WO2012005375A1 - 排気ガス浄化用触媒及びその製造方法 - Google Patents
排気ガス浄化用触媒及びその製造方法 Download PDFInfo
- Publication number
- WO2012005375A1 WO2012005375A1 PCT/JP2011/065767 JP2011065767W WO2012005375A1 WO 2012005375 A1 WO2012005375 A1 WO 2012005375A1 JP 2011065767 W JP2011065767 W JP 2011065767W WO 2012005375 A1 WO2012005375 A1 WO 2012005375A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- exhaust gas
- mass
- gas purifying
- catalyst
- aluminum borate
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 145
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000000919 ceramic Substances 0.000 claims abstract description 21
- 239000007769 metal material Substances 0.000 claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000000746 purification Methods 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910052788 barium Inorganic materials 0.000 claims description 11
- 150000002604 lanthanum compounds Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 129
- 239000007789 gas Substances 0.000 description 100
- 239000010948 rhodium Substances 0.000 description 50
- 239000010410 layer Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 34
- 229910002651 NO3 Inorganic materials 0.000 description 29
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 29
- 239000002002 slurry Substances 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 19
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 description 13
- 239000002131 composite material Substances 0.000 description 13
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000010970 precious metal Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 2
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 2
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- RPTMBSNRRRJARX-UHFFFAOYSA-N C(C)OC([O-])C.[B+3].C(C)OC([O-])C.C(C)OC([O-])C Chemical compound C(C)OC([O-])C.[B+3].C(C)OC([O-])C.C(C)OC([O-])C RPTMBSNRRRJARX-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- OXMKQIVTFWEMRJ-UHFFFAOYSA-N [B+3].CCCC[O-].CCCC[O-].CCCC[O-] Chemical compound [B+3].CCCC[O-].CCCC[O-].CCCC[O-] OXMKQIVTFWEMRJ-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 1
- 229940094800 barium oxalate Drugs 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 238000012512 characterization method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 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
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 125000005374 siloxide group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical compound [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 description 1
- RQNVJDSEWRGEQR-UHFFFAOYSA-N tris(prop-2-enyl) borate Chemical compound C=CCOB(OCC=C)OCC=C RQNVJDSEWRGEQR-UHFFFAOYSA-N 0.000 description 1
- OEJSTGAKVVRHER-UHFFFAOYSA-N tris[2-(2-ethoxyethoxy)ethoxy]alumane Chemical compound [Al+3].CCOCCOCC[O-].CCOCCOCC[O-].CCOCCOCC[O-] OEJSTGAKVVRHER-UHFFFAOYSA-N 0.000 description 1
- TVHGQPXBJLWLCS-UHFFFAOYSA-N tris[ethenyl(dimethyl)silyl] borate Chemical compound C=C[Si](C)(C)OB(O[Si](C)(C)C=C)O[Si](C)(C)C=C TVHGQPXBJLWLCS-UHFFFAOYSA-N 0.000 description 1
- ZMCWFMOZBTXGKI-UHFFFAOYSA-N tritert-butyl borate Chemical compound CC(C)(C)OB(OC(C)(C)C)OC(C)(C)C ZMCWFMOZBTXGKI-UHFFFAOYSA-N 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
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- 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
- 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
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- B01J37/0201—Impregnation
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- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/908—O2-storage component incorporated in the catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
- B01D2255/9207—Specific surface
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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 present invention relates to an exhaust gas purifying catalyst and a method for producing the same, and more specifically, an exhaust gas purifying catalyst having excellent exhaust gas purifying performance after high-temperature durability and excellent dispersibility of noble metals, particularly Pd, such as automobiles.
- the present invention relates to a catalyst for purifying harmful components contained in exhaust gas discharged from an internal combustion engine and a method for producing the same.
- Exhaust gas discharged from an internal combustion engine such as an automobile contains harmful components such as hydrocarbon (HC), carbon monoxide (CO), and nitrogen oxide (NO x ). Therefore, conventionally, a three-way catalyst for purifying and detoxifying these harmful components has been used.
- HC hydrocarbon
- CO carbon monoxide
- NO x nitrogen oxide
- noble metals such as Pt, Pd, and Rh are used as a catalytic active component, and alumina, ceria, zirconia, a ceria-zirconia composite oxide having an oxygen storage ability, and the like are used as a carrier.
- a catalyst support having a shape such as a honeycomb, a plate, or a pellet made of a ceramic or metal material is used.
- Patent Documents 1, 2, and 3 There is also an example in which aluminum borate is used as a carrier, and the catalyst component is supported on a green compact including a powdery body that is covered with an aluminum borate whisker and has a hollow portion formed therein. The diffusibility is improved (see Patent Document 4).
- An object of the present invention is to provide an exhaust gas purifying catalyst excellent in exhaust gas purifying performance after high-temperature durability and excellent in dispersibility of noble metals, particularly Pd, and a method for producing the same.
- the present inventors have carried out intensive investigations and found that in order to achieve the above object, a material obtained by modifying an excellent aluminum borate heat resistance of the formula 9Al 2 O 3 ⁇ 2B 2 O 3 with La 2 O 3 as a carrier
- a material obtained by modifying an excellent aluminum borate heat resistance of the formula 9Al 2 O 3 ⁇ 2B 2 O 3 with La 2 O 3 as a carrier When Pd is supported thereon, La-stabilized alumina is used as a carrier, and Pd is supported on the support, which is superior in exhaust gas purification performance after high-temperature durability and excellent in Pd dispersion.
