GB2522976A - Noble metal-molecular sieve catalysts - Google Patents
Noble metal-molecular sieve catalysts Download PDFInfo
- Publication number
- GB2522976A GB2522976A GB1421740.0A GB201421740A GB2522976A GB 2522976 A GB2522976 A GB 2522976A GB 201421740 A GB201421740 A GB 201421740A GB 2522976 A GB2522976 A GB 2522976A
- Authority
- GB
- United Kingdom
- Prior art keywords
- catalyst
- molecular sieve
- exhaust gas
- noble metal
- gas catalyst
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 268
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 175
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 175
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 47
- 239000011148 porous material Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 28
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 28
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims description 77
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 238000002485 combustion reaction Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011449 brick Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 13
- 239000010457 zeolite Substances 0.000 abstract description 13
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 11
- 239000007789 gas Substances 0.000 description 96
- 230000018537 nitric oxide storage Effects 0.000 description 25
- 239000002002 slurry Substances 0.000 description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 229910001868 water Inorganic materials 0.000 description 14
- 238000011068 loading method Methods 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011230 binding agent Substances 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
- 238000005470 impregnation Methods 0.000 description 5
- -1 platinum group metals Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000019635 sulfation Effects 0.000 description 5
- 238000005670 sulfation reaction Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 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
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012956 testing procedure Methods 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 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 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
-
- 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
-
- 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
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- 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
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
-
- 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
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
- B01D53/9468—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick in different layers
-
- 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
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
- B01D53/9472—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick in different zones
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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
- B01D53/9481—Catalyst preceded by an adsorption device without catalytic function for temporary storage of contaminants, e.g. during cold start
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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
- B01D53/9481—Catalyst preceded by an adsorption device without catalytic function for temporary storage of contaminants, e.g. during cold start
- B01D53/9486—Catalyst preceded by an adsorption device without catalytic function for temporary storage of contaminants, e.g. during cold start for storing hydrocarbons
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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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0354—Noble metals
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Abstract
A noble metal-molecular sieve catalyst effective to adsorb NOx and hydrocarbons (HC), comprises a first molecular sieve catalyst, such as a zeolite, having a first noble metal, such as palladium and a second molecular sieve catalyst, such as a zeolite, having a second noble metal, such as palladium. The noble metal, such as palladium, is located inside pores of the molecular sieves, in an amount greater than 5 percent. The first and second molecular sieves are different. Also disclosed is a method for treating an exhaust gas using the noble metal-molecular sieve catalyst.
Description
NOBLE METAL-MOLECULAR SIEVE CATALYSTS
FIELD OF THE INVENTION
The invention relates to exhaust gas catalysts and their use in an exhaust system for internal combustion engines.
BACKGROUND OF THE INVENTION
Internal combustion engines produce exhaust gases containing a variety of pollutants, including nitrogen oxides ("NOr"), carbon monoxide, and uncombusted hydrocarbons, which are the subject of governmental legislation.
Emission control systems are widely utilized to reduce the amount of these pollutants emitted to atmosphere, and typically achieve very high efficiencies once they reach their operating temperature (typically, 200°C and higher). However, these systems are relatively inefficient below their operating temperature (the "cold start" period).
For instance, current urea based selective catalytic reduction (5CR) applications implemented for meeting Euro Gb emissions require that the temperature at the urea dosing position be above about 180°C before urea can be dosed and used to convert NON. NO conversion below 180°C is difficult to address using the current systems, and future European and US legislation will stress the low temperature NO storage and conversion. Currently this is achieved by heating strategies but this has a detrimental effect of CO2 emissions.
As even more stringent national and regional legislation lowers the amount of pollutants that can be emitted from diesel or gasoline engines, reducing emissions during the cold start period is becoming a major challenge. Thus, methods for reducing the level of NO emitted during cold start condition continue to be explored.
For instance, U.S. AppI. Pub. No. 2012/0308439 teaches a cold start catalyst that comprises (1) a zeolite catalyst comprising a base metal, a noble metal, and a zeolite, and (2) a supported platinum group metal catalyst comprising one or more platinum group metals and one or more inorganic oxide carriers.
PCT Intl. AppI. WO 2008/047 170 discloses a system wherein NO from a lean exhaust gas is adsorbed at temperatures below 200°C and is subsequently thermally desorbed above 200°C. The NO adsorbent is taught to consist of palladium and a cerium oxide or a mixed oxide or composite oxide containing cerium and at least one other transition metal.
U.S. AppI. Pub. No. 2011/0005200 teaches a catalyst system that simultaneously removes ammonia and enhances net NO conversion by placing an ammonia-selective catalytic reduction ("NH3-SCR") catalyst formulation downstream of a lean NO trap. The NH3-SCR catalyst is taught to adsorb the ammonia that is generated during the rich pulses in the lean NO trap. The stored ammonia then reacts with the NO emitted from the upstream lean NO trap, which increases NC conversion rate while depleting the stored ammonia.
ACT Intl. AppI. WO 2004/076829 discloses an exhaust-gas purification system which includes a NC storage catalyst arranged upstream of an 5CR catalyst. The NO storage catalyst includes at least one alkali, alkaline earth, or rare earth metal which is coated or activated with at least one platinum group metal (Pt, Pd, Rh, or Ir). A particularly preferred NO storage catalyst is taught to include cerium oxide coated with platinum and additionally platinum as an oxidizing catalyst on a support based on aluminum oxide. EP 1027919 discloses a NO adsorbent material that comprises a porous support material, such as alumina, zeolite, zirconia, titania, and/or lanthana, and at least 0.1 wt% precious metal (Pt, Pd, and/or Rh). Platinum carried on alumina is exemplified.
As with any automotive system and process, it is desirable to attain still further improvements in exhaust gas treatment systems, particularly under cold start conditions. We have discovered an exhaust gas catalyst and system that can reduce cold start emissions during the low temperature period. The new exhaust gas catalyst also exhibits improved sulfur tolerance.
