CN107921366A - Rhodium iron catalyst for TWC converter systems - Google Patents
Rhodium iron catalyst for TWC converter systems Download PDFInfo
- Publication number
- CN107921366A CN107921366A CN201680041916.9A CN201680041916A CN107921366A CN 107921366 A CN107921366 A CN 107921366A CN 201680041916 A CN201680041916 A CN 201680041916A CN 107921366 A CN107921366 A CN 107921366A
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- CN
- China
- Prior art keywords
- oxide
- catalyst
- external coating
- antigravity system
- washcoat
- 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.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- OMEXLMPRODBZCG-UHFFFAOYSA-N iron rhodium Chemical compound [Fe].[Rh] OMEXLMPRODBZCG-UHFFFAOYSA-N 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 58
- 230000003197 catalytic effect Effects 0.000 claims abstract description 29
- 230000004913 activation Effects 0.000 claims abstract description 19
- 230000008878 coupling Effects 0.000 claims abstract description 18
- 238000010168 coupling process Methods 0.000 claims abstract description 18
- 238000005859 coupling reaction Methods 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims description 82
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 71
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 66
- 239000010948 rhodium Substances 0.000 claims description 60
- 239000011248 coating agent Substances 0.000 claims description 55
- 238000000576 coating method Methods 0.000 claims description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 47
- 239000002184 metal Substances 0.000 claims description 47
- 238000007598 dipping method Methods 0.000 claims description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 36
- 229910052703 rhodium Inorganic materials 0.000 claims description 31
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 21
- 229910052763 palladium Inorganic materials 0.000 claims description 21
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 229910052684 Cerium Inorganic materials 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 229910052779 Neodymium Inorganic materials 0.000 claims description 14
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052788 barium Inorganic materials 0.000 claims description 13
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 12
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 12
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000002485 combustion reaction Methods 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- 238000004891 communication Methods 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 6
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000011232 storage material Substances 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 2
- 229910052726 zirconium Inorganic materials 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000013589 supplement Substances 0.000 abstract description 4
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- 230000035508 accumulation Effects 0.000 description 61
- 238000009825 accumulation Methods 0.000 description 61
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 42
- 229910002091 carbon monoxide Inorganic materials 0.000 description 42
- 238000012360 testing method Methods 0.000 description 42
- 230000006641 stabilisation Effects 0.000 description 21
- 238000011105 stabilization Methods 0.000 description 21
- 238000010586 diagram Methods 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 230000004087 circulation Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 230000001133 acceleration Effects 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- RWFBQHICRCUQJJ-NUHJPDEHSA-N (S)-nicotine N(1')-oxide Chemical compound C[N+]1([O-])CCC[C@H]1C1=CC=CN=C1 RWFBQHICRCUQJJ-NUHJPDEHSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- -1 hydrogen compound Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000008450 motivation Effects 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 239000012041 precatalyst Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229920001247 Reticulated foam Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- FTAHXGPNHBWWDP-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-].[O+]#[C-] FTAHXGPNHBWWDP-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 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
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite 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
- B01D53/9445—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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0234—Impregnation and coating simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
- F01N13/0093—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series the purifying devices are of the same type
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/101—Three-way catalysts
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2825—Ceramics
- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1025—Rhodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2042—Barium
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- B01D2255/2066—Praseodymium
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- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
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- B01D2255/2068—Neodymium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
- B01D2255/9022—Two layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/90—Physical characteristics of catalysts
- B01D2255/903—Multi-zoned catalysts
- B01D2255/9032—Two zones
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/014—Stoichiometric gasoline engines
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2340/00—Dimensional characteristics of the exhaust system, e.g. length, diameter or volume of the apparatus; Spatial arrangements of exhaust apparatuses
- F01N2340/02—Dimensional characteristics of the exhaust system, e.g. length, diameter or volume of the apparatus; Spatial arrangements of exhaust apparatuses characterised by the distance of the apparatus to the engine, or the distance between two exhaust treating apparatuses
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01N2340/00—Dimensional characteristics of the exhaust system, e.g. length, diameter or volume of the apparatus; Spatial arrangements of exhaust apparatuses
- F01N2340/04—Dimensional characteristics of the exhaust system, e.g. length, diameter or volume of the apparatus; Spatial arrangements of exhaust apparatuses characterised by the arrangement of an exhaust pipe, manifold or apparatus in relation to vehicle frame or particular vehicle parts
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
- F01N2510/0682—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having a discontinuous, uneven or partially overlapping coating of catalytic material, e.g. higher amount of material upstream than downstream or vice versa
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- F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
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Abstract
Disclose (UF) three-way catalyst under the close coupling (CC) manufactured according to different material compositions and catalyst configuration and floor.CC catalyst and UF catalyst include the Rh compositions for providing the Fe activation of bigger catalysis.These CC catalyst and UF catalyst are integrated into engine system as the part of TWC converters, the part as the TWC systems for controlling and reducing engine exhaust emission.The conversion performance of these TWC systems is assessed and compared using the United States Federal's test program (FTP 75) and supplement FTP US06 agreements in turbine gasoline direct injection engine.Compared with the catalytic performance of original equipment manufacturer (OEM) catalyst based on high PGM used in TWC applications, these TWC systems show improved catalytic performance.
Description
Technical field
The present disclosure generally relates to three-way catalyst (TWC) system application, and relate more specifically to include being used to reduce coming
From the TWC systems of the Rh-Fe material compositions of the discharge of engine exhaust system.
Background technology
Three-way catalyst (TWC) system is located in the exhaust system of internal combustion type gas engine, to promote unburned carbon
The oxidation of hydrogen compound (HC) and carbon monoxide (CO), and reduce the nitrogen oxides (NO in exhaust streamX).For controlling/subtracting
Few HC, CO and NOXThere is complexity in antigravity system mainly due to (a) in the cost increase of the conventional TWC systems of discharge
Metallic compound group and (b) obtain the cost of the metal.
Catalyst in TWC systems usually contains platinum group metal (PGM), such as platinum (Pt), palladium (Pd) and rhodium (Rh) etc..
Pt and Pd is commonly used in the conversion of HC and CO, and Rh is to NOXReduction it is more effective.Although the price of Rh tends to fluctuate, its
NOXThe performance of higher makes Rh become most common element in TWC systems in conversion.
The growth trend that the PGM that having three factors influences to be used to reduce motor vehicle exhaust emission is consumed.First factor be with
The related automobile making of world population incremental portion is continuously increased, it is desirable to meets its people's transport need.Second factor is complete
The tightening of ball discharge standard, because government uses tightened up NOX, hydrocarbon and granular material discharged regulation.Pass through the U.S.
3 discharge standards of reinforcement Tier of Bureau for Environmental Protection (EPA) and the low emission vehicle (LEV for adding state Air Resources Board to implement
III) plan, in the U.S., the nearest revision to vehicular emission standards confirms this factor.3rd factor is current reduction two
The power of carbon emission is aoxidized, this uses steer motor manufacturer reduces engine exhaust temperature because engine thermal efficiency improves
The engine technology of degree.
Since the supply of PGM is limited, increase in demand may cause supply discontinuity, and PGM and rely on its peculiar property
The price of technology is excessive.Accordingly, it has been required to provide a kind of TWC systems, wherein the catalytic performance of the PGM of per unit mass is by most
Bigization and improved level of conversion is capable of providing, so as to cost-effectively realize discharge limitation.
The content of the invention
The present disclosure describes under the close coupling (CC) and floor manufactured according to different material compositions and catalyst configuration
(UF) three-way catalyst.In certain embodiments, PGM compositions include platinum (Pt), palladium (Pd), ruthenium (Ru), iridium (Ir) and rhodium
(Rh) itself or its use the combination of different loading amount.In an example, PGM compositions include individually or with Ba loading capacities
The about 10g/ft of combination3To about 100g/ft3In the range of Pd loading capacities.In another example, PGM compositions include individually
Or use Fe2O3The about 1g/ft of activation3To about 10g/ft3In the range of Rh loading capacities.
In certain embodiments, FTPUS06 (SFTP- are added according to the United States Federal's test program (FTP-75) and the U.S.
US06) test protocol, various TWC systems are constructed to assess its catalytic performance by measuring intermediate bed and tailpipe thing.
In these embodiments, TWC systems are configurable to include CC catalyst and UF catalyst or only include CC catalyst.Further to
These embodiments, being coupled to the TWC system mechanics constructed internal combustion engine, (such as, such as 4 type turbine gasoline of Tier 2bin is straight
Connect injection (TGDI) engine etc.) and it is in flow communication, for the discharge certification according to FTP-75 and SFTP-US06 agreements
Test.
In other embodiments, conventional TWC systems are configured with the commercially available original equipment manufacturer (OEM) based on high PGM
CC catalyst and OEM UF catalyst, which are used as, refers to antigravity system.In these embodiments, conventional TWC system mechanics ground coupling
Close for the substantially similar engine according to the above-mentioned TWC systems of FTP-75 and SFTP-US06 protocol tests and and its
It is in fluid communication.
