CN111715302B - 抗中毒金属氧化物脱硝催化剂及其制备方法 - Google Patents
抗中毒金属氧化物脱硝催化剂及其制备方法 Download PDFInfo
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- CN111715302B CN111715302B CN202010277796.0A CN202010277796A CN111715302B CN 111715302 B CN111715302 B CN 111715302B CN 202010277796 A CN202010277796 A CN 202010277796A CN 111715302 B CN111715302 B CN 111715302B
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- Prior art keywords
- metal oxide
- poisoning
- catalyst
- metal
- trimethyl ammonium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 48
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 48
- 230000000607 poisoning effect Effects 0.000 title claims abstract description 29
- 231100000572 poisoning Toxicity 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 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 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 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 37
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 239000013049 sediment Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 5
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 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
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 49
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 34
- 239000003513 alkali Substances 0.000 abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 18
- 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
- 239000002028 Biomass Substances 0.000 abstract description 5
- 239000004568 cement Substances 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 5
- 239000011521 glass Substances 0.000 abstract description 5
- 206010027439 Metal poisoning Diseases 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 27
- 230000000694 effects Effects 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000011056 performance test Methods 0.000 description 18
- 239000003546 flue gas Substances 0.000 description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 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
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 150000003839 salts Chemical class 0.000 description 6
- 238000005303 weighing Methods 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
- 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
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 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
- 239000011258 core-shell material Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000006872 improvement Effects 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
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 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
- 239000000356 contaminant Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 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
- 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 incinerator Chemical class 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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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- 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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- 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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- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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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
- B01J23/32—Manganese, technetium or rhenium
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Abstract
本发明公开了一种抗中毒金属氧化物脱硝催化剂及其制备方法,本发明催化剂是一种同时具有高抗碱/碱土金属和抗硫金属氧化物脱硝催化。该催化剂主要通过硅源和铝源在金属氧化物共沉淀前驱体表面原位生长壳层,经煅烧形成介孔硅铝酸盐包覆的金属氧化物催化剂。本发明的催化剂中低温脱硝性能优异、制备方法简单,对合成设备要求低,并具有极强的抗碱/碱土金属中毒和硫中毒能力等优点,其可适用于含碱/碱土金属飞灰和SO2的固定源烟气脱硝,如垃圾焚烧炉、水泥炉窑、生物质燃料锅炉以及玻璃炉窑等。
Description
技术领域
本发明涉及一种脱硝催化剂及其制备方法,特别是涉及一种金属氧化物脱硝催化剂及其制备方法,应用于环境保护中氮氧化物控制与净化技术领域。
背景技术
