JP5827286B2 - 自動車用排ガス浄化触媒 - Google Patents
自動車用排ガス浄化触媒 Download PDFInfo
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- JP5827286B2 JP5827286B2 JP2013185497A JP2013185497A JP5827286B2 JP 5827286 B2 JP5827286 B2 JP 5827286B2 JP 2013185497 A JP2013185497 A JP 2013185497A JP 2013185497 A JP2013185497 A JP 2013185497A JP 5827286 B2 JP5827286 B2 JP 5827286B2
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- Prior art keywords
- oxide
- exhaust gas
- catalyst
- composite oxide
- gas purification
- 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.)
- Expired - Fee Related
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- 239000003054 catalyst Substances 0.000 title claims description 78
- 238000000746 purification Methods 0.000 title claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 100
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 85
- 239000002131 composite material Substances 0.000 claims description 55
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 40
- 229910052742 iron Inorganic materials 0.000 claims description 40
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 31
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- 229910052746 lanthanum Inorganic materials 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- 238000002296 dynamic light scattering Methods 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 4
- -1 platinum group metals Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 description 53
- 239000007789 gas Substances 0.000 description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 26
- 239000001301 oxygen Substances 0.000 description 26
- 229910052760 oxygen Inorganic materials 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- 238000003860 storage Methods 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 229910052747 lanthanoid Inorganic materials 0.000 description 13
- 150000002602 lanthanoids Chemical class 0.000 description 13
- 239000002002 slurry Substances 0.000 description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 10
- 229910052684 Cerium Inorganic materials 0.000 description 8
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- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
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- 229910052777 Praseodymium Inorganic materials 0.000 description 6
- 239000007900 aqueous suspension Substances 0.000 description 6
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- 229910052779 Neodymium Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
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- 239000000126 substance Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
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- 229910052771 Terbium Inorganic materials 0.000 description 3
- 229910052769 Ytterbium Inorganic materials 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910017771 LaFeO Inorganic materials 0.000 description 2
- RCITVHFNWJIDNA-UHFFFAOYSA-K [NH4+].[NH4+].[NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O RCITVHFNWJIDNA-UHFFFAOYSA-K 0.000 description 2
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- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 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 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-K azane;2-hydroxypropane-1,2,3-tricarboxylate;iron(3+) Chemical compound N.[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-K 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
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- 239000004570 mortar (masonry) 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
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- 230000002093 peripheral effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
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- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
