CN111715302A - Anti-poisoning metal oxide denitration catalyst and preparation method thereof - Google Patents
Anti-poisoning metal oxide denitration catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN111715302A CN111715302A CN202010277796.0A CN202010277796A CN111715302A CN 111715302 A CN111715302 A CN 111715302A CN 202010277796 A CN202010277796 A CN 202010277796A CN 111715302 A CN111715302 A CN 111715302A
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- China
- Prior art keywords
- metal oxide
- poisoning
- catalyst
- denitration catalyst
- denitration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 51
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 29
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 231100000572 poisoning Toxicity 0.000 claims abstract description 22
- 230000000607 poisoning effect Effects 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- 239000012702 metal oxide precursor Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 22
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- 229910052751 metal Inorganic materials 0.000 claims description 21
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- 238000003756 stirring Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 4
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 3
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
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- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 33
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 18
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- 239000011593 sulfur Substances 0.000 abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 abstract description 18
- 239000010881 fly ash Substances 0.000 abstract description 6
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- 229910000069 nitrogen hydride Inorganic materials 0.000 description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 10
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- 239000007789 gas Substances 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 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 description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- WSHADMOVDWUXEY-UHFFFAOYSA-N manganese oxocobalt Chemical compound [Co]=O.[Mn] WSHADMOVDWUXEY-UHFFFAOYSA-N 0.000 description 5
- 235000010333 potassium nitrate Nutrition 0.000 description 5
- 239000004323 potassium nitrate Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
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- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
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- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
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- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
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- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 description 1
- -1 garbage incinerators Chemical class 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
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- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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Abstract
The invention discloses an anti-poisoning metal oxide denitration catalyst and a preparation method thereof. The catalyst is a metal oxide catalyst coated by mesoporous aluminosilicate, which is formed by in-situ growth of a shell layer on the surface of a metal oxide coprecipitation precursor through a silicon source and an aluminum source and calcination. The catalyst has the advantages of excellent low-temperature denitration performance, simple preparation method, low requirement on synthesis equipment, extremely strong alkali/alkaline earth metal poisoning and sulfur poisoning resistance and the like, and can be suitable for fly ash containing alkali/alkaline earth metal and SO2The fixed source flue gas denitration, such as a garbage incinerator, a cement kiln, a biomass fuel boiler, a glass kiln and the like.
Description
Technical Field
The invention relates to a denitration catalyst and a preparation method thereof, in particular to a metal oxide denitration catalyst and a preparation method thereof, which are applied to the technical field of control and purification of nitrogen oxides in environmental protection.
Background
With the rapid development of economy in China, the problem of environmental pollution is gradually highlighted. Nitrogen Oxides (NO)x) As a major atmospheric pollutant, haze, acid rain, ozone voids and photochemical smog can be caused, damaging the natural environment and causing damage to living beings. In order to control nitrogen oxides, the national regulations such as the emission standard of air pollutants for thermal power plants (GB16723-2011), the emission standard of air pollutants for boilers (GB 16767-. Currently, ammonia selective catalytic reduction (NH)3-SCR) technology is a fixed source flue gas denitration technology widely adopted at home and abroad, but commercial V2O5-WO3(MoO3)/TiO2The catalyst has certain problems in domestic fixed source denitration application.
Due to the complex composition of the flue gas of industrial boilers, alkali/alkaline earth metal oxides (K) are present2O、Na2O, CaO) and SO2And the like, resulting in a catalyst that needs to be replaced or regenerated once in about 3 years. In the practical application conditions of denitration catalysts such as garbage incinerators, cement kilns, biomass fuel boilers, glass kilns and the like, the flue gas contains a large amount of alkali metal fly ash to accelerate the inactivation of the catalysts. Although toxic substances in the flue gas can be greatly reduced after the dust removal and desulfurization processes, the residual alkali metal fly ash can cover the surface of the catalyst and be combined with the acid center on the catalytic surface, so that the acid amount on the surface of the catalyst is reduced, the adsorption of reducing agent ammonia is influenced, the reduction of the catalyst active center to the ammonia is inhibited, and the activation of the ammonia is reduced. In addition, at lower temperatures, NH3SCR catalyst self-reactivity and SO2The tolerance is a serious challenge, and the residual SO of the desulfurization process2May form inactive sulfate with the active components of the catalyst; in addition, SO at 300 ℃ or below2Possibly with NH3The formed ammonium (hydrogen) sulfate covers catalytic active sites and blocks pore channel structures, thereby seriously affecting the activity of the denitration catalyst.