随着我国经济的快速发展,环境污染问题也逐渐凸显。氮氧化物(NOx)作为一种主要的大气污染物,能够引起雾霾、酸雨、臭氧空洞和光化学烟雾,损害自然环境并对生物造成伤害。为了控制氮氧化物,国家近年来出台了如《火电厂大气污染物排放标准》(GB16723-2011)、《锅炉大气污染物排放标准》(GB 16767-2014)、《大气污染防治法》(2016)、等法律法规进行限制。目前,氨选择性催化还原(NH3-SCR)技术是国内外广泛采用的固定源烟气脱硝技术,但商用V2O5-WO3(MoO3)/TiO2催化剂在国内固定源脱硝应用中存在一定的问题。
由于工业锅炉的烟气组成较为复杂,存在碱/碱土金属氧化物(K2O、Na2O、CaO)和SO2等毒物,导致催化剂大约3年需要更换或再生一次。在垃圾焚烧炉、水泥炉窑、生物质燃料锅炉以及玻璃炉窑等脱硝催化剂的实际应用工况中,烟气中含有大量的碱金属飞灰加速了催化剂的失活。虽然经过除尘和脱硫工艺之后,烟气中的有毒物质能大幅减少,但是残存的碱金属飞灰将会覆盖催化剂的表面并与催化表面酸中心结合,降低了催化剂表面的酸量,影响了对还原剂氨气的吸附,同时抑制催化剂活性中心对氨气的还原,降低了对氨气的活化。另外,在较低温度下,NH3-SCR催化剂自身反应活性以及SO2耐受性都面临严峻的挑战,脱硫工艺残留的SO2可能与催化剂活性组分生成非活性硫酸盐;此外,在300℃以下,SO2可能与 NH3形成的硫酸(氢)铵覆盖催化活性位点、堵塞孔道结构,从而严重影响脱硝催化剂活性。
目前国内外专利主要集中于脱硝催化剂活性的提升及制备,对于其抗性的研究较少,并且在文献报道的工作中,只关注抗碱、碱土金属或抗SO2中毒,对于其共存状态下抗性的提升报道较少。
发明内容
为了解决现有技术问题,本发明的目的在于克服已有技术存在的不足,提供一种抗中毒金属氧化物脱硝催化剂及其制备方法,本发明催化剂是一种性能良好的核壳结构选择性还原脱硝催化剂,能够改善碱/碱土金属和SO2共存时的中毒效应。本发明开发的催化剂在保证催化剂优良中低温活性的基础上,同时增强了催化剂抗碱/碱土金属和抗硫性能,能够极大延长催化剂在固定源烟气脱硝中的使用寿命。
为达到上述发明创造目的,本发明采用如下技术方案:
一种抗中毒金属氧化物脱硝催化剂,以金属活性组分和金属助剂为核,在液相中原位构筑介孔硅铝酸盐壳层;所述催化剂金属活性组分为锰、钒、铁、铈的氧化物中的至少一种,金属助剂为钛、钴、锆、钼、钨、铌的氧化物中的至少一种。
作为本发明优选的技术方案,所述金属氧化物活性组分和助剂组分是通过共沉淀方式进行结合,形成前驱体,通过硅源和铝源在金属氧化物共沉淀前驱体表面原位生长壳层,经煅烧形成介孔硅铝酸盐包覆的金属氧化物催化剂。
作为本发明优选的技术方案,所述介孔硅铝酸盐壳层合成使用的溶剂为甲醇、乙醇、异丙醇、乙二醇、水中的至少一种。
作为本发明优选的技术方案,所述介孔硅铝酸盐壳层质量与催化剂前驱体的质量比为 (0.1~10):1。
作为本发明优选的技术方案,所述介孔硅铝酸盐壳层中硅和铝的摩尔比为(0.1~50):1。
一种本发明抗中毒金属氧化物脱硝催化剂的制备方法,包括如下步骤:
a.金属氧化物前驱体的制备:
以金属活性组分和金属助剂为原料,溶于去离子水中,调整混合液pH为碱性,使活性组分和助剂共沉淀,获得金属氧化物前驱体沉淀,过滤并烘干产物,得到前驱体,备用;
b.介孔硅铝酸盐的制备:
将在所述步骤a中烘干后得到的金属氧化物前驱体分散于醇和水的混合溶剂中,并加入模板剂,使用氨水调节pH至8-10,然后分别加入硅源和铝源,在充分搅拌后进行过滤并洗涤,然后使用马弗炉在450~550℃下煅烧,从而得到产物,即为抗中毒金属氧化物脱硝催化剂。
作为本发明优选的技术方案,在所述步骤a中,金属活性组分和金属助剂的质量比为 (1-3):(1.5-2.5)。
作为本发明优选的技术方案,在所述步骤a中,金属活性组分的前驱体盐采用金属的可溶性盐;助剂的前驱体盐采用金属的可溶性盐。
作为本发明优选的技术方案,在所述步骤a中,加入氨水调节混合液pH为8-10。
作为本发明优选的技术方案,在所述步骤b中,模板剂采用十四烷基三甲基溴化铵、十四烷基三甲基氯化铵、十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十八烷基三甲基溴化铵、十八烷基三甲基氯化铵中的至少一种。
作为本发明优选的技术方案,在所述步骤b中,煅烧至少4h。
作为本发明优选的技术方案,在所述步骤b中,上述醇为甲醇、乙醇、异丙醇、乙二醇中的至少一种。
作为本发明优选的技术方案,在所述步骤b中,硅源为正硅酸乙酯。
作为本发明优选的技术方案,在所述步骤b中,铝源为氯化铝、硫酸铝、硝酸铝、异丙醇铝中的至少一种。
