JP6512911B2 - Method for producing noble metal-supported catalyst for exhaust gas purification - Google Patents
Method for producing noble metal-supported catalyst for exhaust gas purification Download PDFInfo
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- JP6512911B2 JP6512911B2 JP2015080916A JP2015080916A JP6512911B2 JP 6512911 B2 JP6512911 B2 JP 6512911B2 JP 2015080916 A JP2015080916 A JP 2015080916A JP 2015080916 A JP2015080916 A JP 2015080916A JP 6512911 B2 JP6512911 B2 JP 6512911B2
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- noble metal
- zirconia
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- oxide
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- 239000003054 catalyst Substances 0.000 title claims description 80
- 238000000746 purification Methods 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000002245 particle Substances 0.000 claims description 124
- 229910000510 noble metal Inorganic materials 0.000 claims description 71
- 239000000758 substrate Substances 0.000 claims description 62
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 53
- 238000001556 precipitation Methods 0.000 claims description 51
- 239000007789 gas Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 34
- 230000000536 complexating effect Effects 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 25
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 20
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 239000000919 ceramic Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000002923 metal particle Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052773 Promethium Inorganic materials 0.000 claims description 3
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 161
- 239000002002 slurry Substances 0.000 description 107
- 239000000843 powder Substances 0.000 description 102
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 98
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 72
- 239000000243 solution Substances 0.000 description 70
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 62
- 239000006185 dispersion Substances 0.000 description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 229910052751 metal Inorganic materials 0.000 description 46
- 239000002184 metal Substances 0.000 description 46
- 239000000047 product Substances 0.000 description 43
- 230000006866 deterioration Effects 0.000 description 39
- 238000010438 heat treatment Methods 0.000 description 38
- 229910052763 palladium Inorganic materials 0.000 description 37
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 35
- 235000011114 ammonium hydroxide Nutrition 0.000 description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 34
- 238000012360 testing method Methods 0.000 description 30
- 238000010668 complexation reaction Methods 0.000 description 29
- 238000005259 measurement Methods 0.000 description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 239000006228 supernatant Substances 0.000 description 24
- 239000010948 rhodium Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 239000004570 mortar (masonry) Substances 0.000 description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 229910052703 rhodium Inorganic materials 0.000 description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 13
- 239000012295 chemical reaction liquid Substances 0.000 description 12
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 150000003141 primary amines Chemical class 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 8
- -1 heteroaromatic hydrocarbons Chemical class 0.000 description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 238000002525 ultrasonication Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 6
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- JSKUQVBNGZGWIN-UHFFFAOYSA-N [Ce].[Pr] Chemical compound [Ce].[Pr] JSKUQVBNGZGWIN-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 3
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 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 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 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 2
- 239000003446 ligand Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- LKSVMAKMHXTSQX-UHFFFAOYSA-K samarium(3+);triacetate;hydrate Chemical compound O.[Sm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LKSVMAKMHXTSQX-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Description
本発明は、排ガス浄化用貴金属担持触媒の製造方法に関し、特に、過酷な使用環境下でも触媒金属の粒成長を抑制でき、高い触媒活性寿命が得られる排ガス浄化用貴金属担持触媒の製造方法に関するものである。 The present invention relates to a method for producing a noble metal-supported catalyst for exhaust gas purification, and more particularly to a method for producing a noble metal-supported catalyst for exhaust gas purification which can suppress grain growth of catalyst metal and obtain high catalyst activity life even under severe usage environment. It is.
貴金属触媒は、通常、酸化物粒子等の担体に担持されて使用される。例えば、自動車排ガス等の内燃機関から排出されるガスの浄化触媒では、白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）等の貴金属を組み合わせた金属触媒が広く使用され、これら金属触媒は、そのまま触媒として使用されるのではなく、通常、活性アルミナ（γ−アルミナ、ρ−アルミナ、χ−アルミナ、η−アルミナ、δ−アルミナ、κ−アルミナ、θ−アルミナ、無定形アルミナ等）系酸化物やセリア・ジルコニア系酸化物等の微粒子の表面に担持された触媒として使用される。前記担体とする酸化物微粒子は、金属粒子を高分散化して凝集を防ぎ、有効な金属触媒の表面積を維持する目的で使用される。 The noble metal catalyst is usually used by being supported on a carrier such as oxide particles. For example, as a catalyst for purifying gas discharged from an internal combustion engine such as automobile exhaust gas, a metal catalyst in which a noble metal such as platinum (Pt), palladium (Pd), rhodium (Rh) or the like is combined is widely used. Instead of being used as a catalyst as it is, usually, activated alumina (γ-alumina, −-alumina, χ-alumina, −-alumina, δ-alumina, −-alumina, −-alumina, θ-alumina, amorphous alumina, etc.) based oxidation It is used as a catalyst supported on the surface of fine particles such as metals and ceria-zirconia oxides. The oxide fine particles used as the carrier are used for the purpose of highly dispersing metal particles to prevent aggregation and maintaining the surface area of an effective metal catalyst.
自動車排ガス浄化では、貴金属等の触媒金属を酸化物微粒子に担持した触媒は、更に、金属ハニカムあるいはセラミックスハニカムの内壁にウォッシュコート（被覆）され、触媒コンバーター（ハニカム触媒構造体）として使用される。例えば、自動車排ガス中のＣＯ、ＮＯｘ、ＨＣを全て浄化する触媒として三元触媒（Ｔｈｒｅｅ ｗａｙ ｃａｔａｌｙｓｔｓ：ＴＷＣ）が知られている。 In automobile exhaust gas purification, a catalyst in which a catalyst metal such as a noble metal is supported on oxide fine particles is further washcoated (coated) on the inner wall of a metal honeycomb or a ceramic honeycomb, and used as a catalytic converter (honeycomb catalyst structure). For example, a three-way catalyst (TWC) is known as a catalyst that purifies all of CO, NOx and HC in automobile exhaust gas.
近年の排ガス規制の強化に伴い、触媒の高活性や高寿命等の性能を向上すべく、触媒金属及びその担体酸化物についてそれぞれ検討されている。特に、より過酷な使用環境下でも触媒金属の凝集・シンタリングや粒成長を抑制して高寿命化する技術の要求が高い。 With the recent tightening of exhaust gas regulations, catalyst metals and their support oxides are being studied in order to improve the performance such as high activity and long life of catalysts. In particular, there is a high demand for a technology for prolonging the life by suppressing the aggregation / sintering and the grain growth of the catalyst metal even in a more severe use environment.
貴金属等の触媒金属を酸化物等の担体に担持する方法は、触媒金属となる金属塩や金属コロイドと担体粒子の両方を水や有機溶媒に溶解又は分散し、その後、溶媒を蒸発させて熱処理する。溶媒を蒸発する前に還元剤を添加して溶解させた金属塩を還元して担体表面に析出する処理をすることもある。また、熱処理する際に還元雰囲気で行って担持金属を還元させることもある。 In the method of supporting a catalyst metal such as noble metal on a carrier such as oxide, both metal salt and metal colloid serving as catalyst metal and metal particles and carrier particles are dissolved or dispersed in water or an organic solvent, and then the solvent is evaporated and heat treated Do. Prior to evaporation of the solvent, a reducing agent may be added to reduce the dissolved metal salt and deposit on the surface of the carrier. Moreover, when carrying out heat processing, it carries out by a reducing atmosphere and may reduce a carrying | support metal.
前述の担持方法とは異なる方法として、特許文献１には、環境負荷の問題、コストの問題を改善させるのに有利な貴金属触媒担持方法として、貴金属元素を含有する前駆体とマイクロ波吸収性を有する担体とを含有する混合物粉末にマイクロ波を照射させて熱処理することにより、前記前駆体を還元処理させて前記貴金属のナノ粒子を分散させた状態で前記担体に担持させることが開示されている。 As a method different from the above-described supporting method, Patent Document 1 discloses a precursor containing noble metal element and microwave absorption as a noble metal catalyst supporting method which is advantageous for solving the problem of environmental load and the problem of cost. It is disclosed that the mixture powder containing the carrier and the powder is irradiated with microwaves and heat treated to reduce the precursor and support the noble metal nanoparticles in a dispersed state on the carrier. .
金属触媒の担持方法ではないが、特許文献２には、簡便な方法で効率よく貴金属ナノ材料を製造する方法として、貴金属酸化物分散液にアルコール類等の還元剤を添加し、マイクロ波を照射して前記貴金属酸化物分散液を加熱還元してナノロッド等の貴金属ナノ粒子を作製する方法が開示されている。更に、前記分散液に担体を含有させると貴金属を担体に担持できることも開示されている。 Although it is not a supporting method of a metal catalyst, as a method of efficiently producing a noble metal nanomaterial by a simple method, Patent Document 2 adds a reducing agent such as alcohol to a noble metal oxide dispersion and irradiates microwaves There is disclosed a method of thermally reducing the noble metal oxide dispersion to produce noble metal nanoparticles such as nanorods. Furthermore, it is also disclosed that when the dispersion liquid contains a carrier, the noble metal can be supported on the carrier.
特許文献３には、酸化物担体に担持させるクラスターを構成する貴金属の原子数を容易に制御する方法として、有機多座配位子と貴金属原子からなる多核錯体を酸化物担体上に析出させ、該析出酸化物担体にマイクロ波を照射して有機多座配位子を分解もしくは燃焼させて除去して、酸化物担体の表面に貴金属のクラスターを担持させる方法が開示されている。 In Patent Document 3, as a method of easily controlling the number of atoms of a noble metal constituting a cluster supported on an oxide carrier, a polynuclear complex composed of an organic polydentate ligand and a noble metal atom is precipitated on the oxide carrier, A method is disclosed in which the precipitated oxide support is irradiated with microwaves to decompose or burn away the organic multidentate ligand, thereby supporting the noble metal clusters on the surface of the oxide support.
特許文献４には、炭化水素の水素化処理触媒の製造方法として、結晶性アルミノシリケートゼオライトおよび／または多孔性無機酸化物からなる担体に貴金属を含有する水素化活性成分含有水溶液を含浸した後、マイクロ波を照射する方法が開示されている。前記方法によれば、水素化活性成分である貴金属が均一に高分散しているため、軽油、芳香族及び複素芳香族炭化水素等の水素処理に使用して高い水素化脱硫活性と水素化活性を有し、硫黄および窒素化合物に対して高い耐性を示し、活性劣化が少ないとしている。 In Patent Document 4, as a method for producing a hydrocarbon hydrotreating catalyst, a carrier comprising a crystalline aluminosilicate zeolite and / or a porous inorganic oxide is impregnated with an aqueous solution containing a hydrogenation active component containing a noble metal, A method of microwave irradiation is disclosed. According to the above-mentioned method, since the noble metal which is the hydrogenation active component is uniformly dispersed highly, high hydrodesulfurization activity and hydrogenation activity can be obtained by using it for hydroprocessing such as light oil, aromatic and heteroaromatic hydrocarbons, etc. It has high resistance to sulfur and nitrogen compounds, and less activity deterioration.
特許文献５には、パラジウムナノ粒子の製造方法として脂肪族アミンであるオレイルアミンで保護されたパラジウムナノ粒子及び前記パラジウムナノ粒子とパラジウム以外の貴金属を含む二元系金属ナノ粒子の製造方法が開示されている。 Patent Document 5 discloses, as a method for producing palladium nanoparticles, palladium nanoparticles protected with oleylamine which is an aliphatic amine, and a method for producing binary metal nanoparticles comprising the palladium nanoparticles and a noble metal other than palladium. ing.