In a further embodiment and before the emission test according to FTP-75 and SFTP-US06 agreements, use
Improved quick aging test (RAT) circulation agreement carries out aging to above-mentioned the CC catalyst and UF catalyst in TWC systems.
In these embodiments, CC catalyst using improved RAT circulation agreement aging about 50 is small under about 1000 DEG C of bed temperature when.Into one
Step for these embodiments, using improved RAT circulate agreement under about 900 DEG C of bed temperature UF catalyst aging about 50 is small
When.
In certain embodiments, according to FTP-75 and SFTP-US06 agreement assessments TWC systems intermediate bed and tailpipe
The catalytic efficiency (weighting bag result) of foregoing the CC catalyst and UF catalyst of measurement, and further with to the OEM based on high PGM
The weighting discharge for the amount that CC catalyst and UF catalyst are surveyed is compared.
In one embodiment, the present invention provides a kind of catalyst system for the exhaust stream for being used to handle combustion engine
System, including:Combustion engine;Close coupling catalytic converter, it is configured to receive at least one from the combustion engine
A exhaust stream, the close coupling catalytic converter include:
Base material;
Washcoat, it is covered on the substrate;
Subregion impregnates layer, it is impregnated into the washcoat, and subregion dipping layer includes the containing platinum group metal
One region and the second area containing platinum group metal, wherein, the loading capacity of the platinum group metal in the first area is less than
The loading capacity of the platinum group metal in the second area;And
External coating, it covers the subregion dipping layer and the rhodium comprising iron activation and the storage oxygen material based on rare earth element
Material.
In one embodiment, the platinum group metal in subregion dipping layer is selected from the group for including platinum, palladium, ruthenium, iridium and rhodium, and
It is preferred that palladium has about 10g/ft3To 100g/ft3, preferably from about 49g/ft3Loading capacity.
In one embodiment of the antigravity system of at least one or more section in first two sections, subregion dipping layer
Barium can also be included.
In one embodiment of the antigravity system of at least one or more section in above three sections, subregion leaching
The arrival end of the first area of stain layer towards catalytic converter is set, and the second area layer of subregion dipping is towards catalytic converter
The port of export is set.
In one embodiment of the antigravity system of at least one or more section in above four sections, the secondth area
The amount of platinum group metal in domain is about 2.5 to 4 times of the amount of the platinum group metal in first area.
In one embodiment of the antigravity system of at least one or more section in above five sections, the secondth area
The loading capacity of platinum group metal in domain is about 3 times of the loading capacity of the platinum group metal in first area.
In one embodiment of the antigravity system of at least one or more section in above six sections, external coating
Comprising with about 1 to 10g/ft3Loading capacity rhodium.
In one embodiment of the antigravity system of at least one or more section in above seven sections, external coating
Comprising with 4.25g/ft3Loading capacity rhodium.
In one embodiment of the antigravity system of at least one or more section in above seven sections, external coating
In gross weight of the amount based on external coating of iron be about 1 to 10 percentage by weight.
In one embodiment of the antigravity system of at least one or more section in above eight sections, external coating
The amount of middle iron is about 7 percentage by weights based on external coating gross weight.
In the antigravity system of at least one or more section in above nine sections, washcoat is included based on dilute
The hydrogen-storing material and support oxide of earth elements, the support oxide be selected from include aluminium oxide, doped aluminium, zirconium oxide,
Doped zirconia, cerium oxide, titanium oxide, niobium oxide, silica and the group of their combinations.
In one embodiment of the antigravity system of at least one or more section in above ten sections, doping
Support oxide doped with oxide, the oxide be selected from include calcium, strontium, barium, yttrium, lanthanum, neodymium, praseodymium, niobium, silicon, tantalum and they
The group of combination.
In one embodiment of the antigravity system of at least one or more section in above 11 sections, outer painting
Rare earth element in layer and washcoat, which is selected from, includes praseodymium, cerium, neodymium and the group of their combinations.
In one embodiment of the antigravity system of at least one or more section in above 12 sections, activation
Coating includes the aluminium oxide (La-Al of La doped2O3) and cerium-based oxygen storage material (Ce-based OSM).
In one embodiment of the antigravity system of at least one or more section in above 13 sections, this is
System can further include underfloor catalyst converter, the underfloor catalyst converter in the close coupling downstream catalytic converter and
It is in fluid communication with the close coupling catalytic converter, the underfloor catalyst converter includes:Base material;Washcoat, it is covered
On the substrate;Layer is impregnated, it is impregnated into the washcoat;And external coating, it includes iron activation rhodium and be based on
The hydrogen-storing material of rare earth element.
In one embodiment, the washcoat of underfloor catalyst converter include hydrogen-storing material based on rare earth element and
Support oxide, the support oxide be selected from include aluminium oxide, doped aluminium, zirconium oxide, doped zirconia, cerium oxide,
Titanium oxide, niobium oxide, silica and the group of their combinations.
In one embodiment, the support oxide of doping is doped with oxide, the oxide be selected from include calcium, strontium,
Barium, yttrium, lanthanum, neodymium, praseodymium, niobium, silicon, tantalum and the group of their combinations.
In one embodiment, the rare earth element in the external coating and washcoat of underfloor catalyst converter is selected from and includes
Praseodymium, cerium, neodymium and the group of their combinations.
In one embodiment, the washcoat of underfloor catalyst converter includes the aluminium oxide (La-Al of La doped2O3)
With cerium-based oxygen storage material (Ce-based OSM).
In one embodiment, impregnate layer and include the platinum group metal for being selected from the group for including platinum, palladium, ruthenium, iridium and rhodium, and it is excellent
Select palladium that there is about 10g/ft3To 100g/ft3Loading capacity, preferably from about 25.5g/ft3Loading capacity.
In one embodiment, dipping layer can also include barium.
In one embodiment, the external coating of underfloor catalyst converter, which includes, has about 1 to 10g/ft3Loading capacity
Rhodium.
In one embodiment, the external coating of underfloor catalyst converter, which includes, has about 4g/ft3Loading capacity rhodium.
In one embodiment, gross weight of the amount based on external coating of the iron in the external coating of underground catalytic converter is about
1 percentage by weight to 10 percentage by weights.
In one embodiment, gross weight of the amount based on external coating of the iron in the external coating of underfloor catalyst converter is
About 7 percentage by weights.
In one embodiment of the antigravity system of at least one or more section in the first two 12 section, base material
Including ceramics.
It can also relate to a kind of method for preparing catalytic converter in terms of claimed invention, it includes following step
Suddenly:
Washcoat is deposited on base material;
The first solution comprising platinum group metal is impregnated on the first area of the washcoat;
Roast the first area of the dipping of the washcoat and be impregnated into firstth area of the washcoat to limit
The first subregion dipping layer on domain;
The second solution comprising platinum group metal is impregnated on the second area of the washcoat;
Roast the second area of the dipping of the washcoat and be impregnated into secondth area of the washcoat to limit
The second subregion dipping layer on domain;
The overcoat layer on subregion dipping layer, wherein external coating include the rhodium of iron activation and the storage oxygen based on rare earth element
Material.
In one embodiment according to the last period, the platinum group metal in subregion dipping layer, which is selected from, includes platinum, palladium, ruthenium, iridium
With the group of rhodium.
In one embodiment of at least one or more section in first two sections, the platinum group metal in subregion dipping layer
It is that there is about 10g/ft3To 100g/ft3Loading capacity, preferably from about 49g/ft3Loading capacity palladium.
In one embodiment of at least one or more section in above three sections, subregion dipping layer also includes
Barium.
In one embodiment of at least one or more section in above four sections, subregion impregnates the firstth area of floor
The arrival end of domain towards catalytic converter is set, and the port of export of second area towards the catalytic converter of subregion dipping layer is set
Put.
In basis above one embodiment of at least one or more section of five sections, the platinum group metal in second area
Amount be about 2.5 to 4 times of amount of platinum group metal in first area.
In basis above one embodiment of at least one or more section of six sections, the platinum group metal in second area
Loading capacity be about 3 times of loading capacity of platinum group metal in first area.
According in above one embodiment of at least one or more section of seven sections, external coating include have about 1 to
10g/ft3Loading capacity rhodium.
According in above one embodiment of at least one or more section of eight sections, external coating includes about 4.25g/
ft3Rhodium loading capacity.
In one embodiment of at least one or more section in above nine sections, the amount base of the iron in external coating
In the gross weight of external coating be about 1 to 10 percentage by weight.
In one embodiment of at least one or more section in above ten sections, the amount base of the iron in external coating
In the gross weight of external coating be about 7 percentage by weights.
According in above one embodiment of at least one or more section of 11 sections, washcoat is included based on dilute
The hydrogen-storing material and support oxide of earth elements, the support oxide be selected from include aluminium oxide, doped aluminium, zirconium oxide,
Doped zirconia, cerium oxide, titanium oxide, niobium oxide, silica and the group of their combinations.
