CN101711185A - 用于选择性氨氧化的双功能催化剂 - Google Patents
用于选择性氨氧化的双功能催化剂 Download PDFInfo
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- CN101711185A CN101711185A CN200880013740A CN200880013740A CN101711185A CN 101711185 A CN101711185 A CN 101711185A CN 200880013740 A CN200880013740 A CN 200880013740A CN 200880013740 A CN200880013740 A CN 200880013740A CN 101711185 A CN101711185 A CN 101711185A
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- Prior art keywords
- catalyst
- zeolite
- gram
- ammonia
- platinum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 210
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 58
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 56
- 230000003647 oxidation Effects 0.000 title claims abstract description 51
- 230000001588 bifunctional effect Effects 0.000 title description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 138
- 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 85
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 81
- 239000010457 zeolite Substances 0.000 claims abstract description 81
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 26
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 26
- 239000003870 refractory metal Substances 0.000 claims abstract description 26
- 230000000737 periodic effect Effects 0.000 claims abstract description 21
- 230000032683 aging Effects 0.000 claims abstract description 16
- 230000007423 decrease Effects 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 57
- 239000000758 substrate Substances 0.000 claims description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 37
- 229910052742 iron Inorganic materials 0.000 claims description 27
- 239000002912 waste gas Substances 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
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- 238000011144 upstream manufacturing Methods 0.000 claims description 3
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- 230000001747 exhibiting effect Effects 0.000 abstract 1
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- 238000011068 loading method Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
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- 239000004215 Carbon black (E152) Substances 0.000 description 4
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
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- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 229910052759 nickel Inorganic materials 0.000 description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- YBRRALJPLAUIIQ-UHFFFAOYSA-N [O-2].[Ba+2].[O-2].[Al+3] Chemical compound [O-2].[Ba+2].[O-2].[Al+3] YBRRALJPLAUIIQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WIHPHLVFNOYYAP-UHFFFAOYSA-N aluminum barium(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Ba+2] WIHPHLVFNOYYAP-UHFFFAOYSA-N 0.000 description 1
