CN114570412A - Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application - Google Patents
Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 49
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 49
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 49
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002808 molecular sieve Substances 0.000 claims abstract description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 239000011258 core-shell material Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000003223 protective agent Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004642 ferric ammonium citrate Drugs 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 235000000011 iron ammonium citrate Nutrition 0.000 claims description 2
- 239000004313 iron ammonium citrate Substances 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical group [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims 1
- 159000000021 acetate salts Chemical class 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 150000002696 manganese Chemical class 0.000 claims 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical group O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims 1
- 239000012286 potassium permanganate Substances 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000011257 shell material Substances 0.000 description 33
- 239000010410 layer Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
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- 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 Fe2O3@SiO2Molecular sieves, Fe2O3The shape of the active metal oxide is disc-shaped, cage-shaped, polyhedral, cubic or spindle-shaped; SiO 22The shell layer is of an amorphous structure; the molecular sieve is a porous hierarchical structure. The catalyst prepared by the invention has low reaction temperature, simple preparation process and high yield, and the porous single-core double-shell catalyst with different shapes and shell thicknesses can be obtained by controlling the reaction conditions2O3The shape of the nucleus is dish, cage, polyhedron,Cubic or spindle shaped. The selectivity of the aromatic hydrocarbon of the catalyst prepared by the invention can reach 70 wt%; in addition, the catalyst prepared by the method has controllable shape and adjustable size, different limited space is provided for Fischer-Tropsch reaction, and high activity and high selectivity of the Fischer-Tropsch reaction can be realized.
Description
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 thickness2O3@SiO2A molecular sieve Fischer-Tropsch catalyst and a preparation method thereof, belonging to the technical field of catalyst nano confinement.
Background
The core-shell structure catalyst can effectively eliminate the structural collapse caused by the inconsistent pressure of the inner surface and the outer surface of the nano particles in the Fischer-Tropsch reaction process and the nano particles growth caused by an Ostwald ripening mechanism, and can also solve the problems of carbon deposition and sintering. The core-shell structure is favored by researchers by virtue of higher catalytic activity and stability. Fischer-Tropsch synthesis gas (H)2+ CO) catalyzes the conversion to liquid fuel, a polymerization reaction that takes place on the surface of the catalyst. The filling 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 and reduce the nano confinement effect, thereby reducing the catalytic activity and the product selectivity. The preparation of the core-shell catalyst can inhibit the structural collapse caused by the inconsistent internal and external pressures of the active particles in the Fischer-Tropsch reaction, thereby effectively improving the nano confinement effect of pores, avoiding the sintering of active sites and not influencing the contact of synthesis gas and the active sites. The selectivity of 100 percent to the target product can be realized while the catalytic activity and the stability are maintained. In order to effectively improve the yield of the aromatic hydrocarbon, the porosity, the pore size and the thickness of the shell layer can be regulated to regulate the diffusion speed of reactants and products to an active site; 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 catalyst with a core-shell structure is prepared by coating a required material on a template core or adsorbing the required material on a template shell by using a template as a core layer or a shell layer through a vacuum filtration means, and removing impurities through calcination. The documents "C Wu, L Dong, J Onwudili, PT Williams, J Huang [ J ]. Acs Sustainable Chemistry & Engineering, 2013, 1, 1083-; the synthesized nano particles and the carrier have strong interaction, which affects the contact of the synthesis gas and the active site to a certain extent and is not beneficial to the improvement of catalytic activity and selectivity of target products. 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. Documents "J Bao, J He, Y Zhang, Y Yoneyama, N Tsubaki [ J ]. Angewandte Chemie International Edition, 2008, 120, 359-: general, 2013, 456, 11-22 "discloses a synthesis method of a dual-shell catalyst, in which a core-shell structure is synthesized by a dipping 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 structure catalyst.
The synthesis of the core-shell Fischer-Tropsch catalyst needs to adopt an impregnation method to obtain the core-shell catalyst through vacuum filtration, and impurities are removed after calcination; the final core-shell structure is then obtained by synthesis of the template material in solution by hydrothermal methods and calcination. The process is relatively complicated, the morphology and the size of the prepared active particles are not controllable, and the required core-shell catalyst cannot be conveniently and quickly prepared according to the requirement.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the Fischer-Tropsch aromatic hydrocarbon catalyst, and the structure has the advantages of controllable appearance, adjustable shell thickness, adjustable size and convenience in application.
