JP6438480B2 - 2つの異なる貴金属モレキュラーシーブ触媒を含有する排気ガス触媒 - Google Patents
2つの異なる貴金属モレキュラーシーブ触媒を含有する排気ガス触媒 Download PDFInfo
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- JP6438480B2 JP6438480B2 JP2016536604A JP2016536604A JP6438480B2 JP 6438480 B2 JP6438480 B2 JP 6438480B2 JP 2016536604 A JP2016536604 A JP 2016536604A JP 2016536604 A JP2016536604 A JP 2016536604A JP 6438480 B2 JP6438480 B2 JP 6438480B2
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- catalyst
- molecular sieve
- exhaust gas
- gas catalyst
- noble metal
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 255
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims description 171
- 239000002808 molecular sieve Substances 0.000 title claims description 166
- 229910000510 noble metal Inorganic materials 0.000 title claims description 39
- 239000000758 substrate Substances 0.000 claims description 76
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 62
- 239000011148 porous material Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- 229930195733 hydrocarbon Natural products 0.000 claims description 26
- 150000002430 hydrocarbons Chemical class 0.000 claims description 26
- 229910052763 palladium Inorganic materials 0.000 claims description 24
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 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
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 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
- 239000011449 brick Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 98
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 39
- 238000003860 storage Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 17
- 239000002002 slurry Substances 0.000 description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000011068 loading method Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 239000010948 rhodium Substances 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
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 229910052878 cordierite Inorganic materials 0.000 description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000019635 sulfation Effects 0.000 description 3
- 238000005670 sulfation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 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
- 239000000969 carrier Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 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
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 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
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- -1 platinum group metals Chemical class 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
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 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
