JP2019531874A - Scr活性材料 - Google Patents
Scr活性材料 Download PDFInfo
- Publication number
- JP2019531874A JP2019531874A JP2019506677A JP2019506677A JP2019531874A JP 2019531874 A JP2019531874 A JP 2019531874A JP 2019506677 A JP2019506677 A JP 2019506677A JP 2019506677 A JP2019506677 A JP 2019506677A JP 2019531874 A JP2019531874 A JP 2019531874A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- scr active
- aluminum oxide
- material according
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011149 active material Substances 0.000 title claims abstract description 76
- 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 63
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 58
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000010949 copper Substances 0.000 claims abstract description 51
- 229910052802 copper Inorganic materials 0.000 claims abstract description 43
- 239000011148 porous material Substances 0.000 claims abstract description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 42
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 59
- 239000003054 catalyst Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims description 19
- 229910052676 chabazite Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 229910052675 erionite Inorganic materials 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007900 aqueous suspension Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 229910021529 ammonia Inorganic materials 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 12
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910001593 boehmite Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 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
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 5
- -1 natural clays Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000243 solution Substances 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
- 230000032683 aging Effects 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 101100502609 Caenorhabditis elegans fem-1 gene Proteins 0.000 description 3
- 101100334582 Drosophila melanogaster Fem-1 gene Proteins 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 239000007864 aqueous solution Substances 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 230000000694 effects Effects 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
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 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
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 101100372662 Caenorhabditis elegans vem-1 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910018565 CuAl Inorganic materials 0.000 description 1
- 229910002089 NOx Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 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
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 238000000746 purification Methods 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
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010972 statistical evaluation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
- B01D53/9409—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