- the present invention has been completed.
- the carrier for the exhaust gas purifying catalyst of the present invention has the formula 9Al 2 O 3 .multidot. Modified with La 2 O 3 in an amount of 0.3 to 2% by mass based on the mass of aluminum borate. It contains aluminum borate represented by 2B 2 O 3 .
- Exhaust gas purifying catalyst of the present invention is represented by the formula 9Al 2 O 3 ⁇ 2B 2 O 3 modified with an amount of La 2 O 3 as a 0.3 to 2 wt% based on the weight of aluminum borate And a carrier containing aluminum borate and Pd supported on the carrier.
- the exhaust gas purifying catalyst of the present invention have the formula 9Al 2 O 3 ⁇ 2B 2 O 3 modified with an amount of La 2 O 3 as a 0.3 to 2 wt% based on the weight of aluminum borate
- carrier are characterized by the above-mentioned.
- the exhaust gas purifying catalyst component of the present invention includes a catalyst support made of a ceramic or a metal material, and the exhaust gas purifying catalyst layer of the present invention supported on the catalyst support.
- the exhaust gas purifying catalyst component of the present invention includes a catalyst support made of a ceramic or a metal material, the layer of the exhaust gas purifying catalyst supported on the catalyst support, and the exhaust gas purifying. And a rhodium catalyst layer supported on the catalyst layer.
- a method of producing an exhaust gas purifying catalyst of the present invention by mixing a solution of the formula 9Al 2 O 3 ⁇ 2B aluminum borate represented by 2 O 3 and a lanthanum compound, evaporated to dryness and baking La 2 O 3 modified to produce aluminum borate represented by the formula 9Al 2 O 3 2B 2 O 3 , and then the modified aluminum borate and a solution of a Pd compound are mixed or the modified It is characterized by mixing a solution of aluminum borate, Ba compound and Pd compound, and then evaporating to dryness and baking.
- the carrier for the exhaust gas purifying catalyst of the present invention is excellent in exhaust gas purifying performance after high temperature durability, and is useful for producing an exhaust gas purifying catalyst excellent in precious metal, especially Pd dispersibility
- the exhaust gas purifying catalyst of the present invention and the exhaust gas purifying catalyst component of the present invention are excellent in exhaust gas purifying performance after high-temperature durability and excellent in the degree of dispersion of Pd, and the production method of the present invention is the present invention. It is suitable for producing an exhaust gas purifying catalyst.
- Aluminum borate of the formula 9Al 2 O 3 ⁇ 2B 2 O 3 used in the present invention for example, Siba P. Ray, "Preparation and Characterization of Aluminum Borate", J. Am. Ceram. Soc., 75 [9], p2605-2609 (1992).
- aluminum borate of the formula 9Al 2 O 3 ⁇ 2B 2 O 3 is known to have a cavity inside diameter of about 0.4nm crystal structure.
- Such an aluminum borate in an amount of 0.3 to 2% by weight, preferably 0.4 to 2% by weight, more preferably 0.5 to 1.5% by weight, based on the weight of the aluminum borate.
- the carrier for the exhaust gas purifying catalyst of the present invention can be obtained by modifying with La 2 O 3 .
- the amount of La 2 O 3 is less than 0.3% by mass or more than 2% by mass based on the mass of aluminum borate, high temperature durability is evident from the examples and comparative examples described later. The degree of improvement in the exhaust gas purification performance of the later catalyst is insufficient.
- Carrier for exhaust gas purifying catalyst of the present invention may comprise only aluminum borate modified with the above La 2 O 3, and aluminum borate modified with the above La 2 O 3 It may be a mixture with a binder such as alumina commonly used in a three-way catalyst or a support such as CeO 2 —ZrO 2 having an oxygen storage capacity (OSC). That is, the carrier for the exhaust gas purifying catalyst of the present invention contains aluminum borate modified with La 2 O 3 described above.
- a binder such as alumina commonly used in a three-way catalyst or a support such as CeO 2 —ZrO 2 having an oxygen storage capacity (OSC). That is, the carrier for the exhaust gas purifying catalyst of the present invention contains aluminum borate modified with La 2 O 3 described above.
- the carrier for the exhaust gas purifying catalyst of the present invention described above can suppress the deterioration rate of the precious metal dispersion after high temperature endurance regardless of any precious metal of Pd, Rh and Pt, and precious metal sintering after high temperature endurance However, the effect is remarkable when the noble metal is Pd.
- the exhaust gas purifying catalyst of the present invention is obtained by supporting Pd on a carrier containing aluminum borate modified with La 2 O 3 described above.
- the amount of Pd supported is preferably 0.3 to 3% by mass, more preferably 0.4 to 2% by mass based on the mass of the carrier in terms of the mass of Pd metal.
- the exhaust gas purifying catalyst of the present invention is one in which Pd and Ba are supported on a carrier containing aluminum borate modified with La 2 O 3 described above.
- Pd and Ba By supporting Pd and Ba, the oxygen dissociation temperature of PdO can be increased, and the catalytic action of Pd can be enhanced.
- the amount and effect of Pd are as described above.
