CN112536066A - Preparation method of mesoporous Fe-Beta molecular sieve catalyst containing core-shell structure - Google Patents
Preparation method of mesoporous Fe-Beta molecular sieve catalyst containing core-shell structure Download PDFInfo
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- CN112536066A CN112536066A CN202011515494.9A CN202011515494A CN112536066A CN 112536066 A CN112536066 A CN 112536066A CN 202011515494 A CN202011515494 A CN 202011515494A CN 112536066 A CN112536066 A CN 112536066A
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- molecular sieve
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- beta molecular
- sieve catalyst
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 68
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000011258 core-shell material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 21
- 229910001868 water Inorganic materials 0.000 claims abstract description 21
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000012452 mother liquor Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- -1 ammonium ions Chemical class 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 239000000499 gel Substances 0.000 description 20
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 9
- 239000011790 ferrous sulphate Substances 0.000 description 8
- 235000003891 ferrous sulphate Nutrition 0.000 description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 8
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 7
- 239000000264 sodium ferrocyanide Substances 0.000 description 7
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 7
- 239000011148 porous material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002149 hierarchical pore Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2807—Metal other than sintered metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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
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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
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Abstract
The invention discloses a preparation method of a mesoporous Fe-Beta molecular sieve catalyst containing a core-shell structure, belonging to the field of molecular sieve catalyst preparation. The method comprises the following specific steps: a) dispersing an iron source, a carbon source and an aluminum source in deionized water, and stirring and mixing. Reacting the mixed solution at constant temperature, filtering the precipitate, and drying; b) roasting the precipitate to obtain a Fe-C-Al precursor containing a core-shell structure; c) uniformly mixing Fe-C-Al, a silicon source, an alkali source and a template agent in water, and transferring the mixture into a pressure kettle for crystallization reaction; d) and (3) carrying out mother liquor removal, washing, exchange, drying and roasting on the reaction product to obtain the mesoporous Fe-Beta molecular sieve catalyst containing the core-shell structure. Fe-C-Al precursor prepared by the inventionThe prepared Fe-Beta molecular sieve catalyst has a mesoporous structure communicated with the core shell, and the product has high crystallinity, high specific surface area, rich mesopores and uniform iron distribution. Application to ammonia selective catalytic reduction (NH)3-SCR) reaction, the catalytic performance is excellent.
Description
Technical Field
The invention relates to a preparation method of a mesoporous Fe-Beta molecular sieve catalyst containing a core-shell structure, belonging to the field of molecular sieve catalyst preparation.
Background
The Beta molecular sieve is a high-silicon molecular sieve, the silica-alumina ratio of the Beta molecular sieve is wider than the range of about 10-200, and the Beta molecular sieve has higher hydrothermal stability than other synthetic zeolites. The Beta molecular sieve has a twelve-membered ring three-dimensional channel structure, a stacking layer structure is stacked by three ordered prototype structures of A type (tetragonal system), B type (monoclinic system) and C type (monoclinic system), a straight channel with twelve-membered rings is arranged along the directions of a and B axes, the pore diameter is about 0.73nm multiplied by 0.60nm, a twisted twelve-membered ring channel is arranged along the direction of C axis, and the pore diameter is about 0.56nm multiplied by 0.56 nm. A. B, C the prototype structure has similar occurrence probability of 0.31, 0.36 and 0.33, and the occurrence probability is not influenced by the silicon-aluminum ratio of Beta molecular sieve, and the channel structure is shown in FIG. 4. Due to the high hydrothermal stability, good shape selection property and acidity, the Beta molecular sieve shows excellent catalytic performance in the reactions of isomerization, hydrocracking, preparation of isopropylbenzene from benzene and propylene, alkylation of aromatic hydrocarbon, disproportionation of toluene and the like.