The invention also provides active metal oxides Fe with different morphologies2O3Fe with controllable thickness of core and shell2O3@SiO2The preparation method of the core-shell structure and the hierarchical porous molecular sieve is simple, feasible, convenient and quick, and the shape and the size of the prepared core-shell catalyst with controllable shape and size are easier to control.
The invention also provides the application of the Fischer-Tropsch aromatic hydrocarbon catalyst in the preparation of aromatic hydrocarbons.
The invention provides a simple and convenient method for preparing a Fischer-Tropsch aromatic hydrocarbon catalyst with controllable morphology and size and Fe obtained by the method2O3@SiO2The molecular sieve Fischer-Tropsch catalyst has the following specific technical scheme:
a Fischer-Tropsch aromatic hydrocarbon catalyst has the performance parameters that: is Fe2O3The shape of the nucleus is dish, cage, polyhedron, cubic or spindle.
Disc shape Fe2O3The diameter of the glass is 100-300 nanometers, and the thickness of the glass is 6-15 nanometers; cage shape Fe2O3The diameter of (A) is 1000-3000 nm; polyhedral Fe2O3The length of (a) is 30-100 nm; cubic shape of Fe2O3Has a length of 20-80 nm and spindle-shaped Fe2O3The length of the glass is 500-3000 nm; SiO 22The 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 of different shapes2O3The preparation of (1): dissolving ferric salt in deionized water to prepare a solution; dissolving a hydrolysis promoter 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 hours;
(2) and (3) post-treatment: centrifugally separating and washing the product obtained in the step (1) to obtain disc-shaped, cage-shaped, polyhedral, cubic and spindle-shaped Fe2O3；
(3) Core-shell Fe2O3@SiO2The preparation of (1): fe with different shapes and synthesized in the step (1)2O3Dispersing tetraethyl orthosilicate and absolute ethyl alcohol, stirring and reacting for a certain time, introducing ammonia water and deionized water, and continuing stirring and reacting;
(4) and (3) post-treatment: centrifugally separating and washing the product obtained in the step (3) to obtain the core-shell Fe2O3@SiO2；
(5) Preparation of the molecular sieve: dissolving aluminum isopropoxide, tetraethyl orthosilicate and tetrapropyl ammonium hydroxide in deionized water, and carrying out reflux reaction; stirring and adding triaminotrimethoxylsilane;
(6) and (3) post-treatment: and (5) centrifugally separating, washing and calcining the product obtained in the step (5) to obtain the molecular sieve.
(7) Mixing Fe2O3@SiO2Physically mixing with molecular sieve, tabletting and granulating to obtain Fe2O3@SiO2Molecular sieve core-shell Fischer-Tropsch catalyst。
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 hexadecyl trimethyl ammonium bromide.
In the step (1), the concentration ratio of the ferric salt, the hydrolysis promoter and the 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 Fe2O3The performance parameter of (c).
In the step (1), the reaction temperature is 150-.
In step (3) of the present invention, Fe2O3The volume ratio of the absolute ethyl alcohol is 1: 40-90.
In the step (3), the volume ratio of the absolute ethyl alcohol to the tetraethyl orthosilicate to the ammonia water to the water is 300: 0.5-1.5: 2-8: 10-30, and the hydrolysis speed can be regulated and controlled by regulating the proportional relationship of the absolute ethyl alcohol to the tetraethyl orthosilicate to the ammonia water to regulate and control the SiO2Shell thickness and pore size.
In the step (3), the stirring reaction time is 2-5 h and 3-6 h in sequence, and the SiO can be adjusted by adjusting the reaction time2Thickness of the shell layer.
In the step (5), the mass ratio of aluminum isopropoxide to tetraethyl orthosilicate to tetrapropylammonium hydroxide to triaminotrimethoxysilane 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 4-8 h.
In step (7) of the present invention, Fe2O3@SiO2The mass ratio of the zeolite to the molecular sieve is 1.0: 0.3 to 1.0.