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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
- B01J29/005—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
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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
- B01J29/50—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
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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
- B01J29/70—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
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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
- B01J29/70—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
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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
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
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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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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Abstract
Description
(i)小細孔ゼオライトと、
(ii)酸化アルミニウムと、
(iii)銅と、
を含むSCR活性材料であって、材料全体に対して5〜25重量%の酸化アルミニウムを含有し、銅が第1の濃度で酸化アルミニウム上に存在し、小細孔ゼオライト上に第2の濃度で存在することを特徴とする、SCR活性材料に関する。
a)
(i)小細孔ゼオライトと、
(ii)酸化アルミニウムと、
(iii)銅と、
を含むSCR活性材料であって、材料全体に基づいて5〜25重量%の酸化アルミニウムを含有し、銅が第1の濃度で酸化アルミニウム上に存在し、小細孔ゼオライト上に第2の濃度で存在する、SCR活性材料と、
b)水と、を含む。一実施形態では、本発明によるコーティング懸濁液は、それぞれコーティング懸濁液の重量に基づいて、20〜55重量%のSCR活性材料及び45〜80重量%の水を含有する。
別の実施形態では、本発明によるコーティング懸濁液は、それぞれコーティング懸濁液の重量に基づいて、30〜50重量%のSCR活性材料及び50〜70重量%を含有する。
1.SCR活性材料の調製中に既に使用されており、フロースルー型基材上の触媒活性材料の接着強度を改善するためだけではない。
2.銅の一部は酸化アルミニウム上に存在する。
3.酸化アルミニウム又は酸化アルミニウム前駆体を含有するSCR活性材料は、基材上にコーティングする前にか焼され、それによって典型的なバインダ特性が失われる。
4.酸化アルミニウムはまた、フィルタ基材の多孔質ウォールをコーティングする場合(例えば、ウォールフロー型フィルタのインウォールコーティングにおいて)触媒活性材料の熱安定性を増大させるために、本発明によるSCR活性材料の調製に使用される。触媒活性材料がフィルタの細孔の内側に配置されている場合にはバインダの結合特性は必要とされないので、この際バインダの使用は不要である。また、バインダを追加すると、フィルタ間の背圧が望ましくないほど更に上昇することになるが、バインダを追加しなければ、コーティングされた触媒活性材料の量は同じままである。
5.本発明によるSCR活性材料の熱エージング後におけるNOx転化率の増加に寄与し、かつ触媒的に不活性として分類されない。
a)本発明による材料EM−1の調製
100.4グラムの銅(II)−アセテート−1−水和物及び960グラムのアンモニウムチャバザイトを、30のSiO2/Al2O3比で、2500グラムの水中においてスラリー化する。得られた懸濁液を2時間撹拌する。この懸濁液に、20重量%のAl2O3の含有量を有する400グラムのベーマイトゾルを添加する。次いで撹拌を2時間続ける。最終懸濁液をスプレー乾燥機中で乾燥粉末に変換し、次いでこの乾燥粉末を空気中500℃で2時間か焼する。
工程a)に従って得られた材料EM−1は、ポリマー樹脂中に微細に分散した形で埋め込まれている。その後、薄片試料を調製し、透過型電子顕微鏡で検査する。材料の例示的なTEM画像を図1に示す。酸化アルミニウム及びゼオライトの領域は、EDX及び形態によって測定されるアルミニウム含有量に基づいて明確に区別することができる。酸化アルミニウムケーシングを有するゼオライト結晶子の断面を示す。酸化アルミニウム(領域A)とゼオライト領域(領域B)との間の違いを説明するために、容器内に2つの領域をマークした。これら2つの位置で、銅濃度をEDXによって重量パーセントで測定し、領域Aで測定された濃度を領域Bで測定された濃度で除算した。
比較材料VM−1の調製
100.4グラムの銅(II)−アセテート−1−水和物及び960グラムのアンモニウムチャバザイトを、30のSiO2/Al2O3比で、2500グラムの水中においてスラリー化する。得られた懸濁液を2時間撹拌する。実施例1とは異なり、ベーマイトゾルは添加されていない。最終懸濁液をスプレー乾燥機中で乾燥粉末に変換し、この乾燥粉末を空気中500℃で2時間か焼する。このため、ゼオライトに基づくこの調製に使用される銅の量は、実施例1と同じである。しかしながら、銅が分布する可能性がある材料には追加のAl2O3は存在しない。
EM−1材料及びVM−1材料のSCR活性を粉末反応器で試験する。この目的のため、200mgの対応する材料をそれぞれ石英ガラスのU字管反応器に導入し、石英ウールで固定する。
EM−1材料によりコーティングされたハニカム体WEM−1の調製
20重量%のAl2O3を含有する、950グラムのEM−1材料及び250グラムのベーマイトゾルを、水で懸濁液にする。添加されたベーマイトゾルは、市販のコーディエライトハニカム体へ、EM−1材料を良好に付着させるためのバインダシステムとして機能する。
VM−1材料によりコーティングされたハニカム体WVM−1の調製