According in above one embodiment of at least one or more section of 12 sections, the support oxide of doping is used
Selected from including calcium, strontium, barium, yttrium, lanthanum, neodymium, praseodymium, niobium, silicon, tantalum and the group of their combinations.
In basis above one embodiment of at least one or more section of 13 sections, in external coating and washcoat
Rare earth element be selected from include praseodymium, cerium, neodymium and they combinations group.
In one embodiment of at least one or more section according to first 14 sections, washcoat includes the oxygen of La doped
Change aluminium (La-Al2O3) and cerium-based oxygen storage material (Ce-based OSM).
According to detailed description below in conjunction with the accompanying drawings, many other aspects, feature and the benefit of the disclosure can become aobvious
And it is clear to.
Brief description of the drawings
The disclosure may be better understood with reference to the following drawings.Component in attached drawing is not drawn necessarily to scale, but will
Focus in the principle of the explanation disclosure.In the accompanying drawings, corresponding part is represented through different views, reference numeral.
Fig. 1 is to show the three-way catalyst according to the embodiment for including (UF) catalyst under close coupling (CC) and floor
(TWC) functional block diagram of the construction of system.
Fig. 2 is the functional block diagram for showing the catalyst configuration based on PGM according to the embodiment for CC applications.
Fig. 3 is the functional block diagram for showing the catalyst configuration based on PGM according to the embodiment for UF applications.
Fig. 4 is shown according to catalytic performance of the embodiment for testing, measuring and diagnosing TWC systems as shown in Figure 1
The United States Federal's test program (FTP-75) driving phase diagram.
Fig. 5 is to show the catalytic according to the embodiment for being used to testing, measure and diagnosing TWC systems as shown in Figure 1
The diagram of the driving phase of U.S.'s supplement federal test program (SFTP-US06) of energy.
Fig. 6 is to show directly to be sprayed in turbine gasoline using the FTP-75 test protocols described in Fig. 4 according to embodiment
(TGDI) diagram of weighting CO (gram/mile) value at tail pipe (TP) place of the TWC systems 1,2 and 3 used in engine.
Fig. 7 is to show to be used in TGDI engines using FTP-75 test protocols as shown in Figure 4 according to embodiment
TWC systems 1,2 and 3 TP at Weighted N MHC (gram/mile) value diagram.
Fig. 8 is to show to be used in TGDI engines using FTP-75 test protocols as shown in Figure 4 according to embodiment
TWC systems 1,2 and 3 TP at Weighted N OXThe diagram of (gram/mile) value.
Fig. 9 is to show to be sent out in TGDI with given speed using FTP-75 test protocols as shown in Figure 4 according to embodiment
The outer NO of accumulation intermediate bed (MB) and engine of the TWC systems 1 and 3 used in motivationXThe diagram of emission result.
Figure 10 is to show to be sent out in TGDI with given speed using FTP-75 test protocols as shown in Figure 4 according to embodiment
Accumulation MB and the TP NO of the TWC systems 3 and 4 used in motivationXThe diagram of emission result.
Figure 11 is to show to use the SFTP-US06 test protocols described in Fig. 5 with given speed in TGDI according to embodiment
Accumulation MB and the TP NO of the TWC systems 1 and 3 used in engineXThe diagram of emission result.
Embodiment
The disclosure is described in detail with reference to the embodiment being shown in the drawings herein, attached drawing forms a part of this paper.
In the case where not departing from the scope of the present disclosure or spirit, other embodiments can be used and/or other modifications can be made.Tool
Illustrative embodiment described in body embodiment is not intended to limit presented theme.
Definition
As used herein, following term has defined below:
" roast and be calcined " refer in the presence of air be applied to solid material heat treatment process, with
Cause the removal of thermal decomposition, phase transformation or volatile part at a temperature of fusing point less than solid material.
" catalyst " refers to can be used for one or more materials in the conversion of one or more other materials.
" antigravity system " refers to include any system of at least two layers of catalyst, the catalyst include base material,
Washcoat and/or external coating.
" close coupling (CC) catalyst " refers to the catalyst close to enmgine exhaust.
" conversion " refers at least one materials chemistry changing over one or more other materials.
" federal test program (FTP) emission test " refers to the discharge authentication test program of U.S.'s light vehicle.
" dipping (IMP) " refers to be filled with liquid compound or is impregnated with solid layer or some elements is passed through medium or material
The process of diffusion.
" initial wetting (IW) " refers to be added to the solution of catalysis material in dry support oxide powder, Zhi Daozai
All pore volumes of oxide body are filled by solution and mixture is slightly close to saturation point.
" inlet region " refers to the position of the arrival end positioned at catalyst layer in catalyst, which is that exhaust gas initially enters
End, and terminate in the axial distance along catalyst layer towards the port of export, but extended distance is less than catalyst layer
Whole distance.
" grinding " refers to the operation that solid material is broken into required particle or granularity.
" non-methane hydro carbons (NMHC) " refers to the total of all hydrocarbon-air pollutants in addition to methane
With.
" original equipment manufacturer (OEM) " refers to the manufacturer of new vehicle or the original discharge for being installed on new vehicle certification
The manufacturer of any parts or component in control system.
" outlet area " refers to the position for the port of export for originating in catalyst layer, which is the end for discharging gas, and
And terminate at towards the axial distance above the catalyst layer of arrival end, but extend less than the whole distance of catalyst layer.
" external coating (OC) layer " refers to that at least one coating at least one washcoat or dipping layer can be deposited to
Catalyst layer.
" hydrogen-storing material (OSM) " refers to absorb oxygen from oxygen-enriched stream and oxygen further can be discharged into anoxic air-flow
In material.
" platinum group metal (PGM) " refers to platinum, palladium, ruthenium, iridium, osmium and rhodium.
" base material " refers to any shape or any material of construction, its generation is used for depositing activating coating and/or external coating
Enough surface areas.
" support oxide " refers to porosu solid oxide, is typically mixed-metal oxides, it is used to provide for high table
Area, this contributes to oxygen distribution and catalyst is exposed to reactant, such as NOX, CO and hydrocarbon.
" three-way catalyst (TWC) " refers to that performing nitrogen oxides at the same time is reduced to nitrogen and oxygen, is two by Oxidation of Carbon Monoxide
Carbonoxide and the catalyst by unburned oxidizing hydrocarbon for three tasks of carbon dioxide and water.
" (UF) catalyst under floor " refers to be attached to the catalyst in motor vehicle exhaustion system, it typically lies in vehicle
Below floor, in close coupling (CC) catalyst downstream mechanical couplings.
" washcoat (WC) layer " refers to the catalyst layer of at least one coating, it, which includes at least one, can be deposited on base material
On oxide solid.
Disclosed explanation
(UF) three-way catalyst under the close coupling (CC) produced according to various catalyst configurations and floor,
It includes the Rh compositions of Fe activation.These CC catalyst and UF catalyst are integrated into hair as the part of TWC converters
In motivation system, the part as the TWC systems for controlling and reducing engine exhaust emission.Use the United States Federal's test program
(FTP-75) these TWC are assessed and compared to agreement (2014) and the driving phase supplemented described in FTP US06 agreements (2014)
The conversion performance of system.Catalytic performance with original equipment manufacturer (OEM) catalyst based on high PGM applied for TWC
Compare, these TWC systems show improved catalytic performance.
TWC systems construct
Fig. 1 is to show the three-way catalyst according to the embodiment for including (UF) catalyst under close coupling (CC) and floor
(TWC) functional block diagram of the construction of system.In Fig. 1, engine system 100 includes engine 102 and TWC systems 104.TWC
System 104 further includes (UF) catalyst 108 under close coupling (CC) catalyst 106 and floor.As shown in Figure 1, the machinery of engine 102
It is coupled to TWC systems 104 and in flow communication.In TWC systems 104, CC catalyst 106 is mechanical coupling to UF catalyst
108 and connected with UF catalyst flows.
In certain embodiments, engine 102 may be implemented as the internal combustion engine used in motor vehicles, such as Tier
4 type turbine gasoline of 2bin directly sprays (TGDI) engine etc..In these embodiments, CC catalyst 106 and UF catalyst
108 are implemented as the catalyst based on PGM.Further to these embodiments, a variety of TWC systems can be configured to assessment and
Compare when catalytic performance when engine 102 is used together.
TWC systems 1
In certain embodiments, the TWC systems 104 for being referred to herein as TWC systems 1 are implemented as including based on height
Original equipment manufacturer's (OEM) the CC catalyst and OEM UF catalyst of PGM.In these embodiments, CC catalyst 106 is tool
There is about 98g/ft3Palladium (Pd) and about 8.50g/ft3The OEM CC catalyst based on high PGM of the PGM loading capacities of rhodium (Rh), causes
About 106.50g/ft3Total PGM loading capacities and with about 1.7L volume base material.Further to these embodiments, UF is urged
Agent 108 is that have about 51g/ft3Pd and about 8g/ft3The OEM UF catalyst based on high PGM of the PGM loading capacities of Rh, causes
About 59g/ft3Total PGM loading capacities and with about 1.3L volume base material.
