CN109562364A - Scr活性材料 - Google Patents
Scr活性材料 Download PDFInfo
- Publication number
- CN109562364A CN109562364A CN201780049001.7A CN201780049001A CN109562364A CN 109562364 A CN109562364 A CN 109562364A CN 201780049001 A CN201780049001 A CN 201780049001A CN 109562364 A CN109562364 A CN 109562364A
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- CN
- China
- Prior art keywords
- scr activity
- activity material
- aluminium oxide
- copper
- scr
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000463 material Substances 0.000 title claims abstract description 118
- 230000000694 effects Effects 0.000 title claims abstract description 74
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 162
- 239000010457 zeolite Substances 0.000 claims abstract description 71
- 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 70
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 66
- 239000010949 copper Substances 0.000 claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- 239000011148 porous material Substances 0.000 claims abstract description 38
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 53
- 238000000576 coating method Methods 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 20
- 229910052675 erionite Inorganic materials 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 150000004645 aluminates Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims 2
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical group [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 18
- 229910021529 ammonia Inorganic materials 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 229910052593 corundum Inorganic materials 0.000 description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000004411 aluminium Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011149 active material Substances 0.000 description 8
- 229910002089 NOx Inorganic materials 0.000 description 7
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 7
- 229910001593 boehmite Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 6
- 239000012876 carrier material Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052878 cordierite Inorganic materials 0.000 description 5
- 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 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 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 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 101100502609 Caenorhabditis elegans fem-1 gene Proteins 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 101100334582 Drosophila melanogaster Fem-1 gene Proteins 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 101100372662 Caenorhabditis elegans vem-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910018576 CuAl2O4 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 241001083492 Trapa Species 0.000 description 1
- 235000014364 Trapa natans Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000746 body region Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-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
- 238000003618 dip coating Methods 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- YOWAEZWWQFSEJD-UHFFFAOYSA-N quinoxalin-2-amine Chemical compound C1=CC=CC2=NC(N)=CN=C21 YOWAEZWWQFSEJD-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/72—Copper
-
- 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
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- 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
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
- B01J29/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing iron group metals, noble metals or copper
- B01J29/56—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
-
- 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
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
本发明题为“SCR活性材料”。本发明涉及包含小孔沸石、氧化铝和铜的SCR活性材料,其特征在于,该SCR活性材料包含相对于整个材料计5重量%至25重量%的氧化铝,并且铜以第一浓度存在于氧化铝上并且以第二浓度存在于小孔沸石上。
Description
本发明涉及用于降低内燃机废气中的氮氧化物的SCR活性材料。