上述のように自動車排ガス浄化触媒において、より過酷な使用環境下でも触媒金属の凝集・シンタリング・粒成長と呼ばれる粗大化（以下、「粒成長」と記す。）を抑制して高寿命化する技術の要求が高くなっている。触媒金属の粒成長を抑制して触媒活性寿命を延ばすためには、担持触媒金属及び担体のそれぞれを工夫することも大切であるが、本発明者らは触媒金属の担持方法によって前記問題解決ができるのではないかと着想した。 As described above, in an automobile exhaust gas purification catalyst, the catalyst metal is prevented from coarsening (hereinafter referred to as "grain growth") called aggregation, sintering, and grain growth even in a more severe use environment to prolong the life. The demand for technology is high. It is also important to devise each of the supported catalyst metal and the support in order to suppress the grain growth of the catalyst metal and extend the catalyst active life, but the present inventors have solved the above problems by the method of supporting the catalyst metal. I thought that I could do it.
触媒金属の担持方法については、上述のような一般的な方法の他に特許文献１〜４に記載のようにマイクロ波を利用する方法が開示されている。しかしながら、触媒金属の粒成長を抑制するようなマイクロ波利用の仕方ではなく、それに関する示唆もなされていない。 With respect to the method of supporting the catalytic metal, in addition to the general methods as described above, methods using microwaves as disclosed in Patent Documents 1 to 4 are disclosed. However, it is not the way of microwave utilization which suppresses the grain growth of the catalytic metal, nor is there any suggestion regarding it.
特許文献１には、貴金属前駆体とマイクロ波吸収性を有する担体との固体状態、もしくは溶剤がわずかに残っている状態の混合物にマイクロ波を照射している。そのため、担体への局所的な選択加熱により温度分布が不均一となる。その結果、貴金属族触媒粒子に一部凝集が見られ、得られる貴金属触媒粒子の粒度分布も大きいという問題点がある。 In Patent Document 1, microwaves are applied to a solid state of a noble metal precursor and a carrier having microwave absorption, or a mixture in which a solvent is slightly left. Therefore, the temperature distribution becomes uneven due to the local selective heating of the carrier. As a result, there is a problem that aggregation is partially observed in the noble metal group catalyst particles, and the particle size distribution of the obtained noble metal catalyst particles is also large.
特許文献２、４には、「担持状態は強固で且つ均一となる」、「活性劣化が少ない」等の記載があるが、具体的にどの程度であるかの記載も示唆もなく、触媒金属の粒成長をどの程度抑制できるがどうかは明確ではない。 Patent Documents 2 and 4 describe such as "the supported state is strong and uniform", "the activity is less deteriorated" and the like, but there is no suggestion of the specific degree of the catalyst metal, and the catalyst metal It is not clear how much the grain growth can be suppressed.
特許文献５には、オレイルアミンを用いてパラジウムナノ粒子及びパラジウムとパラジウム以外の貴金属との二元系金属ナノ粒子の製造方法が記載されている。しかしながら、担体への担持方法の記載も示唆もない。 Patent Document 5 describes a method for producing palladium nanoparticles and binary metal nanoparticles of palladium and a noble metal other than palladium using oleylamine. However, there is no description or suggestion of a method of supporting on a carrier.
本発明では、上記問題点に鑑みてなされたものであり、過酷な使用環境下でも触媒金属の粒成長を抑制でき、触媒の高活性や高寿命等の性能を有する排ガス浄化用貴金属担持触媒の製造方法を提供することを目的とする。 The present invention has been made in view of the above problems, and it is possible to suppress the grain growth of a catalyst metal even under a severe use environment, and to provide a noble metal-supported catalyst for exhaust gas purification having high catalytic activity and long life. The purpose is to provide a manufacturing method.
本発明者らは、触媒金属の担持方法によって、過酷な使用環境下でも触媒金属の粒成長を抑制できる排ガス浄化用貴金属担持触媒を作製できるのではないかという着想のもとに種々の検討をした結果、触媒金属を担持する際にマイクロ波を照射することによって、目的とする排ガス浄化用貴金属担持触媒を作製できることを見出した。 The present inventors have made various studies based on the idea that it is possible to produce a noble metal-supported catalyst for exhaust gas purification capable of suppressing particle growth of the catalyst metal even in a severe use environment by the method of supporting the catalyst metal. As a result, it was found that the target noble metal supported catalyst for exhaust gas purification can be produced by irradiating the microwave when supporting the catalyst metal.
更に、本発明者らは、前記のようにして触媒金属を担持した後、更に表面沈殿処理を施すと触媒金属の粒成長を抑制できる効果がより優れたものになることも見出した。また、本発明で担持した触媒金属は、表面沈殿処理する際に担持金属の溶出が抑制されるという効果も見出して、本発明を完成した。 Furthermore, the present inventors also found that the effect of suppressing the grain growth of the catalyst metal becomes more excellent if surface precipitation treatment is further performed after supporting the catalyst metal as described above. In addition, the catalyst metal supported in the present invention was found to have the effect that the elution of the supported metal is suppressed when performing surface precipitation treatment, and the present invention was completed.
すなわち、本発明の要旨は、以下のとおりである。 That is, the gist of the present invention is as follows.
（１）還元性を有する溶媒に、セラミック基材粒子を分散し、かつ貴金属塩を溶解した錯化反応溶液を調製する第一工程、前記錯化反応溶液に、マイクロ波照射による加熱を行い、前記貴金属イオンを還元し、還元した貴金属微粒子を前記セラミック基材粒子に担持する第二工程、及び、溶媒を除去する第三工程、更に、表面沈殿処理により、前記セラミック基材粒子の表面に酸化物被膜を形成する第四工程を含むことを特徴とする排ガス浄化用貴金属担持触媒の製造方法。
(1) A first step of preparing a complexing reaction solution in which ceramic base particles are dispersed and a noble metal salt is dissolved in a solvent having reducibility, the complexing reaction solution is heated by microwave irradiation, The second step of reducing the noble metal ions and supporting the reduced noble metal particles on the ceramic base particles, and the third step of removing the solvent, and further, the surface precipitation treatment oxidizes the surface of the ceramic base particles. manufacturing method of the exhaust gas purifying noble metal loaded catalyst you comprising a fourth step of forming an object coating.
（２）前記表面沈殿処理で、酸素イオン伝導酸化物が形成されることを特徴とする上記（１）に記載の排ガス浄化用貴金属担持触媒の製造方法。
(2) The method for producing a noble metal-supported catalyst for exhaust gas purification according to the above (1) , wherein an oxygen ion conductive oxide is formed by the surface precipitation treatment.
（３）前記表面沈殿処理で、酸素吸放出可能な酸化物が形成されること特徴とする上記（１）又は（２）に記載の排ガス浄化用貴金属担持触媒の製造方法。
(3) The method for producing a noble metal-supported catalyst for exhaust gas purification according to the above (1) or (2) , wherein an oxide capable of absorbing and releasing oxygen is formed by the surface precipitation treatment.
（４）前記表面沈殿処理で形成される成分が、セリア単独、またはさらにイットリウム及び原子番号５７から７１までの希土類元素（セリウム、プロメチウムを除く）から選ばれた１種以上の希土類の酸化物を含むことを特徴とする上記（１）〜（３）のいずれかに記載の排ガス浄化用貴金属担持触媒の製造方法。
(4) The component formed by the surface precipitation treatment is ceria alone, or an oxide of at least one rare earth selected from yttrium and rare earth elements having atomic numbers 57 to 71 (except cerium and promethium). The method for producing a noble metal-supported catalyst for exhaust gas purification according to any one of the above (1) to (3) , which comprises
（５）前記表面沈殿処理で形成される成分が、アルミナまたはシリカを含むことを特徴とする上記（１）〜（４）のいずれかに記載の排ガス浄化用貴金属担持触媒の製造方法。
(5) The method for producing a noble metal-supported catalyst for exhaust gas purification according to any one of the above (1) to (4) , wherein the component formed in the surface precipitation treatment contains alumina or silica.
以上のように、本発明の排ガス浄化用貴金属担持触媒の製造方法によれば、これまで以上に過酷な使用環境下でも触媒金属の粒成長を抑制でき、触媒の高活性や高寿命等の性能を有する排ガス浄化用貴金属担持触媒が得られる。排ガス浄化用貴金属担持触媒は、特に高い温度に曝される自動車排ガス浄化用貴金属担持触媒として有効である。 As described above, according to the method for producing a precious metal-supported catalyst for exhaust gas purification of the present invention, particle growth of the catalyst metal can be suppressed even under a more severe usage environment, and the performance such as high activity and long life of the catalyst can be suppressed. A noble metal-supported catalyst for exhaust gas purification is obtained. The noble metal-supported catalyst for exhaust gas purification is effective as a noble metal-supported catalyst for automobile exhaust gas purification which is particularly exposed to high temperatures.
本発明者らは、還元性を有する溶媒に分散したセラミック基材粒子と、溶解した貴金属塩との両方が存在する錯化反応溶液にマイクロ波を照射して、貴金属触媒をセラミック基材粒子に担持させると、過酷な使用環境下でも触媒金属の粒成長を抑制でき、触媒の高活性や高寿命等の性能を有する排ガス浄化用貴金属担持触媒とすることができることを見出し、本発明に至った。更に酸化物被膜の表面沈殿処理を施すことによって担持金属の溶出を抑制できることも見出して、本発明をなしたものである。 The inventors of the present invention irradiate a microwave on a complexing reaction solution in which both a ceramic base particle dispersed in a solvent having reducibility and a dissolved noble metal salt are present to thereby apply a noble metal catalyst to the ceramic base particle. It was found that when supported, it is possible to suppress the grain growth of the catalyst metal even under a severe use environment, and to obtain a noble metal-supported catalyst for exhaust gas purification having performance such as high activity and long life of the catalyst. . Furthermore, it has also been found that the elution of the supported metal can be suppressed by performing the surface precipitation treatment of the oxide film, and the present invention has been made.
本発明の排ガス浄化用貴金属担持触媒の製造方法は、還元性を有する溶媒に、セラミック基材粒子を分散し、かつ貴金属塩を溶解した錯化反応溶液を調製する第一工程、前記溶液にマイクロ波を照射する第二工程、及び、溶媒を除去する第三工程、更に、酸化物被膜の表面沈殿処理する第四工程を含むことを特徴とするものである。
The method for producing a noble metal-supported catalyst for exhaust gas purification according to the present invention comprises the steps of: dispersing a ceramic base particle in a solvent having reducibility and preparing a complexing reaction solution in which a noble metal salt is dissolved; a second step of irradiating the waves, and a third step of removing the solvent, the further and is characterized in that it comprises a fourth step of surface precipitation treatment of oxides coating.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の溶媒とは、還元性を有し、貴金属塩と錯体を形成することができれば、特に限定するものではなく、常温で固体又は液体のものが使用できる。ここで常温とは、２０℃±１５℃をいう。特に、溶媒としての１級アミンは貴金属塩と錯体を形成することができ、貴金属錯体に対する還元能を効果的に発揮するため好ましい。１級アミンは貴金属微粒子の生成時に表面修飾剤として機能するため、１級アミンの除去後においても貴金属微粒子の二次凝集を抑制することができる。また、１級アミンは貴金属錯体を還元して貴金属微粒子を得るときの反応制御の容易性の観点からは還元温度より沸点の高いものが好ましい。 The solvent of the present invention is not particularly limited as long as it has reducibility and can form a complex with a noble metal salt, and those which are solid or liquid at normal temperature can be used. Here, normal temperature means 20 ° C. ± 15 ° C. In particular, a primary amine as a solvent can form a complex with a noble metal salt and is preferable because it effectively exerts a reducing ability to the noble metal complex. Since the primary amine functions as a surface modifier at the time of formation of the noble metal fine particles, secondary aggregation of the noble metal fine particles can be suppressed even after removal of the primary amine. In addition, from the viewpoint of the ease of reaction control when reducing the noble metal complex to obtain noble metal fine particles, the primary amine preferably has a boiling point higher than the reduction temperature.