SUMMARY OF THE INVENTION
The invention is exhaust gas catalysts that are effective to adsorb NO and hydrocarbons (HC) at or below a low temperature and to convert and release the adsorbed NO and HO at temperatures above the low temperature. One exhaust gas catalyst comprises a noble metal and a molecular sieve, and has an infrared spectrum having a characteristic absorption peak in a range of from 750 cm1 to 1050 cm1 in addition to the absorption peaks for the molecular sieve itself. The exhaust gas catalyst also comprises a noble metal and a molecular sieve, having greater than 5 percent of the noble metal amount located inside pores of the molecular sieve. The exhaust gas catalyst also comprises a first and second molecular sieve catalyst. The first molecular sieve catalyst comprises a first noble metal and a first molecular sieve, and the second molecular sieve catalyst comprises a second noble metal and a second molecular sieve, wherein the first and second molecular sieves are different. The invention also includes exhaust systems comprising the exhaust gas catalysts, and a method for treating exhaust gas utilizing the exhaust gas catalysts.
DETAILED DESORIPTION OF THE INVENTION
The exhaust gas catalysts of the invention are effective to adsorb NO and hydrocarbons (HO) at or below a low temperature and to convert and release the adsorbed NO and HO at temperatures above the low temperature. Preferably, the low temperature is in the range of about 200°O to 250°O, more preferably about 200°O.
One exhaust gas catalyst of the invention comprises a noble metal and a molecular sieve. The exhaust gas catalyst has an infrared (IR) spectrum having a characteristic absorption peak in a range of from 750 cm4 to 1050 cm4, more preferably in the range of from 800 cm1 to 1000 cm4, or in the range of from 850 cm4 to 975 cm4. This characteristic absorption peak is in addition to the absorption peaks for an IR spectrum of the molecular sieve itself (i.e., the unmodified molecular sieve).
In another embodiment, the exhaust gas catalyst of the invention comprises a noble metal and a molecular sieve, wherein some of the noble metal (more than 1 percent of the total noble metal added) in the exhaust gas catalyst is located inside the pores of the molecular sieve. Preferably, more than 5 percent of the total amount of noble metal is located inside the pores of the molecular sieve; and more preferably may be greater than 10 percent or greater than 25% or greater than 50 percent of the total amount of noble metal that is located inside the pores of the molecular sieve.
In another embodiment, the exhaust gas catalyst of the invention comprises a noble metal and a molecular sieve, and has an infrared (IR) spectrum having a characteristic absorption peak in a range of from 750 cm4 to 1050 cm4, (more preferably in the range of from 800 cm1 to 1000 cm4, or in the range of from 850 cm4 to 975 cm4.), and some of the noble metal (more than 1 percent of the total noble metal added, and preferably more than 5 percent of the total noble metal added) in the exhaust gas catalyst is located inside the pores of the molecular sieve. More preferably, greater than 10 percent or greater than 25% or greater than 50 percent of the total amount of noble metal is located inside the pores of the molecular sieve.
The noble metal is preferably palladium, platinum, rhodium, gold, silver, iridium, ruthenium, osmium, or mixtures thereof; more preferably, palladium, platinum, rhodium, or mixtures thereof. Palladium is particularly preferred.
The molecular sieve may be any natural or a synthetic molecular sieve, including zeolites, and is preferably composed of aluminum, silicon, and/or phosphorus. The molecular sieves typically have a three-dimensional arrangement of Si04, A104, and/or PD4 that are joined by the sharing of oxygen atoms, but may also be two-dimensional structures as well. The molecular sieve frameworks are typically anionic, which are counterbalanced by charge compensating cations, typically alkali and alkaline earth elements (e.g., Na, K, Mg, Ca, Sr, and Ba), ammonium ions, and also protons.
Preferably, the molecular sieve is selected from an aluminosilicate molecular sieve, a metal-substituted aluminosilicate molecular sieve, an aluminophosphate molecular sieve, or a metal-substituted aluminophosphate molecular sieve.
Preferably, the molecular sieve is a small pore molecular sieve having a maximum ring size of eight tetrahedral atoms, a medium pore molecular sieve having a maximum ring size of ten tetrahedral atoms, or a large pore molecular sieve having a maximum ring size of twelve tetrahedral atoms.
If the molecular sieve is a small pore molecular sieve, it is preferably a molecular sieve having the Framework Type of ACO, AFI, AEN, AFN, AFT, AFX, ANA, ARC, ARD, ATI, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, COO, IHW, lIE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAy, Sly, THO, ISC, UEI, UFI, VNI, YUG, and ZON, as well as mixtures or intergrowths of any two or more. More preferably, the small pore zeolite is AEI or CHA. Particularly preferred intergrowths of the small pore molecular sieves include KFI-SIV, IIE-RIH, AEW-UEI, AEI-CHA, and AEI-SAV. Most preferably, the small pore molecular sieve is AEI or CHA, or an AEI-CHA intergrowth.
If the molecular sieve is a medium pore molecular sieve, it is preferably a molecular sieve having the Framework Type of MFI, FER, MV, or EUO. If the molecular sieve is a large pore molecular sieve, it is preferably a molecular sieve having the Framework Type of CON, BEA, FAU, MOR, or EMT.
The exhaust gas catalyst may be prepared by any known means. For instance, the noble metal may be added to the molecular sieve to form the exhaust gas catalyst by any known means, the manner of addition is not considered to be particularly critical. For example, a noble metal compound (such as palladium nitrate) may be supported on the molecular sieve by impregnation, adsorption, ion-exchange, incipient wetness, precipitation, or the like. Other metals may also be added to the exhaust gas catalyst.
Preferably, the exhaust gas catalyst further comprises a flow-through substrate or filter substrate. In one embodiment, the exhaust gas catalyst is coated onto the flow-through or filter substrate, and preferably deposited on the flow-through or filter substrate using a washcoat procedure to produce an exhaust gas catalyst system.