20重量%のAl2O3を含有する、880グラムのVM−1材料及び600グラムのベーマイトゾルを、水で懸濁液にする。一般的な浸漬法により、コーディエライトハニカム体(直径14.4cm(5.66インチ)、長さ7.6cm(3インチ)、セルラ文字62cpscm(400cpsi)及び壁厚0.15mm(6ミル))を、触媒体積150g/Lのウォッシュコート担持量でコーティングし、90℃で乾燥、500℃でアニールする。
a)得られたばかりの状態
2つのハニカム体WEM−1及びWVM−1から直径2.54cm(1インチ)及び長さ7.6cm(3インチ)のボアコア(bore core)を穿孔し、モデルガスシステムにおいてそれらの触媒活性について試験した。
WEM−1及びWVM−1の2つのドリルコアを、運転中の触媒のエージングをシミュレーションするために、10体積%の水、10体積%の酸素及び80体積%の窒素のガス混合物中で750℃で16時間処理した。
本発明による材料EM−1を、炭化ケイ素フィルタ基材上に、インウォールコーティングとして100g/Lのウォッシュコート担持量でコーティングする。コーティングされたフィルタFEM−1が得られる。
実施例3と同様に、炭化ケイ素フィルタ基材を比較材料VEM−1でコーティングする。コーティングされたフィルタFVM−1が得られる。
いずれの場合も、実施例3及び比較例3に従って、1つのドリルコアを両方のコーティングされたフィルタから取り外す。このドリルコアを、運転中にSCR活性材料でコーティングされた微粒子フィルタのハードエージングをシミュレーションするために、10体積%の水、10体積%の酸素及び80体積%の窒素のガス混合物中で800℃で16時間処理する。
Claims (21)
- (i)小細孔ゼオライトと、
(ii)酸化アルミニウムと、
(iii)銅と、
を含むSCR活性材料であって、材料全体に基づいて5〜25重量%の酸化アルミニウムを含有し、前記銅が第1の濃度で前記酸化アルミニウム上に存在し、前記小細孔ゼオライト上に第2の濃度で存在することを特徴とする、SCR活性材料。 - 全SCR活性材料に基づいてCuOとして計算される銅の総量が1〜15重量%であることを特徴とする、請求項1に記載のSCR活性材料。
- 前記第1の濃度が前記第2の濃度より高いことを特徴とする、請求項1又は2に記載のSCR活性材料。
- 前記第1の濃度が前記第2の濃度の少なくとも1.5倍高いことを特徴とする、請求項1〜3のいずれか一項に記載のSCR活性材料。
- 前記ゼオライト中に浸漬した銅の骨格アルミニウムに対する原子比が、前記ゼオライト中で0.25〜0.6であることを特徴とする、請求項1〜4のいずれか一項に記載のSCR活性材料。
- 前記小細孔ゼオライトが、アルミノシリケートであり、構造型AEI、CHA(チャバザイト)、ERI(エリオナイト)、LEV(レビエン)、AFX、DDR、又はKFIに属することを特徴とする、請求項1〜5のいずれか一項に記載のSCR活性材料。
- 前記小細孔ゼオライトのSAR値が5〜50であることを特徴とする、請求項6に記載のSCR活性材料。
- 前記小細孔ゼオライトが、シリコアルミノシリケート又はアルミノホスフェートであり、構造型AEI、CHA(チャバザイト)、ERI(エリオナイト)、LEV(レビエン)、AFX、DDR、又はKFIに属することを特徴とする、請求項1〜4のいずれか一項に記載のSCR活性材料。
- 前記小細孔ゼオライトの平均結晶子サイズ(d50)が、0.1〜20μmであることを特徴とする、請求項1〜8のいずれか一項に記載のSCR活性材料。
- 前記小細孔ゼオライトがコアを形成し、前記酸化アルミニウムが前記コアを包むシェルを形成することを特徴とする、請求項1〜9のいずれか一項に記載のSCR活性材料。
- 粉末形態で存在することを特徴とする、請求項1〜10のいずれか一項に記載のSCR活性材料。
- 担体基材上にコーティングの形態で存在すること、又はマトリックス成分によって基材に押し出されていることを特徴とする、請求項1〜10のいずれか一項に記載のSCR活性材料。
- コーティング懸濁液の形態で存在することを特徴とする、請求項1〜10のいずれか一項に記載のSCR活性材料であって、前記コーティング懸濁液は、
a)
(i)小細孔ゼオライトと、
(ii)酸化アルミニウムと、
(iii)銅と、
を含むSCR活性材料であって、材料全体に基づいて5〜25重量%の酸化アルミニウムを含有し、前記銅が第1の濃度で前記酸化アルミニウム上に存在し、前記小細孔ゼオライト上に第2の濃度で存在する、SCR活性材料と、
b)水と、を含む、SCR活性材料。 - リーン運転の燃焼エンジンの排気ガスを浄化するための方法であって、前記排気ガスを、請求項1〜12のいずれか一項に記載のSCR活性材料上を通すことを特徴とする、方法。
- 請求項1〜12のいずれか一項に記載のSCR活性材料と、還元剤を提供する手段と、を含むことを特徴とする、リーン運転の燃焼エンジンの排気ガスを浄化するための装置。
- 前記還元剤を提供するための手段が、尿素水溶液用の注入器であることを特徴とする、請求項15に記載の装置。
- 酸化触媒を含むことを特徴とする、請求項15又は16に記載の装置。
- 前記還元剤を提供するための手段が、窒素酸化物吸蔵触媒であることを特徴とする、請求項15に記載の装置。
- 小細孔ゼオライト、銅塩及び酸化アルミニウムの水性懸濁液、又は酸化アルミニウムの前駆体化合物の水性懸濁液を乾燥させた後にか焼することを特徴とする、請求項1〜11のいずれか一項に記載のSCR活性材料の製造方法。
- 前記乾燥は噴霧乾燥であることを特徴とする、請求項19に記載の方法。
- 前記か焼が、空気中又は空気/水雰囲気中で500℃〜900℃の温度で行われることを特徴とする、請求項19又は20に記載の方法。
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US20230191376A1 (en) * | 2020-04-28 | 2023-06-22 | Basf Corporation | A composition for scr catalysts |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011519722A (ja) * | 2008-05-07 | 2011-07-14 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | 分子ふるいをベースとするscr触媒の使用下での炭化水素を含有する排気ガス中の窒素酸化物を減少する方法 |
JP2012522636A (ja) * | 2009-04-03 | 2012-09-27 | ビーエーエスエフ コーポレーション | アンモニア生成触媒およびscr触媒を備える排出処理システム |
JP2012215166A (ja) * | 2011-03-29 | 2012-11-08 | Ibiden Co Ltd | 排ガス浄化システム及び排ガス浄化方法 |
JP2012250149A (ja) * | 2011-05-31 | 2012-12-20 | Jgc Catalysts & Chemicals Ltd | 酸化燐含有金属担持結晶性シリコアルミノフォスフェート成型体触媒およびその製造方法 |
JP2014512940A (ja) * | 2011-03-03 | 2014-05-29 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | 窒素酸化物の選択的触媒還元を行うための触媒活性材料および触媒コンバータ |