すなわち、１級アミンとしては、貴金属塩と錯体を形成させることができる沸点が１４０℃以上のものが好ましく、１８０℃以上のものがより好ましい。脂肪族アミンの炭素数が７〜１８のものが該当し、脂肪族１級アミンを好適に用いることができ、例えば炭素数が８である脂肪族アミンのＣ７Ｈ１７Ｎ（ヘプチルアミン）の沸点は１５７℃である。沸点とハンドリングの容易性から、オクチルアミン、ドデシルアミン、オレイルアミンの３種類が特に好ましい。１級アミンは溶剤兼２電子還元剤として働くので、１級アミンの量は貴金属塩中に含まれる金属換算の貴金属１ｍｏｌに対して１ｍｏｌ以上用いることが好ましく、１．２ｍｏｌ以上用いることがより好ましく、２ｍｏｌ以上用いることがさらに望ましい。１級アミンの量が１．２ｍｏｌ未満では、還元剤としての１級アミンが不足するため、十分に還元反応が進行せずに収率が悪化する。また、１級アミンの量の上限は特にはないが、例えば生産性の観点からは、貴金属塩中に含まれる金属換算の貴金属１ｍｏｌに対して２０ｍｏｌ以下とすることが好ましい。 That is, as a primary amine, the boiling point which can form a complex with a noble metal salt is preferably 140 ° C. or more, more preferably 180 ° C. or more. Aliphatic amines having 7 to 18 carbon atoms are suitable, and aliphatic primary amines can be suitably used, for example, C 7 H 17 N (heptylamine) of aliphatic amines having 8 carbon atoms The boiling point is 157 ° C. From the viewpoint of boiling point and ease of handling, three types of octylamine, dodecylamine and oleylamine are particularly preferable. Since the primary amine works as a solvent and a two-electron reducing agent, the amount of the primary amine is preferably 1 mol or more, more preferably 1.2 mol or more, per mol of noble metal in metal conversion contained in the noble metal salt. It is more preferable to use 2 mol or more. If the amount of primary amine is less than 1.2 mol, the primary amine as a reducing agent is insufficient, so the reduction reaction does not proceed sufficiently and the yield is deteriorated. Although the upper limit of the amount of primary amine is not particularly limited, for example, from the viewpoint of productivity, it is preferably 20 mol or less with respect to 1 mol of metal equivalent noble metal contained in the noble metal salt.
本発明のセラミック基材粒子とは、貴金属を担持できる酸化物粒子であり、公知の酸化物粒子を用いることができる。前記セラミック基材粒子（酸化物粒子）の例としては、セリア・ジルコニア系複合酸化物、セリウム・プラセオジウム系酸化物、ジルコニア、イットリア安定化ジルコニア、アルミナ、チタニア、シリカ等の粒子が挙げられる。 The ceramic substrate particles of the present invention are oxide particles capable of supporting a noble metal, and known oxide particles can be used. Examples of the ceramic base particles (oxide particles) include particles of ceria / zirconia based composite oxide, cerium / praseodymium based oxide, zirconia, yttria stabilized zirconia, alumina, titania, silica and the like.
前記セラミック基材粒子は、貴金属を高分散して担持する観点から、比表面積１０ｍ２／ｇ以上であるのが好ましい。より好ましくは比表面積３５ｍ２／ｇ以上である。比表面積は大きいほど貴金属を高分散して担持することができるのでより好ましいが、酸化物粒子では大きな比表面積は通常１５０ｍ２／ｇまでであるのが現実的である。より耐久性に優れた排ガス浄化触媒とするには、基材粒子の比表面積が耐久試験で低下し難いのが好ましい。特に好ましい基材粒子の表面積は、１１５０℃で２４時間の耐久試験後でも３０％以上維持できる変化率の小さいものである。セラミック基材粒子が、セリア、セリア・ジルコニア系複合酸化物、またはジルコニア、またはイットリア安定化ジルコニア、またはアルミナであるのがより耐熱性に優れている（比表面積の変化率が小さくできる）のでより好ましい。 The ceramic substrate particles preferably have a specific surface area of 10 m 2 / g or more from the viewpoint of highly dispersing and supporting a noble metal. More preferably, the specific surface area is 35 m 2 / g or more. The larger the specific surface area is, the more preferable it is because the noble metal can be supported with high dispersion, but in the oxide particles, it is practical that the large specific surface area is usually up to 150 m 2 / g. In order to make the exhaust gas purification catalyst more excellent in durability, it is preferable that the specific surface area of the substrate particles is hard to reduce in the durability test. The particularly preferred surface area of the substrate particles is one having a small rate of change which can be maintained at 30% or more even after the endurance test at 1150 ° C. for 24 hours. The ceramic substrate particles are superior in heat resistance to be ceria, ceria-zirconia-based composite oxide, or zirconia, or yttria-stabilized zirconia, or alumina (the rate of change in specific surface area can be reduced). preferable.
また、セラミック基材粒子が、酸素吸放出可能な酸化物であるのが三元触媒等の触媒活性が高くなるのでより好ましい。酸素吸放出可能な酸化物としては、例えば、セリア、セリア・ジルコニア系酸化物、セリウム・プラセオジウム系酸化物等が挙げられる。 Further, it is more preferable that the ceramic base particles be oxides capable of absorbing and releasing oxygen, because the catalytic activity of a three-way catalyst or the like becomes high. Examples of the oxide capable of absorbing and releasing oxygen include ceria, ceria-zirconia based oxide, cerium-praseodymium based oxide and the like.
セラミック基材粒子（以下単に基材粒子と言うことがある）を溶媒に分散する方法は、どのような方法でもよいが、例えば、ペイントシェーカー分散、超音波分散、ビーズミル分散、高せん断ホモジナイザー分散等がある。より好ましい方法は、超音波分散である。 Any method may be used to disperse the ceramic substrate particles (hereinafter sometimes referred to simply as substrate particles) in a solvent, for example, paint shaker dispersion, ultrasonic dispersion, bead mill dispersion, high shear homogenizer dispersion, etc. There is. A more preferred method is ultrasonic dispersion.
本発明の貴金属とは、金（Ａｕ）、銀（Ａｇ）、白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）、イリジウム（Ｉｒ）、ルテニウム（Ｒｕ）、オスミウム（Ｏｓ）である。排ガス浄化触媒としてより好ましいのは、銀、白金、パラジウム、ロジウムである。 The noble metals of the present invention are gold (Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru) and osmium (Os). Silver, platinum, palladium and rhodium are more preferable as the exhaust gas purification catalyst.
本発明の貴金属塩とは、溶媒に溶けて錯体形成化しマイクロ波照射によって分解する貴金属化合物（出発原料）であり、例えば、酢酸パラジウム、塩化パラジウム、硝酸パラジウム、塩化白金酸、塩化白金、塩化ロジウム、硝酸銀等が挙げられる。より好ましい貴金属化合物（貴金属塩）は、酢酸パラジウム、塩化パラジウムである。 The noble metal salt of the present invention is a noble metal compound (starting material) which is dissolved in a solvent to form a complex and is decomposed by microwave irradiation, for example, palladium acetate, palladium chloride, palladium nitrate, chloroplatinic acid, platinum chloride, rhodium chloride And silver nitrate. More preferred noble metal compounds (noble metal salts) are palladium acetate and palladium chloride.
前記第一工程における錯化反応溶液を調製する加熱方法としては、どのような加熱方法でも良いが、例えば、オイルバス、マントルヒーター、マイクロ波等の加熱源を用いる方法がある。加熱温度としては、２０℃以上〜１２０℃以下の範囲内の温度で加熱することが好ましい。加熱温度が２０℃未満であると錯化反応溶液を調製することが困難となり、一方、１２０℃を超えて加熱しても錯化反応が飽和しているので、熱損失となり好ましくない。 The heating method for preparing the complexing reaction solution in the first step may be any heating method, for example, a method using a heating source such as an oil bath, a mantle heater, a microwave or the like. As a heating temperature, it is preferable to heat at a temperature in the range of 20 ° C. or more and 120 ° C. or less. When the heating temperature is less than 20 ° C., it is difficult to prepare a complexing reaction solution, and on the other hand, the complexing reaction is saturated even when heated above 120 ° C., which is not preferable because it causes heat loss.
第一工程で調整された前記錯化反応溶液にマイクロ波照射する第二工程における本発明のマイクロ波とは、周波数３００ＭＨｚから３ＴＨｚの電磁波であり、金属塩が添加された錯化反応液をマイクロ波照射して加熱することにより、貴金属錯体を金属に還元して貴金属微粒子を生成させる。マイクロ波での加熱温度は１４０℃以上で加熱することが好ましい。加熱温度の上限は特に限定するものではないが、２５０℃以下とすることが望ましい。マイクロ波照射で錯化反応液を１４０℃以上で加熱することにより、マイクロ波が錯化反応液内に浸透するため、均一加熱が行われ、かつ、エネルギーを媒体に直接与えることができるため、急速加熱を行うことができる。これにより、錯化反応液全体を所望の均一な温度にすることができ、貴金属錯体の還元、核生成、核成長各々の過程を溶液全体において同時に生じさせ、粒径分布の狭い単分散な粒子を短時間で容易に製造することができる。さらに貴金属触媒粒子はマイクロ波を選択的に吸収することで未反応の貴金属錯体を消費し、核成長しながらセラミック担体と強固に固着させることができる。 The microwave of the present invention in the second step of irradiating the complexing reaction solution prepared in the first step with microwaves is an electromagnetic wave with a frequency of 300 MHz to 3 THz, and the complexing reaction solution to which a metal salt is added is By irradiating with waves and heating, the noble metal complex is reduced to metal to form noble metal fine particles. The heating temperature in the microwave is preferably 140 ° C. or higher. The upper limit of the heating temperature is not particularly limited, but is preferably 250 ° C. or less. By heating the complexing reaction solution at 140 ° C. or higher by microwave irradiation, the microwaves penetrate into the complexing reaction solution, so uniform heating can be performed and energy can be directly given to the medium, Rapid heating can be performed. This makes it possible to bring the entire complexing reaction solution to a desired uniform temperature, and simultaneously cause each process of reduction, nucleation and nucleation of a noble metal complex in the whole solution, and monodisperse particles having a narrow particle size distribution. Can be easily manufactured in a short time. Further, the noble metal catalyst particles can absorb unreacted microwaves selectively by consuming microwaves, and can firmly adhere to the ceramic support while growing as nuclei.