The catalyst is used for Fischer-Tropsch reaction, and the reaction conditions are 300-350 ℃, 2MPa,The flow rate is 2000-3000 mlh-1gcat -1Synthetic gas (H)2the/CO) is 1:1, the Fischer-Tropsch product is an 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 morphologies2O3(ii) a Secondly, a certain amount of Fe2O3Dispersing the core and tetraethyl orthosilicate in a certain amount of absolute ethyl alcohol, stirring and reacting at room temperature for a certain time, then respectively adding a certain amount of ammonia water and deionized water, and continuously stirring and reacting at room temperature for a certain time to obtain the porous core-shell Fe2O3@SiO2(ii) a Thirdly, dissolving aluminum isopropoxide, tetraethyl orthosilicate and tetrapropyl ammonium hydroxide in deionized water, and carrying out reflux reaction; stirring and adding triaminotrimethoxylsilane, and carrying out hydrothermal reaction to obtain a molecular sieve; finally, Fe2O3@SiO2Physically mixing with molecular sieve, tabletting and granulating to obtain Fe2O3@SiO2Molecular sieve core-shell Fischer-Tropsch catalyst. The invention synthesizes Fe with controllable shape and size by simple hydrothermal reaction2O3@SiO2Molecular sieve Fischer-Tropsch catalyst due to SiO2The presence of a shell layer can avoid active metal oxide (Fe)2O3) The collapse of the structure caused by the inconsistent internal and external surface pressures of the active particles during the Fischer-Tropsch reaction process. The method is also applicable to other SiO types2The preparation of the stable catalyst provides technical support. Fe2O3The shape and size of the core are determined by the concentration of the initial reactants, the types of the hydrolysis promoter and the protective agent, the reaction temperature and the reaction time, and the shape and size of the core are determined by the Fe content of the core shell2O3@SiO2SiO 22The thickness of the shell layer is related to the volume ratio of absolute ethyl alcohol, tetraethyl orthosilicate, ammonia water and the reaction time, and the Si/Al ratio of the molecular sieve is determined by the concentration of the initial reactants. Therefore, Fe of a desired size and shell thickness can be obtained by adjusting the relationship of these reaction conditions2O3@SiO2Molecular sieveA Fischer-Tropsch catalyst. Compared with the existing impregnation method and coprecipitation method, the method of the invention has the advantages of simplicity, good repeatability of preparation, easier control of morphology, size and shell thickness, and narrow particle size and pore size distribution.
The catalyst prepared by the invention has low reaction temperature, simple preparation process and high yield, and the porous single-core double-shell catalyst with different shapes and shell thicknesses can be obtained by controlling the reaction conditions2O3The shape of the nucleus is dish, cage, polyhedron, cubic or spindle. Disc shape Fe2O3The diameter of the glass is 100-300 nanometers, and the thickness of the glass is 6-15 nanometers; cage shape Fe2O3The diameter of (A) is 1000-3000 nm; polyhedral Fe2O3The length of (a) is 30-100 nm; cubic shape of Fe2O3Has a length of 20-80 nm and spindle-shaped Fe2O3The length of the glass is 500-3000 nm; SiO 22The 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 SiO2The stabilization of the shell layer can effectively avoid active Fe2O3The deactivation and carbon deposition phenomena caused by the structural collapse of the core in the Fischer-Tropsch reaction process can further greatly improve the catalytic activity and the product selectivity of the Fischer-Tropsch aromatic hydrocarbon catalyst, and compared with the existing iron-based catalyst without shell protection (Wen CX, et al, Fuel 2019,244, 492) 498; Wen CX, et al, Energy&Fuel 2020,34(9),11282-11289), the aromatic selectivity of the catalyst prepared by the invention can reach 70 wt%; in addition, the catalyst prepared by the method has controllable shape and adjustable size, different limited space is provided for Fischer-Tropsch reaction, and high activity and high selectivity of the Fischer-Tropsch reaction can be realized. In addition, the catalyst prepared by the invention has great application value in the aspects of photocatalysis, biomass catalytic conversion and the like.
Drawings
FIG. 1 is a disk-shaped Fe synthesized in example 1 of the present invention2O3Scanning Electron Microscope (SEM) pictures of (a).
FIG. 2 is a Scanning Electron Microscope (SEM) picture of a molecular sieve synthesized in example 1 of the present invention and having a Si/Al ratio of 26
FIG. 3 shows a cage Fe synthesized in example 2 of the present invention2O3Scanning Electron Microscope (SEM) pictures of (a).