At present, domestic and foreign patents mainly focus on the promotion and preparation of the activity of the denitration catalyst, the research on the resistance of the denitration catalyst is less, and only the alkali and alkaline earth metal resistance or SO resistance is concerned in the work reported in the literature2Poisoning, there are few reports of increased resistance in its coexisting state.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the prior art and provide an anti-poisoning metal oxide denitration catalyst and a preparation method thereof2Poisoning effects in coexistence. The catalyst developed by the invention ensures the excellence of the catalystOn the basis of medium-low temperature activity, the alkali/alkaline earth metal resistance and sulfur resistance of the catalyst are enhanced, and the service life of the catalyst in fixed source flue gas denitration can be greatly prolonged.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
an anti-poisoning metal oxide denitration catalyst takes a metal active component and a metal additive as cores, and a mesoporous aluminosilicate shell layer is constructed in situ in a liquid phase; the metal active component of the catalyst is at least one of oxides of manganese, vanadium, iron and cerium, and the metal auxiliary agent is at least one of oxides of titanium, cobalt, zirconium, molybdenum, tungsten and niobium.
As a preferred technical scheme, the metal oxide active component and the auxiliary agent component are combined in a coprecipitation mode to form a precursor, a shell layer grows in situ on the surface of the metal oxide coprecipitation precursor through a silicon source and an aluminum source, and the metal oxide catalyst coated by mesoporous aluminosilicate is formed through calcination.
In a preferred embodiment of the present invention, the solvent used for synthesizing the mesoporous aluminosilicate shell is at least one of methanol, ethanol, isopropanol, ethylene glycol, and water.
As a preferable technical scheme of the invention, the mass ratio of the mesoporous aluminosilicate shell layer to the catalyst precursor is (0.1-10): 1.
as a preferable technical scheme of the invention, the molar ratio of silicon to aluminum in the mesoporous aluminosilicate shell is (0.1-50): 1.
the invention relates to a preparation method of an anti-poisoning metal oxide denitration catalyst, which comprises the following steps:
a. preparation of metal oxide precursor:
dissolving a metal active component and a metal auxiliary agent serving as raw materials in deionized water, adjusting the pH of a mixed solution to be alkaline, coprecipitating the active component and the auxiliary agent to obtain a metal oxide precursor precipitate, filtering and drying a product to obtain a precursor for later use;
b. preparation of mesoporous aluminosilicate:
dispersing the metal oxide precursor obtained after drying in the step a in a mixed solvent of alcohol and water, adding a template, adjusting the pH to 8-10 by using ammonia water, then respectively adding a silicon source and an aluminum source, filtering and washing after fully stirring, and then calcining at 450-550 ℃ by using a muffle furnace to obtain a product, namely the anti-poisoning metal oxide denitration catalyst.
In the step a, the mass ratio of the metal active component to the metal auxiliary agent is (1-3): (1.5-2.5).
In the step a, soluble salts of metals are used as precursor salts of the metal active components; the precursor salt of the auxiliary agent adopts soluble salt of metal.
In the preferable technical scheme of the invention, in the step a, ammonia water is added to adjust the pH of the mixed solution to 8-10.
In the step b, at least one of tetradecyltrimethyl ammonium bromide, tetradecyltrimethyl ammonium chloride, hexadecyltrimethyl ammonium bromide, hexadecyltrimethyl ammonium chloride, octadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium chloride is used as the template.
As a preferred technical scheme of the invention, in the step b, the calcination is carried out for at least 4 h.
In a preferred embodiment of the present invention, in the step b, the alcohol is at least one of methanol, ethanol, isopropanol and ethylene glycol.
In the preferred technical scheme of the present invention, in the step b, the silicon source is tetraethoxysilane.
In a preferred embodiment of the present invention, in the step b, the aluminum source is at least one of aluminum chloride, aluminum sulfate, aluminum nitrate and aluminum isopropoxide.
As a preferable embodiment of the present invention, in the step b, the mass ratio of the amount of the aluminum source to the amount of the metal salt for preparing the metal active component is (1-3): (0.1-0.4).