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 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
- 239000012876 carrier material 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
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000007726 management method Methods 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
- 229910017604 nitric acid 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 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
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000000717 retained effect Effects 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
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- 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
-
- 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
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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
- B01D53/9459—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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Description
パラジウムは、種々の異なるモレキュラーシーブに、以下の一般手順により加えられる:粉末触媒は、前駆体として硝酸パラジウムを使用するモレキュラーシーブのウエット含浸により調製される。100℃での乾燥後、試料は500℃でか焼される。試料は、その後、H2Oを10%含有する空気雰囲気中、750℃で水熱的にエージングされる。全ての試料に対するPd充填量は、1重量%である。モレキュラーシーブ担持されたPd触媒の実施例は、表1に列挙される。
比較触媒2A(Pd/CeO2)は、WO2008/047170で報告された手順の後に、CeO2担体上へPdを含浸することにより調製され、かつH2Oを10%含有する空気雰囲気中、750℃で水熱的にエージングされる。Pd充填量は、1重量%である。
触媒(0.4g)は、300Lhr−1g−1のMHSVで毎分2リットル流れるNO含有ガス混合物中で、2分間、約80℃の吸着温度で保持される。この吸着段階の後に、更なる試験のために、貯蔵されたNOxの全てを触媒からパージするために、NO含有ガスの存在下、床温度が約400℃に達するまで、10℃/分のランピング速度で温度プログラムされた放出(TPD)が続く。試験は、その後、80℃の代わりに100℃の温度から始まり繰り返される;150℃の温度から始まり再び繰り返される;及び170℃の温度から始まり再び繰り返される。
比較触媒2Aと共に排気ガス触媒1E、1H、及び1Kは、触媒のグラム毎に約64mgのSを加えるように、300℃でそれらをSO2含有ガス(100ppmのSO2、10%のO2、5%のCO2及びH2O、残部N2)と接触させることにより高レベルのサルフェーションにかけられる。サルフェーション前後の触媒のNOx貯蔵容量は、実施例3の手順に従い、100℃で測定される。結果は、表2に列挙される。
パラジウムは、実施例1の手順に従い、異なるモレキュラーシーブに加えられる。Pd充填量は、0.25から2重量%まで変化される。試料は、H2Oを10%含有する空気雰囲気中、750℃で、水熱的にエージングされる。エージングされた試料は、その後、実施例3の手順に従い、それらのNOx貯蔵容量について試験される。種々の温度における試料のNOx貯蔵容量は、表3に列挙される。
モレキュラーシーブ担持されたパラジウム触媒は、第一に、実施例1の手順に従い個々に調製される。触媒は、続いて、それらの重さベースの同等の比で互いに混合される。混合された触媒は、その後、H2Oを10%含有する空気雰囲気中で、750℃で、水熱的にエージングされる。混合された触媒の実施例は、表4に列挙される。
個々の触媒(0.2g)及びそれらの混合物(0.4g)は、300Lhr−1g−1のMHSVで毎分2リットル流れるNO含有ガス混合物中で、1分間、80℃の吸着温度で保持される。この吸着段階の後に、NO含有ガスの存在下、100℃/分のランピング速度で、床温度が約400℃に達するまで、昇温脱離(TPD)が続く。吸着及び放出の双方の間のNO含有ガス混合物は、12体積%のO2、200ppmのNO、5体積%のCO2、200ppmのCO、50ppmのC10H22及び5体積%のH2Oを含む。
モレキュラーシーブ担持されたパラジウム触媒粉末は、実施例1の手順に従い調製される。Pd充填量は、全ての試料に対して1.4重量%である。粉末試料のそれぞれは、その後、スラリー化され、アルミナバインダーと混合される。混合物は、50g/ft3のPd充填量を達成するように、フロースルーコーディエライト基材上にコーティングされる。コーティングされた触媒は、乾燥され、その後、4時間500℃で熱によりか焼される。触媒の実施例は、表5に列挙される。
実施例8のウォッシュコーティングされた触媒は、アルミナ担持されたPt触媒の第二層で更にコーティングされる。硝酸白金は、Pt/アルミナ触媒スラリーを形成するように、アルミナ粒子(直径10ミクロン未満の平均粒径になるように粉砕された)の水スラリーに加えられる。Pt/アルミナ触媒スラリーは、その後、25g/ft3のPt充填量を達成するように、Pd/モレキュラーシーブコーティングされた基材上にコーティングされ、かつ最終のコーティングされた基材は、乾燥され、その後、4時間500℃で熱することによりか焼される。Pt含有する触媒の実施例も、表5に列挙される。
