CN103402634A - 用于氮氧化物的选择性催化还原的催化活性材料和催化转化器 - Google Patents
用于氮氧化物的选择性催化还原的催化活性材料和催化转化器 Download PDFInfo
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- CN103402634A CN103402634A CN2012800114177A CN201280011417A CN103402634A CN 103402634 A CN103402634 A CN 103402634A CN 2012800114177 A CN2012800114177 A CN 2012800114177A CN 201280011417 A CN201280011417 A CN 201280011417A CN 103402634 A CN103402634 A CN 103402634A
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- catalyst
- oxide
- zeolite
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- exhaust
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000011149 active material Substances 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title description 7
- 238000010531 catalytic reduction reaction Methods 0.000 title 1
- 239000010457 zeolite Substances 0.000 claims abstract description 60
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 53
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 51
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 51
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical group 0.000 claims abstract description 9
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940119177 germanium dioxide Drugs 0.000 claims abstract description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 146
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- -1 zeolite compound Chemical class 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 230000001413 cellular effect Effects 0.000 claims description 11
- 150000004703 alkoxides Chemical class 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 7
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 7
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004176 ammonification Methods 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold 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
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 238000011144 upstream manufacturing Methods 0.000 description 27
- 239000011162 core material Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- 239000000725 suspension Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000032683 aging Effects 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 238000007598 dipping method Methods 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000005342 ion exchange Methods 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 206010000269 abscess Diseases 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 210000002421 cell wall Anatomy 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
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- 150000002500 ions Chemical class 0.000 description 4
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- 229910016874 Fe(NO3) Inorganic materials 0.000 description 3
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- 230000007613 environmental effect Effects 0.000 description 3
- 229910001657 ferrierite group Inorganic materials 0.000 description 3
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- 239000004071 soot Substances 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- 241000269350 Anura Species 0.000 description 2
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- NXKGJIRLCQBHFD-UHFFFAOYSA-N CO[SiH](OC)CC(C)C Chemical compound CO[SiH](OC)CC(C)C NXKGJIRLCQBHFD-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 description 1
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- 229910002089 NOx Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical class 0.000 description 1
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- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- B01J29/88—Ferrosilicates; Ferroaluminosilicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- 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
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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
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
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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
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
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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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