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the denitration catalyst takes a metal oxide precursor as a core, and mesoporous aluminosilicate is constructed in situ as a shell layer; along with the increase of the thickness of the shell layer and the mass of the aluminum source, the alkali/alkaline earth metal resistance of the catalyst is greatly improved and the catalyst has better sulfur resistance;
2. the invention has the advantages of simple preparation method, low cost, low requirement on synthesis equipment, and extremely strong alkali/alkaline earth metal poisoning and sulfur poisoning resistance, and is suitable for fly ash containing alkali/alkaline earth metal and SO2The fixed source flue gas denitration, like waste incinerator, cement kiln, biomass fuel boiler and glass kiln field, can greatly prolong the life of catalyst in fixed source flue gas denitration.
Drawings
Fig. 1 is a TEM image of the mesoporous aluminosilicate coated manganese cobalt oxide prepared in example 1 of the present invention.
Fig. 2 is a pore size distribution curve diagram of the mesoporous aluminosilicate coated manganese cobalt oxide prepared in example 1 of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
the first embodiment is as follows:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparation of metal oxide precursor: weighing 1.5g of manganese nitrate tetrahydrate and 2g of cobalt nitrate hexahydrate, dissolving in deionized water, adding ammonia water to adjust the pH value to 8, obtaining a metal oxide precursor precipitate, filtering and drying for later use.
Preparation of mesoporous aluminosilicate: weighing 5ml of methanol and 55ml of deionized water to prepare a mixed solution, adding 1.5g of dodecyl trimethyl ammonium bromide and 0.5g of octadecyl trimethyl ammonium bromide, and adding 2ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 2ml of ethyl orthosilicate, and then adding 0.2g of aluminum nitrate nonahydrate; and after stirring for 1h, filtering and washing the product, drying and calcining for 4h at 450 ℃ to obtain the product, namely the anti-poisoning metal oxide denitration catalyst.
Testing the denitration performance of the catalyst: granulating the prepared catalyst to 40-60 meshes, putting the granulated catalyst into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 90-250 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 90 percent under the condition of (1), and N is generated at the temperature of 150 DEG C2The O yield was less than 10 ppm. Simulated flue gas is O 25％，NO 500ppm，NH3500ppm, N2 is the diluent gas.
Alkali/alkaline earth metal and sulfur simultaneous poisoning resistance test: the simulated poisoned catalyst obtained by loading 0.1g of sodium nitrate on the catalyst by the impregnation method and calcining the catalyst at 500 ℃ for 3 hours was tested again for 20ppm SO2SCR denitration activity under the condition that the reaction temperature is 90-250 ℃ and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 85 percent under the condition of (1), N is below 150 DEG C2The amount of O produced is small. Experimental tests were performed on the anti-poisoning metal oxide denitration catalyst prepared in this example as a sample, and referring to fig. 1-2, fig. 1 is a TEM image of the mesoporous aluminosilicate coated manganese cobalt oxide prepared in this example. Fig. 2 is a pore size distribution curve diagram of the mesoporous aluminosilicate coated manganese cobalt oxide prepared in this embodiment. It can be seen that the anti-poisoning metal oxide denitration catalyst prepared by the embodiment has a small particle size, and the mesoporous aluminosilicate coated manganese cobalt oxide particles have uniform pore sizes. The catalyst of the embodiment is a selective reduction denitration catalyst with a good core-shell structure, has high alkali/alkaline earth metal resistance and sulfur resistance, and can improve alkali/alkaline earth metal and SO2Poisoning effects in coexistence. The catalyst of the embodiment enhances the alkali/alkaline earth metal resistance and the sulfur resistance of the catalyst on the basis of ensuring the excellent medium and low temperature activity of the catalyst, and can greatly prolong the service life of the catalyst in fixed source flue gas denitration. The catalyst has excellent low-temperature denitration performance, simple preparation method, low requirement on synthesis equipment, extremely strong alkali/alkaline earth metal poisoning resistance and sulfur poisoning resistance and the like, and is suitable for garbage incinerators and cementAlkali/alkaline earth metal-containing fly ash and SO for furnaces, biomass boilers, glass furnaces and the like2Fixed source denitrification requirements.