FIG. 4 shows the synthesis of cage Fe according to example 2 of the present invention2O3@SiO2Transmission Electron Microscope (TEM) pictures of (a).
FIG. 5 is a Scanning Electron Microscope (SEM) picture of a molecular sieve synthesized in example 3 of the present invention and having a Si/Al ratio of 26.
FIG. 6 is polyhedral Fe synthesized in example 5 of the present invention2O3Scanning Electron Microscope (SEM) pictures of (a).
FIG. 7 is a cubic Fe synthesized in example 6 of the present invention2O3Scanning Electron Microscope (SEM) pictures of (a).
FIG. 8 shows spindle-shaped Fe synthesized in example 7 of the present invention2O3Scanning Electron Microscope (SEM) pictures of (a).
FIG. 9 shows a spindle-shaped Fe with a shell thickness of 22nm synthesized in example 7 of the present invention2O3@SiO2Transmission Electron Microscope (TEM) pictures of (a).
FIG. 10 shows a 66nm thick spindle Fe shell synthesized in example 8 of the present invention2O3@SiO2Transmission Electron Microscope (TEM) pictures of (a).
FIG. 11 shows a shell of 48nm thick spindle Fe synthesized in example 9 of the present invention2O3@SiO2Transmission Electron Microscope (TEM) pictures of (a).
Detailed Description
The invention is further illustrated by the following specific examples. The following examples are intended to illustrate the technical aspects of the present invention, and it should be understood that the following descriptions are only illustrative and not intended to limit the present invention.
Example 1
1.1 dissolving 0.5g of ferric chloride hexahydrate in 30mL of ethanol, stirring, adding 1g of polyvinylpyrrolidone, then adding 0.3mL of ammonia water, and then placing in a hydrothermal reaction kettle at 180 ℃ for reaction for 8 hours;
1.2 after the reaction is finished, the reaction solution is centrifugally washed with distilled water to 3 to4 times (the centrifugal speed is 6000rpm) to obtain the dished Fe2O3(ii) a FIG. 1 shows Fe synthesized in this example2O3SEM picture of (1), it can be seen from the figure that Fe is obtained2O3Is disc-shaped, has an average diameter of 250nm and an average thickness of 13 nm;
1.3 0.5g Fe2O3Dispersing in 300mL of absolute ethanol, simultaneously adding 1.0mL of tetraethyl orthosilicate into the absolute ethanol solution, stirring at normal temperature for 3h, adding 5mL of ammonia water and 20mL of water into the solution, and continuing stirring for 4 h;
1.4 after the reaction, centrifugally washing the reaction solution with distilled water and absolute ethyl alcohol for 3-4 times (centrifugal speed 12000rpm) to obtain Fe2O3@SiO2，SiO2The average thickness of the shell layer was 6 nm.
1.5 dissolving 0.5g of aluminum isopropoxide, 15g of tetraethyl orthosilicate and 10g of tetrapropylammonium hydroxide in 30ml of deionized water, and placing the mixed solution in a device at 90 ℃ for refluxing for 20 hours; stirring and adding 0.6g of triaminotrimethoxysilane; stirring for 6h, and then placing the mixed solution in a hydrothermal reaction kettle at the temperature of 170 ℃ for reaction for 120 h;
1.6 after the reaction is finished, centrifugally washing the reaction solution for 3-4 times by using distilled water and absolute ethyl alcohol (centrifugal speed is 12000rpm), drying, and calcining at 550 ℃ for 5 hours to obtain the molecular sieve with Si/Al of 26. FIG. 2 is an SEM picture of the molecular sieve synthesized in this example, and it can be seen that the molecular sieve obtained has a hierarchical porous structure and an average size of 500 nm.
1.7 mixing 0.4gFe2O3@SiO2Physically mixing with 0.4g molecular sieve, tabletting and granulating to obtain catalyst, placing in a fixed bed reactor, and making the catalyst be placed at 330 deg.C, 2MPa and flow rate of 3000mlh-1gcat -11:1 Synthesis gas (H)2Reaction is carried out in a/CO) atmosphere to obtain the aromatic hydrocarbon.