The flow-through or filter substrate is a substrate that is capable of containing catalyst components. The substrate is preferably a ceramic substrate or a metallic substrate. The ceramic substrate may be made of any suitable refractory material, e.g., alumina, silica, titania, ceria, zirconia, magnesia, zeolites, silicon nitride, silicon carbide, zirconium silicates, magnesium silicates, aluminosilicates, metallo aluminosilicates (such as cordierite and spudomene), or a mixture or mixed oxide of any two or more thereof. Cordierite, a magnesium aluminosilicate, and silicon carbide are particularly preferred.
The metallic substrates may be made of any suitable metal, and in particular heat-resistant metals and metal alloys such as titanium and stainless steel as well as ferritic alloys containing iron, nickel, chromium, and/or aluminum in addition to other trace metals.
The flow-through substrate is preferably a flow-through monolith having a honeycomb structure with many small, parallel thin-walled channels running axially through the substrate and extending throughout from an inlet or an outlet of the substrate. The channel cross-section of the substrate may be any shape, but is preferably square, sinusoidal, triangular, rectangular, hexagonal, trapezoidal, circular, or oval.
The filter substrate is preferably a wall-flow monolith filter. The channels of a wall-flow filter are alternately blocked, which allow the exhaust gas stream to enter a channel from the inlet, then flow through the channel walls, and exit the filter from a different channel leading to the outlet. Particulates in the exhaust gas stream are thus trapped in the filter.
The exhaust gas catalyst may be added to the flow-through or filter substrate by any known means. A representative process for preparing the exhaust gas catalyst using a washcoat procedure is set forth below. It will be understood that the process below can be varied according to different embodiments of the invention.
The pre-formed exhaust gas catalyst may be added to the flow-through or filter substrate by a washcoating step. Alternatively, the exhaust gas catalyst may be formed on the flow-through or filter substrate by first washcoating unmodified molecular sieve onto the substrate to produce a molecular sieve-coated substrate. Noble metal may then be added to the molecular sieve-coated substrate, which may be accomplished by an impregnation procedure, or the like.
The washcoating procedure is preferably performed by first slurrying finely divided particles of the exhaust gas catalyst (or unmodified molecular sieve) in an appropriate solvent, preferably water, to form the slurry. Additional components, such as transition metal oxides, binders, stabilizers, or promoters may also be incorporated in the slurry as a mixture of water soluble or water-dispersible compounds. The slurry preferably contains between 10 to 70 weight percent solids, more preferably between 20 to 50 weight percent. Prior to forming the slurry, the exhaust gas catalyst (or unmodified molecular sieve) particles are preferably subject to a size reduction treatment (e.g., milling) such that the average particle size of the solid particles is less than 20 microns in diameter.
The flow-through or filter substrate may then be dipped one or more times into the slurry or the slurry may be coated on the substrate such that there will be deposited on the substrate the desired loading of catalytic materials. If noble metal is not incorporated into the molecular sieve prior to washcoating the flow-through or filter substrate, the molecular sieve-coated substrate is typically dried and calcined and then, the noble metal may be added to the molecular sieve-coated substrate by any known means, including impregnation, adsorption, or ion-exchange, for example, with a noble metal compound (such as palladium nitrate). Preferably, the entire length of the flow-through or filter substrate is coated with the slurry so that a washcoat of the exhaust gas catalyst covers the entire surface of the substrate.
After the flow-through or filter substrate has been coated with the exhaust gas catalyst, and impregnated with noble metal if necessary, the coated substrate is preferably dried and then calcined by heating at an elevated temperature to form the exhaust gas catalyst-coated substrate. Preferably, the calcination occurs at 400 to 600°C for approximately 1 to 8 hours.
In an alternative embodiment, the flow-through or filter substrate is comprised of the exhaust gas catalyst. In this case, the exhaust gas catalyst is extruded to form the flow-through or filter substrate. The exhaust gas catalyst extruded substrate is preferably a honeycomb flow-through monolith.
Extruded molecular sieve substrates and honeycomb bodies, and processes for making them, are known in the art. See, for example, U.S. Pat. Nos. 5,492,883, 5,565,394, and 5.633,217 and U.S. Pat. No. Re. 34,804.
Typically, the molecular sieve material is mixed with a permanent binder such as silicone resin and a temporary binder such as methylcellulose, and the mixture is extruded to form a green honeycomb body, which is then calcined and sintered to form the final molecular sieve flow-through monolith. The molecular sieve may contain the noble metal prior to extruding such that an exhaust gas catalyst monolith is produced by the extrusion procedure. Alternatively, the noble metal may be added to a pre-formed molecular sieve monolith in order to produce the exhaust gas catalyst monolith.
In a separate embodiment, the exhaust gas catalyst comprises a first molecular sieve catalyst and a second molecular sieve catalyst. The first molecular sieve catalyst comprises a first noble metal and a first molecular sieve.
The second molecular sieve catalyst comprises a second noble metal and a second molecular sieve. The first and second molecular sieves are different. In this embodiment, the exhaust gas catalyst may comprise one or more additional molecular sieve catalysts (e.g., a third molecular sieve catalyst and/or a fourth molecular sieve catalyst), provided that the additional molecular sieve(s) are different than the first and second molecular sieves.
The first noble metal and the second noble metal are independently selected from platinum, palladium, rhodium, gold, silver, iridium, ruthenium, osmium, or mixtures thereof; preferably, they are independently selected from palladium, platinum, rhodium, or mixtures thereof. More preferably, the first noble metal and the second noble metal are both palladium.