配备主要以稀燃操作的内燃机的机动车辆的废气具体地包含除了颗粒排放物之外的主要排放物一氧化碳CO、碳氢化合物HC、以及氮氧化物NOx。由于相对高的氧气含量为至多15体积%,因此一氧化碳和碳氢化合物可相对容易地借助于氧化而变得无害;然而,使氮氧化物还原为氮气要困难得多。
用于在存在氧气的情况下从废气中去除氮氧化物的一种已知方法是在合适的催化剂上借助于氨的选择性催化还原方法(SCR方法)。在该方法中,利用氨将废气中待去除的氮氧化物转化为氮气和水。用作还原剂的氨可通过将氨前体化合物例如尿素、氨基甲酸铵或甲酸铵进料到废气流中并且随后水解而可用。
某些金属交换的沸石可用作例如SCR催化剂。沸石通常通过其最大孔开口的环尺寸被细分为大孔、中孔和小孔沸石。大孔沸石具有12的最大环尺寸,并且中孔沸石具有10的最大环尺寸。小孔沸石具有8的最大环尺寸。
虽然例如基于铁交换的β-沸石(即大孔沸石)的SCR催化剂已经并将继续广泛用于重型车辆,但基于小孔沸石的SCR催化剂却变得越来越重要,参见例如WO2008/106519 A1、WO2008/118434 A1和WO2008/132452 A2。具体地,基于铜菱沸石的SCR催化剂最近致力于该方面。
已知的SCR催化剂能够用氨作为还原剂使氮氧化物以高选择性转化为氮气和水。然而,从约350℃起始,在基于铜菱沸石的催化剂中发生所谓的寄生性氨氧化并与期望的SCR反应产生竞争。此处,还原剂氨在一系列副反应中与氧气反应形成氮分子、一氧化二氮、一氧化氮或二氧化氮,使得还原剂未被有效地利用或者由氨形成了甚至附加量的氮氧化物。该竞争在500℃至650℃范围内的高温下尤为显著,因为其可能发生在SCR催化剂的废气管线内柴油机微粒过滤器(DPF)的再生中。此外,必须确保催化剂材料耐老化,以便能够在机动车辆的整个使用寿命中实现高污染物转化率。因此,为了在DPF再生期间和使用寿命内甚至在反应温度下实现高转化率,存在对改善的SCR催化剂材料的需要。
WO 2008/132452 A2描述了一种例如用铜交换的小孔沸石,其可作为修补基面涂料被涂布到合适的单块基材上或者被挤出以形成基材。修补基面涂料可包含选自氧化铝、二氧化硅、(非沸石)硅铝、天然粘土、TiO2、ZrO2和SnO2的粘结剂。
WO 2013/060341 A1描述了来自呈质子形式或呈铁促进形式的酸性沸石或类沸石与例如Cu/Al2O3的物理混合物的SCR活性催化剂组合物。
ACS Catal.2012,2,1432-1440描述了NH3-SCR反应期间氨在CuO/□-Al2O3上的途径。虽然氨与0.5重量%CuO/□-Al2O3,具体地与一氧化氮反应形成氮气,但其也与10重量%CuO/□-Al2O3,具体地与氧气反应形成氮氧化物。
JP 2012-215166描述了一种方法,其中SAPO型沸石与勃姆石混合并且由该混合物挤出柱形蜂窝体,该蜂窝体随后被浸入硝酸铜溶液中。
现已令人惊奇地发现,基于小孔沸石、氧化铝和铜的某些SCR材料满足上述要求。
本发明涉及一种SCR活性材料,该SCR活性材料包含
(i)小孔沸石,
(ii)氧化铝,以及
(iii)铜,
其特征在于,该SCR活性材料包含基于整个材料计5重量%至25重量%的氧化铝,并且铜以第一浓度存在于氧化铝上并且以第二浓度存在于小孔沸石上。
根据措词“铜存在于沸石上”在本发明的范围之内包括铜作为沸石的晶格骨架的一部分存在,铜以离子交换形式在沸石骨架的孔内存在,以及铜可在三维沸石骨架内或在其表面上结合的任何其它形式。
另外,根据措词“铜存在于铝上”包括铜可在三维氧化铝骨架内或在其表面上结合的所有形式。这还包括混合氧化物,诸如铝酸铜(CuAl2O4)。
在任何情况下,术语“铜”包括金属铜和离子铜两者,以及氧化铜。
此外,在本发明的语境中,术语“氧化铝”不包括沸石的沸石晶格中氧化铝的比例。“氧化铝”因此仅包括根据(ii)的组分而不包括来自沸石的SiO2/Al2O3比率(SAR)的氧化铝的比例。
铜的总量以CuO计算并且基于总SCR活性材料计具体地为1重量%至15重量%,优选地1重量%至10重量%,并且更优选地2重量%至5重量%。
应当考虑的是相对于沸石而言铜的优选量取决于沸石的SiO2/Al2O3比率。通常适用的是,可交换铜的量随着沸石的SiO2/Al2O3比率的增大而减小。根据本发明,沸石中交换的铜与沸石中骨架铝的优选的原子比(在本文中被称为Cu/Al比率)具体地为0.25至0.6。
这对应于50%至120%的铜与沸石的理论交换程度,假设沸石中经由二价Cu离子的完全电荷平衡给出100%的交换程度。特别优选的为0.35至0.5的Cu/Al值,这对应于70%至100%的理论Cu交换程度。
