WO2016163488A1 - 内燃機関排気ガスの浄化触媒及び該触媒を用いた排気ガス浄化方法 - Google Patents
内燃機関排気ガスの浄化触媒及び該触媒を用いた排気ガス浄化方法 Download PDFInfo
- Publication number
- WO2016163488A1 WO2016163488A1 PCT/JP2016/061462 JP2016061462W WO2016163488A1 WO 2016163488 A1 WO2016163488 A1 WO 2016163488A1 JP 2016061462 W JP2016061462 W JP 2016061462W WO 2016163488 A1 WO2016163488 A1 WO 2016163488A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cerium
- palladium
- exhaust gas
- catalyst
- oxide
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- 238000000746 purification Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 36
- 239000007789 gas Substances 0.000 title description 72
- 238000002485 combustion reaction Methods 0.000 title description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 209
- 239000002131 composite material Substances 0.000 claims abstract description 138
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 87
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 27
- 239000011574 phosphorus Substances 0.000 claims abstract description 27
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 25
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 20
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 phosphorus compound Chemical class 0.000 claims abstract description 9
- 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 claims abstract 3
- 239000010948 rhodium Substances 0.000 claims description 42
- 229910052703 rhodium Inorganic materials 0.000 claims description 32
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 32
- 238000002441 X-ray diffraction Methods 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 230000006866 deterioration Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 57
- 239000002002 slurry Substances 0.000 description 53
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 46
- 239000000843 powder Substances 0.000 description 42
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 24
- 229910052809 inorganic oxide Inorganic materials 0.000 description 23
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 22
- 229910052878 cordierite Inorganic materials 0.000 description 21
- 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 21
- 229910000510 noble metal Inorganic materials 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 19
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 238000005303 weighing Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000004898 kneading Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 208000005374 Poisoning Diseases 0.000 description 13
- 231100000572 poisoning Toxicity 0.000 description 13
- 230000000607 poisoning effect Effects 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 238000005245 sintering Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010298 pulverizing process Methods 0.000 description 11
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 10
- 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 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- 239000011232 storage material Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 150000001342 alkaline earth metals Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052777 Praseodymium Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 150000001242 acetic acid derivatives Chemical class 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 5
- 150000002823 nitrates Chemical class 0.000 description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 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
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- 229910010413 TiO 2 Inorganic materials 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
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- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- 239000010705 motor oil Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
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- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- 150000003755 zirconium compounds Chemical class 0.000 description 1
Images
Classifications
-
- 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]
-
- 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
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Definitions
- the present invention relates to an internal combustion engine exhaust gas purification catalyst and an exhaust gas purification method using the catalyst. More specifically, the present invention relates to a technique for suppressing a decrease in the performance of palladium under long-term exposure to internal combustion engine exhaust gas.
- Patent Document 3 a technique comprising an alumina carrier, platinum supported on the alumina carrier, and a cerium oxide layer covering the supported platinum and the alumina carrier.
- Non-patent Document 1 phosphorus poisoning is known to occur when a phosphorus compound derived from a lubricating oil additive such as zinc dialkyldithiophosphate contained in exhaust gas accumulates and penetrates into the catalyst layer. It is known that when this phosphorus poisoning occurs, the catalyst performance decreases (Non-patent Document 1).
- Patent Document 4 In order to suppress phosphorus poisoning, it has been disclosed that in a catalyst using palladium, a reduction in performance can be reduced with respect to cerium alone by using a composite oxide of ceria and zirconia (Patent Document 4).
- an object of the present invention is to suppress sintering of noble metal and suppress deterioration of catalyst performance even when exposed to high temperature exhaust gas containing phosphorus for a long period of time.
- An exhaust gas purification catalyst in which palladium is supported on a cerium-aluminum composite oxide containing 3 to 60% by mass of cerium in terms of cerium oxide.
- the catalyst of the present invention By using the catalyst of the present invention, sintering of noble metal particles can be suppressed even when exposed to a high-temperature phosphorus-containing exhaust gas for a long period of time, without reducing the performance of the catalyst. A high exhaust gas processing capacity can be maintained.
- (A) It is a figure which shows the result of carrying out the line analysis of the particle
- the exhaust gas purifying catalyst according to the present invention is a catalyst for purifying exhaust gas containing a phosphorus compound, which contains palladium and rhodium and contains 3 to 60% by mass of cerium oxide per cerium-aluminum composite oxide. It is formed by supporting palladium on an oxide.
- the exhaust gas purifying catalyst of the present invention having such a structure has excellent catalytic performance (poisoning resistance) and high temperature durability even after being exposed to an exhaust gas containing a phosphorus compound, and has noble metal sintering.
- exhaust gas from the internal combustion engine particularly nitrogen oxide (NOx), carbon monoxide (CO), and hydrocarbon (HC) in the exhaust gas can be efficiently purified.
- the cerium-aluminum composite oxide of this embodiment is one in which cerium in the cerium-aluminum composite oxide is uniformly dispersed in the cerium-aluminum composite oxide on the nanometer order.
- TEM-EDX energy dispersive X-ray spectrum-transmission electron microscope
- TEM-EDS energy dispersive spectroscopic-transmission electron microscope
- Ce Counts indicates the number of counts related to Ce measured by TEM-EDX or TEM-EDS.
- Al counts indicate the number of counts related to Al measured by TEM-EDX or TEM-EDS.
- the method for preparing the cerium-aluminum composite oxide is not particularly limited as long as it shows the above-mentioned uniform state, and a method for preparing a composite oxide that can be used in the field can be appropriately adopted.
- various methods such as a coprecipitation method and a sol-gel method can be used as a method for preparing the composite oxide.
- the coprecipitation method is more preferable for forming a uniform cerium-aluminum composite oxide.
- the cerium starting material (cerium source) used in these preparation methods is not particularly limited, and materials used in the field can be used. Specific examples include cerium; halides such as cerium chloride; inorganic salts such as cerium nitrate, sulfate and ammonium salts; carboxylates such as acetate; and hydroxides, alkoxides and oxides. . Preferably, nitrates, acetates, sulfates and chlorides are used. Of these, nitrate (cerium nitrate) and sulfate (cerium sulfate) are more preferable. In addition, these cerium sources may be used individually by 1 type, and may use 2 or more types together.
- the starting material (aluminum source) of aluminum used in these preparation methods is not particularly limited, and a raw material used in this field can be used.
- a raw material used in this field can be used.
- Specific examples include aluminum; halides such as aluminum chloride; inorganic salts such as nitrates, sulfates and ammonium salts of aluminum; carboxylates such as acetates; and hydroxides, alkoxides and oxides. .
- nitrates, acetates, sulfates and chlorides are used. Of these, nitrate (aluminum nitrate) and sulfate (aluminum sulfate) are more preferable.
- these aluminum sources may be used individually by 1 type, and may use 2 or more types together.
- the cerium in the cerium-aluminum composite oxide is 3 to 60% by mass, preferably 5 to 25% by mass, more preferably 8 to 20% by mass as cerium oxide.