前記溶液にマイクロ波を照射する方法は、特に限定するものではないが、例えば使用周波数は２．４５ＧＨｚ、錯化反応溶液１ｋｇ当たりのマイクロ波出力は０．５〜５．０ｋＷ／ｋｇ、マルチモード方式の加熱条件で製造することができる。 The method of irradiating the solution with microwaves is not particularly limited. For example, the frequency used is 2.45 GHz, the microwave output per kg of complexing reaction solution is 0.5 to 5.0 kW / kg, multimode It can be manufactured under the heating conditions of the system.
本発明の第三工程における溶媒を除去する方法としては、溶媒を除去して貴金属が担持された基材粒子を回収できる方法であれば、どのような方法でも良いが、例えば、静置分離、遠心分離等の方法がある。より好ましい方法は、遠心分離である。 As a method of removing the solvent in the third step of the present invention, any method may be used, as long as it can remove the solvent and recover the substrate particles on which the noble metal is supported. There is a method such as centrifugation. The more preferred method is centrifugation.
本発明によって基材粒子に担持されている貴金属は、該基材粒子の表面に分散して存在する。分散している貴金属は、金属又は酸化物で存在して１０ｎｍ以下のサイズであるのがより好ましい。貴金属の担持量（＝貴金属／（貴金属＋基材粒子））は、特に特定しないが、０．１質量％〜１０質量％の範囲がより好ましい。 The noble metal supported on the substrate particles according to the present invention is dispersed and present on the surface of the substrate particles. The dispersed noble metal is more preferably present in a metal or oxide and having a size of 10 nm or less. The loading amount of the noble metal (= noble metal / (noble metal + base particle)) is not particularly specified, but the range of 0.1 mass% to 10 mass% is more preferable.
更に、表面沈殿処理により、酸化物被膜を形成する第四工程を含むことで、過酷な使用環境下でも触媒金属の粒成長を抑制できる効果がより優れたものになる。 Furthermore, by including the fourth step of forming an oxide film by surface precipitation treatment, the effect of being able to suppress the grain growth of the catalytic metal even in a severe use environment becomes more excellent.
本発明の表面沈殿処理とは、貴金属を担持した基材粒子を分散させた液相中から水酸化物や酸化物を形成させる処理である。液相中から形成される前記水酸化物や酸化物を熱処理してもよく、本発明の表面沈殿処理では前記熱処理する場合も含まれる。または、貴金属を担持した基材粒子を分散させた液相中から酸化物前駆体を形成し、熱処理して酸化物を形成する場合も本発明の表面沈殿処理である。前記溶液中から水酸化物や酸化物を形成させる表面沈殿処理としては、例えば、酸化物や水酸化物を形成する金属塩を溶解し、溶液のｐＨを変化させて酸化物や水酸化物を形成する方法、溶解している金属塩に添加剤を加えて溶解度の小さな塩に変化させて酸化物前駆体を析出させる方法（この場合には、更に酸化物前駆体を熱処理して酸化物を形成する）、金属アルコキシド等の加水分解反応する化合物を溶解し、水を加えて加水分解させて酸化物や水酸化物を形成する方法、等がある。 The surface precipitation treatment of the present invention is a treatment for forming a hydroxide or an oxide from the liquid phase in which substrate particles supporting a noble metal are dispersed. The hydroxide or oxide formed in the liquid phase may be heat-treated, and the surface precipitation treatment of the present invention also includes the case of heat-treatment. Alternatively, it is also the surface precipitation treatment of the present invention in the case where an oxide precursor is formed from a liquid phase in which substrate particles supporting a noble metal are dispersed and heat treated to form an oxide. As the surface precipitation treatment for forming hydroxides and oxides from the solution, for example, the oxides and metal salts forming the hydroxides are dissolved, and the pH of the solution is changed to carry out the oxides and hydroxides. Method of forming, adding an additive to a dissolved metal salt to convert it into a salt having low solubility and depositing an oxide precursor (in this case, the oxide precursor is further heat-treated to form an oxide) There is a method of dissolving a hydrolytic reaction compound such as metal alkoxide and the like and adding water to hydrolyze to form an oxide or a hydroxide.
本発明の表面沈殿処理で形成される酸化物（以下、表面沈殿膜ともいう。）は、貴金属を担持した基材粒子の表面の一部又は全体に存在することになる。また、表面沈殿膜は、担持された貴金属の周囲に存在してもいいし、一部あるいは全体を覆っていてもよい。 The oxide formed by the surface precipitation treatment of the present invention (hereinafter, also referred to as a surface precipitation film) is present on a part or the whole of the surface of the substrate particle carrying a noble metal. In addition, the surface precipitate film may be present around the supported noble metal, or may be partially or entirely covered.
表面沈殿膜は、酸素イオン伝導酸化物を含む方が三元触媒等の触媒活性が高くなるので好ましい。酸素イオン伝導酸化物としては、例えば、ジルコニア系酸化物、セリア系酸化物、セリア・ジルコニア系酸化物、セリウム・プラセオジウム系酸化物等が挙げられる。 It is preferable that the surface precipitation film contains an oxygen ion conductive oxide because the catalytic activity of a three-way catalyst or the like becomes high. Examples of oxygen ion conductive oxides include zirconia-based oxides, ceria-based oxides, ceria-zirconia-based oxides, cerium-praseodymium-based oxides, and the like.
表面沈殿膜は、酸素吸放出可能な酸化物を含む方が三元触媒等の触媒活性がより高くなるのでより好ましい。酸素吸放出可能な酸化物としては、例えば、セリア系酸化物、セリア・ジルコニア系酸化物、セリウム・プラセオジウム系酸化物等が挙げられる。 It is more preferable that the surface precipitation film contains an oxide capable of absorbing and releasing oxygen because the catalytic activity of a three-way catalyst or the like is higher. Examples of oxides capable of absorbing and releasing oxygen include ceria-based oxides, ceria-zirconia-based oxides, cerium-praseodymium-based oxides, and the like.
また、前記表面沈殿処理によって形成される成分が、セリア単独、またはさらにイットリウム及び原子番号５７から７１までの希土類元素（セリウム、プロメチウムを除く）から選ばれた１種以上の希土類の酸化物を含むのがより好ましい。 In addition, the component formed by the surface precipitation treatment contains ceria alone or an oxide of at least one rare earth selected from yttrium and rare earth elements having atomic numbers 57 to 71 (except cerium and promethium). Is more preferable.
また、前記表面沈殿処理によって形成される成分が、アルミナ又はシリカを含むのがより好ましい。
表面沈殿膜を形成するための出発原料としては、例えば、膜成分となる原料の塩化物、硝酸塩、ケイ酸塩等が挙げられる。
本発明の排ガス浄化用貴金属担持触媒の製造方法によれば、過酷な使用環境下でも触媒金属の粒成長を抑制でき、触媒の高活性や高寿命等の性能を有する排ガス浄化用貴金属担持触媒を製造することができる。
Moreover, it is more preferable that the component formed by the said surface precipitation process contains an alumina or a silica.
As a starting material for forming a surface deposited film, for example, chloride, nitrate, silicate and the like of the material serving as a film component can be mentioned.
According to the method for producing a noble metal-supported catalyst for exhaust gas purification of the present invention, it is possible to suppress grain growth of a catalyst metal even under a severe use environment, and to provide a noble metal-supported catalyst for exhaust gas purification having high activity and long life of the catalyst. It can be manufactured.
以下に発明例、比較例を用いて本発明を説明するが、本発明はこれらに限定されるものではない。以下で用いる％は、特に断らない限り質量％であり、製品を構成する酸化物中の該当する酸化物の質量％である。ここで、参考例はＮｏ．１〜５で、発明例はＮｏ．１〜１８で、比較例はＮｏ．２４〜２６である。
The present invention will be described below using invention examples and comparative examples, but the present invention is not limited to these. Unless otherwise indicated,% used below is mass%, and is the mass% of the applicable oxide in the oxide which comprises a product. Here, the reference example is No. Invention examples No. 1 to 5 1 to 18 , the comparative example is No. 24-26.
本発明の排ガス浄化用貴金属担持触媒は実際の使用時に高温雰囲気中にさらされても担持された貴金属粒子が劣化（成長、粗大化）しないことに特徴がある。この貴金属粒子の劣化の評価には粉末Ｘ線回折法を用い各担持金属の（１１１）面（例：Ａｇ：３７．９２°、Ｒｈ：４１．０５°、Ｐｄ：４０．１１°、Ｐｔ：３９．７４°）の強度、半値幅で判定しており、強度が大きく半値幅が小さくなるにつれ粒子は成長している。 The noble metal-supported catalyst for exhaust gas purification of the present invention is characterized in that the noble metal particles carried are not deteriorated (grown or coarsened) even when exposed to a high temperature atmosphere during actual use. In order to evaluate the deterioration of the precious metal particles, powder X-ray diffraction method is used to measure the (111) face of each supported metal (example: Ag: 37.92 °, Rh: 41.05 °, Pd: 40.11 °, Pt: The strength is determined at 39.74 ° and the half width, and the particles grow as the intensity increases and the half width decreases.
（参考例１）
３００ｇのオレイルアミンに基材粒子として３０ｇのセリア・ジルコニア（ＣＺ、新日本電工株式会社製、商品名；ＮＤＫ２１、比表面積；８５ｍ２／ｇ）を加え、超音波で３０分解砕し、セリア・ジルコニア分散液を得た。その後、セリア・ジルコニア分散液に３．１６ｇの酢酸パラジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって酢酸パラジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１４０℃で５分加熱することによって、セリア・ジルコニアにパラジウムを担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液(溶媒)を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してセリア・ジルコニアにパラジウムを担持した製品粉末を得た（第三工程）。
得られた粉末に対して、空気中１１００℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図１のような粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Reference Example 1 )
Add 30 g of ceria / zirconia (CZ, manufactured by Shin Nippon Denko Co., Ltd., trade name; NDK21, specific surface area: 85 m 2 / g) as substrate particles to 300 g of oleylamine, and decompose 30 by ultrasonic wave, and ceria / zirconia A dispersion was obtained. Thereafter, 3.16 g of palladium acetate was added to the ceria-zirconia dispersion liquid, and palladium acetate was dissolved by heating at 120 ° C. for 20 minutes under a nitrogen flow to obtain a complexing reaction liquid (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 140 ° C. for 5 minutes to obtain a slurry in which palladium is supported on ceria / zirconia (second step).
The slurry is allowed to stand and separated, and after removing the supernatant (solvent), the slurry is washed 3 times each with toluene and then dried for 6 hours in a vacuum dryer maintained at 60 ° C. to load palladium on ceria zirconia Product powder was obtained (third step).