TWC systems 2
In certain embodiments, the TWC systems 104 for being referred to herein as TWC systems 2 are implemented as including living with Fe
Change the CC catalyst (herein referred as 1 type CC catalyst) based on PGM of Rh loading capacities.In these embodiments, CC catalyst 106
It is 1 type CC catalyst, it includes about 49g/ft3Pd and use Fe2O3The about 4.25g/ft of activation3The PGM loading capacities of Rh, cause about
53.25g/ft3Total PGM loading capacities.
TWC systems 3
In certain embodiments, the TWC systems 104 for being referred to herein as TWC systems 3 are implemented as including as above existed
CC catalyst based on PGM described in TWC systems 2 and the Rh loading capacities with Fe activation based on PGM UF catalyst (
Herein referred to as 1 type UF catalyst).In these embodiments, UF catalyst 108 is 1 type UF catalyst, it is included about
25.5g/ft3Pd and use Fe2O3The about 4g/ft of activation3The PGM carrying capacity of Rh, causes about 29.50g/ft3Total PGM loading capacities.
TWC systems 4
In certain embodiments, the TWC systems 104 for being referred to herein as TWC systems 4 are implemented as including being based on PGM
CC catalyst (herein referred as 2 type CC catalyst) and UF catalyst (referred to herein as 2 type UF catalysis based on PGM
Agent).In these embodiments, CC catalyst 106 is 2 type CC catalyst, it includes about 49g/ft3Pd and about 4.25g/ft3Rh's
PGM loading capacities, cause about 53.25g/ft3Total PGM loading capacities.Further to these embodiments, UF catalyst 108 is 2 types
UF catalyst, it includes about 25.50g/ft3Pd and about 4g/ft3The PGM loading capacities of Rh, cause about 29.50g/ft3Total PGM add
Carrying capacity.
In certain embodiments, the TGDI that TWC systems 1,2,3 and 4 are mechanically coupled to for testing above-mentioned TWC systems is sent out
Motivation is simultaneously in flow communication.
The material composition of the PGM layers used in CC catalyst and UF catalyst
In certain embodiments, PGM compositions include platinum (Pt), palladium (Pd), ruthenium (Ru), iridium (Ir) and rhodium (Rh) itself,
Or it uses the combination of different loading amount.In an example, PGM compositions include the pact individually or with Ba loading capacities combined
10g/ft3To about 100g/ft3In the range of Pd loading capacities.In another example, PGM compositions are included individually or used
Fe2O3The about 1g/ft of activation3To about 10g/ft3In the range of Rh loading capacities.
CC catalyst configurations and manufacture
Fig. 2 is the functional block diagram for showing the catalyst configuration based on PGM according to the embodiment for CC applications.In Fig. 2
In, catalyst configuration 200 includes base material 202, washcoat (WC) layer 204, subregion dipping (ZIMP) layer 206 and external coating (OC)
Layer 208.As shown in Fig. 2, ZIMP layers 206 further include inlet region 210 and outlet area 212.In certain embodiments, 204 quilt of WC layers
It is coated on base material 202.In these embodiments, ZIMP layers 206 are impregnated on WC layers 204.Further to these embodiments,
OC layers 208 are applied on ZIMP layers 206.
In certain embodiments, 202 material of base material includes refractive material, ceramic material, honeycomb, metal material, pottery
Porcelain foam, metal foam, reticulated foam or suitable combination etc..In these embodiments, WC layers 204 are implemented as carrier oxygen
The mixture of compound and hydrogen-storing material (OSM) based on rare earth (RE) metal.Further to these embodiments, ZIMP layers 206
It is implemented as the PGM compositions combined individually or with Ba loading capacities.Further for these embodiments, OC layers 208 are by reality
Apply as metallization to the PGM compositions on the base metal oxide being deposited on RE metals-OSM.
In certain embodiments, support oxide includes aluminium oxide (Al2O3), doping Al2O3, zirconium oxide (ZrO2), mix
Miscellaneous ZrO2、CeO2、TiO2、Nb2O5、SiO2Or its mixture etc..In these embodiments, mixing in the support oxide of doping
Miscellaneous material includes Ca, Sr, Ba, Y, La, Ce, Nd, Pr, Nb, Si or Ta oxide etc..Further to these embodiments, it is based on
The OSM of RE includes Pr, Ce and Nd or its mixture etc..
In the first example, manufacture is herein referred as the CC catalyst of 1 type CC catalyst, it includes ceramic base material, such as
600/3 1.7L base materials, its diameter (D) are 118.4mm, and length (L) is 153.9mm.In this example, adulterated comprising La for WC layers
Al2O3With the mixture of Ce bases OSM.Further to the example, ZIMP layers include about 12.43g/ft3Pd loading capacities enter
Mouth region and the about 36.57g/ft with Ba loading capacities3Pd loading capacities outlet area, each region is impregnated into WC layers of dependent part
On point.Further to the example, OC layers are used Fe comprising being deposited on Ce bases OSM2O3The about 4.25g/ft of activation3Rh add
Carrying capacity.
In this example, the preparation for the WC layers of 1 type CC catalyst starts from preparation and includes with a variety of ratios (such as 1:1
Weight ratio) mixing La doping Al2O3With the mixture of Ce bases OSM.Further to the example, the Al that La is adulterated2O3With
The mixture water of Ce bases OSM is ground to produce the Al of La doping2O3With the slurry of Ce bases OSM.Further for the example,
The Al of La doping2O3Then be applied to the slurry of Ce bases OSM on base material, and at about 550 DEG C further roasting about 4 it is small when
To produce WC layers.
In this example, the manufacture for the ZIMP layers of 1 type CC catalyst, which starts from, is prepared separately about 12.43g/ft3Pd's
PGM loading capacities and with about 0.55M Ba loading capacities about 36.57g/ft3The nitric acid Pd solution of the PGM loading capacities of Pd, respectively
For inlet region and outlet area.Further to the example, by the first nitric acid Pd solution (12.43g/ft3) it is impregnated into a part
To manufacture inlet region on WC layers, then roasted at about 550 DEG C about 4 it is small when, to manufacture inlet region IMP layers in ZIMP layers.Again
Further to the example, by the second nitric acid Pd solution (36.57g/ft3) be impregnated on WC layers another part to produce outlet
Area.In this embodiment, after Pd is immersed in WC layers of dorsal area, roasted at about 550 DEG C about 4 it is small when to manufacture
ZIMP layers.
In this example, the manufacture for the OC layers of 1 type CC catalyst starts from the preparation of base metal nitrate solution.Into one
For step for the example, base metal nitrate solution is embodied as nitric acid Fe solution.Further to the example, pass through initial wetting
(IW) nitric acid Fe solution is added dropwise to Ce base OSM powder, this method and uses about 1 percentage by weight to about 10 weight hundred by method
Divide the Fe loading capacities of ratio, it is preferred to use the Fe loading capacities of 7.37 percentage by weights.In this example, the Ce bases then adulterated Fe
OSM is dried overnight at 120 DEG C, and within the temperature range of about 600 DEG C to about 800 DEG C, preferably at a temperature of about 750 DEG C into
When one one-step baking about 5 is small.Further to the example, then by Fe2O3Fine powder is worn into the calcined material of Ce bases OSM, is gone forward side by side
One step water is ground to manufacture Fe2O3The slurry of/Ce bases OSM.Further to the example, with nitric acid Rh solution metals
Fe2O3The slurry of/Ce bases OSM has about 4.25g/ft to produce3The slurry of the Fe activation Rh and Ce bases OSM of the PGM loading capacities of Rh
Material.In this example, the slurry of Fe activation Rh and Ce bases OSM is coated on ZIMP layers, and be further dried and about 550
Roasted at a temperature of DEG C about 4 it is small when to manufacture 1 type CC catalyst.
In the second example, manufacture is herein referred as the CC catalyst of 2 type CC catalyst, it includes ceramic base material, such as
600/3 1.7L base materials, its diameter (D) are 118.4mm, and length (L) is 153.9mm.In this example, as described above, WC layers of bag
The Al of the doping containing La2O3With the mixture of Ce bases OSM.Further to the example, ZIMP layers include about 12.43g/ft3Pd add
The inlet region of carrying capacity and the about 36.57g/ft with Ba loading capacities3Pd loading capacities outlet area, each region is soaked as described above
Stain is to WC layers of relevant portion.Further to the example, OC layers include the about 4.25g/ft being deposited on Ce bases OSM3Rh
Loading capacity.
In this example, for 2 type CC catalyst WC layers and ZIMP layers of manufacture with above to 1 type CC catalyst institute
The substantially similar mode stated carries out.Further to the example, the preparation of the OC layers of 2 type CC catalyst, which starts from preparation, to be had about
4.25g/ft3The nitric acid Rh solution of the PGM loading capacities of Rh.Further for the example, Ce base OSM powder is individually ground simultaneously
With nitric acid Rh solution metals to produce the slurry of Rh/Ce bases OSM.In this embodiment, the slurry of Rh/Ce bases OSM is coated
Onto ZIMP layers, and be further dried and roasted at a temperature of about 550 DEG C about 4 it is small when to manufacture 2 type CC catalyst.