- the content of cerium oxide is 3% or more, palladium particles supported on palladium supported on the cerium-aluminum composite oxide are formed at a high temperature of 800 ° C. or higher to form an aluminum-cerium-palladium composite oxide. It is difficult to move, and palladium can gather together and suppress sintering that becomes giant particles. Further, when it is 60% or less, the heat resistance of alumina can be exhibited, and the heat resistance of the cerium-aluminum composite oxide is exhibited.
- the aluminum-cerium-palladium composite it is considered that the cerium-aluminum composite oxide and palladium form a bond and the movement of the palladium particles is easily suppressed.
- the average particle diameter of the cerium-aluminum composite oxide is preferably 0.5 to 150 ⁇ m, more preferably 1 to 100 ⁇ m, and further preferably 2 to 50 ⁇ m.
- the BET specific surface area is preferably 10 to 300 m 2 / g, more preferably 30 to 200 m 2 / g.
- the palladium-supported cerium-aluminum composite oxide is used by being further supported on a three-dimensional structure. In this case, the amount of the cerium-aluminum composite oxide is not particularly limited. However, when an exhaust gas purification catalyst using a three-dimensional structure is used, it is 5 to 300 g per liter of the catalyst in terms of oxide, More preferably, it is 20 to 200 g.
- palladium functions as a catalyst in a chemical reaction (oxidation / reduction reaction) for purifying harmful substances.
- palladium means “palladium element” or “palladium atom”.
- the amount of palladium supported is 0.005 to 50% by mass, more preferably 0.05 to 50% by mass, and still more preferably 0.5 to 35% by mass with respect to the cerium-aluminum composite oxide. If the amount is less than 0.005% by mass, the amount of Pd is small, the catalyst performance is not significantly lowered by the movement of Pd, and the effect of using the present invention is small. Absent.
- the exhaust gas purifying catalyst of the present invention can use inorganic oxides used in the field of exhaust gas purifying catalysts.
- inorganic oxides used in the field of exhaust gas purifying catalysts.
- refractory inorganic oxides and oxides having oxygen storage ability are used as inorganic oxides. Can do.
- an inorganic oxide having a high melting point more preferably an inorganic oxide having a melting point of 1000 ° C. or higher is preferably used. More preferably, an inorganic oxide having a melting point of 1000 to 3000 ° C., particularly preferably 1500 to 3000 ° C. is used.
- aluminum oxide such as ⁇ -alumina or activated alumina such as ⁇ , ⁇ , ⁇ , ⁇ ; silicon oxide (silica) (SiO 2 ); titanium oxide (titania) (TiO 2 ) 2 ); zirconium oxide (zirconia) (ZrO 2 ); phosphorus oxide (P 2 O 5 ); phosphoric acid zeolite; or composite oxides thereof such as alumina-titania, alumina-zirconia, titania-zirconia, etc. .
- aluminum oxide, zirconium oxide and silicon oxide are preferable, aluminum oxide and zirconium oxide are more preferable, and aluminum oxide is more preferable.
- the refractory inorganic oxide may contain a rare earth metal (excluding Ce).
- the rare earth metal include lanthanum (La), neodymium (Nd), yttrium (Y), scandium (Sc), and praseodymium (Pr). Of these, lanthanum, neodymium, yttrium, and praseodymium are preferable, and lanthanum and praseodymium are more preferable.
- these rare earth metals may be contained independently in a refractory inorganic oxide, and may be contained in combination of 2 or more types.
- the rare earth metal in the refractory inorganic oxide may be in the form of the metal as it is, in the form of an oxide, or in the form of a complex oxide with the refractory inorganic oxide. May be.
- the shape of the refractory inorganic oxide is not particularly limited, and may be, for example, a spherical shape, a cubic shape, a spindle shape, a cylindrical shape, a ring shape, a needle shape, and an indefinite shape.
- the particle size of the inorganic oxide at this time is preferably 0.5 to 150 ⁇ m, more preferably 1 to 100 ⁇ m, still more preferably 2 to 50 ⁇ m.
- the BET specific surface area of the inorganic oxide is not particularly limited, but is preferably 10 to 750 m 2 / g, more preferably 30 to 350 m 2 / g.
- the amount of the refractory inorganic oxide is not particularly limited, but when a three-dimensional structure is used as an exhaust gas purification catalyst, it is 5 to 300 g per liter of the catalyst in terms of oxide, more preferably 10 ⁇ 200 g, more preferably 20 ⁇ 150 g.
- rare earth elements can be used as the oxygen storage material, and lanthanum, cerium, neodymium, yttrium, and praseodymium can be used, and lanthanum, cerium, or praseodymium is preferable.
- the rare earth elements can be used alone, as a mixture or a composite, and can be combined with aluminum oxide, silicon oxide, zirconium oxide, titanium oxide, etc. (except for the combination of cerium and aluminum).
- the shape of the oxygen storage material is not particularly limited, and may be, for example, a spherical shape, a cubic shape, a spindle shape, a cylindrical shape, a ring shape, a needle shape, an indefinite shape, or the like.
- the particle size of the oxygen storage material at this time is preferably 0.5 to 150 ⁇ m, more preferably 1 to 100 ⁇ m, and still more preferably 2 to 50 ⁇ m.
- the BET specific surface area of the oxygen storage material is not particularly limited, but is preferably 10 to 750 m 2 / g, and more preferably 30 to 350 m 2 / g.
- the amount of the oxygen storage material is not particularly limited. However, when an exhaust gas purifying catalyst using a three-dimensional structure is used, it is 5 to 300 g per liter of the catalyst, more preferably 10 to 10 in terms of oxide. 200 g, more preferably 20 to 150 g.
- the catalyst of the present invention may contain an alkali metal and / or an alkaline earth metal.
- the alkali metal include lithium, sodium, potassium, rubidium and cesium, and potassium is preferable.
- the alkaline earth metal include calcium, strontium and barium, and barium is preferred.
- the alkali metal and / or alkaline earth metal may be blended alone or in the form of a mixture of two or more.
- the amount of alkali metal and / or alkaline earth metal used is not particularly limited. However, when an exhaust gas purifying catalyst using a three-dimensional structure is used, the amount is 0. 5 to 40 g, more preferably 1 to 25 g, still more preferably 3 to 18 g.
- the palladium-supported cerium-aluminum composite oxide of the present invention can be used as an exhaust gas purification catalyst for purifying harmful substances in exhaust gas.
- the exhaust gas purifying catalyst contains palladium and rhodium as essential catalyst components, and may contain other noble metals such as platinum as necessary.
- the noble metal other than palladium and rhodium can be present in the same layer.
- the noble metal other than palladium and the noble metal exist in different layers.
- noble metals other than palladium can be included as long as they do not promote the movement of palladium or do not inhibit the resistance to phosphorus poisoning.
- palladium and rhodium are used in combination, it is preferably present in separate layers.
- 50% or more of the amount of palladium used is preferably a layer different from 50% or more of the amount of rhodium used.
- 50% or more of the amount of palladium used is the lower layer, and 50% or more of the rhodium usage is the upper layer.
- the exhaust gas purification catalyst may contain an inorganic oxide such as a refractory inorganic oxide or an oxygen storage material, and these noble metals are supported on the inorganic oxide.