作为本发明优选的技术方案,在所述步骤b中,相对于制备金属活性组分的金属盐的质量计算,铝源的用量和制备金属活性组分的金属盐的质量比为(1-3):(0.1-0.4)。
本发明与现有技术相比较,具有如下显而易见的突出实质性特点和显著优点:
1.本发明脱硝催化剂是以金属氧化物前驱体为核,原位构筑介孔硅铝酸盐为壳层;随着壳层厚度和铝源质量的增加,催化剂抗碱/碱土金属性能得到极大改善并且具有较好的抗硫性能;
2.本发明制备方法简单,成本低廉,对合成设备要求低,并具有极强的抗碱/碱土金属中毒和硫中毒能力的优点,适用于含碱/碱土金属飞灰和SO2的固定源烟气脱硝,如垃圾焚烧炉、水泥炉窑、生物质燃料锅炉以及玻璃炉窑领域,能够极大延长催化剂在固定源烟气脱硝中的使用寿命。
附图说明
图1为本发明实施例1所制备的介孔硅铝酸盐包覆锰钴氧化物TEM图。
图2为本发明实施例1所制备的介孔硅铝酸盐包覆锰钴氧化物的孔径分布曲线图。
具体实施方式
以下结合具体的实施例子对上述方案做进一步说明,本发明的优选实施例详述如下:
实施例一:
在本实施例中,一种抗中毒金属氧化物脱硝催化剂的制备方法,包括如下步骤:
金属氧化物前驱体的制备:称取1.5g四水合硝酸锰和2g六水合硝酸钴,溶于去离子水中,加入氨水调节pH至8,获得金属氧化物前驱体沉淀,过滤并烘干备用。
介孔硅铝酸盐的制备:量取5ml甲醇和55ml去离子水配置成混合溶液,加入1.5g十二烷基三甲基溴化铵和0.5g十八烷基三甲基溴化铵,并加入2ml氨水;然后加入金属氧化物前驱体,搅拌0.5h后加入2ml正硅酸乙酯然后再加入0.2g九水合硝酸铝;搅拌1h后将产物过滤洗涤,烘干后在450℃下煅烧4h,得到产物为抗中毒金属氧化物脱硝催化剂。
催化剂的脱硝性能测试:将上述制备的催化剂造粒40-60目,放入反应炉中进行活性、N2选择性测试,反应温度为90~250℃、空速为50000h-1的条件下,脱硝效率稳定在90%以上, 150℃下N2O产量低于10ppm。模拟烟气为O25%,NO 500ppm,NH3500ppm,N2为稀释气。
抗碱/碱土金属和抗硫同时中毒性能测试:采用浸渍法在催化剂上负载0.1g硝酸钠,在 500℃下煅烧3小时后得到的模拟中毒催化剂再测试其在含20ppm SO2条件下SCR脱硝活性,反应温度为90~250℃、空速为50000h-1的条件下,脱硝效率稳定在85%以上,150℃以下N2O 的生成量较少。对本实施例制备的抗中毒金属氧化物脱硝催化剂作为样品进行实验测试,参见图1-2,图1为本实施例所制备的介孔硅铝酸盐包覆锰钴氧化物TEM图。图2为本实施例所制备的介孔硅铝酸盐包覆锰钴氧化物的孔径分布曲线图。可见本实施例制备的抗中毒金属氧化物脱硝催化剂的粒径较小,介孔硅铝酸盐包覆锰钴氧化物颗粒的孔径均匀。本实施例催化剂是性能良好的核壳结构选择性还原脱硝催化剂,同时具有高抗碱/碱土金属和抗硫性能,该催化剂能够改善碱/碱土金属和SO2共存时的中毒效应。本实施例催化剂在保证催化剂优良中低温活性的基础上,同时增强了催化剂抗碱/碱土金属和抗硫性能,能够极大延长催化剂在固定源烟气脱硝中的使用寿命。该催化剂中低温脱硝性能优异、制备方法简单,对合成设备要求低,并具有极强的抗碱/碱土金属中毒和抗硫中毒能力等优点,其适用于垃圾焚烧炉、水泥炉窑、生物质燃料锅炉以及玻璃炉窑等含碱/碱土金属飞灰和SO2的固定源脱硝需求。
实施例2:
本实施例与实施例1基本相同,特别之处在于:
在本实施例中,一种抗中毒金属氧化物脱硝催化剂的制备方法,包括如下步骤:
金属氧化物前驱体的制备:称取3g九水合硝酸铁和1.5g硫酸钛,溶于去离子水中,加入氨水调节pH至9,获得金属氧化物前驱体沉淀,过滤并烘干备用。
介孔硅铝酸盐的制备:量取10ml乙醇和50ml去离子水配置成混合溶液,加入1g十四烷基三甲基溴化铵和1g十八烷基三甲基溴化铵,并加入1ml氨水;然后加入金属氧化物前驱体,搅拌0.5h后加入3ml正硅酸乙酯然后再加入0.2g硫酸铝;搅拌2h后将产物过滤洗涤,烘干后在 550℃下煅烧4h,得到产物为抗中毒金属氧化物脱硝催化剂。
催化剂的脱硝性能测试:将上述制备的催化剂造粒40-60目,放入反应炉中进行活性、N2选择性测试,反应温度为270~450℃、空速为50000h-1的条件下,脱硝效率稳定在90%以上, N2O产量低于10ppm。模拟烟气为O25%,NO 500ppm,NH3500ppm,N2为稀释气。
抗碱/碱土金属和抗硫同时中毒性能测试:采用浸渍法在催化剂上负载0.1g硝酸钾,在 500℃下煅烧3小时后得到的模拟中毒催化剂再测试其在含1000ppm SO2条件下SCR脱硝活性,反应温度为270~450℃、空速为50000h-1的条件下,脱硝效率稳定在80%以上,N2O的生成量较少。