Cu/Al比率是用于表征铜交换的沸石的广泛使用的量度,参见例如WO 2008/106519A1,Catalysis Today 54(1999)407-418(Torre-Abreu等人),Chem.Commun.,2011,47,800-802(Korhonen等人),或ChemCatChem 2014,6,634-639(Guo等人)。本领域技术人员因此熟知该量。
Cu/Al比率可例如借助于电感耦合等离子体发射光谱(ICP OES)来测定。该方法是本领域技术人员已知的。
如果第一浓度(铜在氧化铝上的浓度)高于第二浓度(铜在沸石上的浓度),这是特别有利的。优选地,第一浓度为第二浓度的至少1.5倍,更优选地至少3倍。例如,第一浓度为第二浓度的1.5至20倍,或3至15倍。
第一浓度与第二浓度的比率可使用透射电子光谱学(TEM)和能量散射X射线光谱学(EDX)来测定。为此,制备出根据本发明的SCR活性材料的薄片,并借助于EDX来测定沸石区域和氧化铝区域内的铜浓度并实现比例。该方法是本领域技术人员已知的并在文献中有所描述。
在一个实施方案中,根据本发明的SCR活性材料不含贵金属,诸如铂、钯和铑。
小孔沸石例如为铝硅酸盐。可使用本领域技术人员已知的该类型的所有沸石。这些包括天然存在的小孔沸石,但优选地合成制备的小孔沸石。
合成制备的小孔沸石的示例属于结构类型ABW、ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATN、ATT、ATV、AWO、AWW、BIK、BRE、CAS、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、ESV、GIS、GOO、IHW、ITE、ITW、JBW、KFI、LEV、LTA、LTJ、MER、MON、MTF、NSI、OWE、PAU、PHI、RHO、RTE、RTH、SAS、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG和ZON。
优选的小孔沸石是属于结构类型AEI、CHA(菱沸石)、ERI(毛沸石)、LEV(插晶菱沸石)、AFX、DDR和KFI的那些,或属于结构类型AEI、CHA(菱沸石)、ERI(毛沸石)、AFX、DDR和KFI的那些。特别优选的是结构类型CHA、AEI、ERI和LEV,或结构类型CHA、AEI和ERI。非常特别优选的是结构类型CHA和LEV或CHA。
在本发明的实施方案中,铝硅酸盐类型的小孔沸石具有5至50,优选地14至40,特别优选地介于20和35之间的SAR值。
在本发明的语境中,术语“沸石”不仅包括上述铝硅酸盐,而且还包括硅铝磷酸盐和铝磷酸盐类型的所谓的沸石样材料。合适的硅铝磷酸盐或铝磷酸盐也具体地属于结构类型AEI、CHA(菱沸石)、ERI(毛沸石)、LEV(插晶菱沸石)、AFX、DDR和KFI。此类材料可在国际沸石协会根据相关材料的结构数据库的相关三字母代码下找到(http://www.iza-structure.org/databases/)。
示例包括SAPO-17、SAPO-18、SAPO-34、SAPO-35、SAPO-39、SAPO-43、SAPO-47和SAPO-56或AlPO-17、AlPO-18、AlPO-34和AlPO-35。铝硅酸盐的上述优选的SAR值不适用于这些材料。
小孔沸石的平均微晶尺寸(d50)例如为0.1μm至20μm,优选地0.5μm至10μm,更优选地1μm至4μm。
BET表面积为30m2/g至250m2/g,优选地100m2/g至200m2/g(根据ISO9277测定)的氧化铝特别适用作氧化铝。此类材料是本领域技术人员已知的并且可商购获得。
此外,可以考虑掺杂有另外元素的氧化铝,以便改善物理或化学特性。已知的元素例如为Si、Mg、Y、La和镧系元素(诸如Ce、Pr、Nd),这些元素可与铝形成混合氧化物,并能够因此例如改变酸性或表面稳定性。掺杂有一种或多种元素的氧化铝应当为基于相应的混合氧化物计小于15重量%,优选地小于10重量%,特别优选地小于5重量%。
氧化铝可原样使用,然而其中优选的是由合适的前体(诸如勃姆石或铝盐,诸如硝酸铝)形成的氧化铝在SCR活性材料制备的范围之内。
在本发明的一个实施方案中,SCR活性材料以小孔沸石形成核且氧化铝形成包裹该核的壳的形式存在。此类结构被称为核/壳结构,并且在例如WO 2012/117042 A2中有所描述。
在本发明的一个实施方案中,SCR活性材料作为粉末存在。
在本发明的另一个实施方案中,SCR活性材料以涂料悬浮液的形式存在,该涂料悬浮液包含
a)SCR活性材料,该SCR活性材料包含
(i)小孔沸石,
(ii)氧化铝,以及
(iii)铜,
其中该SCR活性材料包含基于总材料计5重量%至25重量%的氧化铝,并且铜以第一浓度存在于氧化铝上并且以第二浓度存在于小孔沸石上,以及
b)水。