- IHNDUGMUECOVKK-UHFFFAOYSA-N aluminum chromium(3+) oxygen(2-) Chemical compound [O-2].[Cr+3].[O-2].[Al+3] IHNDUGMUECOVKK-UHFFFAOYSA-N 0.000 description 1
- VCRLKNZXFXIDSC-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[Al+3].[Zr+4] VCRLKNZXFXIDSC-UHFFFAOYSA-N 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 239000003426 co-catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000008642 heat stress Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 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 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/58—Ammonia
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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
- B01D53/92—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
- B01D53/9436—Ammonia
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
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Abstract
本发明描述了用于处理柴油机废气流的催化剂、方法和***。在一个或多个实施方案,该催化剂包含铂、来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的第二金属、耐高温金属氧化物和沸石,该氧化催化剂在低于大约300℃的温度下对于去除氨已经是有效的,并在经受水热老化后不表现出氨氧化效率的显著下降。方法方面包括首先使车辆发动机废气流通过NOx减除催化剂;和使离开该NOx减除催化剂的并含有氨的废气流通过氨氧化催化剂。还提供了包括这类催化剂的***。
Description
对相关申请的交叉引用
本申请依据35 U.S.C.§119(e)要求2007年2月27日提交的美国专利申请60/891,835和2008年2月27日提交的美国专利申请12/038,459的优先权,它们全文经此引用并入本文。
技术领域
本发明公开了用于内燃机的废气排放物处理***和催化剂、它们的制造方法以及用于稀燃发动机(包括柴油机和稀燃汽油机)的用途。
背景技术
柴油机废气是多相混合物,不仅含有气态排放物,例如一氧化碳(“CO”)、未燃烃或部分燃烧的烃或其含氧化合物(“HC”)和氮氧化物(“NOx”),还含有构成所谓微粒或颗粒物的凝相材料(液体和固体)。通常在柴油机排气***中提供催化剂组合物和具有该组合物的基底,以将某些或所有这些废气组分转化成无害组分。例如,柴油机排气***可以含有柴油机氧化催化剂、滤烟器和用于减除NOx的催化剂中的一种或多种。
应用于在稀燃废气条件下的固定源的公认NOx减除技术是氨选择性催化还原(SCR)。在这种方法中,使NOx(=NO+NO2)与氨在通常在由贱金属构成的催化剂的作用下反应,形成分子氮(N2)。该技术能够减少超过90%的NOx,因此代表了用于实现严峻的NOx减除目标的最佳方法之一。只要废气温度在该催化剂的活性温度范围内,SCR就提供NOx的有效转化。
使用NH3将NOx类物质还原成N2有助于达到稀燃发动机中的NOx排放指标。使用NH3作为还原剂的后果是在不完全转化或废气温度上升的情况下,NH3会从车辆废气中逸出。为避免NH3逸出,可以将亚化学计算量的NH3喷入废气流,但NOx转化率会降低。或者,可以将过量NH3加入该***以提高NOx转化率,但之后需要进一步处理该废气,以除去过量或逸出的NH3。即使在NH3的亚化学计算剂量下,废气温度的提高也可能释放出储存在NOx减除催化剂上的氨,造成NH3逸出。传统的贵金属基氧化催化剂,例如负载在氧化铝上的铂,在去除NH3方面非常有效,但它们产生显著的N2O和NOx作为不需要的副产物,而非所需的N2产物。因此,需要在低至225℃的温度下对NH3氧化呈活性并在250℃至400℃之间具有超过大约60%的N2选择性的催化剂组合物。
还需要稳定的抵抗正常车辆运行的长期的热、化学和物理应力的氨氧化催化剂,对典型柴油机用途而言,这包括最多大约450℃的温度。此外,车辆排气***可能在高于800℃的温度下短时间运行,例如在微粒过滤器的热再生过程中。重要的是,氨氧化催化剂也应在这些严苛的热应激源下稳定。为此,确定了模拟这些长期和严苛应激源对催化剂活性的累积影响的加速老化条件。这类老化条件包括催化剂在空气中最多大约10%水蒸气存在下在700℃至800℃的温度暴露5至50小时。
发明概要
