3 Is spindle-shaped and has an average length of 1500nm;
7.3 preparation and washing procedure of sample were the same as in examples 1.3 and 1.4, FIG. 9 shows Fe synthesized in this example 2 O 3 @SiO 2 From the TEM photograph of (C), it can be seen that Fe is obtained 2 O 3 @SiO 2 Is of a core-shell structure, siO 2 The shell thickness was 22nm.
7.4 molecular sieves were prepared and washed as in examples 1.5 and 1.6 above and the Fischer-Tropsch reaction conditions were as in example 4.2 above.
Example 8
8.1 sample preparation and washing procedure were as in examples 1.1 and 1.2 above.
8.2 0.5g Fe 2 O 3 Dispersing in 300mL absolute ethyl alcohol, adding 1.5. 1.5 mL tetraethyl orthosilicate into absolute ethyl alcohol solution, stirring at normal temperature for 3h, adding 5mL ammonia water and 20mL water into the solution, and continuously stirring for 4h;
8.3 washing procedure of sample was the same as in example 1.4 above, FIG. 10 shows Fe synthesized in this example 2 O 3 @SiO 2 From the TEM photograph of (C), it can be seen that Fe is obtained 2 O 3 @SiO 2 Is of a core-shell structure, siO 2 The shell thickness was 66nm.
8.4 molecular sieves were prepared and washed as in examples 1.5 and 1.6 above and the Fischer-Tropsch reaction conditions were as in example 4.2 above.
Example 9
9.1 sample preparation and washing procedure were as in examples 1.1 and 1.2 above.
9.2 0.5g Fe 2 O 3 Dispersed in 300mL of anhydrousAdding 2.0ml of tetraethyl orthosilicate into absolute ethanol solution, stirring at normal temperature for 3h, adding 5ml of ammonia water and 20ml of water into the solution, and continuously stirring for 4h;
9.3 washing procedure of sample was the same as in example 1.4 above, FIG. 11 shows Fe synthesized in this example 2 O 3 @SiO 2 From the TEM photograph of (C), it can be seen that Fe is obtained 2 O 3 @SiO 2 Is of a core-shell structure, siO 2 The thickness of the shell layer is 48nm.
9.4 molecular sieves were prepared and washed as in examples 1.5 and 1.6 above and the Fischer-Tropsch reaction conditions were as in example 4.2 above.
Example 10
10.1 2g of ferric chloride hexahydrate and 1g of anhydrous ammonium acetate were dissolved in 30mL of deionized water, stirred and 1g of cetyltrimethylammonium bromide was added, followed by reaction in a hydrothermal reaction vessel at 180℃for 8 hours.
10.2 the washing procedure for the sample was as in example 1.2 above. Fe in the present example 2 O 3 For classification of porous microspheres, the average diameter was 300 nm.
10.3 preparation of samples and washing procedure were as in examples 1.3, 1.4 above, siO was obtained 2 The thickness of the shell layer is 5nm.
10.4 preparation and washing procedure of molecular sieves were as in examples 1.5 and 1.6 above.
10.5 0.5g of Fe 2 O 3 @SiO 2 After being physically mixed with 0.3g molecular sieve, the mixture is pressed into tablets, granulated and then placed in a fixed bed reactor, and the mixture is subjected to 300 ℃ and 2MPa with the flow rate of 2000mlh -1 g cat -1 1:1 synthesis gas (H) 2 and/CO) in the atmosphere to obtain aromatic hydrocarbon.

Claims (3)

1. A Fischer-Tropsch aromatic hydrocarbon catalyst is characterized in that the catalyst is Fe 2 O 3 @SiO 2 Molecular sieve, fe 2 O 3 The morphology of the active metal oxide is dish-shaped, cage-shaped, polyhedral, cubic or spindle-shaped; siO (SiO) 2 The shell layer is of an amorphous structure; the molecular sieve is of a porous hierarchical structure; the dish-shaped Fe 2 O 3 Is 100-300 nanometers in diameter and thickThe degree is 6-15 nanometers; cage Fe 2 O 3 The diameter of the catalyst is 1000-3000 nanometers; polyhedral Fe 2 O 3 The length of the polymer is 30-100 nanometers; cubic Fe 2 O 3 Length of 20-80 nm, spindle-shaped Fe 2 O 3 The length of the nano-meter is 500-3000 nanometers; siO (SiO) 2 The thickness of the shell layer is 5-40 nanometers, and the aperture is 3-4 nanometers; the Si/Al ratio of the porous molecular sieve is 15-30; fe (Fe) 2 O 3 @SiO 2 Is of core-shell structure, fe 2 O 3 Is nuclear, siO 2 Is a shell.