The first molecular sieve is preferably a small pore molecular sieve having the Framework Type of ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAy, Sly, THO, TSC, UEI, UFI, VNI, YUG, and ZON, as well as mixtures or intergrowths of any two or more. More preferably, the small pore zeolite is AEI or CHA. Particularly preferred intergrowths of the small pore molecular sieves include KFI-SIV, ITE-RTH, AEW-UEI, AEI-CHA, and AEI-SAV. Most preferably, the small pore molecular sieve is AEI or CHA, or an AEI-CHA intergrowth.
The second molecular sieve is preferably a medium or large pore molecular sieve. The medium pore molecular sieve is preferably a molecular sieve having the Framework Type of MFI, FER, MW, or EUO. The large pore molecular sieve is preferably a molecular sieve having the Framework Type of CON, BEA, FAU, MOR, or EMT. More preferably, the medium or large pore molecular sieve is MFI or BEA.
The exhaust gas catalyst may be prepared by processes well known in the prior ad. The first molecular sieve catalyst and the second molecular sieve catalyst may be physically mixed to produce the exhaust gas catalyst.
Preferably, the exhaust gas catalyst further comprises a flow-through substrate or filter substrate. In one embodiment, the first molecular sieve catalyst and the second molecular sieve catalyst are coated onto the flow-through or filter substrate, and preferably deposited on the flow-through or filter substrate using a washcoat procedure to produce the exhaust gas catalyst system.
Suitable flow-through or filter substrates are described above.
The first molecular sieve catalyst and the second molecular sieve catalyst may be added to the flow-through or filter substrate by any known means. A representative process for preparing the exhaust gas catalyst using a washcoat procedure is set forth below. It will be understood that the process below can be varied according to different embodiments of the invention. Also, the order of addition of the first molecular sieve catalyst and the second molecular sieve catalyst onto the flow-through or filter substrate is not considered critical. Thus, the first molecular sieve catalyst may be washcoated on the substrate prior to the second molecular sieve catalyst or the second molecular sieve catalyst may be washcoated on the substrate prior to the first molecular sieve catalyst or both the first molecular sieve catalyst and the second molecular sieve catalyst can be washcoated on the substrate simultaneously.
The pre-formed first molecular sieve catalyst may be added to the flow-through or filter substrate by a washcoating step. Alternatively, the first molecular sieve catalyst may be formed on the flow-through or filter substrate by first washcoating unmodified molecular sieve onto the substrate to produce a molecular sieve-coated substrate. Noble metal may then be added to the molecular sieve-coated substrate, which may be accomplished by an impregnation procedure, or the like.
The washcoating procedure is preferably performed as described above.
Preferably, the entire length of the flow-through or filter substrate is coated with the first molecular sieve catalyst slurry so that a washcoat of the first molecular sieve catalyst covers the entire surface of the substrate.
After the flow-through or filter substrate has been coated with the first molecular sieve catalyst slurry, and impregnated with noble metal if necessary, the coated substrate is preferably dried and then calcined by heating at an elevated temperature to form the molecular sieve catalyst-coated substrate.
Preferably, the calcination occurs at 400 to 600°C for approximately 1 to 8 hours.
The washcoat addition of the second molecular sieve catalyst is preferably accomplished by the procedure described above. Preferably, the entire length of the flow-through or filter substrate is coated with the supported PGM catalyst slurry so that a washcoat of the supported PGM catalyst covers the entire surface of the substrate.
After the flow-through or filter substrate has been coated with the both the first and second molecular sieve catalyst slurries, it is preferably dried and then calcined by heating at an elevated temperature to produce the exhaust gas catalyst. Preferably, the calcination occurs at 400 to 600°C for approximately 1 to 8 hours.
In an alternative embodiment, the flow-through or filter substrate is comprised of the first molecular sieve catalyst, the second molecular sieve catalyst, or both the first and second molecular sieve catalysts. In this case, the first, second, or both molecular sieve catalysts are extruded to form the flow-through or filter substrate. If not included in the extruded substrate, the first or second molecular sieve catalyst is coated onto the extruded flow-through or filter substrate. The extruded substrate is preferably a honeycomb flow-through monolith.
Preferably, the exhaust gas catalyst comprises a first layer comprising the first molecular sieve catalyst and a second layer comprising the second molecular sieve catalyst. Typically, the first layer may be disposed on a substrate and the second layer is disposed on the first layer. Alternatively, the second layer may be disposed on a substrate and the first layer disposed on the second layer.
In a separate embodiment, the exhaust gas catalyst comprises a first zone comprising the first molecular sieve catalyst and a second zone comprising the second molecular sieve catalyst. The first zone may be upstream of the second zone such that the first zone contacts the exhaust gas prior to the second zone, or alternatively the second zone may be upstream of the first zone such that the second zone contacts the exhaust gas prior to the first zone. Preferably, the second zone is located upstream of the first zone such that the exhaust gas contacts the second molecular sieve catalyst prior to contacting the first molecular sieve catalyst. The two zones may be on the same catalyst component (or catalyst brick), or the first zone comprising the first molecular sieve catalyst may be located on a separate brick (or catalyst component) than the second zone comprising the second molecular sieve catalyst.
The invention also includes an exhaust system for internal combustion engines comprising the exhaust gas catalyst. The exhaust system preferably comprises one or more additional after-treatment devices capable of removing pollutants from internal combustion engine exhaust gases at normal operating temperatures. Preferably, the exhaust system comprises the exhaust gas catalyst and one or more other catalyst components selected from: (1) a selective catalytic reduction (8CR) catalyst, (2) a particulate filter, (3) a 8CR filter, (4) a NO adsorber catalyst, (5) a three-way catalyst, (6) an oxidation catalyst, or any combination thereof. The exhaust gas catalyst is preferably a separate component from any of the above after-treatment devices.
Alternatively, the exhaust gas catalyst can be incorporated as a component into any of the above after-treatment devices.