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Abstract
本发明涉及用于在烃类存在下使氮氧化物与氨反应的一种催化活性材料。该材料由一个内部的芯(1)组成,该内芯是由用一种或多种过渡金属交换的一种沸石或用一种或多种过渡金属交换的一种类沸石化合物构成。该催化活性材料的内芯由一个外壳(2)包围,该外壳是由一种或多种氧化物构成,这些氧化物选自下组,该组由以下各项组成:二氧化硅、二氧化锗、氧化铝、氧化钛、氧化锡、氧化铈、二氧化锆以及它们的混合氧化物。
Description
本发明涉及一种催化活性材料和一种以其生产的催化剂,并且涉及其用于清洁柴油排气,尤其在汽车应用中的用途,该催化剂用于在柴油发动机排气中的氮氧化物的选择性催化还原,并且具有对同样存在于该柴油排气中烃类的改进的耐受性。
柴油发动机的排气包括炭烟颗粒(PM)和氮氧化物(NOx),连同由燃料的不完全燃烧产生的一氧化碳(CO)和烃(HC)污染气体。另外,柴油发动机的排气包含高达按体积计15%的氧。已知,这些可氧化的CO和HC污染物气体可以通过将它们传送经过一种适合的氧化催化剂而转化为无害的二氧化碳(CO2),并且微粒通过将该排气穿过一个适合的炭烟颗粒过滤器。在氧存在时从排气中去除氮氧化物的方法学在现有技术中也是众所周知的。这些“去氮氧方法”的一种是所谓的SCR方法(SCR=选择性催化还原),即,这些氮氧化物与还原剂氨在一种对其适合的催化剂(SCR催化剂)上进行选择性催化还原。在这个方法中,氨可以按原样或者以环境条件下可分解成氨的前体化合物的形式来添加到该排气流中,“环境条件”被理解为是指在SCR催化剂上游的排气流中该化合物可分解成氨的环境。该SCR方法的完成要求一个用于提供还原剂的来源、一种用于将该还原剂经计量后该如所要求地添加到排气中的注射装置、以及布置在该排气的流动路径中的SCR催化剂。被布置在该SCR催化剂的流入侧上的一种还原剂源、SCR催化剂、以及注射装置的整体还被称为一个SCR***。
考虑到今后将会应用的法律限制,用于去除由发动机排放的所有污染气体的一种排气后处理通常将会对于所有新登记的柴油车辆是不可或缺的。因此,将柴油氧化催化剂、柴油微粒过滤器以及SCR***进行组合对于柴油排气后处理的当前应用是必须的,并且这些单元的组合将必然引起尤其该SCR催化剂的改变的工作条件。目前,正在测试这种类型的三个***:在根据EP1 054 722的“***”中,一种柴油氧化催化剂、一种柴油微粒过滤器和一个SCR***被串联地安排在该排气的流动方向上。可替代地,该SCR***还可能被安排在一种紧密联接的柴油催化剂与在机动车辆底部的一个柴油微粒过滤器之间(DOC-SCR-DPF)或在一个由柴油氧化催化剂和柴油微粒过滤器组成的单元的上游(SCR-DOC-DPF)。
在一个排气线中柴油微粒过滤器和SCR***的组合意味着该SCR催化剂,在特殊的工作点上,被显著长时间地暴露于比在现有应用中的情况的更高的HC浓度。对于这些增加的HC浓度,存在几个原因:
首先,发动机内燃烧现在不再是以省去昂贵的排气后处理阶段为目标而进行校准,而是从功率最优化的角度来看,具有对于作为排放物的微粒和HC类以及氮氧化物的相等的耐受性。这导致该排气后处理***的HC污染的某一个基础水平,该排气已经具有比在使用SCR***的迄今为止常规的应用中高得多的HC浓度。第二,该柴油微粒过滤器必须定期进行再生,并且在一种方式中,这是通过该微粒负载的受控烧尽而完成的。为此目的,该过滤器必须被加热至一个高于该碳烟点燃温度的温度。这个加热通过将燃料后注射至该缸的输出活塞冲程中或至该排气线中,并且通过在一种氧化催化剂(被称为“加热催化剂”)上的未燃烧的烃类的催化转化而进行的。通常,一种上游柴油氧化催化剂承担该加热催化剂的功能。如果这是不存在的,则该SCR催化剂可能在某些情况下也承担加热功能。在每个情况下,在该过滤器再生过程中在该SCR催化剂的上游存在较高的HC浓度,因为在点火后注入的烃类在该加热过程中是不完全催化燃烧的。在一个***中,在其中柴油氧化催化剂和柴油微粒过滤器是在该SCR催化剂的上游,在一定的使用寿命后,存在该SCR催化剂的额外地永久的HC负载,这可归因于在柴油氧化催化剂和任选地催化涂覆的过滤器中氧化功能的水热老化。
独立于该柴油微粒过滤器的任何再生,另外的加热措施由于燃料后注入而可能是必须的,例如来补偿冷启动延迟,并且导致在该SCR催化剂的上游短暂地显著增加的HC浓度。
这些影响的结果是在现代排气清洁组合***中的SCR催化剂被暴露于改变的工作条件,存在于该SCR催化剂的上游的排气中的HC浓度比在现有应用中的高得多。在这些条件下,常规的SCR催化剂与在不包含烃类的排气中的其活性相比通常显示出在氮氧化物转化性能上明显的下降。最近,在现有技术中也已经有耐烃的SCR催化剂的描述。