モレキュラーシーブ担持されたパラジウム触媒粉末は、実施例1の手順に従い調製される。Pd充填量は、全ての試料に対して1.4重量%である。2つの選択された粉末試料は、その後、スラリー化されて、1:1の重量比で混合され、その後、混合されたスラリーに対するアルミナバインダーの添加が続く。この混合物は、50g/ft3のPd充填量を達成するように、フロースルーコーディエライト基材上にコーティングされる。コーティングされた触媒は、乾燥され、その後、4時間500℃で熱によりか焼される。触媒の実施例は、表5に列挙される。
実施例10のウォッシュコーティングされた触媒は、アルミナ担持されたPt触媒の第二層で更にコーティングされる。硝酸白金は、Pt/アルミナ触媒スラリーを形成するように、アルミナ粒子(直径10ミクロン未満の平均粒径になるように粉砕された)の水スラリーに加えられる。Pt/アルミナ触媒スラリーは、その後、25g/ft3のPt充填量を達成するように、Pd/モレキュラーシーブコーティングされた基材上にコーティングされ、かつ最終のコーティングされた基材は、乾燥され、その後、4時間500℃で熱することによりか焼される。Pt含有触媒の実施例も、表5に列挙される。
全てのウォッシュコーティングされた触媒は、フロースルー触媒コーティングされたコーディエライト基材のコア試料(直径2.54cmx長さ7.62cm)上で、試験される。触媒コアは、第一に、フロースルー条件下で、炉中で、水熱条件下(5%のH2O、残部空気)で、16時間750℃でエージングされる。個々の排気ガス成分のマス流を調節することにより調製された供給ガス流を使用して、実験室反応器中で、コアはその後、触媒的活性について試験される。ガス流速度は、結果として30,000h−1(GHSV=30,000h−1)のガス時間単位空間速度となる21.2Lmin−1で維持される。
実施例9Cで調製されたPd/BEA下部及びPt/Al2O3上部触媒のコア長の半分と、実施例9Aで調製されたPd/CHA下部及びPt/Al2O3上部触媒のコア長の半分とを組み合わせることにより、ゾーン化された触媒システムは評価される。実施例13Aのシステムは、実施例9Cのコアの半分を、実施例9Aのコアの半分の前に配置する;一方、実施例13Bのシステムは、実施例9Aのコアの半分を、実施例9Cのコアの半分の前に配置する。これらのシステムは、実施例12に概説されるような同一の手順に従い評価される。評価結果は、表5に要約される。
Claims (12)
- 低温度以下でNOx及び炭化水素(HC)を吸着すること、並びに吸着されたNOx及びHCを低温度より上の温度において変換及び放出することに効果的な排気ガス触媒であって、第一のモレキュラーシーブ触媒及び第二のモレキュラーシーブ触媒を含み、ここで第一のモレキュラーシーブ触媒が第一の貴金属及び第一のモレキュラーシーブを含み、第二のモレキュラーシーブ触媒が第二の貴金属及び第二のモレキュラーシーブを含み、第一のモレキュラーシーブが、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、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG及びZON並びに2以上の連晶からなるフレームワークタイプの群から選択される小細孔モレキュラーシーブであり、ここで第一のモレキュラーシーブは第二のモレキュラーシーブと異なり、
第一の貴金属及び第二の貴金属がともにパラジウムであり、かつ
低温度が200℃から250℃の範囲内である、
排気ガス触媒。 - 第一の貴金属の総量の5%より多くが第一のモレキュラーシーブの細孔の内側に位置し、かつ第二の貴金属の総量の5%より多くが第二のモレキュラーシーブの細孔の内側に位置する、請求項1に記載の排気ガス触媒。
- 小細孔モレキュラーシーブがAEI及びCHAからなるフレームワークタイプ群から選択される、請求項1又は2に記載の排気ガス触媒。
- 第二のモレキュラーシーブが、BEA及びMFIからなる群から選択される中又は大細孔モレキュラーシーブである、請求項1から3の何れか一項に記載の排気ガス触媒。
- 排気ガス触媒が、フロースルー又はフィルター基材上にコーティングされる、請求項1から4の何れか一項に記載の排気ガス触媒。
- 排気ガス触媒が押出成形されてフロースルー又はフィルター基材を形成している、請求項1から4の何れか一項に記載の排気ガス触媒。
- 排気ガス触媒が、第一のモレキュラーシーブ触媒を含む第一の層、及び第二のモレキュラーシーブ触媒を含む第二の層を含む、請求項1から4の何れか一項に記載の排気ガス触媒。
- 排気ガス触媒が、第一のモレキュラーシーブ触媒を含む第一のゾーン、及び第二のモレキュラーシーブ触媒を含む第二のゾーンを含む、請求項1から4の何れか一項に記載の排気ガス触媒。
- 第一のモレキュラーシーブ触媒を含む第一のゾーンが、第二のモレキュラーシーブ触媒を含む第二のゾーンとは別のブリック上に位置する、請求項8に記載の排気ガス触媒。
- 請求項1から9の何れか一項に記載の排気ガス触媒、並びに選択的触媒的還元(SCR)触媒、微粒子フィルター、SCRフィルター、NOx吸着触媒、三元触媒、酸化触媒及びそれらの組合せからなる群から選択される触媒コンポーネントを含む、内燃機関のための排気システム。
- 請求項1から9の何れか一項に記載の排気ガス触媒上に、低温度以下でNOx及び炭化水素(HC)を吸着すること、低温度より上の温度において排気ガス触媒からのNOx及びHCを変換及び熱的に放出すること、並びに放出されたNOx及びHCを排気ガス触媒の下流の触媒コンポーネント上で触媒的に除去することを含み、
低温度が200℃から250℃の範囲内である、
内燃機関からの排気ガスを処理するための方法。 - 排気ガスが第一のモレキュラーシーブ触媒と接触する前に第二のモレキュラーシーブ触媒と接触するように、第二のモレキュラーシーブ触媒が第一のモレキュラーシーブ触媒の上流に位置する、請求項11に記載の方法。
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