Example 2:
this embodiment is substantially the same as embodiment 1, and is characterized in that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparation of metal oxide precursor: 3g of ferric nitrate nonahydrate and 1.5g of titanium sulfate are weighed, dissolved in deionized water, added with ammonia water to adjust the pH value to 9, and a metal oxide precursor precipitate is obtained, filtered and dried for later use.
Preparation of mesoporous aluminosilicate: weighing 10ml of ethanol and 50ml of deionized water to prepare a mixed solution, adding 1g of tetradecyl trimethyl ammonium bromide and 1g of octadecyl trimethyl ammonium bromide, and adding 1ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 3ml of ethyl orthosilicate, and then adding 0.2g of aluminum sulfate; and after stirring for 2 hours, filtering and washing the product, drying and calcining the product for 4 hours at 550 ℃ to obtain the product, namely the anti-poisoning metal oxide denitration catalyst.
Testing the denitration performance of the catalyst: granulating the prepared catalyst to 40-60 meshes, putting the granulated catalyst into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 270-450 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 90 percent under the condition of (1), N2The O yield was less than 10 ppm. Simulated flue gas is O 25％，NO 500ppm，NH3500ppm, N2 is the diluent gas.
Alkali/alkaline earth metal and sulfur simultaneous poisoning resistance test: the simulated poisoned catalyst obtained by loading 0.1g of potassium nitrate on the catalyst by the impregnation method after calcination at 500 ℃ for 3 hours was tested again for the presence of 1000ppm SO2SCR denitration activity under the condition that the reaction temperature is 270-450 ℃ and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 80 percent under the condition of (1), N2The amount of O produced is small.
Example 3
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparation of metal oxide precursor: weighing 1g of cerium nitrate hexahydrate and 2g of ammonium metatungstate, dissolving in deionized water, adding ammonia water to adjust the pH value to 10, obtaining metal oxide precursor precipitate, filtering and drying for later use.
Preparation of mesoporous aluminosilicate: weighing 30ml of isopropanol and 30ml of deionized water to prepare a mixed solution, adding 0.5g of hexadecyl trimethyl ammonium chloride and 1g of octadecyl trimethyl ammonium chloride, and adding 0.5ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 4ml of ethyl orthosilicate, and then adding 0.4g of aluminum chloride; and after stirring for 1h, filtering and washing the product, drying and calcining for 4h at 500 ℃ to obtain the product, namely the anti-poisoning metal oxide denitration catalyst.
Testing the denitration performance of the catalyst: granulating the prepared catalyst to 40-60 meshes, putting the granulated catalyst into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 210-450 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 80 percent under the condition of (1), N2The O yield was less than 10 ppm. Simulated flue gas is O 25％，NO 500ppm，NH3500ppm, N2 is the diluent gas.
Alkali/alkaline earth metal and sulfur simultaneous poisoning resistance test: the simulated poisoned catalyst obtained by loading 0.2g of calcium nitrate on the catalyst by impregnation and calcining the catalyst at 500 ℃ for 3 hours was tested again for 100ppm SO2SCR denitration activity under the condition that the reaction temperature is 270-450 ℃ and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 80 percent under the condition of (1), N2The amount of O produced is small.
Example 4
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparation of metal oxide precursor: weighing 1g of manganese acetate tetrahydrate and 2g of phosphotungstic acid, dissolving in deionized water, adding ammonia water to adjust the pH value to 9, obtaining a metal oxide precursor precipitate, filtering and drying for later use.
Preparation of mesoporous aluminosilicate: weighing 40ml of ethylene glycol and 20ml of deionized water to prepare a mixed solution, adding 0.5g of tetradecyltrimethylammonium chloride and 1g of hexadecyltrimethylammonium bromide, and adding 1ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 3ml of ethyl orthosilicate, and then adding 0.3g of aluminum nitrate nonahydrate; and after stirring for 1h, filtering and washing the product, drying and calcining at 550 ℃ for 4h to obtain the product, namely the anti-poisoning metal oxide denitration catalyst.
Testing the denitration performance of the catalyst: granulating the prepared catalyst to 40-60 meshes, putting the granulated catalyst into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 90-300 ℃, and the space velocity is 50000h-1Under the condition of (1), the denitration efficiency is stabilized to be more than 90 percent, and N is generated at 180 DEG C2The O yield was less than 10 ppm. Simulated flue gas is O 25％，NO 500ppm，NH3500ppm, N2 is the diluent gas.