本发明的各方面涉及用于处理废气的催化剂、方法和***。根据本发明的一个或多个实施方案,提供了处理在柴油车辆废气流中生成的排放物的方法。使车辆发动机废气流通过NOx减除催化剂。使离开该NOx减除催化剂的、可能含有氨的废气流通过氧化催化剂。该氧化催化剂包含铂、来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的第二金属、耐高温金属氧化物和沸石。该氧化催化剂在低于大约300℃、优选低于250℃的温度可以有效去除氨。该氧化催化剂可以在经受水热老化后不表现出氨去除效率的显著下降。根据一个或多个实施方案,水热老化是指将催化剂在空气中大约10%水蒸气存在下在最高达大约700℃、尤其最高达约800℃的温度老化最多50小时,例如大约5至大约25小时。
本发明的另一些实施方案涉及用于将氨氧化的催化剂。该催化剂包含两种具有互补功能的有区别的材料:负载在耐高温金属氧化物或沸石上的铂组分;和负载着出自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的第二金属的沸石。该第二金属可以作为与沸石骨架上的离子交换位点结合的金属阳离子存在于沸石上。负载的铂组分提供高度活性和热稳定的氨氧化功能。负载在沸石上的第二金属通过选择性催化还原反应提供消耗NH3和NOx的额外途径,其用于提高该催化剂对生成N2的选择性。该金属/沸石组分也可以被设计成将N2O(其由NH3在低温下被铂/耐高温金属氧化物组分氧化而生成)分解成N2,进一步提高N2选择性。该氧化催化剂可以在低于大约300℃、优选低于250℃的温度有效去除氨。该氧化催化剂可以在最高达大约700℃的水热老化后不表现出氨去除效率的显著下降。根据一个或多个实施方案,所述第二金属是铜,以与沸石上的离子交换位点结合的铜(II)离子形式存在。
本发明的进一步实施方案涉及用于含NOx的废气流的处理***。该处理***包含有效减少NOx的上游催化剂;和有效地将氨氧化的下游氧化催化剂。该氧化催化剂包含铂、来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的第二金属、耐高温金属氧化物和沸石。该氧化催化剂可以在低于大约300℃、优选低于250℃的温度有效去除氨。该氧化催化剂可以在经受水热老化后不表现出氨去除效率的显著下降。
根据一个或多个实施方案,该方法或***中所用的催化剂NOx减除催化剂包含SCR催化剂、LNT催化剂或用于破坏NOx(其造成氨从该NOx减除催化剂中逸出)的其它催化剂。在一个或多个实施方案中,该NOx减除催化剂和氧化催化剂组合物位于分离的基底上。在另一些实施方案中,该NOx减除催化剂和氧化催化剂位于相同基底上。
在一个或多个实施方案中,铂分布在所述耐高温金属氧化物上。铂也可以分布在所述沸石上。在一个或多个实施方案中,基于总催化剂体积,铂以大约0.1克/立方英尺至大约10克/立方英尺的量存在。
在一个或多个实施方案中,所述来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的金属分布在所述沸石上。所述金属可以以沸石的0.1重量%至5重量%的量分布在所述沸石上。在具体实施方案中,该金属是铜或铁或这二者的混合物。
根据一个或多个实施方案,所述耐高温金属氧化物选自氧化铝、二氧化硅、氧化锆、二氧化钛、二氧化铈、和它们的物理混合物或化学组合,包括原子掺杂组合。在某些实施方案中,基于总催化剂体积,所述耐高温金属氧化物载体在基底上的总载量为大约0.01克/立方英寸至2.0克/立方英寸。在一个或多个实施方案中,该沸石具有下述晶体结构之一:CHA、BEA、FAU、MOR、MFI。在一个实施方案中,所述沸石中二氧化硅与氧化铝的摩尔比为大约2至大约250。在具体实施方案中,基于总催化剂体积,所述沸石在基底上的总载量为大约0.1克/立方英寸至4.0克/立方英寸。
附图简述
图1显示了排放物处理***的一个实施方案的示意图;
图2显示了两种催化剂的稳态NH3氧化图:实心符号=0.57%Pt在Al2O3上,催化剂载量0.5克/立方英寸,Pt载量5克/立方英尺;空心符号=0.57%Pt在Al2O3上,催化剂载量0.5克/立方英寸,Pt载量5克/立方英尺+2.5克/立方英寸铁交换的β沸石(Fe=1.1%,以Fe2O3测量,SAR=30)。NH3=500ppm,NO=0,O2=10%(空气形式),H2O=5%,余量=N2,GHSV=100,000/hr。实线是数据点之间的线性插值;
图3显示了用于瞬时NH3氧化评测的脉冲-升温NH3消耗实验的NH3入口浓度图和反应器温度图。气体组成:O2=10%,H2O=5%,CO2=5%,余量=N2,GHSV=100,000/hr;
图4显示了通过脉冲-升温消耗试验评测的代表性双功能氨氧化催化剂的瞬时排放图。催化剂=1.8重量%Pt在Al2O3上,1.0克/立方英寸,Pt载量=30克/立方英尺+0.5克/立方英寸β沸石;
图5显示了通过脉冲-升温消耗试验评测的代表性双功能氨氧化催化剂的瞬时排放图。催化剂=1.8重量%Pt在Al2O3上,1.0克/立方英寸,Pt载量=30克/立方英尺+0.5克/立方英寸β沸石;
图6显示了通过脉冲-升温消耗试验评测的一系列在催化剂中具有不同的铁交换β沸石含量的双功能氨氧化催化剂对NOx(=NO+NO2)的选择性。实线是与数据拟合的线性最小二乘方;
图7显示了对于通过脉冲-升温消耗试验评测的一系列双功能氨氧化催化剂而言,作为催化剂中铁交换β沸石的量的函数的氨转化分数。实线是与数据拟合的线性最小二乘方;
图8显示了两种催化剂的稳态NH3氧化图:实心符号=0.57%Pt在Al2O3上,催化剂载量0.5克/立方英寸,Pt载量5克/立方英尺;空心符号=0.57%Pt在Al2O3上,催化剂载量0.5克/立方英寸,Pt载量5克/立方英尺+铜交换的菱沸石,催化剂载量=2.5克/立方英寸(铜=2.5%,以CuO测量,SAR=30)。NH3=500ppm,NO=0,O2=10%(空气形式),H2O=5%,余量=N2,GHSV=100,000/hr。实线是数据点之间的线性插值。
发明详述