Due to the fact that the Beta molecular sieve modified by metal ions is in NH3The catalytic activity and selectivity of the SCR reaction are good, so that the modification of Beta molecular sieves by different metal ions is also a research hotspot gradually. The modification of Beta molecular sieves has mainly focused on both iron and copper ion types. The modified Fe-Beta molecular sieve catalyst has good NH3SCR reactivity and hydrothermal stability, with different iron species in Fe-Beta, and the type of iron species is loaded and preparedTogether with the influence.
In molecular sieve catalytic reactions, in addition to acidic factors, diffusion limitations are the primary cause of deactivation of molecular sieve catalysts. In order to solve the diffusion problem, researchers introduce mesoporous/macroporous channels on the molecular sieve, so that the diffusion performance and the hydrothermal stability can be guaranteed. Chinese patent CN 110078089A discloses a preparation method of a hierarchical pore Beta molecular sieve, which mainly comprises the steps of carrying out alkali treatment on the Beta molecular sieve, and then supplementing an aluminum source and a template agent in a desilication solution for crystallization to obtain the hierarchical pore Beta molecular sieve. Chinese patent CN 108455629A discloses a method for synthesizing a hierarchical pore Beta molecular sieve in a one-step guiding manner, which utilizes quaternary ammonium salts with three branched chain structures and rigid benzene rings as template agents and tetraethoxysilane as silicon sources to synthesize the hierarchical pore Beta molecular sieve in a one-step guiding manner. The conventional hard template method mainly uses carbon-aerogel, carbon nanoparticles, mesoporous carbon, carbon nanotubes, etc. However, due to the characteristics of the hydrophobicity of the carbon material, the weak acting force between the carbon material and silicon species and the like, the carbon material is often in a phase-separated state in the zeolite synthesis process and cannot play a role in pore forming of a template. And even if the mesoporous or macroporous pore channels are prepared, the mesoporous or macroporous porous channels can be blocked or damaged during subsequent metal loading or roasting.
Therefore, a mesoporous molecular sieve catalyst product loaded with metal can be directly obtained by selecting a proper reaction system to effectively regulate and control the reaction temperature and time without using a special organic template agent (surfactant) or post-treatment and other methods. The preparation method of the mesoporous Fe-Beta molecular sieve catalyst with the core-shell structure, which is stable in process flow, is urgently needed to be developed, and has important significance for preparing the high-performance molecular sieve catalyst.
Disclosure of Invention
Aiming at the problems existing in the modification post-treatment and application of the Fe-Beta molecular sieve in the prior art, the invention aims to provide a preparation method of a mesoporous Fe-Beta molecular sieve catalyst containing a core-shell structure. The method has the advantages of simple and convenient operation process, controllable reaction parameters, high product crystallinity, high specific surface area, abundant mesopores, uniform iron distribution, high yield, capability of greatly improving the hydrothermal resistance and the catalytic performance of the molecular sieve and stable process flow.
The invention has the following specific technical scheme that the preparation method of the mesoporous Fe-Beta molecular sieve catalyst containing the core-shell structure is realized by the following steps:
a) preparing a dilute solution from an iron source, a carbon source and an aluminum source, dispersing the dilute solution into deionized water, and continuously stirring. Stirring the mixed solution at the constant temperature of 5-20 ℃ for reaction for 0.1-2 hours; filtering and washing the precipitate until no soluble salt exists, wherein the drying temperature of the product is not higher than 80 ℃;
b) and C) rotating and roasting the precipitate in the step a) in an inert atmosphere to obtain the Fe-C-Al precursor.
c) Uniformly mixing the Fe-C-Al precursor obtained in the step b), a silicon source, an alkali source and a template agent in water, transferring the mixture into a pressure kettle, and crystallizing under certain conditions;
d) and c) carrying out mother liquor removal, washing, exchange, drying and roasting on the reaction product in the step c) to obtain the mesoporous Fe-Beta molecular sieve catalyst containing the core-shell structure.