UF catalyst configurations and manufacture
Fig. 3 is the functional block diagram for showing the catalyst configuration based on PGM according to the embodiment for UF applications.In Fig. 3
In, catalyst configuration 300 includes base material 202, WC layers 204, dipping (IMP) layer 302 and OC layers 208.In certain embodiments, WC
Layer 204 is applied on base material 202.In these embodiments, IMP layers 302 are impregnated on WC layers 204.Further to these
Embodiment, OC layers 208 are applied on IMP layers 302.In figure 3, there is the member of the element number substantially similar with foregoing figures
Part works in a substantially similar manner.In certain embodiments, IMP layers 302 are implemented as the PGM groups combined with Ba loading capacities
Compound.
In the 3rd example, manufacture UF catalyst (referred to herein as 1 type UF catalyst), it includes ceramic base material, such as
400/3 1.3L base materials, its diameter (D) are 118.4mm, and length (L) is 118.0mm.In this example, as described above, WC layers of bag
The Al of the doping containing La2O3With the mixture of Ce bases OSM.Further to the example, IMP layers include the pact with Ba loading capacities
25.5g/ft3Pd loading capacities.Further for the example, as described above, the OC layers of use for including being deposited on Ce bases OSM
Fe2O3The about 4g/ft of activation3Rh loading capacities.
In this example, for 1 type UF catalyst WC layers and OC layers of manufacture with it is previous with above to 1 type CC catalyst
The substantially similar mode carries out.Further to the example, IMP layers of manufacture starts from the Ba loads prepared with about 0.5M
The about 25.50g/ft of amount3The nitric acid Pd solution of the PGM loading capacities of Pd.Further for the example, by nitric acid Pd+Ba solution
Be impregnated on WC layers, and further roast at about 550 DEG C about 4 it is small when to manufacture IMP layers.
In the 4th example, manufacture is referred to herein as the UF catalyst of 2 type UF catalyst, it includes ceramic base material, example
Such as 400/3 1.3L base materials, its diameter (D) is 118.4mm, and length (L) is 118.0mm.In this example, as it was noted above, WC
Layer includes the Al of La doping2O3With the mixture of Ce bases OSM.Further to the example, as described above, IMP layers include and have Ba
The about 25.5g/ft of loading capacity3Pd loading capacities.Further to the example, as it was noted above, OC layers include and are deposited on Ce bases
About 4g/ft on OSM3Rh loading capacities.
In this embodiment, for 2 type UF catalyst WC layers and OC layers of manufacture with above for 2 type CC catalyst
The substantially similar mode carries out.Further to the example, for 2 type UF catalyst IMP layers with described previously for 1
Substantially similar mode described in type UF catalyst carries out.
The aging of CC catalyst and UF catalyst and test condition
In certain embodiments, before the emission test according to FTP-75 and SFTP-US06, using improved quick old
Change test (RAT) circulation agreement and aging is carried out to above-mentioned the CC catalyst and UF catalyst in TWC systems 1,2,3 and 4.At these
In embodiment, using improved RAT circulation agreement it is small to CC catalyst aging about 50 under about 1000 DEG C of bed temperature when.Further
For these embodiments, using improved RAT circulate agreement under about 900 DEG C of bed temperature by UF catalyst aging about 50 it is small when.
The United States Federal's test program (FTP-75)
Fig. 4 is illustrated according to catalytic performance of the embodiment for testing, measuring and diagnosing TWC systems as described in Figure 1
The diagram of the driving phase of the United States Federal's test program (FTP-75).In Fig. 4, FTP-75 agreements 400 include cold-start phase
402nd, stabilization sub stage 404 and thermal starting stage 406.
In certain embodiments, cold-start phase 402 shows the intermediate bed for measuring above-mentioned TWC systems and tail pipe row
Put the stage of the FTP-75 tests of thing and performance.In these embodiments, the driving phase is when from about 0 to 505 second
Between section perform about 20 DEG C to about 30 DEG C of environment temperature under cold start-up transient phases.Further to these embodiments, surely
Determine the stage that the stage 404 shows the riving condition from about 506 seconds to about 1372 seconds performed after cold-start phase 402.
Further to these embodiments, after the stabilization sub stage 404 terminates, engine stop about 10 minutes and then thermal starting stage
406 start.In these embodiments, the thermal starting stage 406 shows the following two sections of driving performed after the stabilization sub stage 404
Condition:(1) about 540 seconds shortest time section or about 660 seconds maximum duration section perform hot dipping, and (2) from zero to
The thermal starting transient phases performed in the period of about 505 seconds.Further to these embodiments, by each stage
Between bed and tailpipe thing collect in single bag, analyze and represented with gram/mile.
U.S. supplement FTP US06
Fig. 5 is shown according to catalytic performance of the embodiment for testing, measuring and diagnosing TWC systems as described in Figure 1
The diagram of the driving phase of U.S.'s supplement federal test program (SFTP-US06).In Figure 5, SFTP-US06 agreements 500 include
First city stage 502,504 and second city stage 506 of highway stage.
In certain embodiments, SFTP-US06 test loops are solved drives radical, high speed and/or high acceleration
Behavior is sailed, in terms of the expression of the driving behavior after quick velocity perturbation and startup the shortcomings that FTP-75 test loops.
In these embodiments, SFTP-US06 test loops are related to the speed of the rate of acceleration and higher than other regular authentications circulation higher
(up to 80MPH).Further to these embodiments, SFTP-US06 test loops include being designated as " city " and " public at a high speed
Multiple stages on road ".Further to these embodiments, the SFTP-US06 cities stage be in whole test loop starting and
The combination of the two sseparated sections (the first city stage 502 and the second city stage 506) occurred at end, and be included in
Typical multiple acceleration and deceleration in city driving.In these embodiments, SFTP-US06 highways stage (the highway stage 504)
The prolonged uninterrupted driving being included among the test loop that simulation interstate highway drives.Further to these implementations
Example, the intermediate bed from each stage and tailpipe thing are collected in single bag, analyze and represented with gram/mile.
In certain embodiments, SFTP-US06 test loops are the high speed/quick acceleration circulations for lasting about 596 seconds, with about
The average speed of 48.4 miles per hours (77.9km/h) covers the distance of about 8.01 miles (13km), reach about 80.3 miles/it is small
When (129.2km/h) maximal rate.In these embodiments, SFTP-US06 test loops include four stoppings and with every
The quick acceleration of the speed of second about 8.46mph (13.62km/h).Further to these embodiments, when progress SFTP-US06 surveys
During examination circulation, test engine, and without using air-conditioning at operating temperatures.Further to these embodiments, SFTP- is carried out
Environment temperature (30 DEG C) changes from about 68 ℉ (20 DEG C) to about 86 ℉ during US06 test loops.
For performing the engine specifications of test loop
It is implemented with electronically controlled bi-turbo in certain embodiments and with reference to Fig. 1, engine 102
TGDI engines, Dual Over Head Camshaft (DOHC) engine with continuous variable valve timing, use in DOHC engines
The high pressure fuel pump of actuated by cams, which performs, directly to be sprayed.In these embodiments, TGDI engines include two-stage variable discharge capacity oil
Pump, air-air ICS intercooler system and cast aluminium engine cylinder body.The main specifications of TGDI engines is as shown in table 1 below.
Table 1.TGDI engine specifications.
Specification | Unit | Value |
Displacement | cm3 | 1,998.0 |
Compression ratio | 9.5:1 | |
Peak torque | lb-ft | 295.0@3,000-4,000rpm |
Power | HP | 259.0 |
Weighting drain bag result from FTP-75 tests
Fig. 6 is to show directly to be sprayed in turbine gasoline using the FTP-75 test protocols described in Fig. 4 according to embodiment
(TGDI) the weighting CO (gram/mile) at tail pipe (TP) place of the TWC systems 1,2 and 3 used in engine.In figure 6, TP is weighted
CO discharges 600 include TWC systems 1TP weightings CO 602, TWC systems 2TP weighting CO 610 and TWC systems 3TP weightings CO618.
In certain embodiments, TWC systems 1TP, which weights CO 602, includes the specific TP weightings CO bars of following three:TP adds
Weigh CO bars 604, TP weighting CO bars 606 and TP weighting CO bars 608.In these embodiments, each CO bars are shown as measurement and TWC
The weighting CO's in the cold-start phase, stabilization sub stage and the thermal starting stage that are obtained respectively during the TP CO discharges that system is associated
FTP-75 bags of results (gram/mile).In an example, each CO bars show measuring the TP CO associated with TWC systems 1
The FTP-75 bags knot of the weighting CO in cold-start phase 402, stabilization sub stage 404 and the thermal starting stage 406 obtained respectively during discharge
Fruit (gram/mile).