These after-treatment devices are well known in the art. Selective catalytic reduction (SCR) catalysts are catalysts that reduce NO to N2 by reaction with nitrogen compounds (such as ammonia or urea) or hydrocarbons (lean NO reduction). A typical SCR catalyst is comprised of a vanadia-titania catalyst, a vanadia-tungsta-titania catalyst, or a metal/zeolite catalyst such as iron/beta zeolite, copper/beta zeolite, copperfsSz-13, copper/SAPO-34, Fe/ZSM- 5, or copperfzSM-5.
Particulate filters are devices that reduce particulates from the exhaust of internal combustion engines. Particulate filters include catalyzed particulate filters and bare (non-catalyzed) particulate filters. Catalyzed particulate filters (for diesel and gasoline applications) include metal and metal oxide components (such as Pt, Pd, Fe, Mn, Cu, and ceria) to oxidize hydrocarbons and carbon monoxide in addition to destroying soot trapped by the filter.
Selective catalytic reduction filters (SCRF) are single-substrate devices that combine the functionality of an SCR and particulate filter. They are used to reduce NO and particulate emissions from internal combustion engines. In addition to the 3CR catalyst coating, the particulate filter may also include other metal and metal oxide components (such as Pt, Pd, Fe, Mn, Cu, and ceria) to oxidize hydrocarbons and carbon monoxide in addition to destroying soot trapped by the filter.
NO adsorber catalysts (NACs) are designed to adsorb NO under lean exhaust conditions, release the adsorbed NC under rich conditions, and reduce the released NO to form N2. NACs typically include a NOstorage component (e.g., Ba, Ca, Sr, Mg, K, Na, Li, Cs, La, Y, Pr, and Nd), an oxidation component (preferably Pt) and a reduction component (preferably Rh). These components are contained on one or more supports.
Three-way catalysts (TWOs) are typically used in gasoline engines under stoichiometric conditions in order to convert NO to N2, carbon monoxide to 002, and hydrocarbons to CO2 and H20 on a single device.
Oxidation catalysts, and in particular diesel oxidation catalysts (DOC5), are well-known in the art. Oxidation catalysts are designed to oxidize CO to 002 and gas phase hydrocarbons (HG) and an organic fraction of diesel particulates (soluble organic fraction) to 002 and H20. Typical oxidation catalysts include platinum and optionally also palladium on a high surface area inorganic oxide support, such as alumina, silica-alumina and a zeolite.
The exhaust system can be configured so that the exhaust gas catalyst is located close to the engine and the additional after-treatment device(s) are located downstream of the exhaust gas catalyst. Thus, under normal operating conditions, engine exhaust gas first flows through the exhaust gas catalyst prior to contacting the after-treatment device(s). Alternatively, the exhaust system may contain valves or other gas-directing means such that during the low temperature period (typically below a temperature ranging from about 150 to 25000, preferably 200°C, about as measured at the after-treatment device(s)), the exhaust gas is directed to contact the after-treatment device(s) before flowing to the exhaust gas catalyst. Once the after-treatment device(s) reaches the operating temperature (about 150 to 250°C, preferably 200°C, as measured at the after-treatment device(s)), the exhaust gas flow is then redirected to contact the exhaust gas catalyst prior to contacting the after-treatment device(s). This ensures that the temperature of the exhaust gas catalyst remains low for a longer period of time, and thus improves efficiency of the exhaust gas catalyst, while simultaneously allowing the after-treatment device(s) to more quickly reach operating temperature. U.S. Pat. No. 5,656,244, the teachings of which are incorporated herein by reference, for example, teaches means for controlling the flow of the exhaust gas during cold-start and normal operating conditions.
The invention also includes a method for treating exhaust gas from an internal combustion engine. The method comprises adsorbing NO and hydrocarbons (HO) onto the exhaust gas catalyst at temperatures at or below a low temperature, converting and thermally desorbing NO and HO from the exhaust gas catalyst at a temperature above the low temperature, and catalytically removing the desorbed NO and HO on a catalyst component downstream of the exhaust gas catalyst. Preferably, the low temperature is in the range of about 200°C to 250°C, more preferably about 200°C.
The catalyst component downstream of the exhaust gas catalyst is a 5CR catalyst, a particulate filter, a 5CR filter, a NO adsorber catalyst, a three-way catalyst, an oxidation catalyst, or combinations thereof.
The following examples merely illustrate the invention. Those skilled in the ad will recognize many variations that are within the spirit of the invention and scope of the claims.
EXAMPLE 1: PREPARATION OF NOBLE METAL-MOLECULAR SIEVE
CATALYSTS
Palladium is added to a variety of different molecular sieves according to the following general procedure: The powder catalyst is prepared by wet impregnation of the molecular sieve using palladium nitrate as the precursor. After drying at 100°C, the samples are calcined at 50000. The samples are then hydrothermally aged at 750°C in an air atmosphere containing 10% H2O. The Pd loadings for all the samples are 1 wt.%. Examples of the molecular sieve supported Pd catalysts are listed in Table 1.
EXAMPLE 2: PREPARATION OF COMPARATIVE CATALYST Comparative Catalyst 2A (Pd/CeO2) is prepared following the procedures reported in WO 2008/047170 by impregnating Pd onto a CeO2 support, and hydrothermally aged at 750°C in an air atmosphere containing 10% H2O. The Pd loading is 1 wt.%.
EXAMPLE 3: NO STORAGE CAPACITY TESTING PROCEDURES The catalyst (0.4 g) is held at the adsorption temperature of about 80°C for 2 minutes in an NO-containing gas mixture flowing at 2 liters per minute at a MHSV of 300 L * hr * g1. This adsorption stage is followed by Temperature Programmed Desorption (TPD) at a ramping rate of 10°C/minute in the presence of the NO-containing gas until the bed temperature reaches about 400°C in order to purge the catalyst of all stored NO for further testing. The test is then repeated starting from a temperature of 10000, instead of 80°C; repeated again starting from a temperature of 150°C; and repeated again starting from a temperature of 170°C.