实施例3
本实施例与前述实施例基本相同,特别之处在于:
在本实施例中,一种抗中毒金属氧化物脱硝催化剂的制备方法,包括如下步骤:
金属氧化物前驱体的制备:称取1g六水合硝酸铈和2g偏钨酸铵,溶于去离子水中,加入氨水调节pH至10,获得金属氧化物前驱体沉淀,过滤并烘干备用。
介孔硅铝酸盐的制备:量取30ml异丙醇和30ml去离子水配置成混合溶液,加入0.5g十六烷基三甲基氯化铵和1g十八烷基三甲基氯化铵,并加入0.5ml氨水;然后加入金属氧化物前驱体,搅拌0.5h后加入4ml正硅酸乙酯然后再加入0.4g氯化铝;搅拌1h后将产物过滤洗涤,烘干后在500℃下煅烧4h,得到产物为抗中毒金属氧化物脱硝催化剂。
催化剂的脱硝性能测试:将上述制备的催化剂造粒40-60目,放入反应炉中进行活性、N2选择性测试,反应温度为210~450℃、空速为50000h-1的条件下,脱硝效率稳定在80%以上, N2O产量低于10ppm。模拟烟气为O25%,NO 500ppm,NH3500ppm,N2为稀释气。
抗碱/碱土金属和抗硫同时中毒性能测试:采用浸渍法在催化剂上负载0.2g硝酸钙,在500℃下煅烧3小时后得到的模拟中毒催化剂再测试其在含100ppm SO2条件下SCR脱硝活性,反应温度为270~450℃、空速为50000h-1的条件下,脱硝效率稳定在80%以上,N2O的生成量较少。
实施例4
本实施例与前述实施例基本相同,特别之处在于:
在本实施例中,一种抗中毒金属氧化物脱硝催化剂的制备方法,包括如下步骤:
金属氧化物前驱体的制备:称取1g四水合醋酸锰和2g磷钨酸,溶于去离子水中,加入氨水调节pH至9,获得金属氧化物前驱体沉淀,过滤并烘干备用。
介孔硅铝酸盐的制备:量取40ml乙二醇和20ml去离子水配置成混合溶液,加入0.5g十四烷基三甲基氯化铵和1g十六烷基三甲基溴化铵,并加入1ml氨水;然后加入金属氧化物前驱体,搅拌0.5h后加入3ml正硅酸乙酯然后再加入0.3g九水合硝酸铝;搅拌1h后将产物过滤洗涤,烘干后在550℃下煅烧4h,得到产物为抗中毒金属氧化物脱硝催化剂。
催化剂的脱硝性能测试:将上述制备的催化剂造粒40-60目,放入反应炉中进行活性、N2选择性测试,反应温度为90~300℃、空速为50000h-1的条件下,脱硝效率稳定在90%以上, 180℃下N2O产量低于10ppm。模拟烟气为O25%,NO 500ppm,NH3500ppm,N2为稀释气。
抗碱/碱土金属和抗硫同时中毒性能测试:采用浸渍法在催化剂上负载0.05g硝酸钾和0.2g 硝酸钙,在500℃下煅烧3小时后得到的模拟中毒催化剂再测试其在含50ppm SO2条件下SCR 脱硝活性,反应温度为180~300℃、空速为50000h-1的条件下,脱硝效率稳定在85%以上,180℃以下N2O的生成量较少。
实施例5
本实施例与前述实施例基本相同,特别之处在于:
在本实施例中,一种抗中毒金属氧化物脱硝催化剂的制备方法,包括如下步骤:
金属氧化物前驱体的制备:称取2g醋酸铈和2.5g硝酸锆,溶于去离子水中,加入氨水调节pH至8,获得金属氧化物前驱体沉淀,过滤并烘干备用。
介孔硅铝酸盐的制备:量取20ml甲醇、20ml异丙醇和20ml去离子水配置成混合溶液,加入1g十四烷基三甲基氯化铵和2.5g十六烷基三甲基溴化铵,并加入0.5ml氨水;然后加入金属氧化物前驱体,搅拌0.5h后加入5ml正硅酸乙酯然后再加入0.2g硫酸铝;搅拌1h后将产物过滤洗涤,烘干后在500℃下煅烧4h,得到产物为抗中毒金属氧化物脱硝催化剂。
催化剂的脱硝性能测试:将上述制备的催化剂造粒40-60目,放入反应炉中进行活性、N2选择性测试,反应温度为280~480℃、空速为50000h-1的条件下,脱硝效率稳定在90%以上, 450℃以下N2O产量低于10ppm。模拟烟气为O25%,NO 500ppm,NH3500ppm,N2为稀释气。
抗碱/碱土金属和抗硫同时中毒性能测试:采用浸渍法在催化剂上负载0.1g硝酸钠和0.2g 硝酸钙,在500℃下煅烧3小时后得到的模拟中毒催化剂再测试其在含200ppmSO2条件下SCR 脱硝活性,反应温度为280~480℃、空速为50000h-1的条件下,脱硝效率稳定在85%以上,N2O 的生成量较少。
实施例6
本实施例与前述实施例基本相同,特别之处在于:
在本实施例中,一种抗中毒金属氧化物脱硝催化剂的制备方法,包括如下步骤:
金属氧化物前驱体的制备:称取2g六水合硫酸亚铁铵和2g钼酸铵,溶于去离子水中,加入氨水调节pH至10,获得金属氧化物前驱体沉淀,过滤并烘干备用。