例如,WO2009/135588披露了用于处理包含氮氧化物(NOx)和烃类(HC)的柴油发动机排气的一种方法,包含:a)将氨(NH3)按原样或以一种化合物的形式添加至包含氮氧化物和烃类的排气流中,该化合物在环境条件下产生来自一个源的氨,该源不形成该排气线的一部分;以及b)NOx与添加至该排气的NH3在包含用铜(Cu)和/或铁(Fe)交换的沸石的一种SCR催化剂上的选择性反应,其特征在于,存在于该排气中的烃类被保持远离该催化剂中的活性位点,在该活性位点上该反应通过该沸石的类分子筛作用而发生。所用的这些沸石是小孔沸石,尤其镁碱沸石、菱沸石和毛沸石。因为它们的尺寸,存在于该排气中的烃类不能渗透到这些沸石的孔结构中。
与在无烃排气中的其活性相比,这些耐烃SCR催化剂在含烃排气中具有在其氮氧化物转化活性上小得多的下降。然而,甚至在无烃排气中通过这些催化剂可实现的氮氧化物转化总体上比常规的SCR催化剂显著地更差。这些耐HC催化剂的水热老化稳定性也经常显著地不如常规SCR催化剂的水热老化稳定性。
在该有待清洁的排气中烃类的升高的含量也通常对SCR催化剂的长期稳定性有有害影响。这对于常规的SCR催化剂尤其是如此,该催化剂的功能是基于具有中等或大孔径大小的过渡金属交换的沸石(例如丝光沸石、β-沸石、USY、ZSM-5或ZSM-20)的SCR活性,因为这些烃类可以从该排气被存储在沸石骨架中。存在于该排气中的烃类在比较冷的工作温度下与氨竞争而被存储在该沸石骨架中。如果该催化剂然后被暴露于比用于催化烃氧化的点火温度更高的升高的工作温度,则这些存储的烃类在该沸石中“燃烧”。释放的反应焓然后在该催化剂中产生相当大的放热,并且相应的温度上升可以导致对在该沸石催化剂中的催化活性位点相当大的损害。
本发明的一个目的是提供与常规的基于沸石的SCR催化剂相比具有改进的HC耐受性的SCR催化剂,但同时地该SCR催化剂在水热老化之前和之后具有比根据现有技术的耐HC催化剂更高的SCR活性。
这个目的是通过一种催化活性材料实现的,该材料由一个内芯(1)和包围此芯的一个外壳(2)组成,如在图1中示意性示出的。该催化活性材料的内芯是由已经用除镍和铬以外的一种或多种过渡金属交换的一种沸石或一种类沸石化合物形成的,同时包围此内芯的外壳是由一种或多种氧化物形成的,这些氧化物选自下组,该组由以下各项组成:二氧化硅、二氧化锗、氧化铝、氧化钛、氧化锡、氧化铈、二氧化锆以及它们的混合氧化物。
在本文件背景下“类沸石化合物”被理解为是指形成一种典型的沸石结构(“沸石骨架”)的那些,但不是或不是唯一地由硅酸铝形成的。这些尤其包括磷酸硅铝(SAPO)和磷酸铝(ALPO)。
根据本发明使用的这些沸石和类沸石化合物已经用一种或多种过渡金属进行交换-除了镍和铬之外。这意味着,从这些相应的沸石或类沸石化合物的H形式或NH4 +形式出发,H+离子或NH4 +离子通过离子交换已经被交换成相对应当量的过渡金属阳离子。然而,这不意味着形成这些沸石或这些类沸石化合物的基础晶格的铝、硅和/或磷原子已经被交换成过渡金属。反而,由于这个离子交换的结果,该基础晶格保持未改变。
本发明的催化活性材料的芯优选由用一种或多种过渡金属交换的一种沸石或已用一种或多种过渡金属交换的一种类沸石化合物组成,并且选自由β-沸石、ZSM-5、ZSM-20、USY以及MOR组成的组。这些过渡金属优选地选自下组,该组由以下各项组成:铈、锰、铁、铜、银、金、铂、钯和/或它们的混合物。给予特别优选的是铈、铁和铜。在本文件背景下的术语“过渡金属”既不包括镍也不包括铬。
该外壳优选完全包围该内芯。然而,当该外壳是仅仅几乎完全时,本发明也产生效果。更具体地说,该外壳包围该内芯至所到的程度是90%至100%、更优选95%至100%,在每个情况下基于该内芯的表面面积。
本发明催化活性材料的外壳是优选由二氧化硅、氧化铝、氧化铈、氧化锆或铈锆混合氧化物形成的。给予非常特别优选的是二氧化硅。
为了确保足够的孔隙率用于使所希望的反应物,氨和氮氧化物,穿过同时对在排气中的烃类具有足够的阻挡作用的外壳材料,在该外壳中的氧化物优选具有d50等于或小于100nm的粒度分布。给予特别优选的是具有粒度分布的d50为小于或等于70nm的氧化物。最优选地,该氧化物的粒度分布的d50是小于或等于20nm。一种氧化物的粒度分布的d50表明该氧化物的总体积的50%只包含直径是小于或等于作为d50所报道的值的那些颗粒。
在理想的实施例中,由沸石或类沸石材料形成的催化活性材料的这些内芯颗粒是被一个无定形氧化物层包围。一种“无定形氧化物”被理解为是指一种不具有任何长程结构有序性的氧化材料。
为了生产该催化活性材料,用于形成该内芯的沸石或类沸石化合物是用包含这些氧化物的一种或多种可溶性前体的溶液来浸渍的,这些氧化物是用于形成在最终本发明的催化活性材料中的外壳。在该方法中稍后形成该外壳的这些氧化物然后直接在该颗粒内芯上形成。