In the step a), the iron source is ferrous salt, including any one or a mixture of ferrous sulfate, ferrous chloride and the like, preferably ferrous sulfate; the carbon source is ferrocyanide which comprises any one or a mixture of sodium ferrocyanide, potassium ferrocyanide and ammonium ferrocyanide; the aluminum source is any one or a mixture of aluminum sulfate and aluminum chloride, and aluminum sulfate is preferred. The concentration of the prepared raw material dilute solution is not higher than 1mol/L, the preferable concentration is 0.05-0.5 mol/L, and the more preferable concentration is 0.05-0.2 mol/L.
Keeping the temperature of the mixed solution in the step a) at 5-20 ℃, and stirring for reaction for 0.1-2 hours. Washing the precipitate with water until no soluble salt including sodium, potassium, ammonium ion, etc. Preferably keeping the temperature at 5-15 ℃, and stirring for reaction for 0.1-2 hours. Washing with water until the content of sodium, potassium and ammonium ions is less than 500 ppm. The drying temperature of the precipitate fine is not higher than 80 ℃.
In the step b), the inert atmosphere is one of helium, argon and nitrogen, and the nitrogen is preferred economically; the flow rate of the inert gas is 100-500 ml/min, and the roasting temperature is as follows: 300-500 ℃, roasting time: 2-8 hours. In order to obtain a more preferable effect of the invention, rotary firing is preferable.
In the step b), the Fe-C-Al precursor contains 20-55% of ferric oxide, 17-47% of carbon and 6-68% of aluminum oxide, wherein the percentages are mass percentages.
In the step c), the silicon source is one or a mixture of silica sol, white carbon black and silica gel, and the silica sol is preferred; the alkali source is one or mixture of sodium hydroxide and potassium hydroxide, preferably sodium hydroxide; the template agent is one or a mixture of tetraethyl ammonium hydroxide and tetraethyl ammonium bromide; the mass ratio of each component of the mixture is as follows: fe2O3:SiO2:Al2O3:Na2O/K2O:R:H2O=0.01~0.05:1:0.01~0.05:0.05~0.5:0.1~0.5:5~30。
Step c) crystallization is carried out in two temperature sections: crystallizing at 70-120 ℃ for 12-24 hours, crystallizing at 140-180 ℃ for 24-72 hours, preferably at 100-120 ℃ for 12-24 hours, and crystallizing at 150-170 ℃ for 24-72 hours.
The invention is characterized in that: firstly, preparing a Fe-C-Al precursor with a core-shell structure, then adding the precursor into slurry which is uniformly mixed by a template agent, a silicon source and alkali, and reacting under certain conditions to obtain a target product. The prepared Fe-C-Al precursor has a core-shell structure, the prepared Fe-Beta molecular sieve catalyst has a mesoporous structure communicated with the core shell, and the product has high crystallinity, high specific surface area, rich mesopores and uniform iron distribution. In the selective catalytic reduction of ammonia (NH)3-SCR) reaction, excellent catalytic performance is exhibited.
The invention has the beneficial effects that:
(1) the preparation method of the mesoporous Fe-Beta molecular sieve catalyst containing the core-shell structure comprises the steps of firstly preparing a Fe-C-Al precursor with the core-shell structure, then adding the precursor into slurry which is uniformly mixed by a template agent, a silicon source and alkali, and reacting under certain conditions to obtain a target productA compound (I) is provided. Can be applied to purifying nitrogen oxides in the tail gas of diesel vehicles and performing selective catalytic reduction (NH) on ammonia3-SCR) reaction, excellent catalytic performance is exhibited.
(2) According to the preparation method of the mesoporous Fe-Beta molecular sieve catalyst containing the core-shell structure, the prepared Fe-C-Al precursor has the core-shell structure, and the prepared Fe-Beta molecular sieve catalyst has a mesoporous structure communicated with the core shell, is high in specific surface area and rich in mesopores.
(3) The preparation method of the mesoporous Fe-Beta molecular sieve catalyst containing the core-shell structure has the advantages of simple and convenient process operation, high product crystallinity and uniform iron distribution.
Drawings
FIG. 1 shows X-ray diffraction patterns of examples 1 to 6.
FIG. 2 is a transmission electron micrograph of a sample of the Fe-C-Al precursor in example 1.