在描述本发明的几个示例性实施方案之前,要理解的是,本发明不限于下述描述中阐述的构造或工艺步骤的细节。本发明能有其它实施方案并且能以各种方式实施或进行。
除非文中清楚地另行指明,本说明书和所附权利要求中所用的单数形式“一”、“所述”和“该”包括复数对象。因此,例如,提到“一催化剂”时,包括两种或多种催化剂,诸如此类。本文所用的术语“减除”是指由任何方式引起的量的降低。本文中出现的术语“废气流”和“发动机废气流”是指发动机流出物以及在一个或多个其它催化剂***部件(包括但不限于柴油机氧化催化剂和/或滤烟器)下游的流出物。
根据本发明的一个或多个实施方案,提供了处理稀燃或柴油车辆的废气流中生成的排放物的方法。在一个实施方案中,使车辆发动机废气流通过NOx减除催化剂。使离开该NOx减除催化剂的、可能含有氨的废气流通过氧化催化剂。该氧化催化剂包含铂、来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的第二金属、耐高温金属氧化物和沸石。该氧化催化剂可以在低于大约300℃、优选低于250℃的温度有效去除氨。该氧化催化剂可以在空气中大约10%水蒸气存在下在最高达大约700℃、优选最高达大约800℃的温度老化最多50小时后不表现出氨去除效率的显著下降。
一个或多个实施方案的NOx减除催化剂包含选择性催化还原(SCR)催化剂、稀燃NOx捕集(LNT)催化剂或用于破坏NOx(其导致可能从该NOx减除催化剂中排放或逸出氨)的其它催化剂。
该NOx减除催化剂和氧化催化剂组合物可作为洗涂层位于相同或分离的基底上。此外,SCR催化剂和所述选择性氨氧化催化剂可以在相同的催化剂外罩或在不同的催化剂外罩中。
另一些方面涉及用于将氨氧化的催化剂。在一个实施方案中,该催化剂包含两种具有互补功能的有区别的材料:负载在耐高温金属氧化物或沸石上的铂组分;和负载着来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的第二金属的沸石。该第二金属可以作为与沸石骨架上的离子交换位点结合的金属阳离子存在于沸石上。负载的铂组分提供高度活性和热稳定的氨氧化功能。负载在沸石上的第二金属提供通过选择性催化还原反应消耗NH3和NOx的额外途径,其用于提高该催化剂对生成N2的选择性。该金属/沸石组分也可以被设计成将N2O(其由NH3在低温下被铂/耐高温金属氧化物组分氧化而生成)分解成N2,进一步提高N2选择性。该氧化催化剂可以在低于大约300℃、优选低于250℃的温度有效去除氨。该氧化催化剂可以在空气中大约10%水蒸气存在下在高达大约700℃、优选高达大约800℃的温度老化最多50小时后不表现出氨去除效率的显著下降。根据一个或多个实施方案,该第二金属是铜,以与沸石上的离子交换位点结合的铜(II)离子形式存在。
进一步的实施方案是用于含NOx的废气流的处理***。在一个实施方案中,该处理***包含有效减少NOx的上游催化剂;和有效将氨氧化的下游氧化催化剂。该氧化催化剂包含铂、来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的第二金属、耐高温金属氧化物和沸石。该氧化催化剂可以在低于大约300℃、优选低于250℃的温度有效去除氨。该氧化催化剂可以在空气中大约10%水蒸气存在下在最高达大约700℃、优选最高达大约800℃的温度老化最多50小时后不表现出氨去除效率的显著下降。
根据一个或多个实施方案的该发动机处理***包括计量***,用于将氨或氨前体或不同氨前体的混合物连续或定期地计量加入废气流中。
本发明的排放物处理***的一个实施方案示意性描绘在图1中。在图1中可以看出,将含气态污染物(包括未燃烃、一氧化碳和NOx)和颗粒物的废气送过标作11A的排放物处理***。将所述含气态污染物(包括未燃烃、一氧化碳和NOx)和颗粒物的废气从发动机19送往排气***下游的位置,在此向废气流中加入还原剂,即氨或氨前体。经由喷嘴(未显示)将还原剂以喷雾形式喷入废气流。显示在一个管道25上的脲的水溶液可以充当氨前体,其可以与另一管道26上的空气在混合站24中混合。阀23可用于计量加入精确量的脲的水溶液,其在废气流中转化成氨。
将具有所述添加的氨的废气流送往根据一个或多个实施方案含有CuCHA的SCR催化剂基底12(在本文中,包括在权利要求中,也称作“第一基底”)。在经过第一基底12时,通过用氨将NOx选择性催化还原,使废气流的NOx组分转化成N2和H2O。此外,离开入口区的过量NH3可以通过氧化被也含有CuCHA的下游氨氧化催化剂(未显示)转化,使氨转化为N2和H2O。该第一基底通常是流通型整料基底。可以认识到,在其进入SCR催化剂之前的混合距离后,与废气流垂直的径向氨浓度可能均匀或可能不均匀。在SCR催化剂16中,借助NH3将NOx转化成N2和H2O。残留NH3从SCR催化剂16逸出到下游NH3氧化催化剂16。在NH3氧化催化剂中,残留NH3被转化成N2和H2O。
基底
根据一个或多个实施方案,所述氨氧化催化剂的基底可以是常用于制备汽车催化剂的任何材料,通常包括金属或陶瓷蜂窝结构。可以使用任何合适的基底,例如整料流通型基底,并具有从基底的入口延伸到出口面的多个细的平行气流通道,以使得通道对流体流开放。这些通道从其流体入口到其流体出口基本是直的路径,由涂有“洗涂层”形式的催化材料的壁限定,使得流经通道的气体与该催化材料接触。该整料基底的流道是薄壁通道,它们可以具有任何合适的横截面形状,例如梯形、矩形、正方形、正弦形、六边形、椭圆形、圆形等。这类结构可以含有每平方英寸横截面大约60至大约1200个或更多的气体入口(即小室)(cpsi)。代表性的市售流通型基底是Corning 400/6堇青石材料,其由堇青石构成,并具有400cpsi和6密耳的壁厚。但是,要理解的是,本发明不限于特定基底类型、材料或几何。
所述陶瓷基底可以由任何合适的耐高温材料制成,例如堇青石、堇青石-α氧化铝、氮化硅、锆莫来石、锂辉石、氧化铝-二氧化硅氧化镁、硅酸锆、硅线石、硅酸镁、锆、透锂长石、α氧化铝、硅铝酸盐等。