- the supported amount of Ba is preferably 2 to 3% by mass, more preferably 2 to 2.5% by mass based on the mass of Pd metal in terms of the mass of BaO.
- the exhaust gas purifying catalyst structure of the present invention is formed by forming and supporting a layer made of the above-described exhaust gas purifying catalyst of the present invention on a catalyst support made of a ceramic or metal material.
- the supported amount is preferably 70 to 300 g / L, more preferably 100 to 230 g / L.
- the shape of the catalyst support made of a ceramic or metal material is not particularly limited, but is generally a shape of a honeycomb, a plate, a pellet, etc. A honeycomb shape is preferred.
- Examples of the material for such a catalyst support include ceramics such as alumina (Al 2 O 3 ), mullite (3Al 2 O 3 -2SiO 2 ), cordierite (2MgO-2Al 2 O 3 -5SiO 2 ), and the like. And metal materials such as stainless steel.
- a layer made of the above-described exhaust gas purifying catalyst of the present invention is supported on a catalyst support made of a ceramic or metal material,
- the Rh catalyst layer is formed on and supported.
- the shape and material of the catalyst support made of ceramic or metal material in the exhaust gas purifying catalyst component are the same as described above.
- the amount of Rh supported in the Rh catalyst layer is preferably 0.1 to 0.6% by mass, more preferably 0.1 to 0.4% by mass, based on the mass of the carrier in the Rh catalyst layer.
- the ratio of Pd: Rh is preferably 3 to 20: 1, more preferably 5 to 20: 1.
- the loading amount of the lower layer is preferably 70 to 200 g / L, more preferably 100 to 160 g / L, and the loading amount of the upper layer is preferably 30 in consideration of heat resistance, gas diffusibility to the lower layer, exhaust pressure and the like. -100 g / L, more preferably 50-70 g / L.
- a method of producing an exhaust gas purifying catalyst of the present invention by mixing a solution of the formula 9Al 2 O 3 ⁇ 2B aluminum borate represented by 2 O 3 and a lanthanum compound, evaporated to dryness and baking La 2 O 3 modified to produce aluminum borate represented by the formula 9Al 2 O 3 2B 2 O 3 , and then the modified aluminum borate and a solution of a Pd compound are mixed or the modified A solution of aluminum borate, Ba compound and Pd compound is mixed, then evaporated to dryness and fired.
- the processing steps will be specifically described below.
- the solvent constituting the “solution” is not particularly limited as long as it can form a solution, but water is generally used.
- Aluminum borate of the formula 9Al 2 O 3 ⁇ 2B 2 O 3 used in the method of manufacturing the exhaust gas purifying catalyst of the present invention are commercially available or in the laboratory scale, for example, be prepared in the following manner it can. 1.5 L of solvent (for example, 2-propanol, butanol, ethanol) in a three-necked flask immersed in a 50 ° C.
- solvent for example, 2-propanol, butanol, ethanol
- Al alkoxide for example, aluminum ethoxide, aluminum isopropoxide, aluminum, pulverized in an agate mortar
- Al alkoxide 200 g of triisopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum tributoxide, aluminum phenoxide, aluminum ethoxyethoxyethoxide
- alkoxides of B eg, boron n-propoxide, boron trimethyl
- Siloxide boron ethoxy ethoxide, boron vinyl dimethyl siloxide, boron allyl oxide, boron n-butoxide, boron t-butoxide, boron ethoxide, boron isopro Kishido placed boron methoxide) 40.9 g, and stirred while replacing with N 2 gas.
- 2-propanol is produced when the aluminum isopropoxide is hydrolyzed. Therefore, it is most preferable to use 2-propanol as a solvent.
- a mixed solution of solvent for example, 2-propanol
- the obtained precipitate was washed with ethanol, then washed with pure water, filtered, dried at 120 ° C. overnight (about 15 hours), calcined in air at 300 ° C. for 3 hours, and further in air 1 Calcination at 000 ° C. for 5 hours to obtain aluminum borate as a white product.
- the aluminum borate can be identified as the aluminum borate of the formula 9Al 2 O 3 ⁇ 2B 2 O 3 by X-ray diffraction.
- Exhaust gas purifying formula 9Al 2 O 3 ⁇ 2B 2 O 3 aluminum borate and lanthanum compound represented by the manufacturing method of the catalyst (lanthanum compound soluble of the present invention, for example lanthanum nitrate, lanthanum acetate, lanthanum chloride, lanthanum bromide
- the aluminum borate-containing slurry and the lanthanum compound solution may be mixed, or aluminum borate may be added to the lanthanum compound solution.
- the ratio of the amount of aluminum borate to the amount of lanthanum compound at this time is 0.3 to 2% by mass, preferably 0.4 to 2% by mass, more preferably based on the mass of aluminum borate after firing.
- the amount of La 2 O 3 is 0.5 to 1.5% by mass.
- the lanthanum compound is evaporated to dryness at 120 ° C. overnight (about 15 hours) so that the lanthanum compound adheres almost uniformly to the surface of the aluminum borate, and then calcined in air at 600 ° C. for 3 hours to obtain La 2 O 3 in obtaining aluminum borate represented by modified equations 9Al 2 O 3 ⁇ 2B 2 O 3, i.e., a carrier for an exhaust gas purifying catalyst of the present invention.