- the amount of the noble metal based on the oxide is 0.005 to 20% by mass, preferably 0.01 to 15% by mass, and more preferably 0.05 to 10% by mass in terms of the total amount of palladium and rhodium.
- the supported amount of the noble metal-supported inorganic oxide with respect to 1 liter of the three-dimensional structure is 15 to 350 g, preferably 30 to 300 g, more preferably 60 to 250 g.
- the mass ratio of palladium to rhodium is 0.005 to 40, preferably 0.01 to 35, more preferably 0.1 to 30.
- the three-dimensional structure used in the catalyst of the present invention is not particularly limited, and a three-dimensional structure usually used in the art can be used without limitation.
- the three-dimensional structure include a heat-resistant carrier such as a honeycomb carrier, but a monolithic honeycomb structure is preferable. Examples thereof include a monolith honeycomb carrier, a metal honeycomb carrier, and a plug honeycomb carrier. Moreover, a pellet carrier etc. can be mentioned as an example of what is not a three-dimensional integrated structure.
- the monolith honeycomb carrier what is usually referred to as a ceramic honeycomb carrier may be used.
- a honeycomb carrier made of magnesium silicate or the like is preferred, and cordierite-type material is particularly preferred.
- an integrated structure using an oxidation-resistant heat-resistant metal such as stainless steel or Fe—Cr—Al alloy is used.
- These monolith carriers are manufactured by an extrusion molding method or a method of winding and solidifying a sheet-like element.
- the shape of the gas passage port (cell shape) may be any of a hexagon, a square, a triangle, and a corrugation.
- a cell density (number of cells / unit cross-sectional area) of 100 to 1000 cells / in 2 is sufficient, and preferably 400 to 900 cells / in 2.
- the structure of the catalyst is not particularly limited, but preferably has a structure in which one or two or more catalyst layers containing the palladium-supported cerium-aluminum composite oxide are laminated on a support.
- the structure of the catalyst of the present invention is not particularly limited as long as it contains at least one catalyst layer containing a palladium-supported cerium-aluminum composite oxide. When two or more catalyst layers are laminated, the palladium composite The catalyst layer containing the particles may be present at any position.
- support cerium-aluminum complex oxide of this invention may contain catalyst components other than palladium carrying
- catalyst components other than palladium-supporting cerium-aluminum composite oxide include, for example, noble metals such as platinum, alkali metals, alkaline earth metals, rare earth metals, refractory inorganic oxides, oxygen storage materials, HC adsorbents, and NOx adsorption.
- Catalyst components that can be used in the art, such as materials, can be used without limitation.
- the method for producing a palladium-supported cerium-aluminum composite oxide of the present invention can be produced by supporting palladium on a cerium-aluminum composite oxide.
- support method used with the manufacturing method of this form can be employ
- various methods such as a kneading method, a coprecipitation method, a sol-gel method, an impregnation method, a reverse micelle method, and an ion exchange method can be used.
- the kneading method, the coprecipitation method and the impregnation method are preferably used, and the kneading method and the coprecipitation method are more preferably used.
- palladium can be supported on the cerium-aluminum composite oxide.
- the starting material (palladium source) of palladium used in these loading methods is not particularly limited, and materials used in the field can be used. Specifically, metal palladium; halides such as palladium chloride; inorganic salts such as nitrates, sulfates, ammonium salts, amine salts, and tetraammine salts of palladium; carboxylates such as acetates; and hydroxides and alkoxides And oxides. Nitrate, acetate, ammonium salt, amine salt, tetraammine salt, chloride and carbonate are preferable.
- nitrates (palladium nitrate), chlorides (palladium chloride), acetates (palladium acetate), and tetraammine salts (tetraammine palladium) are preferable, and palladium nitrate is more preferable.
- these palladium sources may be used individually by 1 type, and may use 2 or more types together.
- the aqueous medium used in the above production method is not particularly limited, and an aqueous medium usually used in the field is used in the same manner.
- Specific examples include water, lower alcohols such as cyclohexanol, methanol, ethanol, 2-propanol, and organic alkaline aqueous solutions.
- water or lower alcohol is used, and water is particularly preferably used.
- the palladium-supported cerium-aluminum composite oxide thus obtained is dried at a temperature of 50 to 250 ° C., preferably 100 to 200 ° C., for 1 minute to 10 hours, preferably 5 minutes to 5 hours. Baked. Calcination is usually performed at a temperature of 300 to 700 ° C., preferably 350 to 600 ° C., for 5 minutes to 10 hours, preferably 10 minutes to 5 hours.
- the method for producing the catalyst of the present invention is not particularly limited, and can be produced by appropriately referring to conventionally known knowledge.
- the palladium-supported cerium-aluminum composite oxide of the present invention is dispersed in a suitable aqueous medium to obtain a palladium-supported cerium-aluminum composite oxide dispersion. obtain.
- a three-dimensional structure for example, a honeycomb carrier
- a catalyst in which a catalyst layer containing a palladium-supporting cerium-aluminum composite oxide is formed on a three-dimensional structure can be produced.
- palladium is supported on a cerium-aluminum composite oxide, and the three-dimensional structure is immersed in the palladium-supported cerium-aluminum composite oxide dispersion without drying and firing the palladium-supported cerium-aluminum composite oxide. After the excess dispersion liquid is removed, drying and firing can be performed.
- palladium is supported on the cerium-aluminum composite oxide, and the dispersion contains catalyst components other than the palladium-supported cerium-aluminum composite oxide of the present invention, such as noble metals, alkali metals, alkaline earth metals. , Rare earth metals, refractory inorganic oxides, oxygen storage materials, HC adsorbents, NOx adsorbents, and the like may be included.
- the aqueous medium used in the above production method is not particularly limited, and an aqueous medium usually used in the field is used in the same manner.
- Specific examples include water, lower alcohols such as cyclohexanol, methanol, ethanol, 2-propanol, and organic alkaline aqueous solutions.
- water or lower alcohol is used, and water is particularly preferably used.
- the dispersion may be wet pulverized if necessary.
- the wet pulverization is usually performed by a known method, and is not particularly limited, but a ball mill or the like is preferably used.
- a conventionally known means such as a homogenizer, an ultrasonic dispersion device, a sand mill, a jet mill, or a bead mill can be used.
- the three-dimensional structure is charged and immersed in the dispersion prepared as described above. Thereafter, the three-dimensional structure is pulled up from the slurry to remove excess slurry. Thereafter, it is dried at 50 to 250 ° C., preferably 100 to 200 ° C. for 1 minute to 10 hours, preferably 5 minutes to 5 hours, and further at a temperature of 300 to 700 ° C., preferably 350 to 600 ° C. for 5 minutes.
- a catalyst in which a catalyst layer containing palladium composite particles is formed on a three-dimensional structure can be obtained.
- the palladium-supported cerium-aluminum composite oxide layer is coated with another noble metal-supported inorganic oxide-containing slurry by the same method.
- the exhaust gas purifying catalyst of the present invention is used for purifying phosphorus-containing exhaust gas discharged from an internal combustion engine or the like.