本发明的催化活性材料是通过用包含通式(I)的一种或多种醇盐的溶液浸渍形成该内芯的沸石或形成该内芯的类沸石化合物而获得的
(RO)n-mMeR'm (I)
在其中
n是3或4并且m<n;
Me是硅、锗、铝、钛、锡、铈或锆;
R是(C1-C4)-烷基或苯基;并且
R'是(C1-C8)-烷基、氨基-(C1-C4)-烷基、氨基基团被氨基-(C1-C4)-烷基取代的氨基-(C1-C4)-烷基、或(C1-C4)-甲基丙烯酸烷基。
作为这些醇盐的水解以及这些水解产物的缩合作用来在这些颗粒的表面上形成Me-O链和网络的结果而形成了这些氧化物。如果这些水解和缩合反应是完全的,以这种方式获得的固体是任选地被分离、干燥和煅烧,并且完成了该氧化物的形成。
上述这些烷基基团可能是直链或支链的,并且可能,例如,是甲基、乙基、正丙基、异丙基、正丁基或异丁基。(C1-C8)-烷基另外地,例如,还可能是戊基、己基、庚基或辛基。
R优选是甲基、乙基、异丙基、丁基或苯基。
R'优选是氨基-(C1-C4)-烷基,尤其氨甲基和氨乙基;N-(2-氨基乙基)-3-氨基丙基;异丙基;异丁基;苯基;辛基或(C1-C4)-烷基的甲基丙烯酸酯,尤其甲基丙烯酸甲酯、甲基丙烯酸乙酯或甲基丙烯酸丙酯。
更优选地,Me代表硅。在这种情况下,所用的化学式(I)的这些醇盐尤其是四乙氧基硅烷、二异丁基二甲氧基硅烷、N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷、苯基三乙氧基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷和三乙氧基辛基硅烷。
为了制备粉末形式的催化活性材料,该沸石内芯材料优选用在乙醇或在具有按重量计最高达50%水的一种乙醇-水混合物中的醇盐溶液来浸渍。为了完成该缩合反应,小量值的一种质子酸,例如,硝酸、硫酸、盐酸或乙酸,可以任选地被加入到该混合物中。将所产生的混合物进行干燥;将经干燥的材料进行煅烧。这提供了处于粉末形式的本发明的催化活性材料。
为了获得一种适用的汽车排气催化剂,本发明的催化活性材料必须以涂层的形式施用于一种惰性载体或者被挤出成一个机械稳定的蜂窝状物。本发明的催化活性材料可以被悬浮,例如,在水中并且通过本领域的普通技术人员已知的常规的浸渍、抽吸或泵送方法中的一种而被施用到一种催化惰性载体上。
可替代地,还可能在涂覆悬浮液中有效地“原位”生产本发明的催化活性材料,该悬浮溶液用一个常规的浸渍、抽吸或泵送方法直接用于涂覆一种惰性载体而没有该催化活性材料的中间分离。为此目的,例如,将该沸石内芯材料悬浮在水中并且在搅拌下将醇盐的一种乙醇溶液添加到所产生的悬浮液中。当完成该乙醇的醇盐溶液的添加时,该水解和缩合反应可以通过任选地添加小量值的一种质子酸至该悬浮液中而完成。在一段适当的连续的搅拌时间后,由此产生的悬浮液可以直接用于涂覆该载体。
在生产包含一个本发明催化材料涂层的负载型催化剂的情况下,优选在生产该氧化外壳之前,即在添加该乙醇的醇盐溶液之前通过研磨来进行该沸石基材料的颗粒大小的任何调整(出于涂覆原因是必需的)。如果本发明的催化活性材料经受了一个研磨操作,在这些颗粒上的机械应力可能导致内芯材料和外壳材料的部分的或完全的分离并且因此在所产生的催化剂中HC耐受性的损失。
包含本发明催化活性材料的这些催化剂尤其适合于降低在含烃柴油发动机排气中包含一氧化氮和二氧化氮的氮氧化物的水平。氨或一种可分解为氨的前体化合物作为一种还原剂被添加至有待清洁的排气中。所产生的混合物是排气并且还原剂然后被传送经过具有包含本发明催化活性材料的涂层的一种催化剂。
优选地,在添加氨或一种可分解为氨的前体化合物之前,使有待清洁的排气通过一种氧化催化剂,该催化剂对于将存在于该排气中的一氧化氮的至少一部分转化为二氧化氮是有效的。在该SCR催化剂的上游的氧化催化剂和任何另外的排气清洁单元应该优选被选择为,使得它们影响在有待清洁的排气中的一氧化氮与二氧化氮的比率,这样使得在进入包含本发明的催化活性材料的SCR催化剂之前,有待清洁的排气具有在这些氮氧化物的30%至70%中的二氧化氮含量。具有这些氮氧化物的此种二氧化氮含量,实现了尤其良好的NOx向氮气的转化。在这种情况下,被连接在本发明的SCR催化剂的上游的氧化催化剂优选处于在一个整体式流动蜂窝状物和/或在一个壁流式过滤器基底上的一个催化活性涂层的形式。
本发明催化活性材料的使用提供了SCR催化剂,该催化剂因即使在具有高HC含量的排气中对烃类也有极高的耐受性而值得注意。
下文中通过一些附图以及实例来更详细展示本发明。这些图示出:
图1:本发明的催化活性材料的示意图,该材料由一个内部的芯(1)和一个外壳(2)组成,该内芯是由用一种或多种过渡金属交换的一种沸石或由用一种或多种过渡金属交换的一种类沸石化合物形成的,该外壳包围该内芯并且是由一种或多种氧化物形成的,这些氧化物选自下组,该组由以下各项组成:二氧化硅、二氧化锗、氧化铝、氧化钛、氧化锡、氧化铈、氧化锆以及它们的混合氧化物。