The NO-containing gas mixture during both the adsorption and desorption comprises 12 vol.% 02, 200 ppm NO, 5 vol.% C02, 200 ppm CC, 50 ppm C10H22, and 5 vol.% H20.
The NO storage is calculated as the amount of NO2 stored per liter of catalyst with reference to a monolith containing a catalyst loading of about 3 gun3. The results at the different temperatures are shown in Table 1.
The results at Table 1 show that all the molecular sieve supported catalysts, similar to the Comparative Catalyst 2A, can store N0 at low temperatures. In general, the small pore molecular sieve supported catalysts have higher NO storage capacity at temperatures above 150°C; whereas the large pore molecular sieve supported catalysts have higher NO storage capacity at temperatures below 100°C.
EXAMPLE 4: NO STORAGE CAPACITY AFTER SULFUR EXPOSURE
TESTING PROCEDURES
Exhaust gas catalysts 1 E, 1 H, and 1K, together with Comparative Catalyst 2A, are subjected to a high level of sulfation by contacting them with a SO2 containing gas (100 ppm SO2, 10% 02, 5% CO2 and H2O, balance N2) at 300°C to add about 64 mg S per gram of catalyst. The NO storage capacity of the
IS
catalysts before and after sulfation is measured at 100°C following the procedures of Example 3. The results are listed in Table 2.
The results shown in Table 2 indicate that the exhaust gas catalysts of the invention retain a significant amount of the NO storage capacity even after high a level of sulfur exposure. In contrast, Comparative Catalyst 2A (Pd/CeO2) loses almost all of its NO adsorption ability under the same sulfation conditions. The exhaust gas catalysts of the invention exhibits much improved sulfur tolerance.
EXAMPLE 5: PREPARATION AND EVALUATION OF MOLECULAR SIEVE
SUPPORTED CATALYSTS WITH DIFFERENT PALLADIUM LOADINGS
Palladium is added to different molecular sieves following the procedure of Example 1. The Pd loading is varied from 0.25 to 2 wt.%. The samples are hydrothermally aged at 750°C in an air atmosphere containing 10% H20. The aged samples are then tested for their NO storage capacities following the procedure of Example 3. The NO storage capacities of the samples at various temperatures are listed in Table 3.
The results in Table 3 show that increasing Pd loading increases the NO storage capacity.
EXAMPLE 6: PREPARATION OF MIXED MOLECULAR SIEVE SUPPORTED
PALLADIUM CATALYSTS
Molecular sieve supported palladium catalysts are first prepared individually following the procedures of Example 1. The catalysts are subsequently mixed with each other at an equivalent ratio based on their weight. The mixed catalysts are then hydrothermally aged at 750°C in an air atmosphere containing 10% HO.
Examples of the mixed catalysts are listed in Table 4.
EXAMPLE 7: EVALUATION OF THE MIXED CATALYSTS Individual catalysts (0.2 g) and their mixtures (0.4 g) are held at the adsorption temperature of 80°C for 1 minute in an NO-containing gas mixture flowing at 2 liters per minute at a MHSV of 300 L * hr1 * g1. This adsorption stage is followed by Temperature Programmed Desorption (TPD) at a ramping rate of 100°C/minute in the presence of the NO-containing gas until the bed temperature reaches about 400°C. The NO-containing gas mixture during both the adsorption and desorption comprises 12 vol.% 02, 200 ppm NO, 5 vol.% 002, 200 ppm 00, 50 ppm C10H22, and 5 vol.% H20.
The NO storage capacities are calculated during the 1 minute holding at 80°C, as well as during the subsequent temperature ramping from 80 to 200°C.
The results are summarized in Table 4.
The results in Table 4 show that it is possible to optimize the NO storage capacity at different temperatures by combining different types of molecular sieve supported noble metal catalysts.
EXAMPLE 8: WASHCOATING MOLECULAR SIEVE SUPPORTED PALLADIUM
CATALYSTS
Molecular sieve supported palladium catalyst powders are prepared following the procedure of Example 1. The Pd loadings are 1.4 wt.% for all the samples. Each of the powder samples is then slurried and mixed an alumina binder. The mixture is coated on a flow-through cordierite substrate to achieve a Pd loading of 50 gIft3. The coated catalyst is dried and then calcined by heat at 500°C for 4 hours. Examples of the catalysts are listed in Table 5.
EXAMPLE 9: WASHCOATING MOLECULAR SIEVE SUPPORTED PALLADIUM
CATALYSTS TOGETHER WITH A PLATINUM COMPONENT
The washcoated catalysts in Example 8 are further coated with a second layer of alumina supported Pt catalyst. Platinum nitrate is added to a water slurry of alumina particles (milled to an average particle size of less than 10 microns in diameter) to form a Pt/alumina catalyst slurry. The Pt/alumina catalyst slurry is then coated on the Pd/molecular sieve-coated substrate to achieve a Pt loading of 25 gift3, and the final coated substrate is dried, and then calcined by heating at 500°C for 4 hours. Examples of the Pt-containing catalysts are also listed in
Table 5.
EXAMPLE 10: WASHCOATING MIXED MOLECULAR SIEVE SUPPORTED
PALLADIUM CATALYSTS
Molecular sieve supported palladium catalyst powders are prepared following the procedure of Example 1. The Pd loadings are 1.4 wt.% for all the samples. Two selected powder samples are then slurried and mixed with the weight ratio of 1:1, followed by the addition of alumina binder to the mixed slurry.
This mixture is coated on a flow-through cordierite substrate to achieve a Pd loading of 50 gIft3. The coated catalyst is dried and then calcined by heat at 500°C for 4 hours. Examples of the catalysts are listed in Table 5.