Alkali/alkaline earth metal and sulfur simultaneous poisoning resistance test: a simulated poisoned catalyst obtained by loading 0.05g of potassium nitrate and 0.2g of calcium nitrate on the catalyst by the impregnation method and calcining the catalyst at 500 ℃ for 3 hours was tested again for 50ppm of SO2SCR denitration activity under the condition that the reaction temperature is 180-300 ℃ and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 85 percent under the condition of (1), and N is below 180 DEG C2The amount of O produced is small.
Example 5
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparation of metal oxide precursor: weighing 2g of cerium acetate and 2.5g of zirconium nitrate, dissolving in deionized water, adding ammonia water to adjust the pH value to 8, obtaining a metal oxide precursor precipitate, filtering and drying for later use.
Preparation of mesoporous aluminosilicate: weighing 20ml of methanol, 20ml of isopropanol and 20ml of deionized water to prepare a mixed solution, adding 1g of tetradecyltrimethylammonium chloride and 2.5g of hexadecyltrimethylammonium bromide, and adding 0.5ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 5ml of ethyl orthosilicate, and then adding 0.2g of aluminum sulfate; and after stirring for 1h, filtering and washing the product, drying and calcining for 4h at 500 ℃ to obtain the product, namely the anti-poisoning metal oxide denitration catalyst.
Testing the denitration performance of the catalyst: granulating the prepared catalyst to 40-60 meshes, putting the granulated catalyst into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 280-480 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 90 percent under the condition of (1), and N is below 450 DEG C2The O yield was less than 10 ppm. Simulated flue gas is O 25％，NO 500ppm，NH3500ppm, N2 is the diluent gas.
Alkali/alkaline earth metal and sulfur simultaneous poisoning resistance test: a simulated poisoned catalyst obtained by loading 0.1g of sodium nitrate and 0.2g of calcium nitrate on the catalyst by an impregnation method and calcining the catalyst at 500 ℃ for 3 hours was retested to contain 200ppm SO2SCR denitration activity under the condition that the reaction temperature is 280-480 ℃ and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 85 percent under the condition of (1), N2The amount of O produced is small.
Example 6
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparation of metal oxide precursor: weighing 2g of ammonium ferrous sulfate hexahydrate and 2g of ammonium molybdate, dissolving in deionized water, adding ammonia water to adjust the pH value to 10 to obtain a metal oxide precursor precipitate, filtering and drying for later use.
Preparation of mesoporous aluminosilicate: measuring 10ml of ethanol, 30ml of ethylene glycol and 20ml of deionized water to prepare a mixed solution, adding 0.5g of tetradecyltrimethyl ammonium chloride and 0.5g of hexadecyltrimethyl ammonium bromide, and adding 0.5ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 1ml of ethyl orthosilicate, and then adding 0.4g of aluminum sulfate; and after stirring for 1h, filtering and washing the product, drying and calcining at 550 ℃ for 4h to obtain the product, namely the anti-poisoning metal oxide denitration catalyst.
Testing the denitration performance of the catalyst: granulating the prepared catalyst to 40-60 meshes, putting the granulated catalyst into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 270-450 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 90 percent under the condition of (1), N2The O yield was less than 10 ppm. Simulated flue gas is O 25％，NO 500ppm，NH3500ppm, N2 is the diluent gas.
Alkali/alkaline earth metal and sulfur simultaneous poisoning resistance test: the simulated poisoned catalyst obtained by loading 0.1g of potassium nitrate and 0.05g of sodium nitrate on the catalyst by the impregnation method after calcination at 500 ℃ for 3 hours was retested to contain 500ppm SO2SCR denitration activity under the condition that the reaction temperature is 300-450 ℃ and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 90 percent under the condition of (1), N2The amount of O produced is small.
Example 7
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparation of metal oxide precursor: weighing 2g of ferric chloride and 2g of ammonium metavanadate, dissolving in deionized water, adding ammonia water to adjust the pH value to 10, obtaining a metal oxide precursor precipitate, filtering and drying for later use.