可用于本发明实施方案的双功能催化剂复合材料的基底也可以是金属性质的,并由一种或多种金属或金属合金构成。示例性的金属载体包括耐热金属和金属合金,例如钛和不锈钢,以及以铁为基本或主要组分的其它合金。这类合金可以含有镍、铬和/或铝中的一种或多种,并且这些金属的总量可以占该合金的至少15重量%,例如10至25重量%的铬、3至8重量%的铝和最多达20重量%的镍。该合金也可以含有少量或痕量的一种或多种其它金属,如锰、铜、钒、钛等。金属基底可以以各种形状形式使用,例如波纹板或整料。代表性的市售金属基底由Emitec制造。但是,要理解的是,本发明不限于特定基底类型、材料或几何。金属基底的表面可以在例如1000℃和更高的高温氧化,以在基底表面上形成氧化层,从而提高合金的耐腐蚀性。这种高温诱发的氧化也可以增强耐高温金属氧化物载体和助催化金属组分与基底的粘合。
催化剂载体
根据一个或多个实施方案,使铂沉积在高表面积耐高温金属氧化物载体上。高表面积耐高温金属氧化物的实例包括但不限于氧化铝、二氧化硅、二氧化钛、二氧化铈和氧化锆,以及它们的物理混合物或化学组合,包括原子掺杂组合。该耐高温金属氧化物可以由混合氧化物构成或含有它们,例如二氧化硅-氧化铝、硅铝酸盐(其可以是非晶或结晶的)、氧化铝-氧化锆、氧化铝-氧化镧、氧化铝-氧化钡-氧化镧-氧化钕、氧化铝-氧化铬、氧化铝-氧化钡、氧化铝-二氧化铈等。示例性耐高温金属氧化物包含比表面积为大约50至大约300平方米/克的γ氧化铝。
一些实施方案的沸石组分包含多孔硅铝酸盐,其上沉积有来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的金属。这些金属的实例包括铁和铜。沸石组分可具有International Zeolite Association(IZA)出版的the Database of Zeolite Structures中列举的任一骨架结构。骨架结构包括但不限于CHA、FAU、BEA、MFI和MOR类型的那些。
一些实施方案的铂组分可负载在可以具有International ZeoliteAssociation(IZA)出版的the Database of Zeolite Structures中列举的任一骨架结构的沸石上。骨架结构包括但不限于CHA、FAU、BEA、MFI和MOR类型的那些。
洗涂层
根据一个或多个实施方案,以洗涂层的形式施加催化剂,其沉积在即涂布在基底上并粘附在基底上。合适的制备铂组分的方法是制备铂前体在合的适溶剂(例如水)中的混合物或溶液。通常,考虑到经济和环境因素,铂的可溶化合物或络合物的水溶液是优选的。通常,以化合物或络合物形式利用铂前体,以实现该前体在载体上的分散。对本发明而言,术语“铂前体”是指任何化合物、络合物等,其在煅烧或其使用的初始阶段中分解或以其它方式转化成催化活性形式。合适的铂络合物或化合物包括但不限于铂氯化物(例如[PtCl4]2-、[PtCl6]2-的盐)、铂氢氧化物(例如[Pt(OH)6]2-的盐)、氨络铂(例如[Pt(NH3)4]2+、Pt(NH3)4)4+的盐)、水合铂(例如[Pt(OH2)4]+的盐)、双(乙酰丙酮)合铂,和混合化合物或络合物(例如[Pt(NH3)2(Cl)2])。代表性市售铂源是来自Strem Chemicals,Inc.的99%六氯铂酸铵,其可能含有痕量的其它贵金属。但是,要理解的是,本发明不限于特定类型、组成或纯度的铂前体。通过数种化学手段之一将铂前体的混合物或溶液添加到载体中。这些包括将铂前体溶液浸渍到载体上,然后可以进行并入酸性组分(例如乙酸)或碱性组分(例如氢氧化铵)的固定步骤。这种湿固体可以被化学还原或煅烧或原样使用。或者,可以将载体悬浮在合适的赋形剂(例如水)中,并与在溶液中的铂前体反应。当载体是沸石且希望将铂前体固定到沸石骨架中的离子交换位点上时,后一方法更常用。附加加工步骤可包括通过酸性组分(例如乙酸)或碱性组分(例如氢氧化铵)固定、化学还原或煅烧。
在一个或多个实施方案中,该洗涂层含有沸石,该沸石上已分布着来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的金属。示例性沸石包括但不限于具有下述晶体结构CHA、BEA、FAU、MOR、MFI之一的沸石。这一系列的示例性金属是铜。合适的将该金属分布在沸石上的方法是首先制备金属前体在合适溶剂(例如水)中的混合物或溶液。通常,考虑到经济和环境因素,该金属的可溶化合物或络合物的水溶液是优选的。对本发明而言,术语“金属前体”是指可分散在沸石载体上以产生催化活性金属组分的任何化合物、络合物等。对示例性第IB族金属铜而言,合适的络合物或化合物包括但不限于无水和水合的硫酸铜、硝酸铜、乙酸铜、乙酰丙酮合铜、氧化铜、氢氧化铜和氨络铜盐(例如[Cu(NH3)4]+)。代表性的市售铜源是来自Strem Chemicals,Inc.的97%乙酸铜,其可能含有痕量的其它金属,特别是铁和镍。但是,要理解的是,本发明不限于特定类型、组成或纯度的金属前体。可以将沸石添加到该金属组分的溶液中,以形成悬浮液。可以使该悬浮液反应,以使铜组分分布在沸石上。这可能导致铜分布在沸石的孔隙通道中以及在沸石的外表面上。铜可以以铜(II)离子、铜(I)离子或氧化铜的形式分布。在铜分布在沸石上之后,可以将该沸石与悬浮液的液相分离,洗涤并干燥。也可以将其煅烧以固定铜。
为了将催化剂层施用到基底上,将由铂组分和/或金属沸石组分构成的催化剂的细碎粒子悬浮在合适的赋形剂(例如水)中,以形成浆料。可以以在水或水混溶性赋形剂中的混合物或溶液形式向所述浆料中加入其它助催化剂和/或稳定剂和/或表面活性剂。在一个或多个实施方案中,将该浆料粉碎,以使基本所有固体都具有小于大约10微米、即大约0.1至8微米的粒度(平均直径)。该粉碎可以在球磨机、连续Eiger磨机或其它类似设备中实现。在一个或多个实施方案中,该悬浮液或浆料具有大约2至小于大约7的pH值。如果必要,可以通过向该浆料中加入足量的无机或有机酸来调节该浆料的pH值。该浆料的固含量可以为例如约20至60重量%,更特别大约35至45重量%。可以然后将基底浸渍到该浆料中,或以其它方式将该浆料涂布在基底上,从而在该基底上沉积所需载量的催化剂层。此后,将涂布的基底在大约100℃干燥,并通过例如在300至650℃加热大约1至大约3小时来煅烧。干燥和煅烧通常在空气中进行。如果必要,可以重复涂布、干燥和煅烧过程,以实现该催化剂在载体上的最终所需载量。在一些情况下,在将该催化剂投入使用并经受操作过程中遇到的高温前可以不完成该液体和其它挥发性组分的除去。