EXAMPLE 11: WASHCOATING MIXED MOLECULAR SIEVE SUPPORTED
PALLADIUM CATALYSTS TOGETHER WITH A PLATINUM COMPONENT
The washcoated catalysts in Example 10 are further coated with a second layer of alumina supported Pt catalyst. Platinum nitrate is added to a water slurry of alumina particles (milled to an average particle size of less than 10 microns in diameter) to form a Pt/alumina catalyst slurry. The Pt/alumina catalyst slurry is then coated on the Pd/molecular sieve-coated substrate to achieve a Pt loading of 25 gIft3, and the final coated substrate is dried, and then calcined by heating at 500°C for 4 hours. Examples of the Pt-containing catalysts are also listed in
Table 5.
EXAMPLE 12: EVALUATION OF THE WASHCOATED CATALYSTS All the washcoated catalysts are tested on core samples (2.54 cm in diameter x 7.62 cm in length) of the flow-through catalyst-coated cordierite substrate. Catalyst cores are first aged under flow-through conditions in a furnace under hydrothermal conditions (5% H2O, balance air) at 750°C for 16 hours. The cores are then tested for catalytic activity in a laboratory reactor, using a feed gas stream that is prepared by adjusting the mass flow of the individual exhaust gas components. The gas flow rate is maintained at 21.2 L miri1 resulting in a Gas Hourly Space Velocity of 30,000 h1 (GHSV = 30,000 h1).
IS
The catalysts are tested under lean conditions, using a synthetic exhaust gas feed stream consisting of 200 ppm NO, 200 ppm CO, 50 ppm decane, 10% 02, 5% C02, 5% H20 and the balance nitrogen (volume %). The catalyst is exposed to the feed gas stream, first at an isothermal inlet gas temperature of 80°C for 100 seconds, following which the inlet gas temperature is increased to 650°C with a ramp rate of 100°C/mm.
The NO storage capacities of the catalysts at 80°C for 100 seconds and during the subsequent temperature ramp from 80 to 200°C are summarized in Table 5. The cumulative HC storage and conversion efficiency and the cumulative CO conversion efficiency of the catalyst at temperatures below 200°C are also summarized in Table 5.
The results in Table 5 show that large pore molecular sieve supported catalysts have higher NO storage capacity at low temperatures; whereas small pore molecular sieve supported catalysts have higher N0 storage capacity at higher temperatures. The large pore molecular sieve supported catalysts also exhibit higher HC storage and conversion efficiency. Comparing the results on the mixed catalysts versus the catalysts with the corresponding single type of molecular sieve component, the mixed catalysts in general maintain high N0 storage capacity in a wider temperature window.
EXAMPLE 13: EVALUATION OF ZONED CATALYSTS Zoned catalyst systems are evaluated by combining a half of the core length of a Pd/BEA bottom and Pt/A1203 top catalyst prepared in Example 9C and a half of the core length of a Pd/CHA bottom and Pt/A1203 top catalyst prepared in Example 9A. The Example 1 3A system places a half of the core of Example 9C in front of a half of the core of Example 9A; whereas the Example 1 3B system places a half of the core of Example 9A in front of a half of the core of Example 9C. These systems are evaluated following the same procedures as outlined in Example 12. The evaluation results are summarized in Table 5.
The results in Table 5 show that the zoned systems, especially Example hA, exhibit high NO storage capacities in a much wider temperature range than the corresponding individual catalysts.
TABLE 1: NO storage capacity (g N02/L) Catalyst Molecular sieve NO storage capacity at different temperatures (g N02/L) 80°C 100°C 150°C 170°C 1A CHA (SAR=12) 0.42 0.50 0.62 0.60 lB CHA(SAR=13) 0.34 0.43 0.52 0.51 1C CHA(SAR=17) 0.20 0.36 0.42 0.42 1 D CHA (SAR22) 0.28 0.39 0.43 0.42 1 E CHA (SAR=26) 0.28 0.41 0.43 0.45 1 F ALl (SAR=20) 0.33 0.46 0.60 0.57 1G ERI (SAR=12) 0.08 0.21 0.22 0.20 1H MEl (SAR=23) 0.35 0.49 0.41 0.28 1J FER (SAR=18) 0.16 0.19 0.08 0.07 1K BEA (SAR=28) 0.68 0.53 0.14 0.07 1L BEA (SAR=37) 0.33 0.38 0.01 NM* 1M FAU (SAR3O) 0.11 0.10 0.12 0.14 iN MOR(SAR=30) 0.07 0.06 NM* NM* 1 P CHA (SAPO-34) 0.29 0.34 0.40 0.41 1Q AEI-CHA (SAPO) 0.22 0.22 0.25 0.23 2A** --(PdI CeO2) 0.29 0.31 0.41 0.38 *NM: not measured ** comparative b'ample TABLE 2: NO storage capacity (g N02/L) NO storage capacity at 100°C NO storage capacity at 100°C Catalyst before sulfation after sulfation 1E 0.41 0.28 IH 0.49 0.40 1K 0.53 0.47 2A* 0.31 0.01 * Comparative Example TABLE 3: NO storage capacity (g N02/L) Catalyst Molecular sieve Pd loading NO, storage capacity at different (wt.%) temperatures (g NO2IL) 80°C 100°C 150°C 170°C iF CHA(SAR=26) 1 0.28 0.41 0.43 0.45 5A CHA (SAR=26) 2 0.43 0.60 0.67 0.66 1K BEA(SAR=28) 1 0.68 0.53 0.14 0.07 5B BEA (SAR=28) 0.75 0.63 NM* NM* NM* SC BEA (SAR=28) 0.50 0.50 NM* NM* NM* SD BEA (SAR=28) 0.25 0.31 NM* NM* NM* *NM: not measured TABLE 4: NO storage capacity (g N02/L) Catalyst Molecular sieve NO storage capacity (g N02/L) 1 minute at 80°C During ramp from 80 to 200°C 1E CHA(SAR=26) 0.23 0.09 iF AEI (SAR=20) 0.29 0.13 1H MFI (SAR=23) 0.25 0.07 1K BEA(SAR=28) 0.38 -0.08 6A 1E+ 1H 0.17 0.13 6B iF + 1H 0.16 0.21 6C 1E+ 1K 0.17 0.17 ED iF + 1K 0.17 0.20 6E 1H + 1K 0.18 0.16 TABLE 5: Evaluation of washcoated catalysts Catalyst Molecular NO NO storage Cumulative HC Cumulative sieve storage capacity storage and CO capacity during ramp conversion conversion at 80°C from 