FIG. 3 is a transmission electron micrograph of the Fe-Beta sample in example 1.
FIG. 4 is a schematic diagram of the channel structure of Beta molecular sieve.
Detailed Description
In order to better understand the invention, the following examples further illustrate the content of the invention, but the content of the invention is not limited to the following examples, and the examples should not be construed as limiting the scope of the invention.
Example 1
Preparing a Fe-C-Al precursor: ferrous sulfate, sodium ferrocyanide and aluminum sulfate are respectively prepared into dilute solutions with the concentration of 0.1 mol/L. The dilute solution was dispersed in deionized water with constant stirring. The temperature of the mixed solution is kept at 10 ℃, and the reaction is carried out for 1 hour. The precipitate was filtered and washed repeatedly with deionized water to a sodium content of less than 500 ppm. The washed precipitate was dried in an oven at 70 ℃ and ground. Transferring the fine powder to a rotary roasting furnace, introducing nitrogen at the flow rate of 400ml/min, and roasting at 450 ℃ for 3 hours to obtain the Fe-C-Al precursor. The Fe-C-Al precursor contains 37.3% of ferric oxide, 24.1% of carbon and 38.6% of aluminum oxide.
Preparation of Fe-Beta molecular sieve catalyst: Fe-C-Al precursor, silica sol, sodium hydroxide and tetraethyl hydrogenThe ammonium oxide (R) was mixed in deionized water to prepare a gel. The mass ratio of each component substance in the gel is as follows: fe2O3:SiO2:Al2O3:Na2O:R:H2O =0.03:1:0.03:0.1:0.14:15, and the gel is transferred to a high pressure crystallization kettle for crystallization, crystallized at 110 ℃ for 14 hours, and then crystallized at 150 ℃ for 36 hours. After the reaction is finished, the product is subjected to mother liquor removal, water washing, exchange, drying and roasting to obtain the Fe-Beta molecular sieve catalyst which is marked as S-1.
Example 2
Preparing a Fe-C-Al precursor: ferrous sulfate, sodium ferrocyanide and aluminum sulfate are respectively prepared into dilute solutions with the concentration of 0.05 mol/L. The dilute solution was dispersed in deionized water with constant stirring. The temperature of the mixed solution is kept at 5 ℃, and the reaction is carried out for 2 hours. The precipitate was filtered and washed repeatedly with deionized water to a sodium content of less than 500 ppm. The washed precipitate was dried in an oven at 75 ℃ and ground. Transferring the fine powder into a rotary roasting furnace, introducing argon, roasting at the argon flow speed of 100ml/min for 4 hours at 400 ℃ to obtain the Fe-C-Al precursor. The Fe-C-Al precursor contains 48.8% of iron oxide, 39.6% of carbon and 11.6% of aluminum oxide.
Preparation of Fe-Beta molecular sieve catalyst: mixing Fe-C-Al precursor, silica sol, sodium hydroxide and tetraethyl ammonium hydroxide (R) in deionized water to prepare gel. The mass ratio of each component substance in the gel is as follows: fe2O3:SiO2:Al2O3:Na2O:R:H2O =0.04:1:0.015:0.1:0.14:15, and the gel is transferred to a high pressure crystallization kettle for crystallization, crystallized at 100 ℃ for 18 hours, and then crystallized at 160 ℃ for 32 hours. After the reaction is finished, the product is subjected to mother liquor removal, water washing, exchange, drying and roasting to obtain the Fe-Beta molecular sieve catalyst which is marked as S-2.
Example 3
Preparing a Fe-C-Al precursor: ferrous sulfate, sodium ferrocyanide and aluminum sulfate are respectively prepared into dilute solutions with the concentration of 0.20 mol/L. The dilute solution was dispersed in deionized water with constant stirring. The temperature of the mixed solution is kept at 15 ℃, and the reaction is carried out for 0.5 hour. The precipitate was filtered and washed repeatedly with deionized water to a sodium content of less than 500 ppm. The washed precipitate was dried in an oven at 65 ℃ and ground. Transferring the fine substance to a rotary roasting furnace, introducing argon, roasting at 350 ℃ for 6 hours at the argon flow speed of 100ml/min to obtain a Fe-C-Al precursor. The Fe-C-Al precursor contains 30.9% of ferric oxide, 24.8% of carbon and 44.3% of aluminum oxide.