在煅烧后,可以通过计算涂布和未涂布基底重量的差别来测定催化剂载量。本领域技术人员可看出,可以通过改变涂布浆料的固含量和浆料粘度来改变催化剂载量。或者,可以进行基底在涂布浆料中的反复浸渍,然后如上所述除去过量浆料。在具体实施方案中,洗涂层在该基底上的载量为大约0.2至大约3.0克/立方英寸,或通常大约2.0克/立方英寸。
实施例
实施例1:双功能氨氧化催化剂的制备
双功能AMOx催化剂的典型制备以通过初湿含浸法将碱性Pt(IV)前体浸渍到氧化物载体上开始。通过之后的有机酸浸渍以降低表面pH值和使Pt(IV)沉淀,将Pt(IV)固定到载体上。然后将所得粉末悬浮在去离子水中以产生大约40%固含量的浆料,并用连续磨机或标准球磨机研磨,以产生粒子数的90%小于10微米的粒度分布。监测pH值且不使其超过5,从而避免Pt(IV)的再溶解。单独地,将通常由过渡金属交换的沸石构成的第二组分悬浮在水中,以产生约40%固含量的浆料,并研磨至粒子数的90%小于10微米的集料粒度分布。以乙酸锆溶液形式向该悬浮液中加入大约3%ZrO2(按固体计)。要求这样做是为了防止在将这两种浆料混合时胶凝。将这两种浆料以合适的份数混合,以获得负载的Pt和金属交换的沸石组分的所需比率。分析所得浆料以获得正确的Pt含量,并涂布到尺寸为1.0″OD×3.0″长、小室密度为400个孔隙/平方英寸、且壁厚为6密耳的标准圆柱形陶瓷整料上。通过与通道平行地将该整料浸到该浆料中、用空气流除去过量浆料、并干燥和煅烧所得湿催化剂芯,实现涂布。在一些情况下,需要反复施用以获得目标载量,特别是对大于1.0克/立方英寸的总载量而言。在评测催化剂活性之前,通常在高温下将催化剂芯老化。下面描述各评测用的具体老化条件。
实施例2:双功能PtZAl2O3+FeBEA催化剂的稳态评测
图2显示了对于由Al2O3(0.5克/立方英寸)上的0.57重量%Pt构成(产生5克/立方英尺的总Pt载量)的催化剂(实心符号)的NH3转化百分率和N2选择百分率的图。在评测之前,将该催化剂在空气中在750℃处理5小时。数据表明NH3在250℃几乎完全转化,但这种催化剂具有不合意的随温度升高而稳定降低N2选择性的性质。在400℃,N2选择性仅为36%,这不可能适合车辆用途。在高温下的低选择性是该负载的Pt催化剂根据公式1生成大量NOx的结果。一氧化氮公知是氨在车辆废气的运行温度下在负载的铂上的主要氧化产物。
公式1.4NH3+5O2→4NO+6H2O
图2显示了由Al2O3(0.5克/立方英寸)上的0.57重量%Pt和铁交换的β沸石(2.5克/立方英寸)的混合物构成的催化剂(空心符号)的NH3转化率和N2选择性数据。该整料上的总催化剂载量为3.0克/立方英寸。所述铁交换的β沸石的铁含量为1.1重量%(以Fe2O3测量)。空心符号中的数据显示了与没有铁-β组分的催化剂几乎相等的NH3转化率。这是意料中的,因为负载的Pt组分的总载量与之前相同,且在Pt/Al2O3上的主要氧化过程(公式1)基本不受铁-β组分存在的影响。但是,在铁交换的β沸石组分存在下,在高温下的N2选择性显著提高。在400℃,在含铁-β的催化剂中,N2选择性提高至70%,比Pt/Al2O3催化剂增大了1倍。铁交换的沸石是公知的用于NH3和NO的反应从而通过SCR反应(公式2)以高选择性方式产生N2的催化剂。这有助于理解在铁β沸石存在下选择性增强的起因。负载的Pt组分根据公式1将NH3转化成NO。铁β沸石然后根据公式2中的化学计量SCR反应使用相当的未反应NH3将NO中间体转化成N2。基于这种方案,容易看出,在公式2的速率与公式1的速率不相上下或更快时,获得最佳选择性。因此,我们预计在催化剂中SCR组分的量提高时观察到NOx生成量的减少和N2选择性的提高(参见实施例5)。这些数据因此表明这种双功能概念在设计选择性氨氧化催化剂中的价值。
公式2.4NH3+6NO→5N2+6H2O
实施例3:氨氧化催化剂的脉冲-升温测试
开发脉冲-升温评测以测量氨氧化催化剂在瞬态状况下的活性和选择性。在涂布在圆柱形流通型整料上的催化剂上进行这些试验,所述整料的尺寸为0.75″OD×2.5″长、小室密度为400个孔隙/平方英寸且壁厚为6密耳。该试验包括三个阶段。首先,使催化剂在含有500ppm氨、10%分子氧、5%水蒸气和5%二氧化碳且余量为分子氮的150℃气流中暴露1800秒。基于总催化剂体积,GHSV为100,000/hr。然后切断氨进料,并使催化剂平衡1200秒,此后在气相中没有可观察到的NH3。此时,温度经3000秒从150℃线性地升至500℃。在此升温过程中,将氨以每脉冲0.07毫摩尔定期加入该气流中,脉冲持续时间为5秒,然后是55秒停留时间。在停留时间过程中不加入氨。图3显示了空白堇青石基底的这种实验氨曲线图,显示在氨吸附和解吸预平衡阶段中和在脉冲-升温阶段中的氨浓度。
实施例4:典型的双功能氨氧化催化剂的瞬时排放图
图4显示了负载型铂催化剂的典型瞬时排放图。这种催化剂由1克/立方英寸SBA-150氧化铝(其上负载有30克/立方英尺Pt)以及另外0.5克/立方英寸的β沸石构成。在不消耗氨的低温区域中,数据表明,由于NH3组分被沸石组分留住,NH3脉冲明显增宽。在不含沸石的催化剂中没有观察到这种增宽。随着温度升至高于200℃,由于在该催化剂上开始消耗NH3,出口的NH3量降低。这与出口流中立即出现N2O相关联。N2O是在最高300℃观察到的主要非N2排放物,此后NOx成为最普遍的。这种排放模式是不含附加催化功能的负载型铂催化剂常见的。因此,在催化剂配制物中加入第二催化功能的目的是减少NOx和/或N2O的生成。
实施例5:代表性的双功能氨氧化催化剂的累积排放数据