- the phosphorous compound has high purification ability even in a state where 1 g to 30 g, more preferably 1 g to 15 g, and most preferably 1 g to 10 g are accumulated per liter of the three-dimensional structure as phosphorus oxide (P 2 O 5 ).
- the state containing 1 g or more is a state that can occur after long-term use, and it is necessary to assume 1 g or more to improve long-term durability.
- accumulation of an amount exceeding 30 g is an oil system or engine combustion abnormality and is not considered because it is a state that cannot occur in normal operation.
- the catalyst of this embodiment when palladium is supported on a cerium-aluminum composite oxide under a high temperature condition of 800 ° C. or higher, the catalyst of this embodiment has Al 5.0 Ce at the portion where the cerium-aluminum composite oxide and palladium are in contact. By forming 1.7 Pd 3.3 and suppressing sintering of palladium particles, excellent catalytic performance can be maintained. That is, the present invention also provides an exhaust gas purification method including exposing the above exhaust gas purification catalyst to phosphorus-containing exhaust gas at 800 ° C. or higher.
- exposure to exhaust gas refers to bringing the exhaust gas purifying catalyst into contact with exhaust gas, and is not limited to bringing the entire catalyst surface into contact with exhaust gas, but also a part of the catalyst surface. Is also included in contact with exhaust gas.
- the exhaust gas used in the exhaust gas purification method of the present invention is not particularly limited as long as it is an exhaust gas discharged from an internal combustion engine or the like.
- nitrogen oxide for example, NO, NO 2 , N 2 O
- the temperature of the exhaust gas is 800 ° C. or higher, the effect of the present invention (that is, the sintering suppression effect of palladium particles under a high temperature condition) can be sufficiently exerted. If it is higher, the effect of the present invention can be exhibited more remarkably.
- the temperature of the exhaust gas is preferably 900 ° C. or higher, more preferably 950 ° C. or higher, and further preferably 1000 ° C. or higher.
- a similar or different exhaust gas purification catalyst may be arranged at the front stage (inflow side) or the rear stage (outflow side) of the exhaust gas purification catalyst of the present invention.
- the weight ratio of (Pd): a1 was 4.024: 31.
- the powder (a1) of the cerium-aluminum composite oxide a powder in which cerium was confirmed to be uniformly dispersed in the cerium-aluminum composite oxide as shown in FIG. 1 and Table 1 was used. .
- the powder (a2), the average particle diameter 2.0 ⁇ mCeO 2 -ZrO 2 composite oxide, aluminum oxide and barium hydroxide having an average particle diameter of 38 ⁇ m, a2: CeO 2 -ZrO 2 composite oxide: aluminum oxide: Barium oxide (BaO) was weighed to be 54.024: 31: 15.94: 10.06, and wet pulverized with a ball mill to prepare slurry (a3).
- the prepared slurry (a3) was added to a cordierite carrier having a cell density of 600 cells / square inch of 0.8 liter, and the total of the above components was 111.024 g / liter (hereinafter, the weight per liter of cordierite carrier was g / liter). The amount was expressed as liters), and was wash-coated, dried at 150 ° C. for 15 minutes, and then fired at 500 ° C. for 1 hour.
- aqueous rhodium nitrate solution an aqueous palladium nitrate solution, a CeO 2 —ZrO 2 composite oxide (BET specific surface area of 82 m 2 / g) having an average particle size of 4.3 ⁇ m and an aluminum oxide having an average particle size of 38 ⁇ m are converted into rhodium (Rh): Weigh so that the mass ratio of palladium (Pd): CeO 2 —ZrO 2 composite oxide: aluminum oxide is 0.36: 0.216: 48.7: 34.7, and wet pulverize with a ball mill. Thus, slurry (a4) was produced.
- the prepared slurry (a4) was wash-coated on a cordierite carrier previously coated with the slurry (a3) in an amount such that the total of the above components was 83.976 g / liter, dried at 150 ° C. for 15 minutes, and then heated to 500 ° C. Was then calcined for 1 hour to obtain Catalyst A coated with 4.24 g / liter of palladium and 0.36 g / liter of rhodium.
- a palladium nitrate aqueous solution was supported on alumina by a kneading method, dried at 120 ° C. for 12 hours, and then air baked at 500 ° C. for 1 hour to prepare palladium-supported aluminum oxide powder (b1).
- a result of XRD measurement of the powder (b1) after 10 hours of durability treatment in air at 1000 ° C. Al 5.0 Ce 1.7 Pd 3.3 was not detected.
- the powder (b1), an average particle diameter 2.0 ⁇ mCeO 2 -ZrO 2 composite oxide, aluminum oxide and barium hydroxide having an average particle diameter of 38 ⁇ m, b1: CeO 2 -ZrO 2 composite oxide: aluminum oxide: Barium oxide (BaO) was weighed to be 54.024: 31: 15.94: 10.06, and wet pulverized with a ball mill to prepare slurry (b2).
- the prepared slurry (b2) was wash-coated on a cordierite carrier having a cell density of 600 liters / square inch and a total amount of 111.024 g / liter of the above components, and dried at 150 ° C. for 15 minutes. Then, it baked at 500 degreeC for 1 hour.
- aqueous rhodium nitrate solution, an aqueous palladium nitrate solution, a CeO 2 —ZrO 2 composite oxide (BET specific surface area of 82 m 2 / g) having an average particle size of 4.3 ⁇ m and an aluminum oxide having an average particle size of 38 ⁇ m are converted into rhodium (Rh): Weigh so that the mass ratio of palladium (Pd): CeO 2 —ZrO 2 composite oxide: aluminum oxide is 0.36: 0.216: 48.7: 34.7, and wet pulverize with a ball mill. Thus, slurry (b3) was produced.
- the prepared slurry (b3) was wash-coated on a cordierite carrier previously coated with the slurry (b2) in an amount such that the total of the above components was 83.976 g / liter, dried at 150 ° C. for 15 minutes, and then heated to 500 ° C. Was then calcined for 1 hour to obtain Catalyst B coated with 4.24 g / liter of palladium and 0.36 g / liter of rhodium.
- aqueous palladium nitrate solution is supported on a cerium-alumina composite oxide by kneading, dried at 120 ° C for 12 hours, and then air-fired at 500 ° C for 1 hour to produce a palladium-supported cerium-aluminum composite oxide powder (c1). did.
- XRD measurement of the powder (c1) after 10 hours of durability treatment in air at 1000 ° C. Al 5.0 Ce 1.7 Pd 3.3 was detected.
- the slurry (c2) was prepared by weighing and wet-pulverizing with a ball mill.
- the prepared slurry (c2) was wash-coated on a cordierite carrier having a cell density of 400 cells / square inch of 0.0303 liters so that the total amount of the above components was 114 g / liter, dried at 150 ° C. for 15 minutes, Baked at 500 ° C. for 1 hour.
- aqueous rhodium nitrate solution a CeO 2 —ZrO 2 composite oxide having an average particle diameter of 2.1 ⁇ m, and aluminum oxide having an average particle diameter of 38 ⁇ m are mixed with the mass of rhodium (Rh): CeO 2 —ZrO 2 composite oxide: aluminum oxide.