2. A process for preparing a fischer-tropsch aromatic catalyst as claimed in claim 1, comprising the steps of:
(1) Fe with different morphology 2 O 3 Is prepared from the following steps: dissolving ferric salt, a hydrolysis promoter and a protective agent in a solvent, and then placing the solvent in a reaction kettle for reaction; the ferric salt is ferrous oxalate dihydrate, ferric chloride hexahydrate, ferric nitrate, ferric ammonium citrate or ferrous ammonium sulfate; the hydrolysis promoter is anhydrous potassium acetate, anhydrous sodium acetate, anhydrous ammonium acetate or ammonia water; the protective agent is polyvinylpyrrolidone, N-methyl pyrrolidone, vinyl pyrrolidone, 2-pyrrolidone or cetyl trimethyl ammonium bromide; iron salt in step (1): acetate salt: the concentration ratio of the protective agent is 0.06-0.69: 0.02 to 0.66:0.02 to 0.7; the solvent in the step (1) is deionized water and absolute ethyl alcohol; the reaction temperature in the step (1) is 150-200 ℃ and the reaction time is 6-15 h;
(2) Post-treatment: centrifugally separating and washing the product obtained in the step (1) to obtain Fe with different morphologies 2 O 3 A core;
(3) Core-shell Fe 2 O 3 @SiO 2 Is prepared from the following steps: fe with different morphologies synthesized in the step (2) 2 O 3 Dispersing the core and tetraethyl orthosilicate in absolute ethyl alcohol, introducing ammonia water and deionized water after stirring reaction, and continuing stirring reaction; fe in step (3) 2 O 3 : the volume ratio of the absolute ethyl alcohol is 1:40-90; absolute ethyl alcohol, tetraethyl orthosilicate, ammonia water and water in the volume ratio of 1:130-300: 0.2 to 1.5:1.0 to 8: 5-30; the stirring reaction time is 2 to 5 hours and 3 to 6 hours in sequence;
(4) Post-treatment: centrifugally separating and washing the product obtained in the step (3) to obtain core-shell Fe 2 O 3 @SiO 2 ；
(5) Preparation of a hierarchical porous molecular sieve: dissolving aluminum isopropoxide, tetraethyl orthosilicate and tetrapropylammonium hydroxide in deionized water to prepare a mixed solution, refluxing the mixed solution, and stirring and adding triamino trimethoxysilane; stirring and then placing the mixed solution into a hydrothermal reaction kettle for reaction; in the step (5), the mass ratio of the aluminum isopropoxide to the tetraethyl orthosilicate to the tetrapropylammonium hydroxide to the triamino trimethoxysilane is 1:10-40:10-30:0.5-2; the reflux time is 15-30 h; stirring time is 6h; the hydrothermal reaction temperature is 150-200 ℃; the hydrothermal reaction time is 100-150 h;
(6) Post-treatment: centrifugally separating, washing and calcining the product obtained in the step (5) to obtain a molecular sieve;
（7） Fe 2 O 3 @SiO 2 preparation of molecular sieves: the Fe of the step (4) 2 O 3 @SiO 2 Mixing the core-shell catalyst with the molecular sieve in the step (6), tabletting and granulating;
in the step (6), the calcining temperature is 400-650 ℃; the calcination time is 4-8h;
in step (7), fe 2 O 3 @SiO 2 The mixing mass ratio with the molecular sieve is 1.0:0.3 to 1.0.
3. Use of a fischer-tropsch aromatic catalyst according to claim 1, wherein the catalyst is used in a fischer-tropsch reaction at a temperature of 300 to 350 ℃ at a flow rate of 2000 to 3000mlh at 2MPa -1 g cat -1 Synthesis gas H 2 The ratio of CO to Fischer-Tropsch product is aromatic hydrocarbon, which is 1:1.
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