In other embodiments, TWC systems 2TP, which weights CO 610, includes the specific TP weightings CO bars of following three:TP adds
Weigh CO bars 612, TP weighting CO bars 614 and TP weighting CO bars 616.In another example, each CO bars are shown as measurement and TWC
Cold-start phase 402, stabilization sub stage 404 and the thermal starting stage 406 that the associated TPCO of system 2 is obtained respectively when discharging add
Weigh the FTP-75 bag results (gram/mile) of CO.
In a further embodiment, TWC systems 3TP, which weights CO 618, includes the specific TP weightings CO of following three
Bar:TP weighting CO bars 620, TP weighting CO bars 622 and TP weighting CO bars 624.In another example, each CO bars are shown when survey
Cold-start phase 402, stabilization sub stage 404 and the thermal starting rank that the amount TP CO associated with TWC systems 3 is respectively obtained when discharging
The FTP-75 bag results (gram/mile) of the weighting CO of section 406.
In certain embodiments, the execution FTP- associated with TWC systems 1,2 and 3 is described in detail in following table 2
The TP weighting CO discharges (gram/mile) collected during 75 tests.In these embodiments, compared with TWC systems 1, TWC systems 2
Show that relatively low TP weights CO values with 3.Further to these embodiments, including 1 type CC type catalyst (53.25g/
ft3PGM loading capacities) 2 ratio of TWC systems include OEM CC catalyst and UF catalyst (165.5g/ft3PGM loading capacities) TWC
System 1 shows more efficient TP CO conversion ratios.These results demonstrate that CC1 type catalyst provides improved CO conversion ratios,
Thus dual catalyst TWC systems (such as TWC systems 1) are reduced into single catalyst (such as TWC systems 2).
The TP weighting CO discharge value associated with TWC systems 1,2 and 3 as shown in Figure 6 of table 2.
Fig. 7 is to show to be used in TGDI engines using FTP-75 test protocols as described in Figure 4 according to embodiment
The diagram of Weighted N MHC (gram/mile) value at the TP of TWC systems 1,2 and 3.In the figure 7, TP Weighted Ns MHC discharges 700 include
TWC system 1TP Weighted Ns MHC 702, TWC system 2TP Weighted Ns MHC 710 and TWC system 3TP Weighted Ns MHC 718.
In certain embodiments, TWC systems 1TP Weighted Ns MHC 702 includes three following specific TP Weighted Ns MHC bars:
TP Weighted N MHC bars 704, TP Weighted N MHC bars 706 and TP Weighted N MHC bars 708.In these embodiments, each NMHC bars show
Go out cold-start phase, stabilization sub stage and the thermal starting rank obtained respectively when measuring the TP NMHC associated with TWC systems and discharging
The FTP-75 bag results (gram/mile) of the Weighted N MHC of section.In an example, each NMHC bars are shown in measurement and TWC systems
Cold-start phase 402, stabilization sub stage 404 and the thermal starting stage 406 that the associated TP NMHC of system 1 are obtained respectively when discharging
The FTP-75 bag results (gram/mile) of Weighted N MHC.
In other embodiments, TWC systems 2TP Weighted Ns MHC 710 includes three following specific TP Weighted Ns MHC bars:
TP Weighted N MHC bars 712, TP Weighted N MHC bars 714 and TP Weighted N MHC bars 716.In another example, each NMHC bars are shown
Cold-start phase 402, stabilization sub stage 404 and the heat obtained respectively when measuring the TP NMHC associated with TWC systems 2 and discharging
The FTP-75 bag results (gram/mile) of the Weighted N MHC of startup stage 406.
In a further embodiment, TWC systems 3TP Weighted Ns MHC 718 includes three following specific TP Weighted Ns MHC
Bar:TP Weighted N MHC bars 720, TP Weighted N MHC bars 722 and TP Weighted N MHC bars 724.In another example, each NMHC bars
Cold-start phase 402, the stabilization sub stage 404 obtained respectively when measuring the TP NMHC associated with TWC systems 3 and discharging is shown
With the FTP-75 bag results (gram/mile) of the Weighted N MHC in thermal starting stage 406.
In certain embodiments, the implementation FTP- associated with TWC systems 1,2 and 3 is described in detail in following table 3
The TP Weighted Ns MHC discharges (gram/mile) collected during 75 tests.In these embodiments, TWC systems 2 and 3 are shown substantially
Similar NMHC level of conversion.Further to these embodiments, compared with TWC systems 2 and 3, TWC systems 1 show lower
TP Weighted N MHC values.Further to these embodiments, marked when with being discharged for the U.S. Tier 2bin 3 of light duty engine
When (NMHC=0.055 grams/mile) of standard is compared, TWC systems 2 and 3 show lower TP Weighted N MHC values.
The TP Weighted N MHC discharge value associated with TWC systems 1,2 and 3 as shown in Figure 7 of table 3.
The FTP-75 stages | TWC systems | TP Weighted Ns MHC (gram/mile) | Coherent element |
Cold-start phase 402 | 1 | 0.022 | 704 |
Stabilization sub stage 404 | 1 | 0.004 | 706 |
The thermal starting stage 406 | 1 | 0.002 | 708 |
Cold-start phase 402 | 2 | 0.034 | 712 |
Stabilization sub stage 404 | 2 | 0.003 | 714 |
The thermal starting stage 406 | 2 | 0.006 | 716 |
Cold-start phase 402 | 3 | 0.037 | 720 |
Stabilization sub stage 404 | 3 | 0.002 | 722 |
The thermal starting stage 406 | 3 | 0.004 | 724 |
Fig. 8 is to show to be used in TGDI engines using FTP-75 test protocols as described in Figure 4 according to embodiment
Weighted N O at the TP of TWC systems 1,2 and 3XThe diagram of (gram/mile) value.In fig. 8, TP Weighted Ns OXDischarge 800 includes TWC
System 1TP Weighted Ns OX802nd, TWC systems 2TP Weighted Ns OX810 and TWC system 3TP Weighted Ns OX 818。
In certain embodiments, TWC systems 1TP Weighted Ns OX802 include the specific TP Weighted Ns O of following threeXBar:TP adds
Weigh NOXBar 804, TP Weighted Ns OXBar 806 and TP Weighted Ns OXBar 808.In these embodiments, each NOXBar show when measurement with
The TP NO that TWC systems are associatedXThe Weighted N O in the cold-start phase, stabilization sub stage and the thermal starting stage that are respectively obtained during dischargeX
FTP-75 bag results (gram/mile).In an example, each NOXBar is shown as the measurement TP associated with TWC systems 1
NOXThe Weighted N O in the cold-start phase 402, stabilization sub stage 404 and the thermal starting stage 406 that are obtained respectively during dischargeXFTP-75 bags
As a result (gram/mile).
In other embodiments, TWC systems 2TP Weighted Ns OX810 include three following specific TP Weighted Ns OXBar:TP adds
Weigh NOXBar 812, TP Weighted Ns OXBar 814 and TP Weighted Ns OXBar 816.In another example, each NOXBar show when measurement with
The associated TP NO of TWC systems 2XCold-start phase 402, stabilization sub stage 404 and the thermal starting stage obtained respectively during emission
406 Weighted N OXFTP-75 bag results (gram/mile).
In a further embodiment, TWC systems 3TP Weighted Ns OX818 include three following specific TP Weighted Ns OXBar:
TP Weighted Ns OXBar 820, TP Weighted Ns OXBar 822 and TP Weighted Ns OXBar 824.In another example, each NOXBar is shown when survey
The amount TP NO associated with TWC systems 3XCold-start phase 402, stabilization sub stage 404 and the thermal starting rank obtained respectively during discharge
The Weighted N O of section 406XFTP-75 bag results (gram/mile).
In certain embodiments, the execution FTP-75 associated with TWC systems 1,2 and 3 is described in detail in table 4 below to survey
The TP Weighted Ns O collected during examinationXDischarge (gram/mile).In these embodiments, compared with TWC systems 1 and 2, TWC systems 3
Show lower TP Weighted Ns OXValue.Further to these embodiments, TWC systems 1 and 2 show substantially similar NOXTurn
Change level, so as to confirm to use only 1 type CC catalyst (53.25g/ft3PGM loading capacities) with use the OEM based on high PGM
CC catalyst and UF catalyst (165.50g/ft3PGM loading capacities) carry out NOXConversion is equally effective.
The TP Weighted N O associated with TWC systems 1,2 and 3 as shown in Figure 8 of table 4.XDischarge value
The FTP-75 stages | TWC systems | TP Weighted Ns OX(gram/mile) | Coherent element |
Cold-start phase 402 | 1 | 0.033 | 804 |
Stabilization sub stage 404 | 1 | 0.001 | 806 |
The thermal starting stage 406 | 1 | 0.005 | 808 |
Cold-start phase 402 | 2 | 0.032 | 812 |
Stabilization sub stage 404 | 2 | 0.003 | 814 |
The thermal starting stage 406 | 2 | 0.005 | 816 |
Cold-start phase 402 | 3 | 0.019 | 820 |
Stabilization sub stage 404 | 3 | 0.001 | 822 |
The thermal starting stage 406 | 3 | 0.001 | 824 |
In short, the catalysis behavior that TWC systems 2 are shown during each FTP-75 stages is with using the TWC based on high PGM
System 1 equally effectively confirms significant NOX, CO and NMHC conversion performances.1 type CC catalyst causes the feelings in TWC systems 2
There is improved conversion performance, 1 type CC catalyst includes containing about 4.25g/ft under condition3The Rh combinations of the Fe activation of Rh loading capacities
The OC layers of thing.