- the Pd and Ba to produce a supported exhaust gas purifying catalyst is represented by the formula 9Al 2 O 3 ⁇ 2B 2 O 3 modified with La 2 O 3 obtained as described above
- Aluminum borate followed by Ba compounds eg, barium oxide, barium nitrate, barium acetate, barium oxalate, barium hydroxide, barium carbonate
- Pd compounds soluble Pd compounds such as Pd nitrate, Pd chloride, Pd sulfate
- an ordinary carrier ordinarily used in the three-way catalyst or a carrier such as CeO 2 —ZrO 2 having an oxygen storage capacity (OSC) can coexist.
- the ratio of the amount of the carrier and the amount of the Pd compound at this time is as described above, and the amount of the Ba compound is preferably 2 to 3% by mass, more preferably based on the mass of the Pd metal in terms of the BaO amount. 2 to 2.5% by mass.
- the Pd compound, or both of the Pd compound and the Ba compound was evaporated to dryness at 120 ° C. overnight (about 15 hours) so that the Pd compound and both of the Ba compound and the Ba compound were almost uniformly attached, and then calcined in air at 600 ° C. for 3 hours. and, the aluminum borate of the formula 9Al 2 O 3 ⁇ 2B 2 O 3 modified with La 2 O 3 Pd, or both of Pd and Ba is the exhaust gas purifying catalyst of the present invention which are carried obtain.
- the exhaust gas purifying catalyst component of the present invention can be produced, for example, by the following method.
- a slurry is prepared by mixing with a solution of the compound and wet milling.
- the obtained slurry is applied to a catalyst support made of ceramics or a metal material, preferably a honeycomb-shaped catalyst support, dried and fired according to a known method, and the catalyst support and the catalyst support are coated on the catalyst support.
- An exhaust gas purifying catalyst structure including an exhaust gas purifying catalyst layer carried on the substrate is obtained.
- An exhaust gas purifying catalyst structure having an Rh catalyst layer on the catalyst layer can also be produced.
- the aluminum borate were identified as aluminum borate of the formula 9Al 2 O 3 ⁇ 2B 2 O 3 by X-ray diffraction.
- the aluminum borate obtained above was immersed in an aqueous lanthanum nitrate solution.
- the amount of lanthanum nitrate in the aqueous lanthanum nitrate solution is boric acid La 2 O 3 of borate in the aluminum of the formula 9Al 2 O 3 ⁇ 2B 2 O 3 modified with La 2 O 3 for the purpose
- the amount was 0.5% by mass based on the mass of aluminum.
- An aluminum borate represented by 3 was obtained.
- Example 2 The amount of lanthanum nitrate in the aqueous solution of lanthanum nitrate, the amount of aluminum borate of La 2 O 3 wherein modified with 9Al 2 O 3 ⁇ 2B 2 O 3 with boric acid in the aluminum represented La 2 O 3 for the purpose
- the exhaust gas purifying catalyst of the present invention was produced in the same manner as in Example 1 except that the amount was 1% by mass based on the mass of
- Example 3 The amount of lanthanum nitrate in the aqueous solution of lanthanum nitrate, the amount of aluminum borate of La 2 O 3 wherein modified with 9Al 2 O 3 ⁇ 2B 2 O 3 with boric acid in the aluminum represented La 2 O 3 for the purpose
- the exhaust gas purifying catalyst of the present invention was produced in the same manner as in Example 1 except that the amount was 2% by mass based on the mass of
- Comparative Example 1 Exhaust gas of comparative example in the same manner as in Example 1 except that the step of modifying with La 2 O 3 was not carried out (that is, Pd was supported on aluminum borate without modifying with La 2 O 3 ). A purification catalyst was produced.
- Comparative Example 2 The amount of lanthanum nitrate in the aqueous solution of lanthanum nitrate, the amount of aluminum borate of La 2 O 3 wherein modified with 9Al 2 O 3 ⁇ 2B 2 O 3 with boric acid in the aluminum represented La 2 O 3 for the purpose
- a catalyst for purifying exhaust gas of a comparative example was produced in the same manner as in Example 1 except that the amount became 3% by mass based on the mass of
- Comparative Example 3 The amount of lanthanum nitrate in the aqueous solution of lanthanum nitrate, the amount of aluminum borate of La 2 O 3 wherein modified with 9Al 2 O 3 ⁇ 2B 2 O 3 with boric acid in the aluminum represented La 2 O 3 for the purpose
- a catalyst for exhaust gas purification of a comparative example was produced in the same manner as in Example 1 except that the amount was 5% by mass based on the mass of
- Comparative Example 4 La-stabilized alumina was immersed in an aqueous Pd nitrate solution.
- the amount of Pd nitrate in this aqueous solution of Pd nitrate was an amount that would be 0.4% by mass of La stabilized alumina in terms of the mass of Pd metal.
- the catalyst was evaporated to dryness at 120 ° C. overnight (about 15 hours) and calcined in air at 600 ° C. for 3 hours to produce a comparative exhaust gas purifying catalyst.
- the outlet gas component was measured using a CO / HC / NO analyzer. From the obtained light-off performance evaluation results, the temperatures (T10, T50, and T90) that reached the NO 10%, 50%, and 90% purification rates were determined. The results were as shown in Table 1.
- Example 2 Each exhaust gas purifying catalyst obtained in Example 2 and Comparative Example 4 was endured for 25 hours at 900 ° C., 1000 ° C., 1100 ° C. or 1200 ° C. in an air atmosphere containing 10% of water vapor.