The obtained powder was subjected to an accelerated heat resistance deterioration test at 1100 ° C. for 5 hours in air, and when XRD measurement was carried out, there was no particle growth as shown in FIG. 1 and a chart showing almost no deterioration was obtained. The
（比較例２４）
参考例１と同じ基材粒子として３０ｇのセリア・ジルコニア（ＣＺ）（新日本電工株式会社製、ＮＤＫ２１、比表面積；８５ｍ２／ｇ）に対して、３．１６ｇの硝酸パラジウム水溶液を基材粒子に添加して室温で溶解し、エバポレータで真空引きしながら７０℃で加熱、蒸発乾固し、６００℃で１時間焼成し、さらに、参考例１と同じ熱履歴とするため、７００℃で３時間焼成して、Ｐｄ担持セリア・ジルコニア（ＣＺ）を得た。
得られた粉末に対して、空気中１１００℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図１に示すように参考例１と比較して大きくＰｄ粒子が成長したチャートが得られた。
(Comparative example 24)
As a substrate particle the same as Reference Example 1, 3.16 g of an aqueous solution of palladium nitrate is used as a substrate particle with respect to 30 g of ceria-zirconia (CZ) (manufactured by Shin Nippon Electric Co., Ltd., NDK 21, specific surface area: 85 m 2 / g) Add, dissolve at room temperature, heat at 70 ° C while evaporating vacuum with an evaporator, evaporate to dryness, bake at 600 ° C for 1 hour, and heat at 700 ° C for 3 hours to obtain the same heat history as in Reference Example 1 Calcination was performed to obtain Pd-loaded ceria-zirconia (CZ).
The obtained powder was subjected to a heat resistance deterioration accelerated test in air at 1100 ° C. for 5 hours and subjected to XRD measurement. As shown in FIG. 1, a chart in which Pd particles grew larger compared to Reference Example 1 is shown. It was obtained.
参考例１と比較例２４とを対比すると、図１に示すように、本発明の排ガス浄化用貴金属担持触媒は実際の使用時に高温雰囲気中に曝されても担持された貴金属粒子が劣化（成長、粗大化）しないことが確認された。
Comparing the reference example 1 and the comparative example 24 , as shown in FIG. 1, the noble metal-supported catalyst for exhaust gas purification of the present invention is deteriorated in the noble metal particles supported even when exposed to a high temperature atmosphere during actual use (growth It was confirmed that it did not become coarse.
（比較例２５）
３０ｇの基材粒子としてのセリア・ジルコニア（ＣＺ）（新日本電工株式会社製、ＮＤＫ２１、比表面積；８５ｍ２／ｇ）に対して、３．９８ｇの塩化白金酸水溶液を基材粒子に添加して室温で溶解し、エバポレータで真空引きしながら７０℃で加熱、蒸発乾固し、６００℃で１時間焼成し、さらに、７００℃で３時間焼成して、Ｐｔ担持セリア・ジルコニア（ＣＺ）を得た。
得られた粉末に対して、空気中１１００℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図１の比較例２４と同様に大きくＰｔ粒子が成長したチャートが得られた。
(Comparative example 25)
3.98 g of chloroplatinic acid aqueous solution is added to the substrate particles with respect to 30 g of ceria-zirconia (CZ) as a substrate particle (Shin Nippon Electric Co., Ltd., NDK21, specific surface area: 85 m 2 / g) Dissolve at room temperature, heat at 70 ° C while evacuating with an evaporator, evaporate to dryness, bake at 600 ° C for 1 hour, and bake at 700 ° C for 3 hours to prepare Pt-loaded ceria zirconia (CZ) Obtained.
The obtained powder was subjected to a heat resistance deterioration accelerated test in air at 1100 ° C. for 5 hours, and an XRD measurement was conducted to obtain a chart in which large Pt particles were grown as in Comparative Example 24 of FIG.
（比較例２６）
３０ｇの基材粒子としてのセリア・ジルコニア（ＣＺ）（新日本電工株式会社製、ＮＤＫ２１、比表面積；８５ｍ２／ｇ）に対して、３．０８ｇの塩化ルテニゥム水溶液を基材粒子に添加して室温で溶解し、エバポレータで真空引きしながら７０℃で加熱、蒸発乾固し、６００℃で１時間焼成し、さらに、７００℃で３時間焼成して、Ｐｔ担持セリア・ジルコニア（ＣＺ）を得た。
得られた粉末に対して、空気中１１００℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図１の比較例２４と同様に大きくＲｈ粒子が成長したチャートが得られた。
(Comparative example 26)
3.08 g of an aqueous solution of ruthenium chloride is added to the substrate particles with respect to 30 g of ceria-zirconia (CZ) as a substrate particle (Shin Nippon Electric Co., Ltd., NDK21, specific surface area: 85 m 2 / g) Dissolve at room temperature, heat at 70 ° C. while evaporating vacuum with an evaporator, evaporate to dryness, bake at 600 ° C. for 1 hour, and further bake at 700 ° C. for 3 hours to obtain Pt-loaded ceria zirconia (CZ) The
The obtained powder was subjected to a heat resistance deterioration accelerated test in air at 1100 ° C. for 5 hours, and an XRD measurement was conducted to obtain a chart in which large Rh particles were grown as in Comparative Example 24 of FIG.
（参考例２）
３００ｇのドデシルアミンに基材粒子として３０ｇのジルコニア（ＺｒＯ２）（新日本電工株式会社製、商品名ＰＣＳ、比表面積３１ｍ２／ｇ）を加え、超音波で３０分解砕し、ジルコニア分散液を得た。その後、そのジルコニア分散液に３．９８ｇの塩化白金酸を加え、窒素フロー下、１２０℃で２０分加熱することによって塩化白金酸を溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して２２０℃で５分加熱することによって、ジルコニアに白金を担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してジルコニアに白金を担持した製品粉末を得た（第三工程）。
得られた粉末に対して、空気中１１００℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図１の参考例１と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Reference Example 2)
30 g of zirconia (ZrO2) (made by Shin Nippon Electric Co., Ltd., trade name PCS, specific surface area: 31 m 2 / g) was added to 300 g of dodecylamine as substrate particles, and the mixture was ultrasonically broken down into 30 particles to obtain a zirconia dispersion. . Thereafter, 3.98 g of chloroplatinic acid was added to the zirconia dispersion, and the chloroplatinic acid was dissolved by heating at 120 ° C. for 20 minutes under nitrogen flow to obtain a complexing reaction solution (first step). Next, the complexation reaction solution was irradiated with a microwave and heated at 220 ° C. for 5 minutes to obtain a slurry in which platinum is supported on zirconia (second step).
The slurry is allowed to stand and separated, and after removing the supernatant, each slurry is washed 3 times each with toluene and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to obtain a product powder carrying platinum on zirconia. (Third step).
The obtained powder was subjected to an accelerated heat resistance deterioration test at 1100 ° C. for 5 hours in air, and when XRD measurement was carried out, no particle growth was observed as in Reference Example 1 of FIG. 1 and almost no deterioration was observed A chart was obtained.
（参考例３）
参考例２と同様に、３００ｇのドデシルアミンに基材粒子として３０ｇのイットリア安定化ジルコニア（ＹＳＺ）（新日本電工株式会社製、商品名ＴＺ−８Ｙ、比表面積；１０ｍ２／ｇ）を加え、超音波で３０分解砕し、イットリア安定化ジルコニア分散液を得た。その後、その分散液に３．８４ｇの塩化ロジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって塩化ロジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して２２０℃で５分加熱することによって、イットリア安定化ジルコニアにロジウムを担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してイットリア安定化ジルコニアにロジウムを担持した製品粉末を得た（第三工程）。
得られた粉末に対して、空気中１１００℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図１の参考例１と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Reference Example 3)
In the same manner as in Reference Example 2, 30 g of yttria stabilized zirconia (YSZ) (trade name: TZ-8Y, specific surface area: 10 m 2 / g, manufactured by Shin Nippon Electric Co., Ltd.) was added as substrate particles to 300 g of dodecylamine, The mixture was broken by ultrasonication into 30 to obtain a yttria-stabilized zirconia dispersion. Thereafter, 3.84 g of rhodium chloride was added to the dispersion, and the rhodium chloride was dissolved by heating at 120 ° C. for 20 minutes under a nitrogen flow to obtain a complexation reaction solution (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 220 ° C. for 5 minutes to obtain a slurry in which rhodium is supported on yttria-stabilized zirconia (second step).
The slurry was separated and allowed to stand, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried with a vacuum dryer maintained at 60 ° C. for 6 hours to support rhodium on yttria-stabilized zirconia A powder was obtained (third step).
The obtained powder was subjected to an accelerated heat resistance deterioration test at 1100 ° C. for 5 hours in air, and when XRD measurement was carried out, no particle growth was observed as in Reference Example 1 of FIG. 1 and almost no deterioration was observed A chart was obtained.
（参考例４）
３００ｇのヘプチルアミンに基材粒子として３０ｇのアルミナ（Ａｌ２Ｏ３）（新日本電工株式会社製、商品名ＡＫＰ−Ｇ１５、比表面積；１４８ｍ２／ｇ）を加え、超音波で３０分解砕し、アルミナ分散液を得た。その後、そのアルミナ分散液に３．１６ｇの酢酸パラジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって酢酸パラジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１４０℃で５分加熱することによって、アルミナにパラジウムを担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してアルミナにパラジウムを担持した製品粉末を得た（第三工程）。
得られた粉末に対して、空気中１１００℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図１の参考例１と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Reference Example 4)
Add 30 g of alumina (Al 2 O 3 ) (made by Shin Nippon Electric Co., Ltd., trade name AKP-G15, specific surface area: 148 m 2 / g) as a substrate particle to 300 g of heptylamine, and decompose 30 by ultrasonic wave. Alumina dispersion was obtained. Thereafter, 3.16 g of palladium acetate was added to the alumina dispersion, and palladium acetate was dissolved by heating at 120 ° C. for 20 minutes under nitrogen flow to obtain a complexing reaction liquid (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 140 ° C. for 5 minutes to obtain a slurry in which palladium is supported on alumina (second step).
The slurry is allowed to stand and separated, and after removing the supernatant, the slurry is washed three times each with toluene and then dried for 6 hours in a vacuum dryer maintained at 60 ° C. to obtain a product powder having palladium supported on alumina. (Third step).
The obtained powder was subjected to an accelerated heat resistance deterioration test at 1100 ° C. for 5 hours in air, and when XRD measurement was carried out, no particle growth was observed as in Reference Example 1 of FIG. 1 and almost no deterioration was observed A chart was obtained.
（参考例５）
３００ｇのオレイルアミンに基材粒子として３０ｇのセリア・ジルコニア（ＣＺ）（新日本電工株式会社製、商品名ＮＤＫ２１、比表面積；８５ｍ２／ｇ）を加え、超音波で３０分解砕し、セリア・ジルコニア分散液を得た。その後、そのジルコニア分散液に２．３６ｇの硝酸銀を加え、窒素フロー下、８０℃で１０分加熱することによって硝酸銀を溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１８０℃で５分加熱することによって、セリア・ジルコニアに銀を担持したスラリースラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してジルコニアに銀を担持した基材粉末を得た（第三工程）。
得られた粉末に対して、空気中１１００℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２の参考例５に示すように粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Reference Example 5)
Add 30 g of ceria-zirconia (CZ) (made by Shin Nippon Electric Co., Ltd., trade name: NDK21, specific surface area: 85 m 2 / g) as substrate particles to 300 g of oleyl amine, and decompose 30 by ultrasonic wave, ceria-zirconia A dispersion was obtained. Thereafter, 2.36 g of silver nitrate was added to the zirconia dispersion, and the silver nitrate was dissolved by heating at 80 ° C. for 10 minutes under a nitrogen flow to obtain a complexation reaction solution (first step). Next, the complexation reaction solution was irradiated with a microwave and heated at 180 ° C. for 5 minutes to obtain a slurry in which silver is supported on ceria / zirconia (second step).