图2:根据现有技术的一种SCR催化剂(VK1)的上游和下游的排气温度,该催化剂在这些测量开始之前已经负载有烃类:在反应器温度/催化剂的上游温度上升至400℃导致由HC烧尽引起的明显的放热;
图3:在将反应器温度/催化剂的上游温度提高至400℃后,当该催化剂在测量开始之前已经负载有烃类时,在催化剂的上游与下游的排气温度之间的温度差ΔT=T(催化剂的下游)-T(催化剂的上游):在以刚刚产生的状态中的本发明催化剂K1至K11与根据现有技术的一种催化剂(VK1)上由HC烧尽产生的放热量的比较;
图4:在将反应器温度/催化剂的上游温度提高至400℃后,当该催化剂在测量开始之前已经负载有烃类时,在催化剂的上游与下游的排气温度之间的温度差ΔT=T(催化剂的下游)-T(催化剂的上游):在以水热老化状态的本发明的催化剂K'1至K'6与根据现有技术的一种催化剂(VK'1)上由HC烧尽产生的放热量的比较;
图5:标准化为在不含烃排气中的α值的先前水热老化的催化剂VK'2(现有技术)与K'1(本发明)的NOx转化率。
对比实例1:
生产用于基于离子交换的β-沸石的一种可商购的SCR催化剂的一种涂覆悬浮液。为此目的,一种商用的SiO2粘合剂、一种商用的勃姆石粘合剂(作为涂覆助剂)、九水合硝酸铁(III))以及具有SiO2/Al2O3摩尔比(SAR)为25的可商购的β-沸石被悬浮在水中,并且用一种常规的浸渍方法施用到一个陶瓷流蜂窝状物,该蜂窝状物具有每平方厘米62个泡孔以及0.17毫米的泡孔壁厚度。将该涂覆的组分首先在350℃煅烧15分钟,然后在500℃煅烧2小时。以此方式获得的在催化剂VK1上的涂层在一定程度由90%的β-沸石组成并且具有按重量计4.5%的铁含量,计算为Fe2O3。
对比实例2:
生产根据WO2009/135588的一种耐HC的SCR催化剂。为此目的,具有SiO2/Al2O3摩尔比(SAR)为20的镁碱沸石类型的一种可商购的、小孔的沸石被悬浮在水中。九水合硝酸铁(III)被添加至该悬浮液中。在研磨后,该悬浮液用于用一种常规的浸渍方法涂覆一个整体式流动蜂窝状物,该蜂窝状物具有每平方厘米62个泡孔以及0.17毫米的泡孔壁厚度。将该涂覆的组分首先在350℃煅烧15分钟,然后在500℃煅烧2小时。以此方式获得的催化剂VK2的该涂层由具有按重量计4.5%的铁含量,计算为Fe2O3的镁碱沸石组成。
实例1:
在第一步骤中,通过液体离子交换将铁引入到一种可商购的β-沸石(来自分子筛国际公司(Zeolyst)的CP814T)中。为此目的,将该可商购的β-沸石悬浮在水中,并且将九水合硝酸铁(III)添加至该悬浮液中。将该悬浮液搅拌经过20小时的过程并且然后在80℃至90℃下干燥。然后将以此方式获得的固体在350℃煅烧经过10分钟的一段时间并且在500℃煅烧经过2小时的一段时间。该最终的离子交换的β-沸石包含按重量计5%的铁,作为Fe2O3计算。
1kg的先前已制备的经离子交换的β-沸石在一个粉末浸渍步骤中与在乙醇(60%)中包含7.5g四乙氧基硅烷和2.5g水的一个溶液接触。所用溶液的量值与该沸石的吸水率相匹配,使得获得一种潮湿的但自由流动的粉末。将该粉末在50℃煅烧经过6小时的一段时间,然后在120℃煅烧经过2小时的一段时间并且最后在500℃煅烧经过2小时的一段时间。
将由此获得的粉末悬浮在水中,并且在添加按重量计10%的硅溶胶(作为SiO2计算并且基于在悬浮液中的固体的总量值)作为粘合剂后,该悬浮液作为一个涂层用一种常规的浸渍方法施用于一个陶瓷流动蜂窝状物,该蜂窝状物具有每平方厘米62个泡孔以及0.17毫米的泡孔壁厚度。将由此获得的催化剂K1在350℃后煅烧经过10分钟至15分钟的一段时间,然后在500℃后煅烧经过2小时的一段时间。
实例2:
与实例1完全类似,制备一种另外的催化剂K2,除了所用浸渍溶液是在210g乙醇中的8.1g的N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷与2.7g水的一个溶液。
实例3:
与实例1完全类似,制备一种另外的催化剂K3,除了所用浸渍溶液是在210g乙醇中的7.4g二异丁基二甲氧基硅烷与2.5g水的一个溶液。
实例4:
与实例1完全类似,制备一种另外的催化剂K4,除了所用浸渍溶液是在210g乙醇中的8.7g苯基三乙氧基硅烷与2.9g水的一个溶液。
实例5:
与实例1完全类似,制备一种另外的催化剂K5,除了所用浸渍溶液是在210g乙醇中的9.0g甲基丙烯酰氧基丙基三甲氧基硅烷与3.0g水的一个溶液。
实例6:
与实例1完全类似,制备一种另外的催化剂K6,除了所用浸渍溶液是在210g乙醇中的10.0g三乙氧基辛基硅烷与3.3g水的一个溶液。
实例7:
如在上述实例中,首先通过液体离子交换将铁引入到一种可商购的β-沸石中。该方法和原材料对应于在实例1中指出的程序。该最终的经离子交换的β-沸石包含按重量计5%的铁,作为Fe2O3计算。