在一个实施方案中,在每种情况下基于涂料悬浮液的重量计,根据本发明的涂料悬浮液包含20重量%至55重量%的SCR活性材料以及45重量%至80重量%的水。
在另一个实施方案中,在每种情况下基于涂料悬浮液的重量计,根据本发明的涂料悬浮液包含30重量%至50重量%的SCR活性材料以及50重量%至70重量%的水。
根据本发明的SCR活性材料可例如通过对小孔沸石、铜盐、以及氧化铝或氧化铝前体化合物的水性悬浮液进行干燥并且随后煅烧来制备。
例如,将小孔沸石置于水中,在搅拌下添加可溶性铜盐,并且然后添加氧化铝或对应的氧化铝前体。根据本发明的SCR活性材料的所得悬浮液可直接用作涂料悬浮液。然而,也可对其进行过滤和/或干燥,其中在后一种情况下,根据本发明的SCR活性材料以粉末形式获得。
同样可以例如在对由小孔沸石、氧化铝或氧化铝前体化合物以及铜盐组成的水性悬浮液进行干燥和煅烧之后,使所获得的具有氧化铝或对应的氧化铝前体的材料重悬于水溶液中,使其干燥并且再次煅烧,由此制备呈粉末形式的根据本发明的SCR活性材料。
可通过在搅拌的同时添加水并任选地研磨,以简单的方式由呈粉末形式的SCR活性材料来获得根据本发明的涂料悬浮液。
优选的可溶性铜盐是能够溶于水的盐,诸如硫酸铜、硝酸铜和醋酸铜。硝酸铜和醋酸铜是特别优选的,并且醋酸铜是非常特别优选的。
干燥类型可通过不同的方法进行。例如,喷雾干燥、微波干燥、带式干燥、辊筒式干燥、冷凝干燥、转鼓式干燥、冷冻干燥和真空干燥是本领域技术人员已知的。喷雾干燥、带式干燥、辊筒式干燥和冷冻干燥是优选的。喷雾干燥是特别优选的。在这种情况下,悬浮液借助于喷雾器引入热气体流中,其在极短时间(几秒到几分之一秒)内使之干燥,以形成SCR活性材料。任选地,随后将该材料例如在空气或空气/水混合物中在500℃至900℃的温度下进行煅烧。煅烧优选地在550℃至850℃,最优选地600℃至750℃的温度下进行。
在本发明的另一个实施方案中,可以例如在对由小孔沸石和铜盐(或已经合成的具有铜的沸石)组成的水性悬浮液进行洗涤和干燥,并任选地煅烧之后,使由此获得的具有氧化铝或对应氧化铝前体的材料悬浮于水溶液中,再次干燥和煅烧,由此制备根据本发明的SCR活性材料。该材料可随后重悬于水中,任选地研磨,从而提供粘结剂并涂布。
Al2O3、SiO2、TiO2、或ZrO2、或它们的前体、以及它们的混合物可例如用作粘结剂以涂布流通式基材。在过滤器基材的涂布中通常不需要粘结剂。
为清楚起见,这里指出用于产生根据本发明的SCR活性材料的氧化铝或氧化铝前体与含铝粘结剂材料的差异在于:
1.其已经在SCR活性材料的制备期间被使用,并且不只是改善催化活性材料在流通式基材上的粘合强度
2.铜的一部分存在于氧化铝上
3.包含氧化铝或氧化铝前体的SCR活性材料在涂布于基材之前被煅烧,由此典型的粘结剂特性丧失。
4.当过滤器基材的多孔壁要被涂布时(例如,在壁流式过滤器的壁内涂层中),氧化铝也用于制备根据本发明的SCR活性材料,以便增大催化活性材料的热稳定性。粘结剂的使用在这种情况下并非是必须的,因为当催化活性材料位于过滤器的孔内时并不需要粘结剂的粘结特性。此外,在涂布的催化活性材料的量另外将保持相同的情况下,所添加的粘结剂将进一步导致过滤器中的背压不期望的上升。
5.其有助于在根据本发明的SCR活性材料热老化之后提高NOx的转化率,并且不归类为无催化活性。
在这种情况下,根据本发明的SCR活性材料可满足以上提及的一个或多个或者所有观点。
在本发明的一个实施方案中,根据本发明的SCR活性材料以载体基材上涂层的形式存在。
载体基材可为所谓的流通式基材或壁流式过滤器。它们可由例如碳化硅、钛酸铝、堇青石或金属组成。它们是本领域技术人员已知的并且可商购获得。
根据本发明的SCR活性材料向载体基材的施加可通过本领域技术人员熟悉的方法进行,例如通过常用的浸涂方法或泵涂和吸涂方法,并且随后进行热后处理(煅烧)。
本领域技术人员知道,在壁流式过滤器的情况下,它们的平均孔径和根据本发明的SCR活性材料的平均粒度可彼此适应,使得所得的涂层位于多孔壁上,其形成壁流式过滤器的通道(壁上涂层)。然而,平均孔径和平均粒度优选地彼此适应,使得根据本发明的SCR活性材料位于形成壁流式过滤器的通道的多孔壁中,因此使得发生内孔表面的涂层(壁内涂层)。在这种情况下,根据本发明的SCR活性材料的平均粒度必须足够小以渗透到壁流式过滤器的孔中。
本发明还涉及SCR活性材料借助于基质组分被挤出到基材的实施方案。载体基材在这种情况下由惰性基质组分和根据本发明的SCR活性材料形成。