- the catalytic activity of was evaluated as follows.
- catalyst powder is set in a reaction tube, CO: 0.51%, NO: 500 ppm, C 3 H 6 : 1170 ppm C, O 2 : 0.4%, from the remaining N 2
- the outlet gas component was measured using a CO / HC / NO analyzer. From the obtained light-off performance evaluation result, the temperature (T50) at which the NO purification rate reaches 50% was determined. The results were as shown in Table 2.
- a BET value before durability and a BET value after durability treatment at 1000 ° C. for 25 hours in an air atmosphere containing 10% of water vapor were determined. The reduction rate was calculated from these values. The results were as shown in Table 3.
- aluminum borate has a lower BET value reduction rate due to endurance treatment than La-stabilized alumina, and aluminum borate has higher heat resistance than La-stabilized alumina. I found it excellent. Moreover, when aluminum borate is modified with 1% by mass of La 2 O 3 , a BET value that is the same as that before the durability treatment is obtained after the durability treatment, and further improvement in heat resistance by modification with La 2 O 3 was recognized.
- Pd dispersity Pd amount (mole) corresponding to CO adsorption amount / total amount of Pd contained (mole) Is a value calculated by. The Pd dispersion degree deterioration rate was obtained from these values. The results were as shown in Table 4.
- the degree of precious metal dispersion indirectly represents the level of contact probability with exhaust gas, and it can be said that the higher the degree of precious metal dispersion, the higher the contact efficiency with exhaust gas.
- aluminum borate modified with Pd / 1% by mass of La 2 O 3 has a reduced Pd dispersity degradation rate, and after high-temperature durability by adopting a high heat-resistant material. Pd sintering is suppressed.
- Example 4 (Pd monolayer, Pd support concentration 1.3 g / L) Aluminum borate 59.8 parts by mass represented by 1% by mass of La modified with 2 O 3 the formula 9Al 2 O 3 ⁇ 2B 2 O 3, CeO 2 -ZrO 2 composite oxide 29.6 parts by weight, oxide Barium nitrate in an amount corresponding to 3.3 parts by mass as barium and 6.0 parts by mass of an alumina binder were added to an aqueous Pd nitrate solution and wet pulverized to obtain a Pd-containing slurry. The amount of Pd nitrate in this aqueous solution of Pd nitrate was an amount that would be 1.3% by mass in terms of solid content in terms of the mass of Pd metal. The obtained slurry was applied to a ceramic honeycomb (catalyst support) in an amount of 100 g / L, dried and fired to produce an exhaust gas purifying catalyst structure of the present invention.
- a ceramic honeycomb catalyst support
- Comparative Example 5 (Pd single layer, Pd support concentration 1.3 g / L) 29.6 parts by mass of CeO 2 —ZrO 2 -based composite oxide, 59.8 parts by mass of La-stabilized alumina, barium nitrate in an amount corresponding to 3.3 parts by mass as barium oxide, and 6.0 parts by mass of an alumina binder It was added to a Pd nitrate aqueous solution and subjected to a wet pulverization treatment to obtain a Pd-containing slurry. The amount of Pd nitrate in this aqueous solution of Pd nitrate was an amount that would be 1.3% by mass in terms of solid content in terms of the mass of Pd metal. The obtained slurry was applied to a ceramic honeycomb (catalyst support) in an amount of 100 g / L, dried and fired to produce a catalyst structure for exhaust gas purification of a comparative example.
- a ceramic honeycomb catalyst support
- Example 4 Exhaust gas purification in Example 4 and Comparative Example 5 above was measured using a CO / HC / NO analyzer (Horiba Seisakusho MOTOR EXHAUST GAS ANALYZER MEXA9100). The light-off performance of the catalyst assembly was determined. From the result of the obtained light-off performance evaluation, the temperature (T50) at which 50% purification rate of CO / HC / NO was reached was determined. The results were as shown in Table 5.
- the amount of Pd nitrate in the aqueous Pd nitrate solution was 0.83% by mass in terms of solid content in terms of the mass of Pd metal.
- the obtained slurry was applied to a ceramic honeycomb (catalyst support) in an amount of 100 g / L, dried and fired.
- Nd 2 O 3 —ZrO 2 -based composite oxide 70.3 parts by mass of Nd 2 O 3 —ZrO 2 -based composite oxide, 23.4 parts by mass of La-stabilized alumina, and 6.0 parts by mass of an alumina-based binder were added to the aqueous Rh nitrate solution, and wet pulverization was performed.
- an Rh-containing slurry was obtained.
- the amount of nitric acid Rh in the aqueous nitric acid Rh solution was such that the solid content after firing was 0.33% by mass in terms of the mass of Rh metal.
- the obtained slurry is applied to the Pd-supported ceramic honeycomb obtained above in an amount of 50 g / L, dried and fired to produce the exhaust gas purifying catalyst structure of the present invention consisting of two Pd / Rh layers. did.
- Al borate represented by the formula 9Al 2 O 3 ⁇ 2B 2 O 3 modified with 1% by mass of La 2 O 3
- CeO 2 —ZrO 2 -based composite oxide 45.4 parts by mass of CeO 2 —ZrO 2 -based composite oxide
- the amount of Pd nitrate in the aqueous Pd nitrate solution was 0.91% by mass in terms of solid content in terms of the mass of Pd metal.