Preparation of mesoporous aluminosilicate: weighing 10ml of ethanol, 20ml of ethylene glycol and 30ml of deionized water to prepare a mixed solution, adding 0.5g of tetradecyltrimethyl ammonium chloride and 1.5g of hexadecyltrimethyl ammonium bromide, and adding 1ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 1.5ml of ethyl orthosilicate, and then adding 0.2g of aluminum sulfate; and after stirring for 1h, filtering and washing the product, drying and calcining at 550 ℃ for 4h to obtain the product, namely the anti-poisoning metal oxide denitration catalyst.
Testing the denitration performance of the catalyst: granulating the prepared catalyst to 40-60 meshes, putting the granulated catalyst into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 240-450 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 90 percent under the condition of (1), N2The O yield was less than 10 ppm. Simulated flue gas is O 25％，NO 500ppm，NH3500ppm，N2Is diluent gas.
Alkali/alkaline earth metal and sulfur simultaneous poisoning resistance test: the simulated poisoned catalyst obtained by loading 0.1g of potassium nitrate on the catalyst by the impregnation method after calcination at 450 ℃ for 3 hours was tested again for 50ppm SO2SCR denitration activity under the condition that the reaction temperature is 265-450 ℃ and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 90 percent under the condition of (1), N2The amount of O produced is small.
Example 8
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparation of metal oxide precursor: weighing 2g of cerous nitrate hexahydrate and 2g of niobium oxalate, dissolving in deionized water, adding ammonia water to adjust the pH value to 10 to obtain a metal oxide precursor precipitate, filtering and drying for later use.
Preparation of mesoporous aluminosilicate: measuring 5ml of ethanol, 20ml of ethylene glycol and 35ml of deionized water to prepare a mixed solution, adding 1g of tetradecyltrimethylammonium chloride and 0.5g of hexadecyltrimethylammonium bromide, and adding 1ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 2ml of ethyl orthosilicate, and then adding 0.1g of aluminum sulfate; and after stirring for 1h, filtering and washing the product, drying and calcining at 550 ℃ for 4h to obtain the product, namely the anti-poisoning metal oxide denitration catalyst.
Testing the denitration performance of the catalyst: granulating the prepared catalyst to 40-60 meshes, putting the granulated catalyst into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 300-400 ℃, and the space velocity is 50000h-1Under the condition of (A), the denitration efficiency is stabilized atOver 90 percent, N2The O yield was less than 10 ppm. Simulated flue gas is O 25％，NO 500ppm，NH3500ppm, N2 is the diluent gas.
Alkali/alkaline earth metal and sulfur simultaneous poisoning resistance test: the simulated poisoned catalyst obtained by loading 0.1g of potassium nitrate on the catalyst by the impregnation method after calcination at 500 ℃ for 3 hours was tested again for the presence of 100ppm SO2SCR denitration activity under the condition that the reaction temperature is 300-450 ℃ and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 70 percent under the condition of (1), N2The amount of O produced is small.
Example 9
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparation of metal oxide precursor: weighing 2g of manganese nitrate and 2g of titanium sulfate, dissolving in deionized water, adding ammonia water to adjust the pH value to 10, obtaining a metal oxide precursor precipitate, filtering and drying for later use.
Preparation of mesoporous aluminosilicate: measuring 5ml of ethanol, 10ml of ethylene glycol and 45ml of deionized water to prepare a mixed solution, adding 0.5g of tetradecyltrimethyl ammonium chloride and 1g of hexadecyltrimethylammonium bromide, and adding 0.5ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 1.5ml of ethyl orthosilicate, and then adding 0.4g of aluminum sulfate; and after stirring for 1h, filtering and washing the product, drying and calcining for 4h at 450 ℃ to obtain the product, namely the anti-poisoning metal oxide denitration catalyst.
Testing the denitration performance of the catalyst: granulating the prepared catalyst to 40-60 meshes, putting the granulated catalyst into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 100-250 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 90 percent under the condition of (1), and N is generated at the temperature of 150 DEG C2The O yield was less than 10 ppm. Simulated flue gas is O 25％，NO 500ppm，NH3500ppm, N2 is the diluent gas.
Alkali/alkaline earth metal and sulfur simultaneous poisoning resistance test: by dippingThe simulated poisoned catalyst obtained by loading 0.1g of sodium nitrate on the catalyst by impregnation and calcining the catalyst at 500 ℃ for 3 hours was tested for the presence of 20ppm SO2SCR denitration activity under the condition that the reaction temperature is 100-250 ℃ and the space velocity is 50000h-1Under the condition (A), the denitration efficiency is stabilized to be more than 80 percent and N is lower than 150 DEG C2The amount of O produced is small.