不仅由惰性材料诸如堇青石组成而且还附加地包含催化活性材料的载体基材、流通式基材和壁流式基材是本领域技术人员已知的。为了制备它们,根据本身已知的方法挤出由例如10重量%至95重量%的惰性基质组分和5重量%至90重量%的催化活性材料组成的混合物。在这种情况下,所有也用于生产催化剂基材的惰性材料都可用作基质组分。这些是例如硅酸盐、氧化物、氮化物或碳化物,其中具体地优选硅酸镁铝。
包含根据本发明的SCR活性材料的挤出的载体基材可原样使用以用于废气净化。然而,它们也可通过常规方法用另外的催化活性材料按与惰性载体基材相同的方式进行涂布。
然而,根据本发明的SCR活性材料优选地不作为挤出物存在,具体地不作为仅由根据本发明的SCR活性材料(即不包含基质组分)组成的挤出物存在。
根据本发明的SCR活性材料可有利地用于净化稀燃操作的内燃机,特别是柴油机的废气。其使废气中存在的氮氧化物转化为无害的化合物氮气和水。
本发明因此还涉及一种用于净化稀燃操作的内燃机的废气的方法,其特征在于,使废气经过根据本发明的SCR活性材料。
该经过通常在还原剂的存在下发生。在根据本发明的方法中,氨优选地用作还原剂。例如,具体地在富废气条件下的操作期间,所需的氨可在根据本发明的颗粒过滤器上游的废气系统中形成,例如借助于上游氮氧化物储存催化剂(“少NOx捕集器”-LNT)。这种方法被称为“被动SCR”。
然而,氨也可在“活性SCR方法”中以尿素水溶液的形式携带,该尿素水溶液根据需要经由根据本发明的颗粒过滤器上游的注射器给剂量。
本发明因此还涉及一种用于净化稀燃操作的内燃机的废气的设备,该设备的特征在于其包括优选地呈惰性载体材料上涂层的形式的根据本发明的SCR活性材料,以及用于提供还原剂的装置。
氨通常用作还原剂。在根据本发明的设备的一个实施方案中,用于提供还原剂的装置因此是用于尿素水溶液的喷射器。喷射器通常供给尿素水溶液,其来源于顺流而下的贮存器,即例如罐。
在另一个实施方案中,用于提供还原剂的装置是能够由氮氧化物形成氨的氮氧化物储存催化剂。此类氮氧化物储存催化剂是本领域技术人员已知的并在文献中已有广泛描述。
例如,从SAE-2001-01-3625中已知,如果氮氧化物存在于一氧化氮和二氧化氮的1:1或者在任何情况下接近该比率的混合物中,则与氨的SCR反应进行得更快。由于稀燃操作的内燃机的废气通常具有与二氧化氮相比过量的一氧化氮,因此该文献提出借助于氧化催化剂来增加二氧化氮的比例。
在一个实施方案中,根据本发明的设备因此还包括氧化催化剂。在本发明的实施方案中,载体材料上的铂用作氧化催化剂。
本领域的技术人员为此目的已知的所有材料被认为是载体材料。它们具有30m2/g至250m2/g,优选地100m2/g至200m2/g的BET表面积(根据ISO9277测定),并且具体地氧化铝、氧化硅、氧化镁、氧化钛、氧化锆、氧化铈、以及这些氧化物中的至少两种的混合物或混合氧化物。
氧化铝和铝/硅混合氧化物是优选的。如果使用氧化铝,则特别优选地用例如氧化镧稳定化。
根据本发明的设备被设计成使得首先沿废气流动方向布置氧化催化剂,然后是用于尿素水溶液的喷射器,并且然后是根据本发明的SCR活性材料(优选地呈惰性载体材料上涂层的形式)。
另选地,氮氧化物储存催化剂,并且然后根据本发明的SCR活性材料(优选地呈惰性载体材料上涂层的形式)首先沿废气流动方向布置。在氮氧化物储存催化剂的再生期间,氨可在还原性废气条件下形成。氧化催化剂和用于尿素水溶液的喷射器在这种情况下是多余的。
令人惊奇地,根据本发明的SCR活性材料相比于常规铜交换的小孔沸石具有优点。具体地,其通过在介于500℃和650℃之间的反应温度下较高的氮氧化物转化率加以区分。
本发明在接下来的实施例和附图中有更详细的解释。
实施例1
a)根据本发明的材料EM-1的制备
使100.4克的醋酸铜(II)一水合物和960克的铵菱沸石(SiO2/Al2O3-比率为30)在2500克的水中形成浆液。将所得的悬浮液搅拌2小时。向其中添加400克的勃母石溶胶(具有20重量%Al2O3含量)。然后继续搅拌2小时。
使最终悬浮液在喷雾干燥器中转变为干粉,随后在空气中于500℃煅烧2小时。
b)沸石和氧化铝之间的EM-1的Cu分布表征
使根据步骤a)获得的材料EM-1以细分散的方式嵌入聚合物树脂中。然后制备薄片样品,并且在透射电子显微镜中进行检查。材料的示例性TEM图像示于图1中。氧化铝和沸石的区域可基于通过EDX测定的铝含量以及通过形态来清楚地区分。其示出具有氧化铝壳体的沸石晶粒的截面。在接收器中标记2个区域,以示出氧化铝(A区域)和沸石区域(B区域)之间的差异。在这两个位置处,铜浓度以重量%通过EDX进行测定,并将A区域所测定的浓度除以B区域所测定的浓度。
类似地,该过程在具有氧化铝壳体的沸石晶粒的另外TEM图像上进行。在所有情况下,据发现氧化铝壳体区域中铜的浓度显著高于沸石,如可由下表推断出。
比较例1
比较材料VM-1的制备