- the obtained slurry was applied to a ceramic honeycomb (catalyst support) in an amount of 100 g / L, dried and fired.
- Nd 2 O 3 —ZrO 2 -based composite oxide 70.4 parts by mass of Nd 2 O 3 —ZrO 2 -based composite oxide, 23.5 parts by mass of La-stabilized alumina, and 6.0 parts by mass of an alumina binder were added to the aqueous Rh nitrate solution, and wet pulverization was performed.
- an Rh-containing slurry was obtained.
- the amount of nitric acid Rh in the aqueous nitric acid Rh solution was 0.18% by mass in terms of the solid content after firing in terms of the mass of Rh metal.
- the obtained slurry is applied to the Pd-supported ceramic honeycomb obtained above in an amount of 50 g / L, dried and fired to produce the exhaust gas purifying catalyst structure of the present invention consisting of two Pd / Rh layers. did.
- the amount of Pd nitrate in the aqueous Pd nitrate solution was 0.95% by mass in terms of solid content in terms of the mass of Pd metal.
- the obtained slurry was applied to a ceramic honeycomb (catalyst support) in an amount of 100 g / L, dried and fired.
- Nd 2 O 3 —ZrO 2 -based composite oxide 70.4 parts by mass of Nd 2 O 3 —ZrO 2 -based composite oxide, 23.5 parts by mass of La-stabilized alumina, and 6.0 parts by mass of an alumina binder were added to the aqueous Rh nitrate solution, and wet pulverization was performed.
- an Rh-containing slurry was obtained.
- the amount of nitric acid Rh in the aqueous nitric acid Rh solution was an amount that would be 0.10% by mass of the solid content after firing in terms of the mass of Rh metal.
- the obtained slurry is applied to the Pd-supported ceramic honeycomb obtained above in an amount of 50 g / L, dried and fired to produce the exhaust gas purifying catalyst structure of the present invention consisting of two Pd / Rh layers. did.
- Example 8 Pd monolayer, Pd support concentration 1.0 g / L) 1 mass% of La 2 O 3 wherein 9Al 2 O 3 ⁇ 2B 45.3 parts by weight aluminum borate represented by 2 O 3 modified with, CeO 2 -ZrO 2 composite oxide 45.3 parts by weight, oxide Barium nitrate in an amount corresponding to 2.4 parts by mass as barium and 6.0 parts by mass of an alumina binder were added to an aqueous Pd nitrate solution and wet pulverized to obtain a Pd-containing slurry.
- the amount of Pd nitrate in this aqueous solution of Pd nitrate was an amount that would be 1.00% by mass of the solid content in terms of the mass of Pd metal.
- the obtained slurry was applied to a ceramic honeycomb (catalyst support) in an amount of 100 g / L, dried and fired to produce an exhaust gas purifying catalyst structure of the present invention.
- Comparative Example 9 (Pd single layer, Pd carrying concentration 1.0 g / L) And except for using the same amount of La stabilized alumina in place of aluminum borate represented by 1% by mass of La modified with 2 O 3 the formula 9Al 2 O 3 ⁇ 2B 2 O 3 is in the same manner as in Example 8 A catalyst structure for exhaust gas purification of a comparative example was manufactured.
- the outlet gas components at 100 to 500 ° C. were measured using a CO / HC / NO analyzer (MOTOR EXHAUST GAS ANALYZER MEXA9100, manufactured by Horiba, Ltd.).
- the light-off performance of the exhaust gas purification catalyst components of Examples 6 to 9 was determined.
- the purification rate ( ⁇ 400) at 400 ° C. of each of CO / HC / NO was determined from the result of the obtained light-off performance evaluation. The results were as shown in Table 6.