将图4中的瞬时排放数据积分,得到图5中所示的氨氧化的累积排放图。催化剂部分与实施例3的相同。NH3曲线图中在200℃至250℃之间的拐折指示消耗区,在高于250℃的NH3的平坦线段表明在此温度以上没有氨排放。数据清楚表明,在225℃开始生成N2O,且在300℃开始生成NOx。使用该积分数据,确定各含N物质在试验持续期间的净排放,N2除外。假定NH3氧化的仅有的产物是N2、NO、NO2和N2O,进行质量平衡计算,由该计算确定净分子氮生成。作为所述物质的总排放与转化的总NH3的比率,计算各物质的催化选择性。
实施例6:NOx选择性,作为双功能氨氧化催化剂的铁β基于负载的铂和铁β沸石的含量的函数
图6显示了作为催化剂组合物中铁β沸石含量的函数的催化剂对NOx生成的净选择性的图。在表1中提供了用于产生图6的催化剂的组成。图6显示了负载在氧化铝SBA-150、负载在二氧化硅-氧化铝Siralox 1.5和负载在二氧化钛INE 108上的Pt的数据。对所有这些样品而言,一般趋势是随着铁β沸石含量提高,产生较低量的NOx类物质。
表1
实施例7:氨转化率,作为双功能氨氧化催化剂的铁β基于负载的铂和铁β沸石的含量的函数
重要的是证明该双功能氨氧化催化剂中的两种功能在动力学上独立,因而各组分的活性不受另一组分的负面影响。铁β沸石本身不是用于通过公式1将氨氧化的有效催化剂,因此净氨转化率受负载的铂组分支配。这在图7中清楚证明,该图表明,氨转化率和因此氨氧化速率不受样品中铁β沸石的量的影响。铁β组分不会显著促进氨氧化,也不会抑制在负载的铂组分上的氨氧化的消耗。数据还表明,该铁β组分不影响N2O生成,这与铁基催化剂在低于400℃下不与N2O反应的观察结果一致。这增强了负载的铂组分和铁β组分的动力学独立性。
实施例8:双功能Pt/Al2O3+CuCHA催化剂的稳态评测
体现在图1和2中的示意图表明,通过提高SCR活性组分的量或通过使用本身更具活性的SCR组分,可以提高N2选择性。后一策略如下得到验证:制备含有在Al2O3上的0.57重量%Pt(0.5克/立方英尺载量)和铜交换的菱沸石(CuCHA,2.5克/立方英尺载量)的催化剂,产生3.0克/立方英寸的总催化剂载量。负载的Pt组分的总载量与实施例2中相同(5克/立方英尺Pt)。该催化剂在空气中在750℃老化5小时。在稳态NH3氧化条件下评测该催化剂。NH3转化率和N2选择性作为空心符号绘制在图8中,该图还以实心符号绘制了仅含负载的Pt的对照样品。如在实施例2中那样,对含和不含CuCHA组分的催化剂而言,NH3转化率类似。但是,对含CuCHA的催化剂而言,N2选择性明显高于对照样品,也高于含FeBEA的样品。在400℃,该催化剂将100%的NH3转化成N2且基本不形成NOx,而含FeBEA的催化剂在400℃产生了大约30%NOx。这与CuCHA对SCR反应而言是比FeBEA活性高得多的催化剂的独立观察结果一致。
在本说明书通篇中提到“一个实施方案”、“某些实施方案”、“一个或多个实施方案”或“一实施方案”时,是指联系该实施方案描述的具体要素、结构、材料或特征包含在本发明的至少一个实施方案中。因此,如“在一个或多个实施方案中”、“在某些实施方案中”、“在一个实施方案中”或“在一实施方案中”之类的术语在本说明书通篇中各处的出现不一定是指本发明的相同实施方案。此外,这些具体要素、结构、材料或特征可以以任何合适的方式结合在一个或多个实施方案中。
尽管在本文中已参照具体实施方案描述了本发明,但要理解的是,这些实施方案仅举例说明本发明的原理和用途。本领域技术人员会认识到,可以在不背离本发明的实质和范围的情况下对本发明的方法和装置作出各种修改和变动。因此,本发明旨在包括在所附权利要求及其对等物的范围内的修改和变动。
Claims (34)
1.处理在柴油或稀燃车辆的废气流中生成的排放物的方法,所述方法包括:使车辆发动机废气流至少通过NOX减除催化剂;和使离开所述NOX减除催化剂并可能含有氨的废气流通过氧化催化剂,所述氧化催化剂包含铂、来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的第二金属、耐高温金属氧化物和沸石,所述氧化催化剂在低于大约300℃的温度下对于去除氨已经是有效的,并在经受水热老化后不表现出氨氧化效率的显著下降。
2.权利要求1的方法,其中所述NOX减除催化剂包含SCR催化剂、LNT催化剂或用于破坏造成氨从所述NOX减除催化剂中逸出的NOX的其它催化剂。
3.权利要求1的方法,其中所述NOX减除催化剂和氧化催化剂组合物位于分离的基底上。
4.权利要求1的方法,其中所述NOX减除催化剂和所述氧化催化剂位于相同基底上。
5.权利要求1的方法,其中铂分布在所述耐高温金属氧化物上。
6.权利要求1的方法,其中铂分布在所述沸石上。
7.权利要求1的方法,其中基于总催化剂体积,铂以约0.1克/立方英尺至大约10克/立方英尺的量存在。
8.权利要求1的方法,其中所述来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的金属分布在所述沸石上。
9.权利要求1的方法,其中所述来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的金属以沸石的0.1重量%至5重量%的量存在于所述沸石上。
10.权利要求1的方法,其中所述来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的金属是铜。
11.权利要求1的方法,其中所述来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的金属是铁。
12.权利要求1的方法,其中所述耐高温金属氧化物选自氧化铝、二氧化硅、氧化锆、二氧化钛、二氧化铈、和它们的物理混合物或化学组合,包括原子掺杂的组合。
13.权利要求1的方法,其中基于总催化剂体积,所述耐高温金属氧化物载体在基底上的总载量为大约0.01克/立方英寸至2.0克/立方英寸。
14.权利要求1的方法,其中所述沸石具有下述晶体结构之一:CHA、BEA、FAU、MOR、MFI。
15.权利要求1的方法,其中所述沸石中二氧化硅与氧化铝的摩尔比为大约2至大约250。