Preparation of Fe-Beta molecular sieve catalyst: mixing Fe-C-Al precursor, silica sol, sodium hydroxide and tetraethyl ammonium hydroxide (R) in deionized water to prepare gel. The mass ratio of each component substance in the gel is as follows: fe2O3:SiO2:Al2O3:Na2O:R:H2O =0.02:1:0.045:0.1:0.14:15, the gel was transferred to a high pressure crystallization kettle for crystallization, crystallized at 120 ℃ for 12 hours, and then crystallized at 170 ℃ for 72 hours. After the reaction is finished, the product is subjected to mother liquor removal, water washing, exchange, drying and roasting to obtain the Fe-Beta molecular sieve catalyst which is marked as S-3.
Example 4
Preparing a Fe-C-Al precursor: ferrous sulfate, sodium ferrocyanide and aluminum sulfate are respectively prepared into dilute solutions with the concentration of 0.1 mol/L. The dilute solution was dispersed in deionized water with constant stirring. The temperature of the mixed solution is kept at 10 ℃, and the reaction is carried out for 1 hour. The precipitate was filtered and washed repeatedly with deionized water to a sodium content of less than 500 ppm. The washed precipitate was dried in an oven at 70 ℃ and ground. Transferring the fine powder to a rotary roasting furnace, introducing nitrogen at the flow rate of 500ml/min, and roasting at 500 ℃ for 2 hours to obtain the Fe-C-Al precursor. The Fe-C-Al precursor contains 37.3% of ferric oxide, 24.1% of carbon and 38.6% of aluminum oxide.
Preparation of Fe-Beta molecular sieve catalyst: mixing Fe-C-Al precursor, silica sol, sodium hydroxide and tetraethyl ammonium bromide in deionized water to prepare the gel. The mass ratio of each component substance in the gel is as follows: fe2O3:SiO2:Al2O3:Na2O:R:H2O =0.03:1:0.03:0.1:0.14:15, and the gel is transferred to a high pressure crystallization kettle for crystallization, crystallized at 110 ℃ for 12 hours, and then crystallized at 140 ℃ for 24 hours. After the reaction is finished, the product is subjected to mother liquor removal, water washing, exchange, drying and roasting to obtain the Fe-Beta molecular sieve catalyst which is marked as S-4
Example 5
Preparing a Fe-C-Al precursor: ferrous sulfate, sodium ferrocyanide and aluminum sulfate are respectively prepared into dilute solutions with the concentration of 0.05 mol/L. The dilute solution was dispersed in deionized water with constant stirring. The temperature of the mixed solution is kept at 5 ℃, and the reaction is carried out for 2 hours. The precipitate was filtered and washed repeatedly with deionized water to a sodium content of less than 500 ppm. The washed precipitate was dried in an oven at 75 ℃ and ground. Transferring the fine powder into a rotary roasting furnace, introducing argon, roasting at the argon flow speed of 100ml/min for 6 hours at 400 ℃ to obtain a Fe-C-Al precursor. The Fe-C-Al precursor contains 48.8% of iron oxide, 39.6% of carbon and 11.6% of aluminum oxide.