The slurry was separated and allowed to stand, and after removing the supernatant, the slurry was washed 3 times each with toluene, and then dried for 6 hours in a vacuum dryer maintained at 60 ° C. to support silver powder supported on zirconia. Obtained (third step).
The obtained powder was subjected to an accelerated heat resistance deterioration test at 1100 ° C. for 5 hours in air, and when XRD measurement was performed, there was no particle growth as shown in Reference Example 5 of FIG. There is no chart obtained.
（発明例１）
３００ｇのオレイルアミンに基材粒子として３０ｇのセリア・ジルコニア（ＣＺ）（新日本電工株式会社製、ＮＤＫ２１、比表面積；８５ｍ２／ｇ）を加え、超音波で３０分解砕し、セリア・ジルコニア分散液を得た。その後、そのジルコニア分散液に３．９８ｇの塩化白金酸を加え、窒素フロー下、１２０℃で２０分加熱することによって塩化白金酸を溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して２２０℃で５分加熱することによって、セリア・ジルコニアに白金を担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してジルコニアに白金を担持した基材粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながら酸化ジルコニウム３．２ｇ相当を含むオキシ塩化ジルコニウム溶液及び酸化イットリウム０．８ｇ相当を含む塩化イットリウム溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面に水酸化イットリウム含有水酸化ジルコニウムの表面沈殿膜を沈殿させた。得られたスラリーを、2％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、イットリア安定化ジルコニア表面沈殿膜（ＹＳＺ）を形成した白金を担持したセリア・ジルコニア製品粉末を得た（第四工程）。イットリア安定化ジルコニア（ＹＳＺ）の表面沈殿膜は、基材粒子であるセリア・ジルコニア３０ｇに対する膜質量は４ｇであった。
得られた製品粉末に対して参考例１〜５よりもさらに過酷な空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２の発明例１に示すように粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention Example 1 )
Add 30 g of ceria-zirconia (CZ) (made by Shin Nippon Denko Co., Ltd., NDK21, specific surface area: 85 m 2 / g) as substrate particles to 300 g of oleylamine, and decompose 30 by ultrasonic wave, ceria-zirconia dispersion liquid I got Thereafter, 3.98 g of chloroplatinic acid was added to the zirconia dispersion, and the chloroplatinic acid was dissolved by heating at 120 ° C. for 20 minutes under nitrogen flow to obtain a complexing reaction solution (first step). Next, the complexation reaction solution was irradiated with a microwave and heated at 220 ° C. for 5 minutes to obtain a slurry in which platinum is supported on ceria / zirconia (second step).
The slurry was separated and allowed to stand, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to support platinum powder supported on zirconia. Obtained (third step).
Water is added to the obtained base powder to form a slurry of 150 ml, and a zirconium oxychloride solution containing 3.2 g equivalent of zirconium oxide and a yttrium chloride solution containing 0.8 g equivalent of yttrium oxide are added while stirring, ammonia The pH was adjusted to 9 with water, and a surface precipitated film of zirconium hydroxide containing yttrium hydroxide was precipitated on the surface of the base powder particles. The obtained slurry is washed 3 times with 2% aqueous ammonia, dried at 120 ° C., calcined at 700 ° C., and mortar ground to form a yttria-stabilized zirconia surface precipitated film (YSZ) formed platinum-supported ceria -Obtained a zirconia product powder (fourth step). The surface precipitation film of yttria-stabilized zirconia (YSZ) had a film weight of 4 g with respect to 30 g of ceria-zirconia as a substrate particle.
The resulting make more severe heat degradation accelerated test for 5 hours at 1150 ° C. in air against the product powder in Reference Example 1-5, the particles as shown in Inventive Example 1 in FIG. 2 was subjected to XRD measurement The chart shows no growth and almost no deterioration.
（発明例２）
３００ｇのドデシルアミンに基材粒子として３０ｇのセリア・ジルコニア（ＣＺ）（新日本電工株式会社製、ＮＤＫ２１、比表面積；８５ｍ２／ｇ）を加え、超音波で３０分解砕し、セリア・ジルコニア分散液を得た。その後、そのジルコニア分散液に３．８４ｇの塩化ロジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって塩化ロジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して２２０℃で２０分加熱することによって、セリア・ジルコニアにロジウムを担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してジルコニアにロジウムを担持した基材粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながら酸化セリウム４．０ｇ相当を含む塩化セリウム溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面に酸化セリウム（ＣｅＯ２）の表面沈殿膜を沈殿させた。得られたスラリーを、2％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、酸化セリウム（ＣｅＯ２）の表面沈殿膜形成Ｒｈ担持セリア・ジルコニア製品粉末を得た（第四工程）。酸化セリウム（ＣｅＯ２）の表面沈殿膜は、基材粒子であるセリア・ジルコニア３０ｇに対する膜質量は４ｇであった。得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention Example 2 )
Add 30 g of ceria-zirconia (CZ) (made by Shin Nippon Electric Co., Ltd., NDK21, specific surface area: 85 m 2 / g) as a substrate particle to 300 g of dodecylamine, and decompose 30 by ultrasonication and disperse it into ceria-zirconia I got a liquid. Thereafter, 3.84 g of rhodium chloride was added to the zirconia dispersion, and the rhodium chloride was dissolved by heating at 120 ° C. for 20 minutes under a nitrogen flow to obtain a complexing reaction liquid (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 220 ° C. for 20 minutes to obtain a slurry in which rhodium is supported on ceria / zirconia (second step).
The slurry was separated and allowed to stand, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours in a vacuum drier maintained at 60 ° C. to load the substrate powder having rhodium supported on zirconia. Obtained (third step).
Water is added to the obtained base powder to form a slurry of 150 ml, a cerium chloride solution containing 4.0 g equivalent of cerium oxide is added while stirring, and the pH is adjusted to 9 with aqueous ammonia to obtain base powder particles. A surface precipitation film of cerium oxide (CeO 2 ) was precipitated on the surface. The obtained slurry is washed 3 times using 2% ammonia water, dried at 120 ° C., fired at 700 ° C., ground in a mortar, surface precipitated film of cerium oxide (CeO 2 ) formed Rh supported ceria-zirconia product powder (The fourth step). The surface precipitation film of cerium oxide (CeO 2 ) had a film weight of 4 g with respect to 30 g of ceria-zirconia as a substrate particle. The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out, as in FIG. The
（発明例３）
３００ｇのオクチルアミンに基材粒子として３０ｇのセリア・ジルコニア（ＣＺ）（新日本電工株式会社製、商品名Ｍ４０−Ａ１、比表面積；６９ｍ２／ｇ）を加え、超音波で３０分解砕し、セリア・ジルコニア分散液を得た。その後、そのジルコニア分散液に３．１６ｇの酢酸パラジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって酢酸パラジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１４０℃で５分加熱することによって、セリア・ジルコニアにパラジウムを担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してジルコニアにパラジウムを担持した基材粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながら酸化セリウム１．０ｇ相当を含む硝酸イットリウム溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面に酸化イットリウム（Ｙ２Ｏ３）の表面沈殿膜を沈殿させた。得られたスラリーを、2％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、酸化イットリウム（Ｙ２Ｏ３）表面沈殿膜形成Ｐｄ担持セリア・ジルコニア製品粉末を得た（第四工程）。酸化イットリウム（Ｙ２Ｏ３）の表面沈殿膜は、基材粒子であるセリア・ジルコニア３０ｇに対する膜質量は１ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention Example 3 )
Add 30 g of ceria-zirconia (CZ) (made by Shin Nippon Electric Co., Ltd., trade name M40-A1, specific surface area: 69 m 2 / g) as a substrate particle to 300 g of octylamine, and decompose 30 by ultrasonic wave, A ceria-zirconia dispersion was obtained. Thereafter, 3.16 g of palladium acetate was added to the zirconia dispersion, and palladium acetate was dissolved by heating at 120 ° C. for 20 minutes under a nitrogen flow to obtain a complexing reaction liquid (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 140 ° C. for 5 minutes to obtain a slurry in which palladium is supported on ceria / zirconia (second step).
The slurry was separated and allowed to stand, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to support palladium on palladium supported on zirconia. Obtained (third step).
Water is added to the obtained base powder to form a slurry of 150 ml, a yttrium nitrate solution containing 1.0 g equivalent of cerium oxide is added while stirring, and the pH is adjusted to 9 with aqueous ammonia to obtain base powder particles. A surface precipitation film of yttrium oxide (Y 2 O 3 ) was precipitated on the surface. The obtained slurry is washed 3 times using 2% ammonia water, dried at 120 ° C., fired at 700 ° C., and mortar ground, and yttrium oxide (Y 2 O 3 ) surface precipitated film formed Pd-loaded ceria-zirconia product A powder was obtained (fourth step). The surface precipitation film of yttrium oxide (Y 2 O 3 ) had a film weight of 1 g with respect to 30 g of ceria-zirconia as a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out, as in FIG. The
（発明例４）
３００ｇのオレイルアミンに基材粒子として３０ｇのセリア・ジルコニア（ＣＺ）（新日本電工株式会社製、商品名ＮＤＫ２１、比表面積；８５ｍ２／ｇ）を加え、超音波で３０分解砕し、セリア・ジルコニア分散液を得た。その後、そのジルコニア分散液に２．５０ｇの塩化パラジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって塩化パラジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１４０℃で５分加熱することによって、セリア・ジルコニアにパラジウムを担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してジルコニアにパラジウムを担持した基材粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながら硝酸ランタン１．０ｇ相当を含む硝酸ランタン溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面に酸化ランタン（Ｌａ２Ｏ３）の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、酸化ランタン表面沈殿膜を形成したＰｄ担持セリア・ジルコニア製品粉末を得た（第四工程）。酸化ランタン（Ｌａ２Ｏ３）の表面沈殿膜は、基材粒子であるセリア・ジルコニア３０ｇに対する膜質量は１ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention Example 4 )
Add 30 g of ceria-zirconia (CZ) (made by Shin Nippon Electric Co., Ltd., trade name: NDK21, specific surface area: 85 m 2 / g) as substrate particles to 300 g of oleyl amine, and decompose 30 by ultrasonic wave, ceria-zirconia A dispersion was obtained. Thereafter, 2.50 g of palladium chloride was added to the zirconia dispersion, and palladium chloride was dissolved by heating at 120 ° C. for 20 minutes under a nitrogen flow to obtain a complexation reaction solution (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 140 ° C. for 5 minutes to obtain a slurry in which palladium is supported on ceria / zirconia (second step).
The slurry was separated and allowed to stand, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to support palladium on palladium supported on zirconia. Obtained (third step).