Example 2
2.1 dissolving 1g of ferric chloride hexahydrate in 30mL of deionized water, stirring and adding 1g of polyvinylpyrrolidone, then adding 0.3mL of ammonia water, and then placing in a 200 ℃ hydrothermal reaction kettle for reaction for 10 h.
2.2 washing of the samplesThe washing procedure was as in example 1.2 above. FIG. 3 shows Fe synthesized in this example2O3SEM picture of (1), it can be seen from the figure that Fe is obtained2O3Is cage-shaped and has an average size of 1000 nm.
2.3 preparation of sample and washing procedure same as in examples 1.3 and 1.4, FIG. 4 shows Fe synthesized in this example2O3@SiO2TEM picture of (B), from which it can be seen that Fe is obtained2O3@SiO2Is of a core-shell structure, SiO2The thickness of the shell layer is 160 nm.
2.4 preparation and washing procedures of the molecular sieve are the same as in examples 1.5 and 1.6, and the catalyst prepared is used in the fischer-tropsch reaction, the fischer-tropsch reaction conditions being the same as in example 1.7.
Example 3
3.1 preparation of samples and washing procedure as in examples 2.1, 2.2, 2.3 above.
3.2 dissolving 0.8g of aluminum isopropoxide, 15g of tetraethyl orthosilicate and 10g of tetrapropylammonium hydroxide in 30ml of deionized water, and placing the mixed solution in a device at 90 ℃ for refluxing for 20 hours; stirring and adding 0.6g of triaminotrimethoxysilane; stirring for 6h, and then placing the mixed solution in a hydrothermal reaction kettle at the temperature of 170 ℃ for reaction for 120 h;
3.3 after the reaction is finished, centrifugally washing the reaction solution for 3-4 times by using distilled water and absolute ethyl alcohol (centrifugal speed is 12000rpm), drying, and calcining at 550 ℃ for 5 hours to obtain the molecular sieve with the Si/Al of 18. FIG. 5 is an SEM picture of the molecular sieve synthesized in this example, and it can be seen that the molecular sieve obtained has a hierarchical porous structure and an average size of 350 nm.
3.4 adding 0.4gFe2O3@SiO2Physically mixing with 0.4g molecular sieve, tabletting and granulating to obtain catalyst, placing in a fixed bed reactor, and making reaction at 320 deg.C, 2MPa and flow rate of 3000mlh-1gcat -11:1 Synthesis gas (H)2Reaction is carried out in a/CO) atmosphere to obtain the aromatic hydrocarbon.
Example 4
4.1 preparation of samples and washing procedure as in examples 3.1, 3.2, 3.3.
4.2 0.5g Fe2O3@SiO2Physically mixing with 0.3g molecular sieve, tabletting, granulating, placing in a fixed bed reactor, and treating at 320 deg.C and 2MPa at flow rate of 3000mlh-1gcat -11:1 Synthesis gas (H)2/CO)
Reacting in the atmosphere to obtain the aromatic hydrocarbon.
Example 5
5.1 dissolving 1g of ferric chloride hexahydrate and 2g of anhydrous sodium acetate in 30mL of deionized water, stirring and adding 1g of cetyltrimethylammonium bromide, followed by adding 0.3mL of ammonia water, and then placing in a 200 ℃ hydrothermal reaction kettle for reaction for 10 hours.
5.2 the sample was washed as in example 1.2 above. FIG. 6 shows Fe synthesized in this example2O3SEM picture of (1), it can be seen from the figure that Fe is obtained2O3Is polyhedral and has an average size of 55 nm.
5.3 preparation of samples and washing procedure as in examples 1.3, 1.4, SiO2The thickness of the shell layer is 5 nm.
5.4 preparation and washing of the molecular sieves were 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 dissolving 1g of ferric chloride hexahydrate and 2g of anhydrous sodium acetate in 30mL of deionized water, stirring and adding 1g of polyvinylpyrrolidone, then adding 0.3mL of ammonia water, and then placing in a 200 ℃ hydrothermal reaction kettle for reaction for 10 h. 6.2 the sample was washed as in example 1.2 above. FIG. 7 shows Fe synthesized in this example2O3The SEM picture of (a) is shown,
as can be seen from the figure, the resulting Fe2O3Is cubic and has an average size of 45 nm.
6.3 preparation of samples and washing procedure as in examples 1.3, 1.4, SiO2The thickness of the shell layer is 4.5 nm.