Fig. 9 is to show using FTP-75 test protocols as described in Figure 4 with given speed in TGDI to be started according to embodiment
The outer NO of accumulation intermediate bed (MB) and engine of the TWC systems 1 and 3 used in machineXThe diagram of emission result.In fig.9, accumulate
NOXBeing worth comparison curves 900 includes accumulation NOXCurve 902, accumulation NOXCurve 904, accumulation NOXCurve 906, accumulation NOXCurve 908
With FTP-75 agreements 400.In fig.9, there is the element to element number that foregoing figures are substantially similar with substantially similar side
Formula works.
In certain embodiments, NO is accumulatedXCurve 902 is shown under given speed in the MB associated with TWC systems 1
Locate the accumulation NO obtainedXEmission result.In these embodiments, NO is accumulatedXCurve 904 show under given speed with TWC systems
The accumulation NO obtained at the associated MB of system 3XEmission result.Further to these embodiments, with accumulating NOXCurve 902 and tired
Product NOXThe scale edge accumulation NO that the relative value of curve 904 is associatedXIt is worth the y-axis positioning on the right side of comparison curves 900, and is labeled
NO is accumulated for intermediate bedXDischarge (g).In these embodiments, NO is accumulatedXCurve 906 show under given speed with TWC systems 1
The accumulation NO that outer (pre-catalyst) place of associated engine obtainsXEmission result.Further to these embodiments, NO is accumulatedX
Curve 908 shows outside associated with TWC systems 3 engine under given speed the accumulation NO that (pre-catalyst) place obtainsX
Emission result.Further to these embodiments, with accumulating NOXCurve 906 and accumulation NOXWhat the relative value of curve 908 was associated
Scale edge accumulation NOXIt is worth the y-axis positioning on the left side of comparison curves 900, and is labeled as EOUT(g accumulations), speed (mile).
In certain embodiments, the accumulation MB NO associated with TWC systems 3XValue (accumulation NOXCurve 904) it is substantially less than
The accumulation MB NO associated with TWC systems 1XValue (accumulation NOXCurve 902).In these embodiments, MB NOXDischarge (accumulation
NOXCurve 904) in improvement show that compared with the OEM CC catalyst based on PGM, 1 type CC catalyst shows urging for bigger
Change function.Further to these embodiments, TWC systems 3 reduce accumulation MB NO by using the PGM for reducing 50%XValue.
Further to these embodiments, NO outside the accumulation engine associated with TWC systems 1 and 3XDischarge shows substantially similar
It is horizontal.In short, TWC systems 3 show the NO than 1 higher of TWC systemXTransformation efficiency.
Figure 10 is to show using FTP-75 test protocols as described in Figure 4 with given speed in TGDI to be started according to embodiment
Accumulation MB and the TP NO of the TWC systems 3 and 4 used in machineXThe diagram of emission result.In Fig. 10, NO is accumulatedXIt is worth comparison curves
1000 include accumulation NOXCurve 1002, accumulation NOXCurve 1004, accumulation NOXCurve 1006, accumulation NOXCurve 1008 and FTP-
75 agreements 400.In Fig. 10, there is the element work in a substantially similar manner of substantially similar element number with attached drawing above
Make.
In certain embodiments, NO is accumulatedXCurve 1002 is shown under given speed in the MB associated with TWC systems 4
Locate the accumulation NO obtainedXEmission result.In these embodiments, NO is accumulatedXCurve 1004 show under given speed with
The accumulation NO obtained at the associated TP of TWC systems 4XEmission result.Further to these embodiments, NO is accumulatedXCurve 1006
Show the accumulation NO obtained under given speed at the MB associated with TWC systems 3XEmission result.Further to this
A little embodiments, accumulate NOXCurve 1008 shows the accumulation obtained under given speed at the TP associated with TWC systems 3
NOXEmission result.
In certain embodiments, the accumulation MB NO associated with TWC systems 3XValue (accumulation NOXCurve 1006) it is substantially less than
The accumulation MB NO associated with TWC systems 4XValue (accumulation NOXCurve 1002).In these embodiments, it is related to TWC systems 3
The accumulation TP NO of connectionXValue (accumulation NOXCurve 1008) it is substantially less than the accumulation TP NO associated with TWC systems 4XValue (accumulation
NOXCurve 1004).Further to these embodiments, the accumulative MB and TP NO associated with TWC systems 3XDischarge shows base
This similar level (accumulation NOXCurve 1006 and accumulation NOXCurve 1008).Further to these embodiments, TWC systems 3 exist
Improved NO is shown under the space velocity (for example, second of acceleration in the massif 2 of about 20,000 seconds) of higherXConversion.
In short, TWC systems 3 have the NO of higher than TWC system 4XTransformation efficiency.
Inclusion fruit is discharged in weighting from SFTP-US06 tests
Figure 11 is to show to use the SFTP-US06 test protocols described in Fig. 5 with given speed in TGDI according to embodiment
Accumulation MB and the TP NO of the TWC systems 1 and 3 used in engineXThe diagram of emission result.In fig. 11, NO is accumulatedXValue compares
Curve 1100 includes accumulation NOXCurve 1102, accumulation NOXCurve 1104, accumulation NOXCurve 1106, accumulation NOX1108 He of curve
SFTP-US06 agreements 500.In fig. 11, there is the element of substantially similar element number with substantially similar to attached drawing above
Mode work.
In certain embodiments, NO is accumulatedXCurve 1102 is shown at associated with TWC systems 1 MB under given speed
The accumulation NO of acquisitionXEmission result.In these embodiments, NO is accumulatedXCurve 1104 show under given speed with TWC systems
The accumulation NO obtained at the associated TP of system 1XEmission result.Further to these embodiments, NO is accumulatedXCurve 1106 is shown
The accumulation NO obtained under given speed at the MB associated with TWC systems 3XEmission result.Further to these realities
Example is applied, accumulates NOXCurve 1108 shows the accumulation NO obtained under given speed at the TP associated with TWC systems 3XDischarge
As a result.
In certain embodiments, the accumulation MB NO associated with TWC systems 3XValue (accumulation NOXCurve 1106) it is substantially less than
The accumulation MB NO associated with TWC systems 1XValue (accumulation NOXCurve 1102).In these embodiments, MB NOXDischarge (accumulation
NOXCurve 1106) in improvement show that compared with the OEM CC catalyst based on PGM, 1 type CC catalyst shows bigger
Catalysis.Further to these embodiments, TWC systems 3 reduce accumulation MB NO by using 50% less PGMX
Value.Further to these embodiments, the accumulation TP NO associated with TWC systems 3XValue (accumulation NOXCurve 1108) be less than with
The associated accumulation TP NO of TWC systems 1XValue (accumulation NOXCurve 1104).In short, TWC systems 3 are shown than TWC system 1 more
High NOXTransformation efficiency.
Although having been disclosed for various aspects and embodiment, it is contemplated that other side and embodiment.It is disclosed herein
Various aspects and embodiment be to be for the purpose of illustration, rather than restricted, real scope and spirit are by following right
Claim is pointed out.
Claims (45)
1. a kind of antigravity system for the exhaust stream for being used to handle combustion engine, including:
Combustion engine;
Close coupling catalytic converter, it is configured to receive at least one exhaust stream from the combustion engine, described tight
Coupled catalytic converter includes:
Base material;
Washcoat, it is covered on the substrate;
Subregion impregnates layer, it is impregnated into the washcoat, and the subregion dipping floor includes the firstth area containing platinum group metal
Domain and the second area containing platinum group metal, wherein, the loading capacity of the platinum group metal in the first area is less than described
The loading capacity of the platinum group metal in second area;And
External coating, it covers the subregion dipping layer and the rhodium comprising iron activation and the hydrogen-storing material based on rare earth element.
2. antigravity system according to claim 1, wherein, the platinum group metal in the subregion dipping layer is selected from bag
Include the group of platinum, palladium, ruthenium, iridium and rhodium.
3. antigravity system according to any one of the preceding claims, wherein, the platinum in the subregion dipping layer
Race's metal is that have about 10g/ft3To 100g/ft3Loading capacity palladium.
4. antigravity system according to any one of the preceding claims, wherein, the platinum in the subregion dipping layer
Race's metal is that have about 49g/ft3Loading capacity palladium.
5. antigravity system according to any one of the preceding claims, wherein, the subregion dipping layer also includes barium.