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Abstract
Description
実施例1
50℃の湯浴に浸した三口フラスコ中に2-プロパノール1.5L、瑪瑙乳鉢にて粉砕したアルミニウムイソプロポキシド200g及びボロンn-プロポキシド40.9gを入れ、N2ガスにて置換しながら攪拌した。アルミニウムイソプロポキシドが完全に溶解した(溶液が透明になった)後、2-プロパノール:水=1:1の混合溶液24.6gをゆっくり滴下して徐々に加水分解させると白いゲル状物質が生成した。得られた沈殿物をエタノールで洗浄し、次いで純水で洗浄し、ろ過した。その後、120℃で一晩(約15時間)乾燥し、空気中300℃で3時間焼成し、更に空気中1,000℃で5時間焼成して白色生成物であるホウ酸アルミニウムを得た。このホウ酸アルミニウムはX線回折によって式9Al2O3・2B2O3で表わされるホウ酸アルミニウムであると同定できた。
硝酸ランタン水溶液中の硝酸ランタンの量を、目的とするLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウム中のLa2O3の量がホウ酸アルミニウムの質量を基準にして1質量%となる量とした以外は実施例1と同様にして本発明の排気ガス浄化用触媒を製造した。
硝酸ランタン水溶液中の硝酸ランタンの量を、目的とするLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウム中のLa2O3の量がホウ酸アルミニウムの質量を基準にして2質量%となる量とした以外は実施例1と同様にして本発明の排気ガス浄化用触媒を製造した。
La2O3で修飾させる工程を実施しなかった以外は実施例1と同様にして(即ち、La2O3で修飾させることなしでホウ酸アルミニウムにPdを担持させて)比較例の排気ガス浄化用触媒を製造した。
硝酸ランタン水溶液中の硝酸ランタンの量を、目的とするLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウム中のLa2O3の量がホウ酸アルミニウムの質量を基準にして3質量%となる量とした以外は実施例1と同様にして比較例の排気ガス浄化用触媒を製造した。
硝酸ランタン水溶液中の硝酸ランタンの量を、目的とするLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウム中のLa2O3の量がホウ酸アルミニウムの質量を基準にして5質量%となる量とした以外は実施例1と同様にして比較例の排気ガス浄化用触媒を製造した。
La安定化アルミナを硝酸Pd水溶液中に浸漬させた。この硝酸Pd水溶液中の硝酸Pdの量はPdメタルの質量に換算して、La安定化アルミナの0.4質量%となる量であった。その後、120℃で一晩(約15時間)蒸発乾固させ、空気中600℃で3時間焼成して比較例の排気ガス浄化用触媒を製造した。
実施例1~3及び比較例1~3で得られた各々の排気ガス浄化用触媒を水蒸気10%を含んだ大気雰囲気中で、900℃で25時間耐久処理した後、それらの触媒活性を以下のようにして評価した。即ち、固定床流通型反応装置を用い、反応管に触媒粉をセットし、CO:0.51%、NO:500ppm、C3H6:1170ppmC、O2:0.4%、残余N2から成る完全燃焼を想定した模擬排気ガスをW/F(触媒質量/ガス流量)=5.0×10-4g・min・cm-3となるように反応管に流通させ、100~500℃における出口ガス成分をCO/HC/NO分析計を用いて測定した。得られたライトオフ性能評価結果より、NOの10%、50%及び90%浄化率に到達する温度(T10、T50及びT90)を求めた。その結果は第1表に示す通りであった。
Pd分散度=CO吸着量に相当するPd量(モル)/含まれているPdの総量(モル)
により計算される値である。それらの値からPd分散度劣化率を求めた。それらの結果は第4表に示す通りであった。
1質量%のLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウム59.8質量部、CeO2-ZrO2系複合酸化物29.6質量部、酸化バリウムとして3.3質量部に相当する量の硝酸バリウム及びアルミナ系バインダー6.0質量部を硝酸Pd水溶液に添加し、湿式粉砕処理を施してPd含有スラリーを得た。この硝酸Pd水溶液中の硝酸Pdの量はPdメタルの質量に換算して、固形分の1.3質量%となる量であった。得られたスラリーをセラミックハニカム(触媒支持体)に100g/Lとなる量で塗布し、乾燥し、焼成して本発明の排気ガス浄化用触媒構成体を製造した。
CeO2-ZrO2系複合酸化物29.6質量部、La安定化アルミナ59.8質量部、酸化バリウムとして3.3質量部に相当する量の硝酸バリウム及びアルミナ系バインダー6.0質量部を硝酸Pd水溶液に添加し、湿式粉砕処理を施してPd含有スラリーを得た。この硝酸Pd水溶液中の硝酸Pdの量はPdメタルの質量に換算して、固形分の1.3質量%となる量であった。得られたスラリーをセラミックハニカム(触媒支持体)に100g/Lとなる量で塗布し、乾燥し、焼成して比較例の排気ガス浄化用触媒構成体を製造した。
上記実施例4、比較例5の排気ガス浄化用触媒構成体を1000℃に保持した電気炉にセットし、C3H6:5,000ppmC、O2:0.75%及び残余量のN2から成る完全燃焼を想定した模擬排気ガス(50s)及び空気(50s)を周期させながら流通させて25時間処理した。この模擬排気ガス耐久後の排気ガス浄化用触媒構成体について性能比較を行った。上記と同一組成の完全燃焼を想定した模擬排気ガスを全流量25L/min、SV=100,000h-1となるように上記の耐久後の実施例4、比較例5の排気ガス浄化用触媒構成体に流通させ、100~500℃における出口ガス成分をCO/HC/NO分析計(堀場製作所製 MOTOR EXHAUST GAS ANALYZER MEXA9100)を用いて測定して、上記実施例4、比較例5の排気ガス浄化用触媒構成体のライトオフ性能を求めた。得られたライトオフ性能評価の結果より、CO/HC/NOそれぞれの50%浄化率に到達する温度(T50)を求めた。その結果は第5表に示す通りであった。
1質量%のLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウム45.6質量部、CeO2-ZrO2系複合酸化物45.6質量部、酸化バリウムとして2.0質量部に相当する量の硝酸バリウム及びアルミナ系バインダー6.0質量部を硝酸Pd水溶液に添加し、湿式粉砕処理を施してPd含有スラリーを得た。この硝酸Pd水溶液中の硝酸Pdの量はPdメタルの質量に換算して、固形分の0.83質量%となる量であった。得られたスラリーをセラミックハニカム(触媒支持体)に100g/Lとなる量で塗布し、乾燥し、焼成した。