6.4 preparation and washing of the molecular sieves were 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 ferric chloride hexahydrate and 2g anhydrous sodium acetate are dissolved in 30mL deionized water, stirred and 1g polyvinylpyrrolidone is added followed by 1.0mL ethylenediamine, then placed in a 200 ℃ hydrothermal reaction kettle and reacted for 10 h.
7.2 the sample was washed as in example 1.2 above. FIG. 8 shows Fe synthesized in this example2O3SEM picture of (1), it can be seen from the figure that Fe is obtained2O3Is spindle-shaped, and the average length is 1500 nm;
7.3 preparation of sample and washing procedure same as in examples 1.3 and 1.4, FIG. 9 shows Fe synthesized in this example2O3@SiO2The TEM photograph of (A) shows that Fe was obtained2O3@SiO2Is of a core-shell structure, SiO2The thickness of the shell layer is 22 nm.
7.4 preparation and washing of the molecular sieves were 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 preparation of samples and washing procedure as in examples 1.1, 1.2 above.
8.2 0.5g Fe2O3Dispersing in 300mL of absolute ethyl alcohol, simultaneously adding 1.5mL of tetraethyl orthosilicate into the absolute ethyl alcohol solution, stirring at normal temperature for 3h, adding 5mL of ammonia water and 20mL of water into the solution, and continuing stirring for 4 h;
8.3 washing of samples the same as in example 1.4 above, FIG. 10 shows the Fe synthesized in this example2O3@SiO2TEM of
Photograph, as can be seen from the figure, the resulting Fe2O3@SiO2Is of a core-shell structure, SiO2The thickness of the shell layer is 66 nm.
8.4 preparation and washing of the molecular sieves were 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 preparation of samples and washing procedure as in examples 1.1, 1.2 above.
9.2 0.5g Fe2O3Dispersing in 300mL of absolute ethanol, simultaneously adding 2.0mL of tetraethyl orthosilicate into the absolute ethanol solution, stirring at normal temperature for 3h, adding 5mL of ammonia water and 20mL of water into the solution, and continuing stirringStirring for 4 h;
9.3 sample washing procedure as in example 1.4 above, FIG. 11 is Fe synthesized in this example2O3@SiO2TEM of
Photograph, as can be seen from the figure, the resulting Fe2O3@SiO2Is of a core-shell structure, SiO2The thickness of the shell layer is 48 nm.
9.4 preparation and washing of the molecular sieves were 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 dissolving 2g of ferric chloride hexahydrate and 1g of anhydrous ammonium acetate in 30mL of deionized water, stirring and adding 1g of cetyltrimethylammonium bromide, then placing in a 180 ℃ hydrothermal reaction kettle for reaction for 8 h.
The washing process for the 10.2 sample was the same as in example 1.2 above. Fe in this example2O3The microspheres are graded porous microspheres with an average diameter of 300 nm.
10.3 preparation of samples and washing procedure as in examples 1.3, 1.4, SiO2The thickness of the shell layer is 5 nm.
10.4 preparation of the molecular sieves and washing procedure were as in examples 1.5 and 1.6 above.
10.5 mixing 0.5gFe2O3@SiO2Physically mixing with 0.3g molecular sieve, tabletting, granulating, placing in a fixed bed reactor, and treating at 300 deg.C under 2MPa and flow rate of 2000mlh-1gcat -11:1 Synthesis gas (H)2Reaction is carried out in a/CO) atmosphere to obtain the aromatic hydrocarbon.
Claims (10)
1. The Fischer-Tropsch aromatic hydrocarbon catalyst is characterized in that the catalyst is Fe2O3@SiO2Molecular sieves, Fe2O3The shape of the active metal oxide is disc-shaped, cage-shaped, polyhedral, cubic or spindle-shaped; SiO 22The shell layer is of an amorphous structure; the molecular sieve is a porous hierarchical structure.
2. Fischer-Tropsch aromatic hydrocarbon catalyst according to claim 1, characterised in that the dish-shaped Fe2O3The diameter of the glass is 100-300 nanometers, and the thickness of the glass is 6-15 nanometers; cage shape Fe2O3The diameter of (a) is 1000-3000 nm; polyhedral Fe2O3The length of (a) is 30-100 nm; cubic shape of Fe2O3Has a length of 20-80 nm and spindle-shaped Fe2O3The length of the glass is 500-3000 nm; SiO 22The 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.
