WO2008113457A1 - Palladium-rhodium einfachschicht-katalysator - Google Patents
Palladium-rhodium einfachschicht-katalysator Download PDFInfo
- Publication number
- WO2008113457A1 WO2008113457A1 PCT/EP2008/001450 EP2008001450W WO2008113457A1 WO 2008113457 A1 WO2008113457 A1 WO 2008113457A1 EP 2008001450 W EP2008001450 W EP 2008001450W WO 2008113457 A1 WO2008113457 A1 WO 2008113457A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cerium
- oxide
- zirconium mixed
- zirconium
- way catalyst
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 239000002356 single layer Substances 0.000 title abstract description 7
- XSKIUFGOTYHDLC-UHFFFAOYSA-N palladium rhodium Chemical compound [Rh].[Pd] XSKIUFGOTYHDLC-UHFFFAOYSA-N 0.000 title description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 41
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 15
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 15
- 239000010948 rhodium Substances 0.000 claims abstract description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 10
- 238000002485 combustion reaction Methods 0.000 claims abstract description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 12
- 238000004140 cleaning Methods 0.000 claims abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 15
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 8
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims 1
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 29
- 239000000725 suspension Substances 0.000 description 29
- 239000010410 layer Substances 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- -1 compounds rhodium nitrate Chemical class 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000010198 maturation time Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
Classifications
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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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
- B01J23/38—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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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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
- B01J37/0201—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
- B01J37/0215—Coating
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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
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- 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
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- 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
- B01D2255/40—Mixed oxides
- B01D2255/407—Zr-Ce mixed oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the invention relates to a three-way catalyst with excellent catalytic activity and aging stability for the purification of the exhaust gases of internal combustion engines.
- Three-way catalysts are used in large numbers for the purification of the exhaust gases of substantially stoichiometrically operated internal combustion engines. They are able to simultaneously convert the three main pollutants of the engine, namely hydrocarbons, carbon monoxide and nitrogen oxides into harmless components. Often, double-layered catalysts are used, which allow a separation of different catalytic processes and thus an optimal coordination of the catalytic effects in the two layers. Catalysts of this type are described, for example, in EP 0 885 650 and EP 1 046 423.
- Double-layer catalysts have the disadvantage that their production is more expensive than that of single-layer catalysts. Furthermore, double-layer catalysts tend to increase the exhaust gas back pressure compared to single-layer catalysts, which is at the expense of the performance of the internal combustion engines and their fuel consumption. Therefore, there have always been attempts to produce the good catalytic properties of double-layer catalysts as possible without sacrificing single-layer catalysts.
- Single-layer three-way catalysts are known, for example, from WO 98/09726, EP 1 138 382 and EP 1 541 220.
- the ever-increasing demands on the emission reduction of internal combustion engines necessitate a continuous development of the catalysts with regard to the catalytic activity, aging resistance and production costs. It was therefore the object of this invention to provide a catalyst which, compared with the catalysts from the prior art, has further reduced light-off temperatures and improved temperature stability with lower production costs. This object is achieved by a catalyst according to the claims.
- the catalyst has a single catalytically active coating on an inert catalyst support of ceramic or metal.
- the catalyst is characterized by containing an active alumina and a first and a second cerium / zirconium mixed oxide, wherein the first cerium / zirconium mixed oxide is activated with rhodium and has a higher zirconium oxide content than the second cerium / zirconium mixed oxide, which is catalytically activated with palladium.
- the formulation that a carrier material is activated with a catalytically active element means that the catalytically active element is deposited in highly dispersed form on the impregnated surface of the carrier material.
- the catalyst shows a very good light-off behavior and has a high temperature stability.
- the catalyst has a low exhaust gas back pressure and its manufacturing costs are lower than those of a corresponding double-layer catalyst.
- the active alumina and the cerium / zirconium mixed oxides are introduced into the coating as powdery solids.
- Both mixed oxides may be stabilized with at least one oxide of elements selected from the group consisting of iron, manganese, tin, titanium, silicon, yttrium, lanthanum, praseodymium, neodymium, samarium, and mixtures thereof to improve their temperature stability.
- the amount of doping elements, calculated as oxide, is preferably between 1 and 15, in particular between 5 and 10 wt .-%, based on the total weight of the stabilized mixed oxide.
- the first cerium / zirconium mixed oxide preferably has a weight ratio of cerium oxide to zirconium oxide of from 0.5 to 0.1, and the second cerium / zirconium mixed oxide has a weight ratio of cerium oxide to zirconium oxide of from 0.8 to 1.2.
- the specific surface of these materials is advantageously in a range between 50 and 100 m 2 / g.
- the active alumina may be stabilized with 1 to 10 weight percent lanthana based on the total weight of alumina plus lanthana.
- a further improvement in the temperature stability of the catalyst can be achieved if active aluminum oxide and the cerium / zirconium mixed oxides are additionally impregnated with strontium oxide and / or barium oxide.