- the slurry (c3) was produced by weighing each so that the ratio would be 0.3: 40: 40 and wet pulverizing with a ball mill.
- the prepared slurry (c3) was wash-coated on a cordierite carrier previously coated with the slurry (c2) in an amount such that the total of the above components was 80.3 g / liter, dried at 150 ° C. for 15 minutes, and then heated to 500 ° C. Was calcined for 1 hour to obtain catalyst C coated with 4 g / liter of palladium and 0.3 g / liter of rhodium.
- a palladium nitrate aqueous solution is supported on a cerium-alumina composite oxide by a kneading method, dried at 120 ° C. for 12 hours, and then air-fired at 500 ° C. for 1 hour to produce a palladium-supported cerium-aluminum composite oxide powder (d1). did.
- a palladium-supported cerium-aluminum composite oxide powder (d1) did.
- Al 5.0 Ce 1.7 Pd 3.3 was detected.
- the slurry (d2) was prepared by weighing so as to be wet-ground by a ball mill.
- the prepared slurry (d2) was wash-coated on a cordierite carrier having a cell density of 400 cells / square inch of 0.0303 liters so that the total amount of the above components was 114 g / liter, dried at 150 ° C. for 15 minutes, Baked at 500 ° C. for 1 hour.
- aqueous rhodium nitrate solution a CeO 2 —ZrO 2 composite oxide having an average particle diameter of 2.1 ⁇ m, and aluminum oxide having an average particle diameter of 38 ⁇ m are mixed with the mass of rhodium (Rh): CeO 2 —ZrO 2 composite oxide: aluminum oxide.
- the slurry (d3) was produced by weighing each so that the ratio would be 0.3: 40: 40 and wet pulverizing with a ball mill.
- the prepared slurry (d3) was wash-coated on a cordierite carrier previously coated with the slurry (d2) in an amount such that the total of the above components was 80.3 g / liter, dried at 150 ° C. for 15 minutes, and then subjected to 500 ° C. Was calcined for 1 hour to obtain Catalyst D coated with 4 g / liter of palladium and 0.3 g / liter of rhodium.
- a palladium nitrate aqueous solution is supported on a cerium-alumina composite oxide by a kneading method, dried at 120 ° C. for 12 hours, and then air-fired at 500 ° C. for 1 hour to produce a palladium-supported cerium-aluminum composite oxide powder (e1). did.
- a palladium-supported cerium-aluminum composite oxide powder (e1) did.
- Al 5.0 Ce 1.7 Pd 3.3 was detected.
- the slurry (e2) was prepared by weighing so as to be wet-ground by a ball mill.
- the prepared slurry (e2) was wash-coated on a cordierite carrier having a cell density of 400 cells / square inch of 0.0303 liters so that the total amount of the above components was 114 g / liter, dried at 150 ° C. for 15 minutes, Baked at 500 ° C. for 1 hour.
- aqueous rhodium nitrate solution a CeO 2 —ZrO 2 composite oxide having an average particle diameter of 2.1 ⁇ m, and aluminum oxide having an average particle diameter of 38 ⁇ m are mixed with the mass of rhodium (Rh): CeO 2 —ZrO 2 composite oxide: aluminum oxide.
- the slurry (e3) was prepared by weighing each so that the ratio would be 0.3: 40: 40 and wet pulverizing with a ball mill.
- the prepared slurry (e3) was wash-coated on a cordierite carrier previously coated with the slurry (e2) in an amount such that the total of the above components was 80.3 g / liter, dried at 150 ° C. for 15 minutes, and then subjected to 500 ° C. Was then calcined for 1 hour to obtain Catalyst E coated with 4 g / liter of palladium and 0.3 g / liter of rhodium.
- aqueous palladium nitrate solution is supported on a cerium-alumina composite oxide by kneading, dried at 120 ° C for 12 hours, and then air-fired at 500 ° C for 1 hour to produce a palladium-supported cerium-aluminum composite oxide powder (f1). did.
- XRD measurement of the powder (f1) after 10 hours of durability treatment in air at 1000 ° C. Al 5.0 Ce 1.7 Pd 3.3 was detected.
- the slurry (f2) was prepared by weighing so as to be wet-ground by a ball mill.
- the prepared slurry (f2) was applied to a cordierite carrier having a cell density of 400 cells / square inch of 0.0303 liter, and the amount of each of the above components was 114 g / liter, followed by drying at 150 ° C. for 15 minutes. Baked at 500 ° C. for 1 hour.
- aqueous rhodium nitrate solution a CeO 2 —ZrO 2 composite oxide having an average particle diameter of 2.1 ⁇ m, and aluminum oxide having an average particle diameter of 38 ⁇ m are mixed with the mass of rhodium (Rh): CeO 2 —ZrO 2 composite oxide: aluminum oxide.
- the slurry (f3) was produced by weighing each so that the ratio would be 0.3: 40: 40 and wet pulverizing with a ball mill.
- the prepared slurry (f3) was wash-coated on a cordierite carrier previously coated with the slurry (f2) in an amount such that the total of the above components was 80.3 g / liter, dried at 150 ° C. for 15 minutes, and then subjected to 500 ° C. Was then calcined for 1 hour to obtain catalyst F coated with 4 g / liter of palladium and 0.3 g / liter of rhodium.
- a palladium nitrate aqueous solution is supported on a cerium-alumina composite oxide by a kneading method, dried at 120 ° C. for 12 hours, and then air-fired at 500 ° C. for 1 hour to produce a palladium-supported cerium-aluminum composite oxide powder (g1). did.
- a palladium-supported cerium-aluminum composite oxide powder (g1) did.
- Al 5.0 Ce 1.7 Pd 3.3 was detected.
- the slurry (g2) was prepared by weighing and wet-grinding with a ball mill.
- the prepared slurry (g2) was wash-coated on a cordierite carrier having a cell density of 400 cells / square inch of 0.0303 liter, and the total amount of the above components was 114 g / liter, dried at 150 ° C. for 15 minutes, Baked at 500 ° C. for 1 hour.
- aqueous rhodium nitrate solution a CeO 2 —ZrO 2 composite oxide having an average particle diameter of 2.1 ⁇ m, and aluminum oxide having an average particle diameter of 38 ⁇ m are mixed with the mass of rhodium (Rh): CeO 2 —ZrO 2 composite oxide: aluminum oxide.
- Slurries (g3) were prepared by weighing each so that the ratio was 0.3: 40: 40 and wet pulverizing with a ball mill.
- the prepared slurry (g3) was wash-coated on a cordierite carrier previously coated with the slurry (g2) in an amount such that the total of the above components was 80.3 g / liter, dried at 150 ° C. for 15 minutes, and then subjected to 500 ° C. Was then calcined for 1 hour to obtain catalyst G coated with 4 g / liter of palladium and 0.3 g / liter of rhodium.