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
- B01J23/70—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
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/206—Rare earth metals
- B01D2255/2061—Yttrium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/90—Physical characteristics of catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
Description
(1)基材上に触媒コート層を有する排ガス浄化触媒であって、同一触媒コート層内に、アルミナ担体、白金族金属、酸化鉄−ジルコニア系複合酸化物、および酸化ランタノイドを含む、前記触媒。
(2)酸化鉄−ジルコニア系複合酸化物が、鉄、ジルコニウムおよび希土類元素を含有する複合酸化物であって、Fe2O3とZrO2と希土類元素酸化物との合計含有量が90質量%以上であり、かつFe2O3換算の酸化鉄の含有量が10〜90質量%である、(1)に記載の排ガス浄化触媒。
(3)酸化鉄−ジルコニア系複合酸化物が希土類元素としてランタンまたはイットリウムを含有する、(1)または(2)に記載の排ガス浄化触媒。
(4)同一触媒コート層内に、さらにセリア−ジルコニア系複合酸化物を含む、(1)〜(3)のいずれかに記載の排ガス浄化触媒。
(5)酸化鉄−ジルコニア系複合酸化物に対する酸化ランタノイドの質量比が0.18〜1.1の範囲である、(1)〜(4)のいずれかに記載の排ガス浄化触媒。
(6)動的光散乱法により測定した酸化ランタノイドのD50粒径が15μm以下である、(1)〜(5)のいずれかに記載の排ガス浄化触媒。
(7)酸化ランタノイドがLa2O3である、(1)〜(6)のいずれかに記載の排ガス浄化触媒。
(8)白金族金属がアルミナおよびセリア−ジルコニア系複合酸化物の少なくとも一方に担持されている、(4)〜(7)のいずれかに記載の排ガス浄化触媒。
A.材料
触媒の調製に用いた材料は以下のとおりである。
材料1(Al2O3):1質量%のLa2O3を複合化したAl2O3
材料2(CZ):CeO2−ZrO2−Y2O3−La2O3複合酸化物(各酸化物の含有量は順に30質量%、60質量%、5質量%、5質量%)
材料3(LFZ):Fe:Zr:La:Y=1.0:1.0:1.2:0.109(原子比)であるLaFeO3−La2Zr2O7−(Zr,Y)Ox複合酸化物
材料4(La2O3):La2O3粉末(キシダ化学製)
材料5(Pd):貴金属含有量8.8質量%の硝酸パラジウム水溶液(キャタラー製)
基材:875cc(600H/3−9R−08)のコージェライトハニカム基材(デンソー製)
クエン酸鉄(III)アンモニウム(和光純薬工業製、褐色、鉄含量:16〜19%)、水分散型のイットリア含有アルカリ性ジルコニアゾル(日産化学工業製「ナノユース ZR30−BS」、ゾル粒子径:30〜80nm、ZrO2固形分濃度:30.8%、Zr:Y(原子比)=1:0.109)378.4g、テトラメチルアンモニウムヒドロキシド(TMAH)9gおよび蒸留水約140gを混合し、クエン酸鉄(III)アンモニウムとジルコニアゾルとを含有する混合物を調製した。次に、酸化ランタン微粒子(キシダ化学製、粒子径:15μ以下)165.36gおよび蒸留水約140gを混合して酸化ランタン微粒子分散液を調製した。
(1)比較例1:Pd(1.5)/CZ(105)+Al2O3(113)+バインダー
まず、材料5(Pd)を用いて、1.42質量%のPdを材料2(CZ)に担持させたPd/CZを調製した(材料6)。ここで、Pdの担持は含浸法にておこなった。次に、攪拌しながら蒸留水に材料6、材料1、Al2O3系バインダーを懸濁し、スラリーを調製した。次に、このスラリーを基材へ流し込み、ブロアで不要分を吹き払うことで基材壁面に材料をコーティングした。このコーティング材料は、基材容量に対してPdが1.5g/L、材料1が113g/L、材料2が105g/Lとなるように調製した。最後に、120℃に保持された乾燥機で2時間水分を飛ばした後、電気炉で500℃、2時間の焼成を行い比較例1の触媒を得た。
比較例1のスラリーに材料4(La2O3)を加えてスラリーを調製した。そのスラリーを用いて比較例1と同様に基材をコーティングしたものを比較例2の触媒とした。コーティング材料は、基材容量に対してPdが1.5g/L、材料1が113g/L、材料2が105g/L、材料4が15g/Lとなるように調製した。
比較例1のスラリーに材料3(LFZ)を加えてスラリーを調製した。そのスラリーを用いて比較例1と同様に基材をコーティングしたものを比較例3の触媒とした。コーティング材料は、基材容量に対してPdが1.5g/L、材料1が113g/L、材料2が105g/L、材料3が27.8g/Lとなるように調製した。
比較例1のスラリーに材料3(LFZ)と材料4(La2O3)を加えてスラリーを調製した。そのスラリーを用いて比較例1と同様に基材をコーティングしたものを実施例1の触媒とした。コーティング材料は、基材容量に対してPdが1.5g/L、材料1が113g/L、材料2が105g/L、材料3が27.8g/L、材料4が15g/Lとなるように調製した。
(1)耐久試験
実機エンジンを用いて1000℃(触媒床温)で25時間の劣化促進試験を実施した。その際の排ガス組成については、スロットル開度とエンジン負荷を調整し、リッチ域〜ストイキ〜リーン域を一定サイクルで繰り返すことにより、劣化を促進させた。
実機エンジンを用いて14.1と15.1を目標にA/Fフィードバック制御を行い、ストイキ点とA/Fセンサ出力の差分より、酸素の過不足を以下の式から算出し、最大酸素吸蔵量をOSC値として評価した。
OSC(g)=0.23×ΔA/F×噴射燃料量
図1に耐久試験を行う前(初期)と耐久試験後の各触媒のOSC値をまとめたグラフを示す。
La2O3の添加量を変えた以外は上記1の実施例1と同様に触媒を調製し、上記2と同じ評価試験を行った。図2に耐久試験後のOSC値の推移を表すグラフを示す。試験結果から、La2O3の添加量は5〜30gの範囲が適切であると判断された。
Claims (4)
- 基材上に触媒コート層を有する排ガス浄化触媒であって、
同一触媒コート層内に、アルミナ担体、白金族金属、酸化鉄−ジルコニア系複合酸化物、およびLa 2 O 3 を含み、
前記酸化鉄−ジルコニア系複合酸化物が、鉄、ジルコニウム、およびランタンまたはイットリウムである希土類元素を含有し、Fe 2 O 3 とZrO 2 と希土類元素酸化物との合計含有量が90質量%以上であり、かつFe 2 O 3 換算の酸化鉄の含有量が10〜90質量%であり、
前記酸化鉄−ジルコニア系複合酸化物に対するLa 2 O 3 の質量比が0.18〜1.1の範囲である、前記触媒。 - 同一触媒コート層内に、さらにセリア−ジルコニア系複合酸化物を含む、請求項1に記載の排ガス浄化触媒。
- 動的光散乱法により測定したLa 2 O 3 のD50粒径が15μm以下である、請求項1または2に記載の排ガス浄化触媒。
- 白金族金属がアルミナおよびセリア−ジルコニア系複合酸化物の少なくとも一方に担持されている、請求項2または3に記載の排ガス浄化触媒。
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PCT/IB2014/001687 WO2015033204A1 (en) | 2013-09-06 | 2014-09-03 | Exhaust gas purification catalyst for motor vehicle |
US14/916,862 US10022708B2 (en) | 2013-09-06 | 2014-09-03 | Exhaust gas purification catalyst for motor vehicle |
CN201480048815.5A CN105517704B (zh) | 2013-09-06 | 2014-09-03 | 用于机动车的排气净化催化剂 |
DE112014004050.9T DE112014004050T5 (de) | 2013-09-06 | 2014-09-03 | Abgasreinigungskatalysator für Kraftfahrzeug |
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