- the catalyst carrier is a honeycomb body with a volume V having parallel flow channels for the exhaust gases of the internal combustion engine, wherein the wall surfaces of the flow channels are coated with the catalyst and the concentration of palladium based on the volume of the honeycomb body between 0.1 and 10 g and the concentration of rhodium is between 0.01 and 1 g.
- the first cerium / zirconium mixed oxide may additionally be catalytically activated in addition to rhodium with palladium.
- both cerium / zirconium mixed oxides can still be activated with platinum.
- a coating suspension must be prepared which contains all of the components of the desired catalytic layer, either directly or precursors thereof, which are converted to their final form by the final calcination of the coating.
- the two cerium / zirconium mixed oxides can be coated separately with precursor compounds of rhodium or palladium by known impregnation methods.
- Alumina can be suspended in water.
- the suspension is wet milled until the solids of the suspension have an average particle size of about 3 to 5 microns. Thereafter, the honeycomb body with this suspension by known methods coated, dried and calcined. This method of preparation guarantees that palladium and rhodium are deposited separately on different support materials.
- the first cerium / zirconium mixed oxide is suspended in water.
- a solution of a precursor compound of rhodium, preferably rhodium nitrate is added to this suspension.
- a base for example tetraethylammonium hydroxide (TEAH)
- TEAH tetraethylammonium hydroxide
- the second cerium / zirconium mixed oxide is suspended in the suspension and a solution of a precursor compound of palladium is added.
- the pH of the suspension sinks into the strongly acidic region.
- the pH is raised again to about 6 and thus precipitated the palladium on both mixed oxides.
- alumina is added to the suspension and the suspension finally, as already described, milled and applied to the catalyst support body.
- the catalyst thus prepared contains no alkaline earth metals.
- a basic solution of barium hydroxide and / or strontium oxide can be initially charged.
- the first cerium / zirconium mixed oxide is added and suspended in the solution.
- a solution of rhodium nitrate is added to the suspension, the rhodium precipitating due to the basicity of the suspension on the first cerium / zirconium mixed oxide.
- the suspension is fed with the second cerium / zirconium mixed oxide followed by a palladium nitrate solution.
- alumina is added to the suspension and the suspension milled as already described and applied to the catalyst support.
- both rhodium and palladium are present on the particles of the first cerium / zirconium mixed oxide.
- a catalyst according to EP 1 541 220 was prepared.
- a suspension of barium sulfate in water was first prepared. 1% by weight of nitric acid was added to this suspension and the pH was thus lowered to about 5. Thereafter, a ⁇ -alumina stabilized with 3% by weight of lanthanum oxide was added followed by a cerium-zirconium mixed oxide having a zirconia content of 50% by weight, and the pH was kept approximately constant during addition by nitric acid. After the addition of 10% by weight of sucrose, the suspension was ground and then added with palladium nitrate and rhodium nitrate.
- a cordierite honeycomb body was coated with the suspension, dried and calcined.
- the honeycomb body had a cell density of 93 cm "2, a diameter of 14.4 cm and a length of 10.2 cm
- the finished catalyst contained the following amounts of coating.:
- a catalyst according to the invention was prepared as follows:
- Another catalyst according to the invention was prepared as follows:
- Barium hydroxide was dissolved in water.
- the cerium / zirconium mixed oxide was suspended with 70 wt .-% zirconium oxide and added rhodium nitrate in the suspension. Thereafter, the cerium / zirconium oxide with 50 wt .-% zirconia in the suspension.
- Catalyst contained the following amounts of coating:
- FIG. 1 shows the comparison of light-off temperatures. After aging, the two catalysts according to the invention have significantly lower light-off temperatures for the conversion of the pollutants HC (hydrocarbons), CO (carbon monoxide) and NOx (nitrogen oxides) than the comparative catalyst.
- the diagram of Figure 2 shows the maximum conversions achieved with the catalysts.
- the catalysts had a back pressure of 18.3 mbar at a gas temperature of 30 ° C and an air mass flow of 345 kg / h. This back pressure is about 15% lower than the backpressure of a comparable double-layer catalyst.