- CeO 2 : Al 2 O 3 60: 40, the same applies hereinafter
- a palladium nitrate aqueous solution is supported on a cerium-alumina composite oxide by a kneading method, dried at 120 ° C. for 12 hours, and then air-fired at 500 ° C. for 1 hour to produce a palladium-supported cerium-aluminum composite oxide powder (h1). did.
- a palladium-supported cerium-aluminum composite oxide powder (h1) did.
- Al 5.0 Ce 1.7 Pd 3.3 was detected.
- the slurry (h2) was prepared by weighing and wet-pulverizing with a ball mill.
- the prepared slurry (h2) was wash-coated on a cordierite carrier having a cell density of 400 cells / square inch of 0.0303 liters so that the total amount of the above components was 114 g / liter, dried at 150 ° C. for 15 minutes, Baked at 500 ° C. for 1 hour.
- aqueous rhodium nitrate solution a CeO 2 —ZrO 2 composite oxide having an average particle diameter of 2.1 ⁇ m, and aluminum oxide having an average particle diameter of 38 ⁇ m are mixed with the mass of rhodium (Rh): CeO 2 —ZrO 2 composite oxide: aluminum oxide.
- the slurry (h3) was produced by weighing each so that the ratio would be 0.3: 40: 40 and wet pulverizing with a ball mill.
- the prepared slurry (h3) was wash-coated on a cordierite carrier previously coated with the slurry (h2) in an amount such that the total of the above components was 80.3 g / liter, dried at 150 ° C. for 15 minutes, and then heated to 500 ° C. Was then calcined for 1 hour to obtain catalyst H coated with 4 g / liter of palladium and 0.3 g / liter of rhodium.
- aqueous palladium nitrate solution was supported on aluminum oxide by a kneading method, dried at 120 ° C. for 12 hours, and then air baked at 500 ° C. for 1 hour to prepare palladium-supported aluminum oxide powder (i1).
- XRD measurement of the powder (i1) after 10 hours of durability treatment in air at 1000 ° C. Al 5.0 Ce 1.7 Pd 3.3 was not detected.
- the slurry (i1) was prepared by weighing so as to be wet-ground by a ball mill.
- the prepared slurry (i2) was wash-coated on a cordierite carrier with a cell density of 400 cells / square inch of 0.0303 liter, and the total amount of the above components was 114 g / liter, dried at 150 ° C. for 15 minutes, Baked at 500 ° C. for 1 hour.
- aqueous rhodium nitrate solution a CeO 2 —ZrO 2 composite oxide having an average particle diameter of 2.1 ⁇ m, and aluminum oxide having an average particle diameter of 38 ⁇ m are mixed with the mass of rhodium (Rh): CeO 2 —ZrO 2 composite oxide: aluminum oxide.
- Slurry (i3) was produced by weighing each so that the ratio would be 0.3: 40: 40 and wet pulverizing with a ball mill.
- the prepared slurry (i3) was wash-coated on a cordierite carrier previously coated with the slurry (i2) in an amount such that the total of the above components was 80.3 g / liter, dried at 150 ° C. for 15 minutes, and then heated to 500 ° C. Was then calcined for 1 hour to obtain Catalyst I coated with 4 g / liter of palladium and 0.3 g / liter of rhodium.
- a palladium nitrate aqueous solution was supported on cerium oxide by a kneading method, dried at 120 ° C. for 12 hours, and then air baked at 500 ° C. for 1 hour to prepare palladium-supported cerium oxide powder (j1).
- a result of XRD measurement of the powder (j1) after 10 hours durability treatment at 1000 ° C. in air Al 5.0 Ce 1.7 Pd 3.3 was not detected.
- the remaining raw material was wet pulverized with a ball mill to prepare slurry (j1).
- the prepared slurry (j2) was wash-coated on a cordierite carrier having a cell density of 400 cells / square inch of 0.0303 liter so that the total amount of the above components was 114 g / liter, dried at 150 ° C. for 15 minutes, Baked at 500 ° C. for 1 hour.
- aqueous rhodium nitrate solution a CeO 2 —ZrO 2 composite oxide having an average particle diameter of 2.1 ⁇ m, and aluminum oxide having an average particle diameter of 38 ⁇ m are mixed with the mass of rhodium (Rh): CeO 2 —ZrO 2 composite oxide: aluminum oxide.
- the slurry (j3) was produced by weighing each so that the ratio would be 0.3: 40: 40 and wet pulverizing with a ball mill.
- the prepared slurry (j3) was wash-coated on a cordierite carrier previously coated with the slurry (j2) in an amount such that the total of the above components was 80.3 g / liter, dried at 150 ° C. for 15 minutes, and then subjected to 500 ° C. Was then calcined for 1 hour to obtain Catalyst J coated with 4 g / liter of palladium and 0.3 g / liter of rhodium.
- the catalysts A and C to H obtained in Examples 1 to 7 and the catalysts B, I and J obtained in Comparative Examples 1 to 3 are respectively connected to the exhaust ports of a V type 6 cylinder and 3.0 liter engine.
- the heat treatment was performed using oil having a phosphorus (P) concentration of 3000 ppm in the engine oil.
- the temperature of the catalyst bed was set to 1000 ° C.
- the A / F at the catalyst inlet at the time of heat resistance was operated at 14.6 for 25 seconds, and then the fuel supply was stopped and operated for 2.5 seconds.
- the cycle of second operation was repeated for a total of 40 hours.
- the amount of phosphorus deposited on the catalyst was about 3.5 g per liter of the three-dimensional structure.
- ⁇ XRD peak intensity> The catalyst A obtained in Example 1 and the catalyst B obtained in Comparative Example 1 were subjected to the above heat treatment, and then the peak intensity derived from palladium was measured in X-ray diffraction measurement (XRD) using CuK ⁇ rays. did.
- XRD X-ray diffraction measurement
- the X-ray output was measured at 40 mA, 45 kV, and a step angle of 0.017 °.
- Example 1 The catalyst A obtained in Example 1 and the catalyst B obtained in Comparative Example 1 were subjected to the heat resistance treatment and then placed 30 cm downstream from the in-line 6-cylinder, 2.4-liter MPI gasoline engine exhaust port.
- a / F was 14.6, the catalyst inlet temperature was raised from 100 ° C. to 500 ° C., the gas discharged from the catalyst outlet was sampled, and the purification rates of CO, THC and NO were calculated.
- FIG. 4 shows the results when T10 is the temperature at which each purification rate reaches 10%.
- Catalyst performance evaluation test > Catalysts C to H obtained in Examples 2 to 7 and Catalysts I and J obtained in Comparative Examples 2 and 3 were subjected to the heat treatment, so that A / F was 14.6. NO, CO, C 3 H 6 , O 2 , H 2 and CO 2 are mixed, the catalyst inlet temperature is raised from 100 ° C. to 500 ° C., the gas discharged from the catalyst outlet is sampled, CO, THC and Each purification rate of NO was calculated. Table 2 shows the results when T50 is the temperature at which each purification rate reaches 50%.