Preparation of Fe-Beta molecular sieve catalyst: mixing Fe-C-Al precursor, silica sol, sodium hydroxide and tetraethyl ammonium bromide in deionized water to prepare the gel. The mass ratio of each component substance in the gel is as follows: fe2O3:SiO2:Al2O3:Na2O:R:H2O =0.04:1:0.015:0.1:0.14:15, and the gel was transferred to a high pressure crystallization kettle for crystallization, crystallized at 70 ℃ for 24 hours, and then crystallized at 160 ℃ for 32 hours. After the reaction is finished, the product is subjected to mother liquor removal, water washing, exchange, drying and roasting to obtain the Fe-Beta molecular sieve catalyst which is marked as S-5
Example 6
Preparing a Fe-C-Al precursor: ferrous sulfate, sodium ferrocyanide and aluminum sulfate are respectively prepared into dilute solutions with the concentration of 0.20 mol/L. The dilute solution was dispersed in deionized water with constant stirring. The mixed solution is kept at the constant temperature of 20 ℃ and reacts for 0.1 hour. The precipitate was filtered and washed repeatedly with deionized water to a sodium content of less than 500 ppm. The washed precipitate was dried in an oven at 65 ℃ and ground. Transferring the fine powder into a rotary roasting furnace, introducing argon, roasting for 8 hours at 300 ℃ at the flow rate of 200ml/min of argon to obtain the Fe-C-Al precursor. The Fe-C-Al precursor contains 30.9% of ferric oxide, 24.8% of carbon and 44.3% of aluminum oxide.
Preparation of Fe-Beta molecular sieve catalyst: mixing Fe-C-Al precursor, silica sol, sodium hydroxide and tetraethyl ammonium bromide in deionized water to prepare the gel. The mass ratio of each component substance in the gel is as follows: fe2O3:SiO2:Al2O3:Na2O:R:H2O =0.02:1:0.045:0.1:0.14:15, the gel was transferred to a high pressure crystallization kettle for crystallization, crystallized at 120 ℃ for 12 hours, and then crystallized at 180 ℃ for 24 hours. After the reaction is finished, the product is subjected to mother liquor removal, water washing, exchange, drying and roasting to obtain the Fe-Beta molecular sieve catalyst which is marked as S-6
Comparative example
Using silica sol and aluminum sulfate as silicon and aluminum sources, the mass ratio of each component (Fe) in example 1 was adjusted2O3:SiO2:Al2O3:Na2O:R:H2O =0.03:1:0.03:0.1:0.14:15), preparing gel, transferring the gel into a high-pressure reaction kettle, starting stirring for crystallization for a period of time, and keeping the temperature at 120 ℃ for 18 hours. After the first-stage crystallization is finished, heating to 150 ℃, stopping stirring, and statically crystallizing for 56 hours. And obtaining product slurry after crystallization, and obtaining a comparative sample after mother liquor removal, washing, exchange, drying and roasting of the slurry. Recording as follows: and C-1.
And (3) testing the performance of the catalyst: physical indexes and catalytic performances of the comparative sample and the samples (S-1 to 6) of the examples are detected, and the results are shown in Table 1.
TABLE 1 physical property index and catalytic performance of samples of examples 1-6
As can be seen from the data in Table 1, the catalyst product prepared by the preparation method of the mesoporous Fe-Beta molecular sieve catalyst containing the core-shell structure has the advantages of high specific surface area, rich mesopores and uniform iron distribution. In the selective catalytic reduction of ammonia (NH)3And in the-SCR) reaction, the high NOX conversion rate is realized in the NH3-SCR reaction at the temperature range of 174-555 ℃, the activity window range is wide, and the excellent catalytic performance is shown.
From the X-ray diffraction patterns of the samples of examples 1 to 6 and the sample of the reference example shown in the attached figure 1, the samples show characteristic diffraction peaks of typical Beta-type zeolite, and the products prepared by the invention are all in a pure-phase BEA topological structure peak type. The transmission electron microscope images of the Fe-C-Al and Fe-Beta precursor samples of the example 1 sample shown in the attached figures 2-3 show that the prepared precursor has a perfect crystal structure and is uniform in appearance. The prepared Bate molecular sieve catalyst presents a typical pore channel structure, and uniform distribution of Fe particles in the Bate molecular sieve and extremely fine particles can be observed. The analytical structure of the Bate molecular sieve catalyst prepared in the other examples is basically the same as that in example 1, but is not provided.