介孔硅铝酸盐的制备:量取10ml乙醇、30ml乙二醇和20ml去离子水配置成混合溶液,加入0.5g十四烷基三甲基氯化铵和0.5g十六烷基三甲基溴化铵,并加入0.5ml氨水;然后加入金属氧化物前驱体,搅拌0.5h后加入1ml正硅酸乙酯然后再加入0.4g硫酸铝;搅拌1h后将产物过滤洗涤,烘干后在550℃下煅烧4h,得到产物为抗中毒金属氧化物脱硝催化剂。
催化剂的脱硝性能测试:将上述制备的催化剂造粒40-60目,放入反应炉中进行活性、N2选择性测试,反应温度为270~450℃、空速为50000h-1的条件下,脱硝效率稳定在90%以上, N2O产量低于10ppm。模拟烟气为O25%,NO 500ppm,NH3500ppm,N2为稀释气。
抗碱/碱土金属和抗硫同时中毒性能测试:采用浸渍法在催化剂上负载0.1g硝酸钾和0.05g 硝酸钠,在500℃下煅烧3小时后得到的模拟中毒催化剂再测试其在含500ppmSO2条件下SCR 脱硝活性,反应温度为300~450℃、空速为50000h-1的条件下,脱硝效率稳定在90%以上,N2O 的生成量较少。
实施例7
本实施例与前述实施例基本相同,特别之处在于:
在本实施例中,一种抗中毒金属氧化物脱硝催化剂的制备方法,包括如下步骤:
金属氧化物前驱体的制备:称取2g氯化铁和2g偏钒酸铵,溶于去离子水中,加入氨水调节pH至10,获得金属氧化物前驱体沉淀,过滤并烘干备用。
介孔硅铝酸盐的制备:量取10ml乙醇、20ml乙二醇和30ml去离子水配置成混合溶液,加入0.5g十四烷基三甲基氯化铵和1.5g十六烷基三甲基溴化铵,并加入1ml氨水;然后加入金属氧化物前驱体,搅拌0.5h后加入1.5ml正硅酸乙酯然后再加入0.2g硫酸铝;搅拌1h后将产物过滤洗涤,烘干后在550℃下煅烧4h,得到产物为抗中毒金属氧化物脱硝催化剂。
催化剂的脱硝性能测试:将上述制备的催化剂造粒40-60目,放入反应炉中进行活性、N2选择性测试,反应温度为240~450℃、空速为50000h-1的条件下,脱硝效率稳定在90%以上, N2O产量低于10ppm。模拟烟气为O25%,NO 500ppm,NH3500ppm,N2为稀释气。
抗碱/碱土金属和抗硫同时中毒性能测试:采用浸渍法在催化剂上负载0.1g硝酸钾,在 450℃下煅烧3小时后得到的模拟中毒催化剂再测试其在含50ppm SO2条件下SCR脱硝活性,反应温度为265~450℃、空速为50000h-1的条件下,脱硝效率稳定在90%以上,N2O的生成量较少。
实施例8
本实施例与前述实施例基本相同,特别之处在于:
在本实施例中,一种抗中毒金属氧化物脱硝催化剂的制备方法,包括如下步骤:
金属氧化物前驱体的制备:称取2g六水合硝酸铈和2g草酸铌,溶于去离子水中,加入氨水调节pH至10,获得金属氧化物前驱体沉淀,过滤并烘干备用。
介孔硅铝酸盐的制备:量取5ml乙醇、20ml乙二醇和35ml去离子水配置成混合溶液,加入1g十四烷基三甲基氯化铵和0.5g十六烷基三甲基溴化铵,并加入1ml氨水;然后加入金属氧化物前驱体,搅拌0.5h后加入2ml正硅酸乙酯然后再加入0.1g硫酸铝;搅拌1h后将产物过滤洗涤,烘干后在550℃下煅烧4h,得到产物为抗中毒金属氧化物脱硝催化剂。
催化剂的脱硝性能测试:将上述制备的催化剂造粒40-60目,放入反应炉中进行活性、N2选择性测试,反应温度为300~400℃、空速为50000h-1的条件下,脱硝效率稳定在90%以上, N2O产量低于10ppm。模拟烟气为O25%,NO 500ppm,NH3500ppm,N2为稀释气。
抗碱/碱土金属和抗硫同时中毒性能测试:采用浸渍法在催化剂上负载0.1g硝酸钾,在 500℃下煅烧3小时后得到的模拟中毒催化剂再测试其在含100ppm SO2条件下SCR脱硝活性,反应温度为300~450℃、空速为50000h-1的条件下,脱硝效率稳定在70%以上,N2O的生成量较少。
实施例9
本实施例与前述实施例基本相同,特别之处在于:
在本实施例中,一种抗中毒金属氧化物脱硝催化剂的制备方法,包括如下步骤:
金属氧化物前驱体的制备:称取2g硝酸锰和2g硫酸钛,溶于去离子水中,加入氨水调节 pH至10,获得金属氧化物前驱体沉淀,过滤并烘干备用。
介孔硅铝酸盐的制备:量取5ml乙醇、10ml乙二醇和45ml去离子水配置成混合溶液,加入0.5g十四烷基三甲基氯化铵和1g十六烷基三甲基溴化铵,并加入0.5ml氨水;然后加入金属氧化物前驱体,搅拌0.5h后加入1.5ml正硅酸乙酯然后再加入0.4g硫酸铝;搅拌1h后将产物过滤洗涤,烘干后在450℃下煅烧4h,得到产物为抗中毒金属氧化物脱硝催化剂。