WO2015017516A2 (en) * | 2013-07-30 | 2015-02-05 | Johnson Matthey Public Limited Company | Ammonia slip catalyst |
WO2016023928A1 (de) * | 2014-08-13 | 2016-02-18 | Umicore Ag & Co. Kg | Katalysator-system zur reduktion von stickoxiden |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BRPI0808091A2 (pt) | 2007-02-27 | 2014-07-15 | Basf Catalysts Llc | Catalisador, sistema de tratamento de gás de exaustão, processo para a redução de óxidos de nitrogênio, e, artigo de catalisador. |
CN102319584A (zh) | 2007-03-26 | 2012-01-18 | Pq公司 | 包含具有8元环开孔结构的分子筛或沸石的新型微孔结晶材料及其制备方法和应用 |
JP5777339B2 (ja) | 2007-04-26 | 2015-09-09 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Publiclimited Company | 遷移金属/ゼオライトscr触媒 |
GB2464478A (en) * | 2008-10-15 | 2010-04-21 | Johnson Matthey Plc | Aluminosilicate zeolite catalyst and use thereof in exhaust gas after-treatment |
US10583424B2 (en) * | 2008-11-06 | 2020-03-10 | Basf Corporation | Chabazite zeolite catalysts having low silica to alumina ratios |
EP2687284A1 (en) * | 2009-06-08 | 2014-01-22 | Basf Se | Cu containing silicoaluminophosphate (Cu-SAPO-34) |
KR101952557B1 (ko) * | 2010-12-02 | 2019-02-26 | 존슨 맛쎄이 퍼블릭 리미티드 컴파니 | 금속을 함유하는 제올라이트 촉매 |
WO2013060341A1 (en) | 2011-10-24 | 2013-05-02 | Haldor Topsøe A/S | Catalyst composition for use in selective catalytic reduction of nitrogen oxides |
WO2017216012A1 (en) | 2016-06-13 | 2017-12-21 | Basf Se | CATALYST COMPOSITE AND USE THEREOF IN THE SELECTIVE CATALYTIC REDUCTION OF NOx |
GB2554517B (en) | 2016-07-22 | 2021-02-03 | Johnson Matthey Plc | Catalyst binders for filter substrates |
-
2016
- 2016-08-11 EP EP16183708.3A patent/EP3281698A1/de not_active Withdrawn
-
2017
- 2017-08-11 EP EP17751105.2A patent/EP3496852B1/de active Active
- 2017-08-11 JP JP2019506677A patent/JP7041123B2/ja active Active
- 2017-08-11 KR KR1020197006751A patent/KR102431022B1/ko active IP Right Grant
- 2017-08-11 US US16/323,845 patent/US10799831B2/en active Active
- 2017-08-11 WO PCT/EP2017/070399 patent/WO2018029328A1/de unknown
- 2017-08-11 CN CN201780049001.7A patent/CN109562364A/zh active Pending
-
2020
- 2020-09-08 US US17/014,831 patent/US20200406191A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011519722A (ja) * | 2008-05-07 | 2011-07-14 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | 分子ふるいをベースとするscr触媒の使用下での炭化水素を含有する排気ガス中の窒素酸化物を減少する方法 |
JP2012522636A (ja) * | 2009-04-03 | 2012-09-27 | ビーエーエスエフ コーポレーション | アンモニア生成触媒およびscr触媒を備える排出処理システム |
JP2014512940A (ja) * | 2011-03-03 | 2014-05-29 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | 窒素酸化物の選択的触媒還元を行うための触媒活性材料および触媒コンバータ |
JP2012215166A (ja) * | 2011-03-29 | 2012-11-08 | Ibiden Co Ltd | 排ガス浄化システム及び排ガス浄化方法 |
JP2012250149A (ja) * | 2011-05-31 | 2012-12-20 | Jgc Catalysts & Chemicals Ltd | 酸化燐含有金属担持結晶性シリコアルミノフォスフェート成型体触媒およびその製造方法 |
WO2015017516A2 (en) * | 2013-07-30 | 2015-02-05 | Johnson Matthey Public Limited Company | Ammonia slip catalyst |
WO2016023928A1 (de) * | 2014-08-13 | 2016-02-18 | Umicore Ag & Co. Kg | Katalysator-system zur reduktion von stickoxiden |
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