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Abstract
Description
媒。
本形態のセリウム-アルミニウム複合酸化物は、ナノメートルオーダーでセリウム-アルミニウム複合酸化物中のセリウムがセリウム-アルミニウム複合酸化物中に均一に分散しているものである。均一に分散しているとは、例えば、TEM-EDX(エネルギー分散型X線スペクトル-透過型電子顕微鏡)、TEM-EDS(エネルギー分散型分光-透過型電子顕微鏡)等を用いてエネルギー分散型X線検出器を備えた電子顕微鏡観察の線分析において、セリウム-アルミニウム複合酸化物上の各観測点のセリウムの比率の最大値と最小値の差が10%以内であるとする。セリウムの比率は下記の式(1)で定義される状態を示すものである。
AlのCountsとは、TEM-EDXまたはTEM-EDSで測定したとき、測定されたAlに関するカウント数を示すものである。
本発明において、パラジウムは、有害物質を浄化するための化学反応(酸化・還元反応)において、触媒として機能する。なお、本明細書において、パラジウムとは「パラジウム元素」または「パラジウム原子」を意味する。
本発明の排気ガス浄化用触媒は、排気ガス浄化用触媒分野で用いられる無機酸化物を用いることができ、例えば、耐火性無機酸化物、酸素貯蔵能力を有する酸化物を無機酸化物として用いることができる。
本発明のパラジウム担持セリウム-アルミニウム複合酸化物は、排気ガス中の有害物質を浄化するための排気ガス浄化用触媒として使用できる。
本発明の触媒に使用される三次元構造体は、特に制限はなく、当該分野で通常使用される三次元構造体を制限なく使用することができる。三次元構造体としては、ハニカム担体などの耐熱性担体が挙げられるが、一体成型のハニカム構造体が好ましく、例えば、モノリスハニカム担体、メタルハニカム担体、プラグハニカム担体などが挙げられる。また、三次元一体構造体ではないものの例として、ペレット担体なども挙げることができる。
本発明のパラジウム担持セリウム-アルミニウム複合酸化物の製造方法は、セリウム-アルミニウム複合酸化物に、パラジウムを担持することによって製造されうる。本形態の製造方法で用いられる担持方法は、特に制限はなく、当該分野で使用されうる担持方法を適宜採用することができる。例えば、担持方法として、混練法、共沈法、ゾルゲル法や、含浸法、逆ミセル法およびイオン交換法など各種の方法が用いられうる。このうち、アルミニウム-セリウム-パラジウム複合物形成の観点から、混練法、共沈法および含浸法を用いることが好ましく、混練法および共沈法を用いることがより好ましい。このような担持方法を用いることにより、セリウム-アルミニウム複合酸化物に、パラジウムを担持させることができる。
以下、本発明の触媒の製造方法について説明する。本発明の触媒の製造方法は特に制限はなく、従来公知の知見を適宜参照して製造することができる。当該分野で用いられる触媒の製造方法の一形態によると、まず、本発明のパラジウム担持セリウム-アルミニウム複合酸化物を適当な水性媒体に分散して、パラジウム担持セリウム-アルミニウム複合酸化物の分散液を得る。そして、三次元構造体(例えば、ハニカム担体)を当該分散液に浸し、余剰の分散液を除いた後、乾燥、焼成する。以上の工程によって三次元構造体上にパラジウム担持セリウム-アルミニウム複合酸化物を含む触媒層が形成された触媒を製造することができる。なお、パラジウムをセリウム-アルミニウム複合酸化物に担持し、該パラジウム担持セリウム-アルミニウム複合酸化物を乾燥及び焼成せずに、該パラジウム担持セリウム-アルミニウム複合酸化物分散液へ、三次元構造体を浸し、余剰の分散液を除いた後、乾燥、焼成するを行うことができる。また、パラジウムがセリウム-アルミニウム複合酸化物へ担持されていれば良く、分散液には、本発明のパラジウム担持セリウム-アルミニウム複合酸化物以外の触媒成分、例えば、貴金属、アルカリ金属、アルカリ土類金属、希土類金属、耐火性無機酸化物、酸素貯蔵材、HC吸着材、およびNOx吸着材などが含まれていてもよい。
本発明の排気ガス浄化用触媒は、内燃機関などから排出されるリン含有排気ガスの浄化に使用される。リン化合物が酸化リン(P2O5)として三次元構造体1リットルあたり、好ましくは1g~30g、より好ましくは1g~15g、最も好ましくは1g~10g蓄積した状態においても高い浄化能を有する。1g以上含む状態は長期間使用後に起こり得る状態であり、長期耐久性の向上には1g以上は想定する必要がある。一方、30gを超える量が蓄積することは、オイル系統やエンジン燃焼異常であり、通常運転では起こり得ない状態であるため考慮しない。特に、本形態の触媒は、800℃以上の高温条件下において、セリウム-アルミニウム複合酸化物上にパラジウムを担持すると、セリウム-アルミニウム複合酸化物とパラジウムが接触している部分でAl5.0Ce1.7Pd3.3を形成し、パラジウム粒子のシンタリングが抑制されることで、優れた触媒性能を維持することができる。すなわち、本発明は、上述の排気ガス浄化用触媒を、800℃以上のリン含有排気ガスに曝すことを含む、排気ガス浄化方法をも提供する。なお、本明細書において「排気ガスに曝す」とは、排気ガス浄化用触媒を排気ガスと接触させることをいい、触媒表面の全部分を排気ガスと接触させる場合だけでなく、触媒表面の一部分を排気ガスと接触させる場合も含まれる。
硝酸パラジウム水溶液、平均粒径18.5μmのセリウム-アルミニウム複合酸化物(CeO2:Al2O3=8:92、以下同様)(BET比表面積100m2/g)の粉体(a1)をパラジウム(Pd):a1の質量比が4.024:31、となるように、それぞれ評量した。ここで上記セリウム-アルミニウム複合酸化物の粉体(a1)は、図1及び表1に示すようにセリウムがセリウム-アルミニウム複合酸化物中に均一に分散していることを確認したものを用いた。
硝酸パラジウム水溶液、平均粒径38μmの酸化アルミニウムを、パラジウム(Pd):酸化アルミニウムの質量比が4.024:50となるように、それぞれ評量した。
硝酸パラジウム水溶液、平均粒径59μmのセリウム-アルミニウム複合酸化物(CeO2:Al2O3=3:97、以下同様)(BET比表面積108m2/g)を、パラジウム(Pd):セリウム-アルミニウム複合酸化物の質量比が4:80となるように、それぞれ評量した。
硝酸パラジウム水溶液、平均粒径59μmのセリウム-アルミニウム複合酸化物(CeO2:Al2O3=5:95、以下同様)(BET比表面積108m2/g)を、パラジウム(Pd):セリウム-アルミニウム複合酸化物の質量比が4:80となるように、それぞれ評量した。
硝酸パラジウム水溶液、平均粒径52μmのセリウム-アルミニウム複合酸化物(CeO2:Al2O3=10:90、以下同様)(BET比表面積114m2/g)を、パラジウム(Pd):セリウム-アルミニウム複合酸化物の質量比が4:80となるように、それぞれ評量した。