Water is added to the obtained base powder to form a slurry of 150 ml, and while stirring, a lanthanum nitrate solution containing 1.0 g equivalent of lanthanum nitrate is added, and the pH is adjusted to 9 with aqueous ammonia to obtain base powder particles. A surface precipitation film of lanthanum oxide (La 2 O 3 ) was precipitated on the surface. The obtained slurry was washed 3 times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., and mortar ground to obtain a Pd-loaded ceria-zirconia product powder having a lanthanum oxide surface precipitation film formed. (The fourth step). The surface precipitation film of lanthanum oxide (La 2 O 3 ) had a film weight of 1 g with respect to 30 g of ceria-zirconia as a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out, as in FIG. The
（発明例５）
３００ｇのドデシルアミンに基材粒子として３０ｇのジルコニア（ＺｒＯ２）（新日本電工株式会社製、商品名ＰＣＳ、比表面積；３１ｍ２／ｇ）を加え、超音波で３０分解砕し、ジルコニア分散液を得た。その後、そのジルコニア分散液に２．３６ｇの硝酸銀を加え、窒素フロー下、８０℃で１０分加熱することによって硝酸銀を溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１８０℃で５分加熱することによって、ジルコニアに銀を担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してジルコニアに銀を担持した製品粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながらセリウム１．０ｇ相当を含む塩化セリウム溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面に酸化セリウム（ＣｅＯ２）の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、酸化ランタン表面沈殿膜を形成したＰｄ担持セリア・ジルコニア製品粉末を得た（第四工程）。酸化セリウム（ＣｅＯ２）の表面沈殿膜は、基材粒子であるセリア・ジルコニア３０ｇに対する膜質量は１ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention Example 5 )
Add 30 g of zirconia (ZrO 2 ) (made by Shin Nippon Electric Co., Ltd., trade name PCS, specific surface area: 31 m 2 / g) as a substrate particle to 300 g of dodecylamine, and decompose 30 by ultrasonication and break up the zirconia dispersion I got Thereafter, 2.36 g of silver nitrate was added to the zirconia dispersion, and the silver nitrate was dissolved by heating at 80 ° C. for 10 minutes under a nitrogen flow to obtain a complexation reaction solution (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 180 ° C. for 5 minutes to obtain a slurry in which silver is supported on zirconia (second step).
The slurry is allowed to stand and separated, and after removing the supernatant, the slurry is washed 3 times each with toluene, and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to obtain a product powder having silver supported on zirconia. (Third step).
Water is added to the obtained base powder to form a slurry of 150 ml, a cerium chloride solution containing 1.0 g equivalent of cerium is added while stirring, pH is adjusted to 9 with aqueous ammonia, and the surface of base powder particles The surface precipitation film of cerium oxide (CeO 2 ) was precipitated. The obtained slurry was washed 3 times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., and mortar ground to obtain a Pd-loaded ceria-zirconia product powder having a lanthanum oxide surface precipitation film formed. (The fourth step). The surface precipitation film of cerium oxide (CeO 2 ) had a film weight of 1 g with respect to 30 g of ceria-zirconia as a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out, as in FIG. The
（発明例６）
３００ｇのオレイルアミン（溶媒）に基材粒子として３０ｇのジルコニア（ＺｒＯ２）（新日本電工株式会社製、商品名ＰＣＳ、比表面積；３１ｍ２／ｇ）を加え、超音波で３０分解砕し、ジルコニア分散液を得た。その後、そのジルコニア分散液に３．８４ｇの塩化ロジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって塩化ロジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して２２０℃で２０分加熱することによって、ジルコニアにロジウムを担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してジルコニアにロジウムを担持した粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながらプラセオジム０．４ｇ相当を含む塩化プラセオジム溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面に酸化プラセオジム（Ｐｒ６Ｏ１１）の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、酸化プラセオジム表面沈殿膜を形成したＲｈ担持ジルコニア製品粉末を得た（第四工程）。酸化プラセオジム（Ｐｒ６Ｏ１１）の表面沈殿膜は、基材粒子であるジルコニア３０ｇに対する膜質量は０．４ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention Example 6 )
Add 30 g of zirconia (ZrO 2 ) as substrate particles to 300 g of oleylamine (solvent) (Shin Nippon Electric Co., Ltd., trade name PCS, specific surface area: 31 m 2 / g) A dispersion was obtained. Thereafter, 3.84 g of rhodium chloride was added to the zirconia dispersion, and the rhodium chloride was dissolved by heating at 120 ° C. for 20 minutes under a nitrogen flow to obtain a complexing reaction liquid (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 220 ° C. for 20 minutes to obtain a slurry in which rhodium is supported on zirconia (second step).
The slurry was allowed to stand and separated, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to obtain a powder carrying rhodium on zirconia. (Third step).
Water is added to the obtained base powder to make a slurry of 150 ml, a praseodymium chloride solution containing 0.4 g equivalent of praseodymium is added while stirring, pH is adjusted to 9 with aqueous ammonia, and the surface of base powder particles The surface precipitate film of praseodymium oxide (Pr 6 O 11 ) was precipitated. The obtained slurry was washed 3 times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., and mortar ground to obtain a Rh-loaded zirconia product powder in which a praseodymium oxide surface precipitate film was formed (No. Four steps). The surface precipitation film of praseodymium oxide (Pr 6 O 11 ) had a film weight of 0.4 g with respect to 30 g of zirconia as a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out, as in FIG. The
（発明例７）
３００ｇのドデシルアミンに基材粒子として３０ｇのジルコニア（ＺｒＯ２）（新日本電工株式会社製、商品名ＰＣＳ、比表面積；３１ｍ２／ｇ）を加え、超音波で３０分解砕し、ジルコニア分散液を得た。その後、そのジルコニア分散液に３．１６ｇの酢酸パラジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって酢酸パラジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１４０℃で５分加熱することによって、ジルコニアにパラジウムを担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してジルコニアにパラジウムを担持した粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながらネオジム０．４ｇ相当を含む塩化ネオジム溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面に酸化ネオジム（Ｎｄ２Ｏ３）の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、酸化ランタン表面沈殿膜を形成したＰｄ担持ジルコニア製品粉末を得た（第四工程）。酸化ネオジム（Ｎｄ２Ｏ３）の表面沈殿膜は、基材粒子であるジルコニア３０ｇに対する膜質量は０．４ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention Example 7 )
Add 30 g of zirconia (ZrO 2 ) (made by Shin Nippon Electric Co., Ltd., trade name PCS, specific surface area: 31 m 2 / g) as a substrate particle to 300 g of dodecylamine, and decompose 30 by ultrasonication and break up the zirconia dispersion I got Thereafter, 3.16 g of palladium acetate was added to the zirconia dispersion, and palladium acetate was dissolved by heating at 120 ° C. for 20 minutes under a nitrogen flow to obtain a complexing reaction liquid (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 140 ° C. for 5 minutes to obtain a slurry in which palladium is supported on zirconia (second step).
The slurry was allowed to stand and separated, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours with a vacuum drier maintained at 60 ° C. to obtain a powder wherein palladium was supported on zirconia (Third step).
Water is added to the obtained base powder to make a slurry of 150 ml, a neodymium chloride solution containing 0.4 g equivalent of neodymium is added while stirring, pH is adjusted to 9 with aqueous ammonia, and the surface of base powder particles Surface precipitate film of neodymium oxide (Nd 2 O 3 ). The obtained slurry was washed 3 times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., and ground in a mortar to obtain a Pd-supporting zirconia product powder in which a lanthanum oxide surface precipitation film was formed (No. Four steps). The surface precipitation film of neodymium oxide (Nd 2 O 3 ) had a film weight of 0.4 g with respect to 30 g of zirconia as a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out, as in FIG. The
（発明例８）
３００ｇのヘプチルアミンに基材粒子として３０ｇのジルコニア（ＺｒＯ２）（新日本電工株式会社製、商品名ＯＧ、比表面積；１１ｍ２／ｇ）を加え、超音波で３０分解砕し、ジルコニア分散液を得た。その後、そのジルコニア分散液に３．１６ｇの酢酸パラジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって酢酸パラジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１４０℃で５分加熱することによって、ジルコニアにパラジウムを担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してジルコニアにパラジウムを担持した粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながらサマリウム６ｇ相当を含む酢酸サマリウム溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面に酸化サマリウム（Ｓｍ２Ｏ３）の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、酸化サマリウム表面沈殿膜を形成したＰｄ担持ジルコニア製品粉末を得た（第四工程）。酸化サマリウム（Ｓｍ２Ｏ３）の表面沈殿膜は、基材粒子であるジルコニア３０ｇに対する膜質量は６ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention Example 8 )
Add 30 g of zirconia (ZrO 2 ) (made by Shin Nippon Electric Co., Ltd., trade name: OG, specific surface area: 11 m 2 / g) as a substrate particle to 300 g of heptylamine, and decompose 30 by ultrasonic wave and break it up, zirconia dispersion I got Thereafter, 3.16 g of palladium acetate was added to the zirconia dispersion, and palladium acetate was dissolved by heating at 120 ° C. for 20 minutes under a nitrogen flow to obtain a complexing reaction liquid (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 140 ° C. for 5 minutes to obtain a slurry in which palladium is supported on zirconia (second step).
The slurry was allowed to stand and separated, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours with a vacuum drier maintained at 60 ° C. to obtain a powder wherein palladium was supported on zirconia (Third step).
Water is added to the obtained base powder to form a slurry of 150 ml, a samarium acetate solution containing 6 g of samarium is added while stirring, the pH is adjusted to 9 with aqueous ammonia, and the surface of base powder particles is oxidized A surface precipitation film of samarium (Sm 2 O 3 ) was precipitated. The obtained slurry was washed three times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., and mortar-ground to obtain a Pd-supporting zirconia product powder in which a samarium oxide surface precipitation film was formed (No. Four steps). The surface precipitation film of samarium oxide (Sm 2 O 3 ) had a film weight of 6 g with respect to 30 g of zirconia as a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out. As in FIG. 2, no growth of particles was observed and a chart showing almost no deterioration was obtained. The
（発明例９）
３００ｇのオレイルアミンに基材粒子として３０ｇのジルコニア（ＺｒＯ２）（新日本電工株式会社製、商品名ＯＧ、比表面積；１１ｍ２／ｇ）を加え、超音波で３０分解砕し、ジルコニア分散液を得た。その後、そのジルコニア分散液に３．９８ｇ塩化白金酸を加え、窒素フロー下、１２０℃で２０分加熱することによって塩化白金酸を溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１４０℃で５分加熱することによって、ジルコニアに白金を担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してジルコニアに白金を担持した粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながらガドリウム６ｇ相当を含む硝酸ガドリウム溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面に酸化ガドリウム（Ｇｄ２Ｏ３）の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、酸化ガドリウム表面沈殿膜を形成したＰｄ担持ジルコニア製品粉末を得た（第四工程）。酸化ガドリウム（Ｇｄ２Ｏ３）の表面沈殿膜は、基材粒子であるジルコニア３０ｇに対する膜質量は６ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention Example 9 )
Add 30 g of zirconia (ZrO 2 ) (made by Shin Nippon Electric Co., Ltd., trade name: OG, specific surface area: 11 m 2 / g) as substrate particles to 300 g of oleylamine, and decompose 30 by ultrasonication to break up the zirconia dispersion Obtained. Thereafter, 3.98 g of chloroplatinic acid was added to the zirconia dispersion, and chloroplatinic acid was dissolved by heating at 120 ° C. for 20 minutes under a nitrogen flow to obtain a complexing reaction solution (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 140 ° C. for 5 minutes to obtain a slurry in which platinum is supported on zirconia (second step).