1質量%のLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウム45.4質量部、CeO2-ZrO2系複合酸化物45.4質量部、酸化バリウムとして2.2質量部に相当する量の硝酸バリウム及びアルミナ系バインダー6.0質量部を硝酸Pd水溶液に添加し、湿式粉砕処理を施してPd含有スラリーを得た。この硝酸Pd水溶液中の硝酸Pdの量はPdメタルの質量に換算して、固形分の0.91質量%となる量であった。得られたスラリーをセラミックハニカム(触媒支持体)に100g/Lとなる量で塗布し、乾燥し、焼成した。
1質量%のLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウム45.4質量部、CeO2-ZrO2系複合酸化物45.4質量部、酸化バリウムとして2.3質量部に相当する量の硝酸バリウム及びアルミナ系バインダー6.0質量部を硝酸Pd水溶液に添加し、湿式粉砕処理を施してPd含有スラリーを得た。この硝酸Pd水溶液中の硝酸Pdの量はPdメタルの質量に換算して、固形分の0.95質量%となる量であった。得られたスラリーをセラミックハニカム(触媒支持体)に100g/Lとなる量で塗布し、乾燥し、焼成した。
1質量%のLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウム45.3質量部、CeO2-ZrO2系複合酸化物45.3質量部、酸化バリウムとして2.4質量部に相当する量の硝酸バリウム及びアルミナ系バインダー6.0質量部を硝酸Pd水溶液に添加し、湿式粉砕処理を施してPd含有スラリーを得た。この硝酸Pd水溶液中の硝酸Pdの量はPdメタルの質量に換算して、固形分の1.00質量%となる量であった。得られたスラリーをセラミックハニカム(触媒支持体)に100g/Lとなる量で塗布し、乾燥し、焼成して本発明の排気ガス浄化用触媒構成体を製造した。
1質量%のLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウムの代わりに同量のLa安定化アルミナを用いた以外は実施例5と同様にして比較例の排気ガス浄化用触媒構成体を製造した。
1質量%のLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウムの代わりに同量のLa安定化アルミナを用いた以外は実施例6と同様にして比較例の排気ガス浄化用触媒構成体を製造した。
1質量%のLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウムの代わりに同量のLa安定化アルミナを用いた以外は実施例7と同様にして比較例の排気ガス浄化用触媒構成体を製造した。
1質量%のLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウムの代わりに同量のLa安定化アルミナを用いた以外は実施例8と同様にして比較例の排気ガス浄化用触媒構成体を製造した。
上記実施例5~8、比較例6~9の排気ガス浄化用触媒構成体を1000℃に保持した電気炉にセットし、C3H6:5,000ppmC、O2:0.75%及び残余量のN2から成る完全燃焼を想定した模擬排気ガス(50s)及び空気(50s)を周期させながら流通させて25時間処理した。この模擬排気ガス耐久後の排気ガス浄化用触媒構成体について性能比較を行った。上記と同一組成の完全燃焼を想定した模擬排気ガスを全流量25L/min、SV=100,000h-1となるように上記の耐久後の実施例5~8、比較例6~9の排気ガス浄化用触媒構成体に流通させ、100~500℃における出口ガス成分をCO/HC/NO分析計(堀場製作所製 MOTOR EXHAUST GAS ANALYZER MEXA9100)を用いて測定して、上記実施例5~8、比較例6~9の排気ガス浄化用触媒構成体のライトオフ性能を求めた。得られたライトオフ性能評価の結果より、CO/HC/NOそれぞれの400℃における浄化率(η400)を求めた。その結果は第6表に示す通りであった。
Claims (6)
- ホウ酸アルミニウムの質量を基準にして0.3~2質量%となる量のLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウムを含むことを特徴とする排気ガス浄化用触媒のための担体。
- ホウ酸アルミニウムの質量を基準にして0.3~2質量%となる量のLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウムを含む担体と、該担体に担持されたPdとを含むことを特徴とする排気ガス浄化用触媒。
- ホウ酸アルミニウムの質量を基準にして0.3~2質量%となる量のLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウムを含む担体と、該担体に担持されたPd及びBaとを含むことを特徴とする排気ガス浄化用触媒。
- セラミックス又は金属材料からなる触媒支持体と、該触媒支持体上に担持されている請求項2又は3記載の排気ガス浄化用触媒の層とを含むことを特徴とする排気ガス浄化用触媒構成体。
- セラミックス又は金属材料からなる触媒支持体と、該触媒支持体上に担持されている請求項2又は3記載の排気ガス浄化用触媒の層と、該排気ガス浄化用触媒の層の上に担持されているRh触媒層とを含むことを特徴とする排気ガス浄化用触媒構成体。
- 式9Al2O3・2B2O3で表わされるホウ酸アルミニウムとランタン化合物の水溶液とを混合し、蒸発乾固させ、焼成してLa2O3で修飾された式9Al2O3・2B2O3で表わされるホウ酸アルミニウムを製造し、次いで、該修飾されたホウ酸アルミニウムとPd化合物の水溶液とを混合するか、又は該修飾されたホウ酸アルミニウムとBa化合物とPd化合物の水溶液とを混合し、その後、蒸発乾固させ、焼成することを特徴とする排気ガス浄化用触媒の製造方法。
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WO2013098987A1 (ja) * | 2011-12-28 | 2013-07-04 | 三井金属鉱業株式会社 | 排気ガス浄化用触媒のための担体、排気ガス浄化用触媒及びその製造方法 |
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US20160144344A1 (en) | 2016-05-26 |
US20130116115A1 (en) | 2013-05-09 |
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