80 to efficiency efficiency (g N02/L) 200°C (g below 200°C below 200°C ________ ___________ __________ N02/L) (%) (%) 8A Pd/CHA 0.21 0.33 26 46 SB Pd/MFI 0.19 0.26 95 28 8C Pd/BEA 0.33 0.29 96 39 9A Pd/CHA 0.19 0.28 46 47 with ________ PtIAI2O3 __________ ____________ _____________ ___________ 9B Pd/MFI with 0.18 0.12 97 29 ________ PtIAI2O3 __________ ____________ _____________ ___________ 9C Pd/BEA with 0.33 -0.02 98 50 ________ PtIAI2O3 __________ ____________ _____________ ___________ 1OA PdJBEA + 0.27 0.16 96 35 _________ Pd/MFI ___________ _____________ _______________ ____________ lOB Pd/BEA+ 0.29 0.22 97 42 ________ Pd/CHA __________ ____________ _____________ ___________ hA (Pd/BEAt 0.28 -0.01 98 46 Pd/MFI) w/ ________ PtIAI2O3 __________ ____________ _____________ ___________ 11B (Pd/BEA+ 0.27 0.10 97 46 Pd/CHA) wI ________ P t/ A 12 03 __________ ____________ _____________ ___________ 13A 1⁄29C+1⁄2 0.30 0.12 89 54 _______ 9A _________ __________ ____________ __________ 13B 1⁄29A+1⁄2 0.23 0.07 88 44 _______ 9c _________ __________ ____________ __________
Claims (16)
- We claim: 1. An exhaust gas catalyst effective to adsorb NO and hydrocarbons (HG) at or below a low temperature and to convert and release the adsorbed NO and HG at temperatures above the low temperature, said exhaust gas catalyst comprising a first molecular sieve catalyst and a second molecular sieve catalyst, wherein the first molecular sieve catalyst comprises a first noble metal and a first molecular sieve, and the second molecular sieve catalyst comprises a second noble metal and a second molecular sieve, wherein the first molecular sieve is different than the second molecular sieve.
- 2. The exhaust gas catalyst of claim 1 wherein greater than 5 percent of the total amount of first noble metal is located inside pores of the first molecular sieve and greater than 5 percent of the total amount of second noble metal is located inside pores of the second molecular sieve.
- 3. The exhaust gas catalyst of claim 1 or claim 2 wherein the first noble metal and the second noble metal are independently selected from the group consisting of platinum, palladium, rhodium, gold, silver, iridium, ruthenium, osmium, and mixtures thereof.
- 4. The exhaust gas catalyst of claim 3 wherein the first noble metal and the second noble metal are both palladium.
- 5. The exhaust gas catalyst of any of claims 1 to 4 wherein the first molecular sieve is a small pore molecular sieve selected from the group of Framework Type consisting of AGO, AEI, AEN, AFN, AFT, AFX, ANA, APC, ARD, AlT, CDO, CHA, DDR, DEl, EAB, EDI, ER, ERI, GIS, GOO, IHW, lIE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAy, Sly, THO, TSC, UEI, UFI, VNI, YUG AND ZON, and intergrowths of two or more.
- 6. The exhaust gas catalyst of claim 5 wherein the small pore molecular sieve is selected from the group Framework Type consisting of AEI and CHA.
- 7. The exhaust gas catalyst of any of claims 1 to 6 wherein the second molecular sieve is a medium or large pore molecular sieve selected from the group consisting of BEA and MFI.
- 8. The exhaust gas catalyst of any of claims 1 to 7 wherein the exhaust gas catalyst is coated onto a flow-through or filter substrate.
- 9. The exhaust gas catalyst of claim I to 7 wherein the exhaust gas catalyst is extruded to form a flow-through or filter substrate.
- 10. The exhaust gas catalyst of claim 1 to 7 wherein the exhaust gas catalyst comprises a first layer comprising the first molecular sieve catalyst and a second layer comprising the second molecular sieve catalyst.
- 11. The exhaust gas catalyst of claim I to 7 wherein the exhaust gas catalyst comprises a first zone comprising the first molecular sieve catalyst and a second zone comprising the second molecular sieve catalyst.
- 12. The exhaust gas catalyst of claim 11 wherein the first zone comprising the first molecular sieve catalyst is located on a separate brick than the second zone comprising the second molecular sieve catalyst.
- 13. An exhaust system for internal combustion engines comprising the exhaust gas catalyst of any of the preceding claims and a catalyst component selected from the group consisting a selective catalytic reduction (SCR) catalyst, a particulate filter, a 3CR filter, a NO adsorber catalyst, a three-way catalyst, an oxidation catalyst, and combinations thereof.
- 14. A method for treating an exhaust gas from an internal combustion engine, said method comprising adsorbing NO and hydrocarbons (HC) onto the exhaust gas catalyst of any of the preceding claims at or below a low temperature, converting and thermally desorbing NO and HC from the exhaust gas catalyst at a temperature above the low temperature, and catalytically removing the desorbed NO and HC on a catalyst component downstream of the exhaust gas catalyst.
- 15. The method of claim 14 wherein the low temperature is in the range of 200°C to 250°C.
- 16. The method of claim 14 or claim 15 wherein the second molecular sieve catalyst is located upstream of the first molecular sieve catalyst so that the exhaust gas contacts the second molecular sieve catalyst prior to contacting the first molecular sieve catalyst.
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CN105813745A (en) | 2016-07-27 |
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KR102380570B1 (en) | 2022-03-30 |
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