在第一容器中,生产先前制备的经离子交换的β-沸石的1kg的涂覆悬浮液。用乙酸将该涂覆悬浮液的pH调整至4。
在第二容器中,制备在252g乙醇中含有7.5g四乙氧基硅烷与2.5g水的一种浸渍溶液。
这两种溶液在具有恒定pH的一个注入***中以一个受控的方式进行组合。在添加按重量计10%的硅溶胶(作为SiO2计算并且基于在悬浮液中的固体的总量值)作为粘合剂后,该悬浮液通过一种常规的浸渍方法用于涂覆一个陶瓷流动蜂窝状物,该蜂窝状物具有每平方厘米62个泡孔以及0.17毫米的泡孔壁厚度。首先将所产生的催化剂K7在350℃煅烧经过10分钟至15分钟的一段时间,然后在500℃煅烧经过2小时的一段时间。
实例8:
与实例7完全类似,制备一种另外的催化剂K8,除了该浸渍溶液在125g乙醇中包含70.5g四乙氧基硅烷。
实例9:
与实例7完全类似,制备一种另外的催化剂K9,除了该浸渍溶液在180g乙醇中包含7.2g四乙氧基硅烷并且该涂覆悬浮液的pH被调整至值为7。
实例10:
与实例8完全类似,制备一种另外的催化剂K10,除了该浸渍溶液在108g乙醇中包含72.7g四乙氧基硅烷并且该涂覆悬浮液的pH被调整至值为7。
实例11:
与实例8完全类似,制备一种另外的催化剂K11,除了该浸渍溶液在115g乙醇中包含73.3g四乙氧基硅烷并且该涂覆悬浮液的pH被调整至值为2。
所有制备的催化剂K1至K11以及对比催化剂VK1以刚刚制备的状态经受在以下的条件下的一个HC耐受性的研究。
为此目的,具有一英寸的直径和3英寸的长度的所制备的催化剂的钻孔内芯在100℃下与烃类在一个发动机测试床上接触经过60分钟的一段时间。随后,将该钻孔内芯在一个模型气体***中在反应器温度100℃下预处理10分钟(10%O2、10%CO2、5%H2O、余量为N2、总流速4m3/h)。然后在30秒内以同样的气体混合物将该反应器温度提高至400℃。在进入该催化剂钻孔内芯中的入口上游5毫米的排气温度以及超过该钻孔内芯3英寸的排气温度作为已经出现的放热性的一个量度而被评估。
图2示出,通过举例,在进入对比催化剂VK1的入口上游5毫米的排气温度以及超过该对比催化剂VK176.2毫米的所测量的排气温度。在从t=600秒提高该反应器温度之后不久,观察到一个明显的放热,该放热反映在催化剂下游的排气温度上升至大于800℃。
为了能够更好比较由这些催化剂产生的放热,通过形成在催化剂上游温度与催化剂下游温度之间的温度差ΔT,基于定义ΔT=T(催化剂的下游)-T(催化剂的上游),而考虑在温度控制上的不准确度。在此,T(催化剂的上游)是该钻孔内芯上游5毫米的排气温度并且T(催化剂的下游)是超过该钻孔内芯76.2毫米的排气温度。当在催化剂的下游或上游的温度最大值存在时,在时间t催化剂的上游=t最大,催化剂的上游或t催化剂的下游=t最大,催化剂的下游时记录该温度。
图3示出对于以刚刚制备的状态的所制备的催化剂K1至K11与VK1所确定的温度差的比较。通过上述方法的评估导致了在本发明的催化剂的情况下的负温度差。这些是由这个事实造成的:由反应热引起的温度差被通过该反应器的正常的热量损失掩蔽,该反应器在这种情况下不是绝热的。在本发明的催化剂上,HC烧尽没有产生或几乎没有产生反应热,并且因此经由该反应器(不是绝热的)而存在的热量损失是如此高以至于该催化剂样品的下游的排气比该催化剂样品的上游的更冷。总体上,因此发现由于存储的烃类的烧尽的结果,在本发明的催化剂上没有产生显著的放热。与常规的沸石SCR催化剂VK1相比,本发明的催化剂K1至K11因此以在HC耐受性上显著的改进而值得注意。
从每个催化剂K1至K6以及对比催化剂VK1和VK2中取另一个钻孔内芯。这些经受人工水热老化,是在氮气中含有按重量计10%的水蒸汽和按重量计10%的氧气的气氛中在烘箱中在750℃的温度下经过16小时的一段时间。在这个老化步骤后,所产生的催化剂VK'1以及K'1至K'6再次经受一个放热性测试。
图4示出在老化的催化剂K'1至K'6以及VK'1上所确定的温度差的比较。同样在水热老化状态中,在本发明的催化剂上观察到比根据现有技术VK'1的沸石SCR催化剂的低得多的由HC烧尽引起的放热量。根据现有技术的SCR催化剂(VK1)在水热老化后也具有显著低得多的放热的这个事实可以归因于:对催化活性位点的损害随着该老化已经发生,并且这也不利地影响催化烃燃烧的能力。总体上,因此发现本发明的这些催化剂比常规的SCR催化剂更耐HC。毫无例外地,与根据现有技术的一种常规的经离子交换的沸石催化剂相比,它们具有对烃类明显地改进的耐受性。
为了测试在SCR反应中本发明催化剂的催化活性,对在人工水热老化后在实例1中制备的催化剂的NO转化活性进行了研究。
该研究是在一个具有以下气体浓度的模型气体***中在一个静态测试中进行的:
模型气体组分: | 浓度 |
NO | 500ppmv |
NH3 | 450ppmv |
O2 | 按体积计5% |
H2O | 按体积计5% |
N2 | 余量 |
氨与这些氮氧化物的摩尔比在SCR活性的研究中通常被定义为α:
在该表中列出的这些气体浓度产生一个α值α=0.85。在这些模型气体测试中进行的空间速度是30000h-1。
在本文件的上下文中以一个标准化至α值的形式,即NOx转化率/α值报道了所测量的NOx转化率。
图5示出了之前人工水热老化的催化剂K'1与相对应地老化的对比催化剂VK'2的转化性能相比的SCR活性测试的结果,该对比催化剂VK'2是根据现有技术(WO2009/135588)的更耐HC的SCR催化剂。本发明的催化剂显示了在250℃至450℃温度范围内在NOx转化性能上的显著的改进。
这些实例显示了可能通过本发明的催化活性材料和以其产生的这些催化剂来提供与常规的沸石SCR催化剂相比具有明显改进的HC耐受性的SCR催化剂,并且同时地可能实现比迄今在现有技术中已知的耐HC的SCR催化剂高得多的氮氧化物转化性能。
Claims (11)
1.一种催化活性材料,该材料由一个内部的芯(1)和一个包围此内芯的外壳(2)组成,其中该内芯是由已经用除镍和铬以外的一种或多种过渡金属交换的一种沸石或一种类沸石化合物形成的,并且其中该外壳是由一种或多种氧化物形成的,这些氧化物选自下组,该组由以下各项组成:二氧化硅、二氧化锗、氧化铝、氧化钛、氧化锡、氧化铈、二氧化锆以及它们的混合氧化物。
2.如权利要求1所述的催化活性材料,其特征在于,该沸石或类沸石化合物选自由β-沸石、ZSM-5、ZSM-20、USY以及MOR组成的组。
3.如权利要求1和/或2所述的催化活性材料,其特征在于,这些过渡金属选自下组,该组由以下各项组成:铈、锰、铁、铜、银、金、铂、钯和/或它们的混合物。
4.如以上权利要求中任一项所述的催化活性材料,其特征在于,在该外壳中的氧化物的粒度分布的d50是等于或小于100nm,该氧化物的粒度分布的d50被理解为使得该氧化物的总体积的50%只包含直径小于或等于报道为d50的值的那些颗粒。
5.一种用于生产如以上权利要求中任一项所述的催化活性材料的方法,其特征在于以下方法步骤:
·用包含化学式(I)的一种或多种醇盐的一个溶液浸渍形成该内芯的沸石或类沸石化合物
(RO)n-mMeR'm (I)
在其中
n是3或4并且m<n;
Me是硅、锗、铝、钛、锡、铈或锆;
R是(C1-C4)-烷基或苯基;并且
R'是(C1-C8)-烷基、氨基-(C1-C4)-烷基、氨基基团被氨基-(C1-C4)-烷基取代的氨基-(C1-C4)-烷基、或(C1-C4)-烷基甲基丙烯酸酯,并且
·水解和冷凝该醇盐,并且
·干燥和煅烧来自先前的方法步骤的固体来形成相应的氧化物。
6.如权利要求5所述的方法,其特征在于,R是甲基、乙基、异丙基、丁基或苯基。
7.如权利要求5所述的方法,其特征在于,R'是氨基-(C1-C4)-烷基、N-(2-氨基乙基)-3-氨基丙基、异丙基、异丁基、苯基、辛基或(C1-C4)-烷基甲基丙烯酸酯。
8.一种催化剂,由一种催化惰性载体以及施用到其上的至少一个涂层组成,其特征在于,该涂层包含如权利要求1至4中任一项所述的催化活性材料。
9.一种用于降低在含烃柴油发动机排气中包含一氧化氮和二氧化氮的氮氧化物水平的方法,包含以下方法步骤:
·添加氨或可分解成氨的一种前体化合物至该排气作为还原剂,该排气包含氮氧化物和烃类并且是有待清洁的,并且
·使所产生的排气和还原剂的混合物通过如权利要求8所述的一种催化剂。
10.如权利要求9所述的方法,其特征在于,在添加氨或一种可分解成氨的前体化合物之前,使该排气通过一种氧化催化剂,该氧化催化剂对于存在于该排气中的一氧化氮的至少一部分向二氧化氮的转化是有效的。
11.如权利要求10所述的方法,其特征在于,该氧化催化剂是处于在一个整体式流动蜂窝状物和/或在一个壁流式过滤器基底上的一个催化活性涂层的形式。
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Also Published As
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JP2016203172A (ja) | 2016-12-08 |
JP2014512940A (ja) | 2014-05-29 |
US8911697B2 (en) | 2014-12-16 |
CN103402634B (zh) | 2018-10-26 |
US20130336866A1 (en) | 2013-12-19 |
WO2012117042A2 (de) | 2012-09-07 |
JP5972913B2 (ja) | 2016-08-17 |
WO2012117042A3 (de) | 2012-12-20 |
EP2680965A2 (de) | 2014-01-08 |
JP6316882B2 (ja) | 2018-04-25 |
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