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Toxicology (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020097019617A KR101230272B1 (ko) | 2007-03-19 | 2008-02-23 | 팔라듐-로듐 단층 촉매 |
CN2008800074012A CN101626832B (zh) | 2007-03-19 | 2008-02-23 | 钯-铑单层催化剂 |
JP2010500094A JP5361855B2 (ja) | 2007-03-19 | 2008-02-23 | パラジウム−ロジウム単一層触媒 |
US12/530,586 US9156023B2 (en) | 2007-03-19 | 2008-02-23 | Palladium—rhodium single-layer catalyst |
BRPI0808980A BRPI0808980B1 (pt) | 2007-03-19 | 2008-02-23 | catalisador de paládio-ródio de camada única |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07005548A EP1974810B1 (de) | 2007-03-19 | 2007-03-19 | Palladium-Rhodium Einfachschicht Katalysator |
EP07005548.8 | 2007-03-19 |
Publications (1)
Publication Number | Publication Date |
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WO2008113457A1 true WO2008113457A1 (de) | 2008-09-25 |
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ID=38134095
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2008/001450 WO2008113457A1 (de) | 2007-03-19 | 2008-02-23 | Palladium-rhodium einfachschicht-katalysator |
Country Status (10)
Country | Link |
---|---|
US (1) | US9156023B2 (de) |
EP (1) | EP1974810B1 (de) |
JP (1) | JP5361855B2 (de) |
KR (1) | KR101230272B1 (de) |
CN (1) | CN101626832B (de) |
AT (1) | ATE477849T1 (de) |
BR (1) | BRPI0808980B1 (de) |
DE (1) | DE502007004776D1 (de) |
RU (1) | RU2009138367A (de) |
WO (1) | WO2008113457A1 (de) |
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Cited By (22)
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US8906330B2 (en) | 2009-05-04 | 2014-12-09 | Basf Corporation | Lean HC conversion of TWC for lean burn gasoline engines |
WO2013004456A1 (en) | 2011-07-01 | 2013-01-10 | Treibacher Industrie Ag | Ceria zirconia alumina composition with enhanced thermal stability |
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US9889428B2 (en) | 2011-07-14 | 2018-02-13 | Treibacher Industrie Ag | Ceria zirconia alumina composition with enhanced thermal stability |
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WO2013007809A1 (en) | 2011-07-14 | 2013-01-17 | Treibacher Industrie Ag | Ceria zirconia alumina composition with enhanced thermal stability |
DE102011107702A1 (de) | 2011-07-14 | 2013-01-17 | Sasol Germany Gmbh | Verfahren zur Herstellung von Kompositen aus Aluminiumoxid und Cer-/Zirkonium-Mischoxiden |
US10766018B2 (en) | 2011-07-14 | 2020-09-08 | Sasol Germany Gmbh | Composites of aluminum oxide and cerium/zirconium mixed oxides |
EP2545990A1 (de) | 2011-07-14 | 2013-01-16 | SASOL Germany GmbH | Verfahren zur Herstellung von Kompositen aus Aluminiumoxid und Cer-/Zirkonium-Mischoxiden |
US9289751B2 (en) | 2011-07-14 | 2016-03-22 | Sasol Germany Gmbh | Method for producing composites of aluminum oxide and cerium/zirconium mixed oxides |
WO2013007242A1 (de) | 2011-07-14 | 2013-01-17 | Sasol Germany Gmbh | Verfahren zur herstellung von kompositen aus aluminiumoxid und cer-/zirkonium-mischoxiden |
EP2604337A1 (de) | 2011-12-16 | 2013-06-19 | Treibacher Industrie AG | Ceriumoxid-Zirconiumdioxid-Aluminiumoxid-Zusammensetzung mit verbesserter Wärmebeständigkeit |
US9737850B2 (en) | 2012-03-30 | 2017-08-22 | Honda Motor Co., Ltd. | Exhaust gas purification palladium monolayer catalyst for saddle-riding-type vehicle |
WO2014195196A1 (de) | 2013-06-03 | 2014-12-11 | Umicore Ag & Co Kg | Dreiwegkatalysator |
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DE102013210270A1 (de) | 2013-06-03 | 2014-12-04 | Umicore Ag & Co. Kg | Dreiwegkatalysator |
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US10022672B2 (en) | 2014-03-13 | 2018-07-17 | Umicore Ag & Co. Kg | Catalyst system for gasoline combustion engines, having three-way catalysts and SCR catalyst |
WO2015135983A1 (de) | 2014-03-13 | 2015-09-17 | Umicore Ag & Co. Kg | Katalysatorsystem für benzinverbrennungsmotoren mit dreiwegekatalysatoren und scr-katalysator |
US11352385B2 (en) | 2016-02-26 | 2022-06-07 | Umicore Ag & Co. Kg | Precious metal compounds |
DE102022130469A1 (de) | 2022-11-17 | 2024-05-23 | Umicore Ag & Co. Kg | Verfahren und Vorrichtung zum Herstellen eines Substrats für eine Abgasnachbehandlungseinrichtung |
Also Published As
Publication number | Publication date |
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CN101626832A (zh) | 2010-01-13 |
KR20090121350A (ko) | 2009-11-25 |
JP5361855B2 (ja) | 2013-12-04 |
JP2010521302A (ja) | 2010-06-24 |
CN101626832B (zh) | 2011-12-21 |
KR101230272B1 (ko) | 2013-02-06 |
US20100126154A1 (en) | 2010-05-27 |
BRPI0808980A2 (pt) | 2014-09-09 |
EP1974810A1 (de) | 2008-10-01 |
EP1974810B1 (de) | 2010-08-18 |
US9156023B2 (en) | 2015-10-13 |
ATE477849T1 (de) | 2010-09-15 |
DE502007004776D1 (de) | 2010-09-30 |
BRPI0808980B1 (pt) | 2018-11-13 |
RU2009138367A (ru) | 2011-04-27 |
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