In conclusion, the anti-poisoning metal oxide denitration catalyst is a denitration catalyst which has high alkali/alkaline earth metal resistance and sulfur resistance. The catalyst is a metal oxide catalyst coated by mesoporous aluminosilicate, which is formed by in-situ growth of a shell layer on the surface of a metal oxide coprecipitation precursor through a silicon source and an aluminum source and calcination. The catalyst has the advantages of excellent low-temperature denitration performance, simple preparation method, low requirement on synthesis equipment, extremely strong alkali/alkaline earth metal poisoning and sulfur poisoning resistance and the like, and can be suitable for fly ash containing alkali/alkaline earth metal and SO2Such as garbage incinerators, cement kilns, biomass-fueled boilers, and glass kilns.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitution ways, as long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention as long as the technical principle and inventive concept of the anti-poisoning metal oxide denitration catalyst and the preparation method thereof of the present invention are not departed.
Claims (10)
1. An anti-poisoning metal oxide denitration catalyst is characterized in that: constructing a mesoporous aluminosilicate shell layer in situ in a liquid phase by taking a metal active component and a metal additive as cores; the metal active component of the catalyst is at least one of oxides of manganese, vanadium, iron and cerium, and the metal auxiliary agent is at least one of oxides of titanium, cobalt, zirconium, molybdenum, tungsten and niobium.
2. The poisoning-resistant metal oxide denitration catalyst according to claim 1, wherein: the metal oxide active component and the auxiliary agent component are combined in a coprecipitation mode to form a precursor, a shell layer grows in situ on the surface of the metal oxide coprecipitation precursor through a silicon source and an aluminum source, and the metal oxide catalyst coated by mesoporous aluminosilicate is formed through calcination.
3. The poisoning-resistant metal oxide denitration catalyst according to claim 1, wherein: the solvent used for synthesizing the mesoporous aluminosilicate shell layer is at least one of methanol, ethanol, isopropanol, glycol and water.
4. The poisoning-resistant metal oxide denitration catalyst according to claim 1, wherein: the mass ratio of the mesoporous aluminosilicate shell layer to the catalyst precursor is (0.1-10): 1.
5. the poisoning-resistant metal oxide denitration catalyst according to claim 1, wherein: the mesoporous aluminosilicate shell layer comprises silicon and aluminum in a molar ratio of (0.1-50): 1.
6. a method for preparing the poisoning-resistant metal oxide denitration catalyst of claim 1, wherein: the method comprises the following steps:
a. preparation of metal oxide precursor:
dissolving metal active components and metal additives serving as raw materials in deionized water, adjusting the pH of a mixed solution to be alkaline, obtaining a metal oxide precursor precipitate, filtering and drying to obtain a precursor for later use;
b. preparation of mesoporous aluminosilicate:
dispersing the metal oxide precursor obtained after drying in the step a in a mixed solvent of alcohol and water, adding a template, adjusting the pH to 8-10 by using ammonia water, then respectively adding a silicon source and an aluminum source, filtering and washing after fully stirring, and then calcining at 450-550 ℃ by using a muffle furnace to obtain a product, namely the anti-poisoning metal oxide denitration catalyst.
7. The method for preparing the poisoning-resistant metal oxide denitration catalyst according to claim 6, wherein: in the step a, the mass ratio of the metal active component to the metal auxiliary agent is (1-3): (1.5-2.5).
8. The method for preparing the poisoning-resistant metal oxide denitration catalyst according to claim 6, wherein: in the step a, adding ammonia water to adjust the pH of the mixed solution to 8-10.
9. The method for preparing the poisoning-resistant metal oxide denitration catalyst according to claim 6, wherein: in the step b, the template agent is at least one of tetradecyltrimethyl ammonium bromide, tetradecyltrimethyl ammonium chloride, hexadecyltrimethyl ammonium bromide, hexadecyltrimethyl ammonium chloride, octadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium chloride.
10. The method for preparing the poisoning-resistant metal oxide denitration catalyst according to claim 6, wherein: in said step b, calcining is carried out for at least 4 h.
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