使100.4克的醋酸铜(II)一水合物和960克的铵菱沸石(SiO2/Al2O3-比率为30)在2500克的水中形成浆液。将所得的悬浮液搅拌2小时。不同于实施例1,不添加勃母石溶胶。使最终悬浮液在喷雾干燥器中转变为干粉,将其在空气中于500℃煅烧2小时。
该制剂中所用铜的量(基于沸石)因此与实施例1相同。然而,没有附加的Al2O3存在于铜可铺展于其上的材料中。
EM-1和VM-1催化活性的比较
在粉末反应器(powder reactor)上测试EM-1材料和VM-1材料的SCR活性。为此,将200mg的对应材料各自引入到石英玻璃U型管反应器中并用石英棉固定。
450℃反应温度下氮氧化物的转化率在每种情况下按以下测量条件进行测定:500ppm一氧化氮,750ppm氨,5%水,5%氧气,余量氮气,流速cm3/min(mL/min)。
EM 1-材料提供96%NOx转化率,而VM-1材料仅提供89%NOx转化率。
实施例2
用EM-1材料制备涂布的蜂窝体WEM-1
将950克的EM-1材料和250克的包含20重量%Al2O3的勃姆石溶胶用水制成悬浮液。所添加的勃姆石溶胶充当粘结剂体系,以便实现EM-1材料对可商购获得的堇青石蜂窝体良好的粘附性。
所得的悬浮液因此包含根据样品重量的以下化合物或组分并且铜以CuO计算:
经由常用的浸渍法,将堇青石蜂窝体(14.4cm(5.66英寸)直径、7.6cm(3英寸)长度、62cpscm(400cpsi)孔特征以及0.15mm(6密耳)壁厚)以150g/L催化剂体积的修补基面涂料载量进行涂布,在90℃下干燥并在500℃下退火。
比较例2
用VM-1材料制备涂布的蜂窝体WVM-1
将880克的VM-1材料和600克的包含20重量%Al2O3的勃姆石溶胶用水制成悬浮液。经由常用的浸渍法,将堇青石蜂窝体(14.4cm(5.66英寸)直径、7.6cm(3英寸)长度、62cpscm(400cpsi)孔特征以及0.15mm(6密耳)壁厚)以150g/L催化剂体积的修补基面涂料载量进行涂布,在90℃下干燥并在500℃下退火。
所得的悬浮液因此包含与实施例2按比例相同量的以下组分,其中不同于实施例2,此时氧化铝组分仅来源于粘结剂。
WEM-1和WVM-1催化活性的比较
a)新制状态
将具有2.54cm(1英寸)直径和7.6cm(3英寸)长度的钻芯从两种蜂窝体WEM-1和WVM-1钻出,并且测试其在模型气体系统中的催化活性。
选择以下测量条件:500ppm NO,750ppm NH3,5体积%H2O,10体积%O2,残余N2,空速为60000h-1,反应温度为500℃和650℃。
在两种测量温度下,WEM-1具有比WVM-1更高的NOx转化率。
b)老化之后
为了模拟驾驶操作期间催化剂的老化,将WEM-1和WVM-1的两种钻芯在10体积%水、10体积%氧气和80体积%氮气的气体混合物中于750℃处理16小时。
在该模拟的老化之后,根据以上a)指示的条件对催化活性再次进行测试。相比于比较催化剂WVM-1,基于根据本发明的材料EM-1的催化剂WEM-1具有显著更高的NOx转化率。
实施例3
根据本发明的材料EM-1以100g/L修补基面涂料载量作为壁内涂层涂布到碳化硅过滤器基材上。获得涂布的过滤器FEM-1。
比较例3
类似于实施例3,将碳化硅过滤器基材用比较材料VEM-1进行涂布。获得涂布的过滤器FVM-1。
FEM-1和FVM-1催化活性的比较
在每种情况下,将一个钻芯从根据实施例3和比较例3的两种涂布的过滤器移除。将这些在10体积%水、10体积%氧气和80体积%氮气的气体混合物中于800℃处理16小时,以便模拟驾驶操作期间涂布有SCR活性材料的颗粒过滤器的强老化。
随后,使用模型气体在以下测量条件下测量这两种钻芯:500ppm NO,750ppm NH3,5体积%H2O,10体积%O2,残余N2,空速为100,000h-1,反应温度为650℃。
虽然FVM-1仅实现8%的NOx转化率,但FEM-1样品转化了18%的投入氮氧化物。
Claims (21)
1.一种SCR活性材料,包含
(i)小孔沸石,
(ii)氧化铝,以及
(iii)铜,
其特征在于,所述SCR活性材料包含基于整个材料计5重量%至25重量%的氧化铝,并且所述铜以第一浓度存在于所述氧化铝上并且以第二浓度存在于所述小孔沸石上。
2.根据权利要求1所述的SCR活性材料,其特征在于
铜的总量以CuO计算并且基于总SCR活性材料计为1重量%至15重量%。
3.根据权利要求1和/或2所述的SCR活性材料,其特征在于,所述第一浓度高于所述第二浓度。
4.根据权利要求1至3中任一项所述的SCR活性材料,其特征在于,所述第一浓度为所述第二浓度的至少1.5倍。