It should be noted that the above-mentioned preferred embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of a mesoporous Fe-Beta molecular sieve catalyst containing a core-shell structure is characterized by comprising the following steps:
a) preparing a dilute solution from an iron source, a carbon source and an aluminum source, dispersing the dilute solution into deionized water, and continuously stirring; stirring the mixed solution at the constant temperature of 5-20 ℃ for reaction for 0.1-2 hours; filtering and washing the precipitate until no soluble salt exists, and drying the product;
b) rotating and roasting the precipitate in the step a) in an inert atmosphere to obtain a Fe-C-Al precursor;
c) uniformly mixing the Fe-C-Al precursor obtained in the step b), a silicon source, an alkali source and a template agent in water, and transferring the mixture into a pressure kettle for crystallization reaction;
d) and c) carrying out mother liquor removal, washing, exchange, drying and roasting on the reaction product in the step c) to obtain the mesoporous Fe-Beta molecular sieve catalyst containing the core-shell structure.
2. The preparation method of the mesoporous Fe-Beta molecular sieve catalyst containing the core-shell structure according to claim 1, which is characterized in that: the Fe-C-Al precursor in the step b) contains 20-55% of ferric oxide, 17-47% of carbon and 6-68% of aluminum oxide by mass percent.
3. The preparation method of the mesoporous Fe-Beta molecular sieve based catalyst with the core-shell structure according to claim 1, wherein the weight ratio of each component substance of the mixture in the step c) is as follows: fe2O3:SiO2:Al2O3:Na2O/K2O:R:H2O=0.01~0.05:1:0.01~0.05:0.05~0.5:0.1~0.5:5~30。
4. The method for preparing the mesoporous Fe-Beta molecular sieve catalyst with the core-shell structure according to any one of claims 1 to 3, wherein the method comprises the following steps: the drying temperature of the product described in step a) is < 80 ℃.
5. The method for preparing the mesoporous Fe-Beta molecular sieve catalyst with the core-shell structure according to any one of claims 1 to 3, wherein the method comprises the following steps: the iron source in the step a) is any one or combination of several of ferrous salts; the carbon source is any one or a combination of more of ferrocyanide; the aluminum source is any one or the combination of aluminum sulfate and aluminum chloride.
6. The method for preparing the mesoporous Fe-Beta molecular sieve catalyst with the core-shell structure according to any one of claims 1 to 3, wherein the method comprises the following steps: the concentration of the raw material dilute solution prepared in the step a) is not higher than 1 mol/L.
7. The method for preparing the mesoporous Fe-Beta molecular sieve catalyst with the core-shell structure according to any one of claims 1 to 3, wherein the method comprises the following steps: step a), keeping the temperature at 5-15 ℃, and stirring for reaction for 0.1-2 hours; washing with water until the content of sodium, potassium and ammonium ions is less than 500 ppm; the drying temperature of the fine precipitate is less than or equal to 80 ℃.
8. The method for preparing the mesoporous Fe-Beta molecular sieve catalyst with the core-shell structure according to any one of claims 1 to 3, wherein the method comprises the following steps: the inert atmosphere in the step b) is any one of helium, argon and nitrogen; the flow rate of the inert gas is 100-500 ml/min, and the roasting temperature is as follows: 300-500 ℃, roasting time: 2-8 hours.
9. The method for preparing the mesoporous Fe-Beta molecular sieve catalyst with the core-shell structure according to any one of claims 1 to 3, wherein the method comprises the following steps: in the step c), the silicon source is any one or a combination of more of silica sol, white carbon black and silica gel, the alkali source is any one or a combination of two of sodium hydroxide and potassium hydroxide, and the template agent is any one or a combination of two of tetraethylammonium hydroxide and tetraethylammonium bromide.
10. The method for preparing the mesoporous Fe-Beta molecular sieve catalyst with the core-shell structure according to any one of claims 1 to 4, wherein: and c) crystallizing the crystal in two temperature sections, namely crystallizing the crystal at 70-120 ℃ for 12-24 hours, and then crystallizing the crystal at 140-180 ℃ for 24-72 hours.
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