硝酸パラジウム水溶液、平均粒径32μmのセリウム-アルミニウム複合酸化物(CeO2:Al2O3=20:80、以下同様)(BET比表面積121m2/g)を、パラジウム(Pd):セリウム-アルミニウム複合酸化物の質量比が4:80となるように、それぞれ評量した。
硝酸パラジウム水溶液、平均粒径32μmのセリウム-アルミニウム複合酸化物(CeO2:Al2O3=25:75、以下同様)(BET比表面積120m2/g)を、パラジウム(Pd):セリウム-アルミニウム複合酸化物の質量比が4:80となるように、それぞれ評量した。
硝酸パラジウム水溶液、平均粒径7.3μmのセリウム-アルミニウム複合酸化物(CeO2:Al2O3=60:40、以下同様)(BET比表面積121m2/g)を、パラジウム(Pd):セリウム-アルミニウム複合酸化物の質量比が4:80となるように、それぞれ評量した。
硝酸パラジウム水溶液、平均粒径38μmの酸化アルミニウムを、パラジウム(Pd):酸化アルミニウムの質量比が4:80となるように、それぞれ評量した。
硝酸パラジウム水溶液、酸化セリウムを、パラジウム(Pd):酸化セリウムの質量比が4:80となるように、それぞれ評量した。
酸化アルミニウム、硝酸セリウムを、酸化アルミニウム:酸化セリウムの質量比が92:8となるように、それぞれ評量した。酸化アルミニウムに硝酸セリウムを混練法で担持し、120℃で12時間乾燥後、500℃で1時間焼成することで、酸化セリウム担持酸化アルミニウムの粉体(k1)を得た。ここで上記セリウム-アルミニウム複合酸化物の粉体(k1)は、図2及び表1に示すようにセリウムがセリウム-アルミニウム複合酸化物中に均一に分散していないことを確認した。触媒Aを作成するにあたって、粉体(a1)を粉体(k1)に変えた以外は、同様にして作成する触媒Kは、触媒Aより排ガス浄化性能が低いものである。
上記実施例1~7で得られた触媒A及びC~H、ならびに比較例1~3で得られた触媒B、I及びJを、それぞれ、V型6気筒、3.0リットルエンジンの排気口から25cm下流側に設置し、エンジンオイル中リン(P)濃度が3000ppmのオイルを用いて、耐熱処理を行った。このとき、触媒床部の温度を1000℃とした。また、耐熱時の触媒入口部のA/Fは14.6で25秒運転し、続いて燃料供給を停止して2.5秒運転し、続いてA/Fを12.0で2.5秒運転するサイクルを繰り返し、合計40時間運転を行った。触媒上のリン堆積量は三次元構造体1リットルあたり約3.5gであった。
実施例1に用いているセリウム-アルミニウム複合酸化物(粉体a1)、及び酸化セリウム担持酸化アルミニウム(粉体k1)のTEM-EDS測定(図1(A)および図2(A))において、各粒子の線分析を行い、距離に対してセリウム及びアルミニウムのEDSスペクトル強度をプロットした結果を図1(B)および図2(B)に示す。式(1)で計算した各観測点のセリウムの比率の最大値と最小値、及び最大値と最小値の差を表1に示す。
上記実施例1で得られた触媒Aならびに比較例1で得られた触媒Bを、上記耐熱処理を行った後、CuKα線によるX線回折測定(XRD)において、パラジウムに由来するピーク強度を測定した。XRD装置としてはスペクトリス株式会社製、X‘Pert PROを用いた。X線出力は40mA、45kV、ステップ角度 0.017°で測定した。
得られたX線回析パターンにおいて、回折角2θ=33.5°における酸化パラジウムに由来するピーク強度と、2θ=40.2°におけるパラジウムに由来するピーク強度の比の結果を図3に示す。
上記実施例1で得られた触媒Aならびに比較例1で得られた触媒Bを、上記耐熱処理を行った後、直列6気筒、2.4リットルMPIガソリンエンジン排気口から30cm下流側に設置し、A/Fは14.6で、触媒入口温度を100℃から500℃まで昇温させ、触媒出口から排出されるガスをサンプリングし、CO、THCおよびNOの各浄化率を算出した。各浄化率が10%に達する時の温度をT10として、結果を図4に示す。
上記実施例2~7で得られた触媒C~H並びに比較例2及び3で得られた触媒I及びJを、上記耐熱処理を行った後、TEM測定においてパラジウム粒子径を測定した。測定したパラジウム粒子径を図5に示す。
上記実施例2~7で得られた触媒C~Hならびに比較例2及び3で得られた触媒I及びJを、上記耐熱処理を行った後、A/Fは14.6となるように、NO、CO、C3H6、O2、H2およびCO2を混合し、触媒入口温度を100℃から500℃まで昇温させ、触媒出口から排出されるガスをサンプリングし、CO、THCおよびNOの各浄化率を算出した。各浄化率が50%に達する時の温度をT50として、結果を表2に示す。
Claims (10)
- パラジウムが酸化セリウム換算で3~60質量%のセリウムを含有するセリウム-アルミニウム複合酸化物に担持されてなる排気ガス浄化用触媒。
- 該セリウム-アルミニウム複合酸化物中のセリウムが該セリウム-アルミニウム複合酸化物中に均一に分散してなる請求項1記載の排気ガス浄化用触媒。
- 前記排気ガス浄化用触媒が1000℃以上の高温に曝された後、CuKα線によるX線回折測定において、担持されたパラジウムの一部がアルミニウム-セリウム-パラジウム複合物である請求項1または2に記載の排気ガス浄化用触媒。
- 前記アルミニウム-セリウム-パラジウム複合物が、AlxCeyPdz(ただし、x=9~1、y=5~1、z=7~1)である請求項3に記載の排ガス浄化用触媒。
- 前記アルミニウム-セリウム-パラジウム複合物が、Al5.0Ce1.7Pd3.3である請求項3または4に記載の排気ガス浄化用触媒。
- 該触媒が1000℃以上の高温に曝された後、CuKα線によるX線回折測定において、回折角2θ=38.5°に位置するピーク強度と、40.2°に位置するピーク強度の比が、0.18~0.45である請求項1から5のいずれか一つに記載の排気ガス浄化用触媒。
- 白金およびロジウムの少なくとも1種を含む請求項1~6のいずれか一つに記載の排気ガス浄化用触媒。
- 該パラジウムと該ロジウムとの質量比は、0.005~40である請求項7に記載の排気ガス浄化用触媒。
- 該パラジウムの該セリウム-アルミニウム複合酸化物に対する質量比は0.005~50質量%である請求項1~8のいずれか一つに記載の排気ガス浄化用触媒。
- 請求項1~9のいずれか一つに記載の触媒を用いてリン化合物を含有する排気ガスを処理することを特徴とする排気ガスの処理方法。
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JP6662852B2 (ja) | 2020-03-11 |
CN107530687A (zh) | 2018-01-02 |
US11110396B2 (en) | 2021-09-07 |
JPWO2016163488A1 (ja) | 2017-09-14 |
EP3281697A1 (en) | 2018-02-14 |
US20180133651A1 (en) | 2018-05-17 |
EP3281697A4 (en) | 2018-03-21 |
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