5.根据权利要求1至4中任一项所述的SCR活性材料,其特征在于,铜与埋入所述沸石的骨架铝的原子比在所述沸石中为0.25至0.6。
6.根据权利要求1至5中任一项所述的SCR活性材料,其特征在于,所述小孔沸石为铝硅酸盐并且属于结构类型AEI、CHA(菱沸石)、ERI(毛沸石)、LEV(插晶菱沸石)、AFX、DDR或KFI。
7.根据权利要求6所述的SCR活性材料,其特征在于,所述小孔沸石具有5至50的SAR值。
8.根据权利要求1至4中任一项所述的SCR活性材料,其特征在于,所述小孔沸石为硅铝硅酸盐或铝磷酸盐并且属于结构类型AEI、CHA(菱沸石)、ERI(毛沸石)、LEV(插晶菱沸石)、AFX、DDR或KFI。
9.根据权利要求1至8中任一项所述的SCR活性材料,其特征在于,所述小孔沸石的平均微晶尺寸(d50)为0.1μm至20μm。
10.根据权利要求1至9中任一项所述的SCR活性材料,其特征在于,所述小孔沸石形成核,并且所述氧化铝形成包裹所述核的壳。
11.根据权利要求1至10中任一项所述的SCR活性材料,其特征在于,所述SCR活性材料以粉末形式存在。
12.根据权利要求1至10中任一项所述的SCR活性材料,其特征在于,所述SCR活性材料以载体基材上涂层的形式存在,或者所述SCR活性材料借助于基质组分被挤出到基材。
13.根据权利要求1至10中任一项所述的SCR活性材料,其特征在于,所述SCR活性材料以涂料悬浮液的形式存在,所述涂料悬浮液包含a)SCR活性材料,所述SCR活性材料包含
(i)小孔沸石,
(ii)氧化铝,以及
(iii)铜,
其中所述SCR活性材料包含基于总材料计5重量%至25重量%的氧化铝,并且所述铜以第一浓度存在于所述氧化铝上并且以第二浓度存在于所述小孔沸石上,以及
b)水。
14.一种用于净化稀燃操作的内燃机的废气的方法,其特征在于,使所述废气经过根据权利要求1至12中任一项所述的SCR活性材料。
15.一种用于净化稀燃操作的内燃机的废气的设备,其特征在于,所述设备包括根据权利要求1至12中任一项所述的SCR活性材料,以及用于提供还原剂的装置。
16.根据权利要求15所述的设备,其特征在于,所述用于提供还原剂的装置为用于尿素水溶液的喷射器。
17.根据权利要求15至16中任一项所述的设备,其特征在于,所述设备包括氧化催化剂。
18.根据权利要求15所述的设备,其特征在于,所述用于提供还原剂的装置为氮氧化物储存催化剂。
19.一种用于制备根据权利要求1至11中任一项所述的SCR活性材料的方法,其特征在于,对小孔沸石、铜盐以及氧化铝或氧化铝前体化合物的水性悬浮液进行干燥并且随后煅烧。
20.根据权利要求19所述的方法,其特征在于,所述干燥为喷雾干燥。
21.根据权利要求19和/或20所述的方法,其特征在于,所述煅烧在空气中或在空气/水气氛中于介于500℃和900℃之间的温度下进行。
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EP16183708.3A EP3281698A1 (de) | 2016-08-11 | 2016-08-11 | Scr-aktives material |
PCT/EP2017/070399 WO2018029328A1 (de) | 2016-08-11 | 2017-08-11 | Scr-aktives material |
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EP (2) | EP3281698A1 (zh) |
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CN115485055A (zh) * | 2020-04-28 | 2022-12-16 | 巴斯夫公司 | 用于scr催化剂的组合物 |
CN114433222B (zh) * | 2020-10-20 | 2023-08-29 | 中国石油化工股份有限公司 | 二氧化碳加氢制备低碳烯烃的催化剂及其制备和应用 |
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US10799831B2 (en) | 2020-10-13 |
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JP7041123B2 (ja) | 2022-03-23 |
KR20190039550A (ko) | 2019-04-12 |
JP2019531874A (ja) | 2019-11-07 |
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