6. antigravity system according to any one of the preceding claims, wherein, described the first of the subregion dipping layer
The arrival end of region towards the catalytic converter is set, and the second area of subregion dipping layer is urged described in
The port of export for changing converter is set.
7. antigravity system according to any one of the preceding claims, wherein, the platinum family in the second area
The amount of metal is about 2.5 to 4 times of the amount of the platinum group metal in the first area.
8. antigravity system according to any one of the preceding claims, wherein, the platinum family in the second area
The loading capacity of metal is about 3 times of the loading capacity of the platinum group metal in the first area.
9. antigravity system according to any one of the preceding claims, wherein, the external coating include have about 1 to
10g/ft3Loading capacity rhodium.
10. antigravity system according to any one of the preceding claims, wherein, the external coating, which includes, to be had about
4.25g/ft3Loading capacity rhodium.
11. antigravity system according to any one of the preceding claims, wherein, the amount of the iron in the external coating is based on
The gross weight of the external coating is about 1 percentage by weight to 10 percentage by weights.
12. antigravity system according to any one of the preceding claims, wherein, the amount of the iron in the external coating is based on
The gross weight of the external coating is about 7 percentage by weights.
13. antigravity system according to any one of the preceding claims, wherein, the washcoat includes and is based on rare earth
The hydrogen-storing material and support oxide of element, the support oxide, which is selected from, to be included aluminium oxide, doped aluminium, zirconium oxide, mixes
Miscellaneous zirconium oxide, cerium oxide, titanium oxide, niobium oxide, silica and the group of their combinations.
14. antigravity system according to claim 13, wherein, the support oxide of doping is described doped with oxide
Oxide, which is selected from, includes calcium, strontium, barium, yttrium, lanthanum, neodymium, praseodymium, niobium, silicon, tantalum and the group of their combinations.
15. antigravity system according to any one of the preceding claims, wherein, the external coating and the washcoat
In rare earth element be selected from include praseodymium, cerium, neodymium and they combinations group.
16. antigravity system according to any one of the preceding claims, wherein, the washcoat includes La doped
Aluminium oxide (La-Al2O3) and cerium-based oxygen storage material (Ce-based OSM).
17. antigravity system according to any one of the preceding claims, wherein, the system also includes underfloor catalyst
Converter, the underfloor catalyst converter the close coupling downstream catalytic converter and with the close coupling catalytic converter
It is in fluid communication, the underfloor catalyst converter includes:
Base material;
Washcoat, it is covered on the substrate;
Layer is impregnated, it is impregnated into the washcoat;And
External coating, it is covered on dipping layer and the rhodium comprising iron activation and the hydrogen-storing material based on rare earth element.
18. antigravity system according to claim 17, wherein, the washcoat of the underfloor catalyst converter includes
Hydrogen-storing material and support oxide based on rare earth element, the support oxide, which is selected from, includes aluminium oxide, doped aluminium, oxygen
Change zirconium, doped zirconia, cerium oxide, titanium oxide, niobium oxide, silica and the group of their combinations.
19. antigravity system according to claim 18, wherein, the support oxide of doping is described doped with oxide
Oxide, which is selected from, includes calcium, strontium, barium, yttrium, lanthanum, neodymium, praseodymium, niobium, silicon, tantalum and the group of their combinations.
20. the antigravity system according to any one of claim 17 to 19, wherein, the underfloor catalyst converter
Rare earth element in the external coating and the washcoat, which is selected from, includes praseodymium, cerium, neodymium and the group of their combinations.
21. the antigravity system according to any one of claim 17 to 20, wherein, the underfloor catalyst converter
The washcoat includes La doped aluminium oxide (La-Al2O3) and cerium-based oxygen storage material (Ce-based OSM).
22. the antigravity system according to any one of claim 17 to 21, wherein, the dipping layer, which includes to be selected from, to be included
Platinum, palladium, ruthenium, iridium and rhodium group platinum group metal.
23. antigravity system according to claim 22, wherein, the platinum group metal in the dipping layer is that have about
10g/ft3To 100g/ft3Loading capacity palladium.
24. antigravity system according to claim 23, wherein, the platinum group metal in the dipping layer is that have about
25.5g/ft3Loading capacity palladium.
25. the antigravity system according to any one of claim 22 to 23, wherein, the dipping layer also includes barium.
26. the antigravity system according to any one of claim 17 to 25, wherein, the underfloor catalyst converter
The external coating, which includes, has about 1g/ft3To 10g/ft3Loading capacity rhodium.
27. antigravity system according to claim 26, wherein, the external coating bag of the underfloor catalyst converter
Containing with about 4g/ft3Loading capacity rhodium.
28. the antigravity system according to any one of claim 17 to 27, wherein, the underfloor catalyst converter
Gross weight of the amount of iron in the external coating based on the external coating is about 1 percentage by weight to 10 percentage by weights.
29. antigravity system according to claim 28, wherein, in the external coating of the underfloor catalyst converter
Gross weight of the amount of iron based on the external coating be about 7 percentage by weights.
30. a kind of method for preparing catalytic converter, comprises the following steps:
Washcoat is deposited on base material;
The first solution comprising platinum group metal is impregnated on the first area of the washcoat;
Roast the first area of the dipping of the washcoat and be impregnated into firstth area of the washcoat to limit
The first subregion dipping layer on domain;
The second solution comprising platinum group metal is impregnated on the second area of the washcoat;
Roast the second area of the dipping of the washcoat and be impregnated into secondth area of the washcoat to limit
The second subregion dipping layer on domain;
The overcoat layer on subregion dipping layer, wherein, the external coating includes the rhodium of iron activation and based on rare earth element
Hydrogen-storing material.
31. according to the method for claim 30, wherein, the platinum group metal in the subregion dipping layer, which is selected from, to be included
Platinum, palladium, ruthenium, the group of iridium and rhodium.
32. according to the method for claim 30, wherein, the platinum group metal in the subregion dipping layer is that have about
10g/ft3To 100g/ft3Loading capacity palladium.
33. according to the method for claim 32, wherein, the platinum group metal in the subregion dipping layer is that have about
49g/ft3Loading capacity palladium.
34. the method according to any one of claim 30 to 33, wherein, the subregion dipping layer also includes barium.
35. the method according to any one of claim 30 to 33, wherein, the first area of the subregion dipping layer
Set towards the arrival end of the catalytic converter, and the second area of subregion dipping layer turns towards the catalysis
The port of export for changing device is set.
36. the method according to any one of claim 30 to 35, wherein, the platinum group metal in the second area
Amount be about 2.5 to 4 times of amount of the platinum group metal in the first area.
37. the method according to any one of claim 30 to 36, wherein, the platinum group metal in the second area
Loading capacity be about 3 times of loading capacity of the platinum group metal in the first area.
38. according to the method for claim 30, wherein, the external coating, which includes, has about 1 to 10g/ft3Loading capacity
Rhodium.
39. according to the method for claim 38, wherein, the external coating, which includes, has about 4.25g/ft3Loading capacity
Rhodium.
40. the method according to any one of claim 30 to 39, wherein, the amount of the iron in the external coating is based on described
The gross weight of external coating is about 1 percentage by weight to 10 percentage by weights.
41. the method according to any one of claim 30 to 40, wherein, the amount of the iron in the external coating is based on described
The gross weight of external coating is about 7 percentage by weights.
42. the method according to any one of claim 30 to 41, wherein, the washcoat includes and is based on rare earth element
Hydrogen-storing material and support oxide, the support oxide be selected from include aluminium oxide, doped aluminium, zirconium oxide, adulterate oxygen
Change zirconium, cerium oxide, titanium oxide, niobium oxide, silica and the group of their combinations.
43. the method according to any one of claim 30 to 42, wherein, the support oxide of doping is doped with oxidation
Thing, the oxide, which is selected from, includes calcium, strontium, barium, yttrium, lanthanum, neodymium, praseodymium, niobium, silicon, tantalum and the group of their combinations.
44. the method according to any one of claim 30 to 43, wherein, the rare earth in the external coating and washcoat
Element, which is selected from, includes praseodymium, cerium, neodymium and the group of their combinations.
45. the method according to any one of claim 30 to 43, wherein, the washcoat includes the oxidation of La doped
Aluminium (La-Al2O3) and cerium-based oxygen storage material (Ce-based OSM).
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US62/163,231 | 2015-05-18 | ||
PCT/IB2016/052877 WO2016185386A1 (en) | 2015-05-18 | 2016-05-17 | Rhodium-iron catalysts for twc converter systems |
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CN113924163A (en) * | 2019-06-20 | 2022-01-11 | 巴斯夫公司 | Automobile three-way catalyst system containing tail pipe catalyst |
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EP3778011A4 (en) * | 2018-03-28 | 2021-06-02 | Mitsui Mining & Smelting Co., Ltd. | Exhaust gas purification catalyst |
MY182695A (en) | 2018-03-28 | 2021-02-02 | Mitsui Mining & Smelting Co Ltd | Exhaust gas purification catalyst |
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