催化剂的脱硝性能测试:将上述制备的催化剂造粒40-60目,放入反应炉中进行活性、N2选择性测试,反应温度为100~250℃、空速为50000h-1的条件下,脱硝效率稳定在90%以上, 150℃下N2O产量低于10ppm。模拟烟气为O25%,NO 500ppm,NH3500ppm,N2为稀释气。
抗碱/碱土金属和抗硫同时中毒性能测试:采用浸渍法在催化剂上负载0.1g硝酸钠,在 500℃下煅烧3小时后得到的模拟中毒催化剂再测试其在含20ppm SO2条件下SCR脱硝活性,反应温度为100~250℃、空速为50000h-1的条件下,脱硝效率稳定在80%以上,低于150℃时N2O 的生成量较少。
综上所述,本发明抗中毒金属氧化物脱硝催化剂是一种同时具有高抗碱/碱土金属和抗硫金属氧化物脱硝催化剂。该催化剂主要通过硅源和铝源在金属氧化物共沉淀前驱体表面原位生长壳层,经煅烧形成介孔硅铝酸盐包覆的金属氧化物催化剂。本发明的催化剂中低温脱硝性能优异、制备方法简单,对合成设备要求低,并具有极强的抗碱/碱土金属中毒和硫中毒能力等优点,其可适用于含碱/碱土金属飞灰和SO2的固定源烟气脱硝,如垃圾焚烧炉、水泥炉窑、生物质燃料锅炉以及玻璃炉窑。
上面对本发明实施例结合附图进行了说明,但本发明不限于上述实施例,还可以根据本发明的发明创造的目的做出多种变化,凡依据本发明技术方案的精神实质和原理下做的改变、修饰、替代、组合或简化,均应为等效的置换方式,只要符合本发明的发明目的,只要不背离本发明抗中毒金属氧化物脱硝催化剂及其制备方法的技术原理和发明构思,都属于本发明的保护范围。
Claims (4)
1.一种抗中毒金属氧化物脱硝催化剂,其特征在于:以金属活性组分和金属助剂为核,在液相中原位构筑介孔硅铝酸盐壳层;所述催化剂的金属活性组分为锰、钒、铁、铈的氧化物中的至少一种,金属助剂为钛、钴、锆、钼、钨、铌的氧化物中的至少一种;
所述金属氧化物活性组分和助剂组分是通过共沉淀方式进行结合,形成前驱体,通过硅源和铝源在金属氧化物共沉淀前驱体表面原位生长壳层,经煅烧形成介孔硅铝酸盐包覆的金属氧化物催化剂;
所述介孔硅铝酸盐壳层质量与前驱体的质量比为(0.1~10):1;
所述介孔硅铝酸盐壳层中硅和铝的摩尔比为(0.1~ 50):1;
所述抗中毒金属氧化物脱硝催化剂采用如下制备方法制备而成,包括如下步骤:
a.金属氧化物前驱体的制备:
将金属活性组分源和金属助剂源溶于去离子水中,调整混合液pH为碱性,获得金属氧化物前驱体沉淀,过滤并烘干,得到前驱体,备用;金属活性组分和金属助剂的质量比为(1-3):(1.5-2.5);
b.介孔硅铝酸盐的制备:
将在所述步骤a中烘干后得到的金属氧化物前驱体分散于醇和水的混合溶剂中,并加入模板剂,使用氨水调节pH至8-10,然后分别加入硅源和铝源,在充分搅拌后进行过滤并洗涤,然后使用马弗炉在450~550℃下煅烧,从而得到产物,即为抗中毒金属氧化物脱硝催化剂;
模板剂采用十四烷基三甲基溴化铵、十四烷基三甲基氯化铵、十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十八烷基三甲基溴化铵、十八烷基三甲基氯化铵中的至少一种。
2.一种权利要求1所述抗中毒金属氧化物脱硝催化剂的制备方法,其特征在于:包括如下步骤:
a.金属氧化物前驱体的制备:
将金属活性组分源和金属助剂源溶于去离子水中,调整混合液pH为碱性,获得金属氧化物前驱体沉淀,过滤并烘干,得到前驱体,备用;金属活性组分和金属助剂的质量比为(1-3):(1.5-2.5);
b.介孔硅铝酸盐的制备:
将在所述步骤a中烘干后得到的金属氧化物前驱体分散于醇和水的混合溶剂中,并加入模板剂,使用氨水调节pH至8-10,然后分别加入硅源和铝源,在充分搅拌后进行过滤并洗涤,然后使用马弗炉在450~550℃下煅烧,从而得到产物,即为抗中毒金属氧化物脱硝催化剂;
模板剂采用十四烷基三甲基溴化铵、十四烷基三甲基氯化铵、十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十八烷基三甲基溴化铵、十八烷基三甲基氯化铵中的至少一种。
3.根据权利要求2所述抗中毒金属氧化物脱硝催化剂的制备方法,其特征在于:在所述步骤a中,加入氨水调节混合液pH为8-10。
4.根据权利要求2所述抗中毒金属氧化物脱硝催化剂的制备方法,其特征在于:在所述步骤b中,煅烧至少4h。
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