16.权利要求1的方法,其中基于总催化剂体积,所述沸石在基底上的总载量为大约0.1克/立方英寸至4.0克/立方英寸。
17.用于将氨氧化的催化剂,包含铂、来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的第二金属、耐高温金属氧化物和沸石,所述氧化催化剂在低于大约300℃的温度下对于去除氨已经是有效的,并在经受水热老化后不表现出氨氧化效率的显著下降。
18.权利要求17的催化剂,其中铂分布在所述耐高温金属氧化物上。
19.权利要求17的催化剂,其中铂分布在所述沸石上
20.权利要求17的催化剂,其中基于总催化剂体积,铂以大约0.1克/立方英尺至大约10克/立方英尺的量存在。
21.权利要求17的催化剂,其中所述来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的金属分布在所述沸石上。
22.权利要求17的催化剂,其中所述来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的金属以沸石的0.1重量%至5重量%的量存在于所述沸石上。
23.权利要求17的催化剂,其中所述来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的金属是铜。
24.权利要求17的催化剂,其中所述来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的金属是铁。
25.权利要求17的催化剂,其中所述耐高温金属氧化物选自氧化铝、二氧化硅、氧化锆、二氧化钛、二氧化铈、和它们的物理混合物或化学组合,包括原子掺杂组合。
26.权利要求17的催化剂,其中基于总催化剂体积,所述耐高温金属氧化物载体在基底上的总载量为大约0.01克/立方英寸至2.0克/立方英寸。
27.权利要求17的催化剂,其中所述沸石具有下述晶体结构之一:CHA、BEA、FAU、MOR、MFI。
28.权利要求17的催化剂,其中所述沸石中二氧化硅与氧化铝的摩尔比为大约4至大约250。
29.权利要求17的催化剂,其中基于总催化剂体积,所述沸石在基底上的总载量为大约0.1克/立方英寸至4.0克/立方英寸。
30.用于含NOX的废气流的处理***,所述***包含:至少一种有效减少NOX的上游催化剂;和有效除氨的下游氧化催化剂,所述氧化催化剂包含铂、来自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族之一的第二金属、耐高温金属氧化物和沸石,所述氧化催化剂在低于大约300℃的温度下对于去除氨已经是有效的,并在经受水热老化后不表现出氨氧化效率的显著下降。
31.权利要求30的发动机处理***,其中所述NOX减除催化剂包含SCR催化剂、LNT催化剂或用于破坏造成氨从所述NOX减除催化剂中逸出的NOX的其它催化剂。
32.权利要求30的发动机处理***,其中所述NOX减除催化剂和氧化催化剂组合物位于分离的基底上。
33.权利要求30的发动机处理***,其中所述NOX减除催化剂和所述氧化催化剂位于相同基底上。
34.权利要求30的发动机处理***,包含用于将氨或氨前体计量加入废气流中的计量***。
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JP5110954B2 (ja) | 2007-05-09 | 2012-12-26 | エヌ・イーケムキャット株式会社 | 選択還元型触媒を用いた排気ガス浄化触媒装置並びに排気ガス浄化方法 |
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Also Published As
Publication number | Publication date |
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US20080292519A1 (en) | 2008-11-27 |
KR20150065907A (ko) | 2015-06-15 |
BRPI0807379B1 (pt) | 2017-12-26 |
EP2117702B1 (en) | 2020-11-11 |
KR20170089936A (ko) | 2017-08-04 |
BRPI0807379A2 (pt) | 2014-05-06 |
MX2009009097A (es) | 2009-09-18 |
WO2008106523A3 (en) | 2008-12-04 |
CA2679599C (en) | 2016-01-05 |
JP2010519039A (ja) | 2010-06-03 |
RU2009135861A (ru) | 2011-04-10 |
KR20160079935A (ko) | 2016-07-06 |
WO2008106523A2 (en) | 2008-09-04 |
KR20090114480A (ko) | 2009-11-03 |
PL2117702T3 (pl) | 2021-05-04 |
US7722845B2 (en) | 2010-05-25 |
JP2015166083A (ja) | 2015-09-24 |
JP6125552B2 (ja) | 2017-05-10 |
CN105251359A (zh) | 2016-01-20 |
EP2117702A2 (en) | 2009-11-18 |
JP5761917B2 (ja) | 2015-08-12 |
CA2679599A1 (en) | 2008-09-04 |
MY151931A (en) | 2014-07-31 |
EP3778009A1 (en) | 2021-02-17 |
KR101974704B1 (ko) | 2019-05-02 |
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