3. A process for the preparation of a fischer-tropsch aromatic catalyst as claimed in any one of claims 1 to 2, comprising the steps of:
(1) fe of different shapes2O3The preparation of (1): dissolving ferric salt, a hydrolysis promoter and a surfactant in a solvent, and then placing the solution in a reaction kettle for reaction;
(2) and (3) post-treatment: centrifugally separating and washing the product obtained in the step (1) to obtain Fe with different shapes2O3A core;
(3) core-shell Fe2O3@SiO2The preparation of (1): fe with different morphologies synthesized in the step (2)2O3Dispersing the core and tetraethyl orthosilicate in absolute ethyl alcohol, stirring for reaction, introducing ammonia water and deionized water, and continuing stirring for reaction;
(4) and (3) post-treatment: centrifugally separating and washing the product obtained in the step (3) to obtain the core-shell Fe2O3@SiO2；
(5) Preparing a hierarchical porous molecular sieve: dissolving aluminum isopropoxide, tetraethyl orthosilicate and tetrapropyl ammonium hydroxide in deionized water to prepare a mixed solution, refluxing the mixed solution, and stirring and adding triaminotrimethoxysilane; after stirring, placing the mixed solution in a hydrothermal reaction kettle for reaction;
(6) and (3) post-treatment: centrifugally separating, washing and calcining the product obtained in the step (5) to obtain the molecular sieve;
(7)Fe2O3@SiO2preparation of molecular sieves: subjecting the Fe obtained in the step (4)2O3@SiO2And (4) mixing the core-shell catalyst and the molecular sieve in the step (6), tabletting and granulating.
4. The Fischer-Tropsch aromatic hydrocarbon catalyst preparation method of claim 3, characterized in that: 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 hexadecyl trimethyl ammonium bromide; the manganese salt is manganese acetate tetrahydrate, potassium manganate, potassium permanganate or manganous chloride tetrahydrate.
5. The Fischer-Tropsch aromatic hydrocarbon catalyst preparation method of claim 3, characterized in that: by mass, iron salt in step (1): acetate salt: the concentration ratio of the protective agent is 0.06-0.69: 0.02-0.66: 0.02 to 0.7; in the step (1), the solvent is deionized water and absolute ethyl alcohol; the reaction temperature in the step (1) is 150-.
6. The Fischer-Tropsch aromatic hydrocarbon catalyst preparation method of claim 3, characterized in that: fe in step (3)2O3: the volume ratio of the absolute ethyl alcohol is 1: 40-90; the volume ratio of the absolute ethyl alcohol to the tetraethyl orthosilicate to the ammonia water to the water is 1: 130-300: 0.2-1.5: 1.0-8: 5-30; the stirring reaction time is 2-5 hours and 3-6 hours in sequence.
7. The Fischer-Tropsch aromatic hydrocarbon catalyst preparation method of claim 3, characterized in that: in the step (5), the mass ratio of aluminum isopropoxide to tetraethyl orthosilicate to tetrapropylammonium hydroxide to triaminotrimethoxysilane is 1: 10-40: 10-30: 0.5-2; the reflux time is 15-30 h; the stirring time is 6 h; the hydrothermal reaction temperature is 150-200 ℃; the hydrothermal reaction time is 100-150 h.
8. The Fischer-Tropsch aromatic hydrocarbon catalyst preparation method of claim 3, characterized in that: in the step (6), the calcining temperature is 400-650 ℃; the calcination time is 4-8 h.
9. The Fischer-Tropsch aromatic hydrocarbon catalyst preparation method of claim 3, characterized in that: in step (7), Fe2O3@SiO2The mixing mass ratio of the zeolite to the molecular sieve is 1.0: 0.3 to 1.0.
10. Use of a fischer-tropsch aromatic catalyst as claimed in any one of claims 1 to 2, wherein the catalyst is for use in a fischer-tropsch reaction at a temperature of from 300 to 350 ℃, at a pressure of 2MPa and at a flow rate of from 2000 to 3000mlh-1gcat -1Synthetic gas (H)2the/CO) is 1:1, the Fischer-Tropsch product is an aromatic hydrocarbon.
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