The slurry was allowed to stand and separated, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to obtain a powder carrying platinum on zirconia. (Third step).
Water is added to the obtained base powder to make a slurry of 150 ml, and a gadolinium solution containing 6 g equivalent of gadolium is added while stirring, the pH is adjusted to 9 with aqueous ammonia, and the surface of base powder particles is oxidized A surface sediment film of gadolinium (Gd 2 O 3 ) was precipitated. The obtained slurry was washed 3 times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., and mortar ground to obtain a Pd-loaded zirconia product powder having a gadolinium oxide surface precipitation film formed (No. Four steps). The surface precipitation film of gadolinium oxide (Gd 2 O 3 ) had a film weight of 6 g with respect to 30 g of zirconia as a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out, as in FIG. The
（発明例１０）
３００ｇのオレイルアミンに基材粒子として３０ｇのイットリア安定化ジルコニア（ＹＳＺ）（新日本電工株式会社製、商品名ＴＺ−８Ｙ、比表面積；１０ｍ２／ｇ）ジルコニアを加え、超音波で３０分解砕し、イットリア安定化ジルコニア分散液を得た。その後、そのイットリア安定化ジルコニア分散液に３．１６ｇの酢酸パラジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって酢酸パラジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１４０℃で５分加熱することによって、イットリア安定化ジルコニアにパラジウムを担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してイットリア安定化ジルコニアにパラジウムを担持した粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながらアルミニウム４ｇ相当を含む硝酸アルミニウム溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面にアルミナ（Ａｌ２Ｏ３）の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、アルミナ表面沈殿膜を形成したＰｄ担持イットリア安定化ジルコニア製品粉末を得た（第四工程）。アルミナ（Ａｌ２Ｏ３）の表面沈殿膜は、基材粒子であるイットリア安定化ジルコニア３０ｇに対する膜質量は４ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention example 10 )
Add 30 g of yttria stabilized zirconia (YSZ) (trade name: TZ-8Y, specific surface area; 10 m 2 / g) made of Shiny Nippon Denko Co., Ltd. as a substrate particle to 300 g of oleylamine, and decompose 30 by ultrasonic wave. Yttria stabilized zirconia dispersion was obtained. Thereafter, 3.16 g of palladium acetate was added to the yttria-stabilized zirconia dispersion, and palladium acetate was dissolved by heating at 120 ° C. for 20 minutes under nitrogen flow to obtain a complexing reaction liquid (first step) . Next, the complexation reaction solution was irradiated with microwaves and heated at 140 ° C. for 5 minutes to obtain a slurry in which palladium is supported on yttria stabilized zirconia (second step).
The slurry was allowed to stand and separated, and after removing the supernatant, the slurry was washed 3 times each with toluene, and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to support palladium supported on yttria stabilized zirconia. (Third step).
Water is added to the obtained base powder to make a slurry of 150 ml, an aluminum nitrate solution containing 4 g equivalent of aluminum is added while stirring, the pH is adjusted to 9 with aqueous ammonia, and alumina on the surface of base powder particles. The surface precipitation film of (Al 2 O 3 ) was precipitated. The obtained slurry was washed 3 times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., and mortar ground to obtain a Pd-supported yttria-stabilized zirconia product powder having an alumina surface precipitated film formed thereon. (The fourth step). The surface precipitation film of alumina (Al 2 O 3 ) had a film weight of 4 g with respect to 30 g of yttria-stabilized zirconia as a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out, as in FIG. The
（発明例１１）
３００ｇのドレシルアミンに基材粒子として３０ｇのイットリア安定化ジルコニア（ＹＳＺ）（新日本電工株式会社製、商品名ＴＺ−８Ｙ、比表面積；１０ｍ２／ｇ）ジルコニアを加え、超音波で３０分解砕し、イットリア安定化ジルコニア分散液を得た。その後、そのイットリア安定化ジルコニア分散液に３．１６ｇの酢酸パラジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって酢酸パラジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１４０℃で５分加熱することによって、イットリア安定化ジルコニアにパラジウムを担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してイットリア安定化ジルコニアにパラジウムを担持した粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながらアルミニウム４ｇ相当を含む硝酸アルミニウム溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面にアルミナ（Ａｌ２Ｏ３）の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、アルミナ表面沈殿膜を形成したＰｄ担持イットリア安定化ジルコニア製品粉末を得た（第四工程）。アルミナ（Ａｌ２Ｏ３）の表面沈殿膜は、基材粒子であるイットリア安定化ジルコニア（ＹＳＺ）３０ｇに対する膜質量は４ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention example 11 )
Add 30 g of yttria stabilized zirconia (YSZ) (manufactured by Shin Nippon Electric Co., Ltd., trade name: TZ-8 Y, specific surface area: 10 m 2 / g) zirconia as a base particle to 300 g of dresilamine and decompose 30 by ultrasonic wave Yttria stabilized zirconia dispersion was obtained. Thereafter, 3.16 g of palladium acetate was added to the yttria-stabilized zirconia dispersion, and palladium acetate was dissolved by heating at 120 ° C. for 20 minutes under nitrogen flow to obtain a complexing reaction liquid (first step) . Next, the complexation reaction solution was irradiated with microwaves and heated at 140 ° C. for 5 minutes to obtain a slurry in which palladium is supported on yttria stabilized zirconia (second step).
The slurry was allowed to stand and separated, and after removing the supernatant, the slurry was washed 3 times each with toluene, and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to support palladium supported on yttria stabilized zirconia. (Third step).
Water is added to the obtained base powder to make a slurry of 150 ml, an aluminum nitrate solution containing 4 g equivalent of aluminum is added while stirring, the pH is adjusted to 9 with aqueous ammonia, and alumina on the surface of base powder particles. The surface precipitation film of (Al 2 O 3 ) was precipitated. The obtained slurry was washed 3 times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., and mortar ground to obtain a Pd-supported yttria-stabilized zirconia product powder having an alumina surface precipitated film formed thereon. (The fourth step). The surface precipitation film of alumina (Al 2 O 3 ) had a film mass of 4 g with respect to 30 g of yttria-stabilized zirconia (YSZ) which is a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out, as in FIG. The
（発明例１２）
３００ｇのオクチルアミンに基材粒子として３０ｇのイットリア安定化ジルコニア（ＹＳＺ）（新日本電工株式会社製、商品名ＴＺ−８Ｙ、比表面積；１０ｍ２／ｇ）を加え、超音波で３０分解砕し、イットリア安定化ジルコニア分散液を得た。その後、そのイットリア安定化ジルコニア分散液に２．３６ｇ硝酸銀を加え、窒素フロー下、８０℃で１０分加熱することによって硝酸銀を溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１７０℃で２０分加熱することによって、イットリア安定化ジルコニア（ＹＳＺ）に銀を担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してイットリア安定化ジルコニアに銀を担持した基材粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながらＬａ４ｇ相当を含む硝酸Ｌａ溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面にＬａ２Ｏ３の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、Ｌａ２Ｏ３表面沈殿膜を形成したＡｇ担持イットリア安定化ジルコニア製品粉末を得た（第四工程）。表面沈殿膜（Ｌａ２Ｏ３）は、基材粒子であるイットリア安定化ジルコニア（ＹＳＺ）３０ｇに対する膜質量は４ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention example 12 )
Add 30 g of yttria stabilized zirconia (YSZ) (trade name: TZ-8 Y, specific surface area: 10 m 2 / g, made by Shin Nippon Electric Co., Ltd.) as a substrate particle to 300 g of octylamine, and decompose 30 by ultrasonic wave Yttria stabilized zirconia dispersion was obtained. Thereafter, 2.36 g of silver nitrate was added to the yttria-stabilized zirconia dispersion, and the silver nitrate was dissolved by heating at 80 ° C. for 10 minutes under a nitrogen flow to obtain a complexation reaction solution (first step). Next, the complexing reaction solution was irradiated with microwaves and heated at 170 ° C. for 20 minutes to obtain a slurry in which silver is supported on yttria stabilized zirconia (YSZ) (second step).
The slurry was allowed to stand and separated, and after removing the supernatant, the slurry was washed 3 times each with toluene, and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to load silver on yttria stabilized zirconia. Material powder was obtained (third step).
To the obtained base powder, water is added to make a slurry of 150 ml, a La nitrate solution containing 4 g equivalent of La is added while stirring, pH is adjusted to 9 with aqueous ammonia, and La 2 on the surface of base powder particles. A surface sediment of O 3 was precipitated. The obtained slurry is washed 3 times using 2% ammonia water, dried at 120 ° C., calcined at 700 ° C., and mortar ground to form a La 2 O 3 surface precipitated film, Ag-supported yttria-stabilized zirconia product powder (The fourth step). The surface precipitated film (La 2 O 3 ) had a film weight of 4 g with respect to 30 g of yttria-stabilized zirconia (YSZ) as a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out, as in FIG. The
（発明例１３）
３００ｇのドデシルアミンに基材粒子として３０ｇのイットリア安定化ジルコニア（ＹＳＺ）（新日本電工株式会社製、商品名ＴＺ−８Ｙ、比表面積；１０ｍ２／ｇ）を加え、超音波で３０分解砕し、イットリア安定化ジルコニア分散液を得た。その後、そのイットリア安定化ジルコニア分散液に３．８４ｇ塩化ロジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって塩化ロジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１７０℃で２０分加熱することによって、イットリア安定化ジルコニア（ＹＳＺ）にロジウム（Ｒｈ）を担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してイットリア安定化ジルコニアにロジウムを担持した基材粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながら硝酸Ｚｒ及び硝酸Ｙ溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面にイットリア安定化ジルコニア（ＹＳＺ）の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、ＹＳＺ表面沈殿膜を形成したＲｈ担持イットリア安定化ジルコニア製品粉末を得た（第四工程）。表面沈殿膜（ＹＳＺ）は、基材粒子であるイットリア安定化ジルコニア（ＹＳＺ）３０ｇに対する膜質量は１ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention example 13 )
Add 30 g of yttria stabilized zirconia (YSZ) (trade name: TZ-8 Y, specific surface area: 10 m 2 / g, made by Shin Nippon Denko Co., Ltd.) as a substrate particle to 300 g of dodecylamine and decompose 30 by ultrasonic wave Yttria stabilized zirconia dispersion was obtained. Thereafter, 3.84 g of rhodium chloride was added to the yttria-stabilized zirconia dispersion, and the rhodium chloride was dissolved by heating at 120 ° C. for 20 minutes under nitrogen flow to obtain a complexing reaction solution (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 170 ° C. for 20 minutes to obtain a slurry in which rhodium (Rh) is supported on yttria stabilized zirconia (YSZ) (second step).
The slurry was separated and allowed to stand, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours with a vacuum drier maintained at 60 ° C. to load rhodium on yttria stabilized zirconia. Material powder was obtained (third step).
Water is added to the obtained base powder to make a slurry of 150 ml, Zr nitrate and Y nitrate solutions are added while stirring, pH is adjusted to 9 with aqueous ammonia, and yttria is stabilized on the surface of base powder particles. A surface precipitation film of zirconia (YSZ) was precipitated. The obtained slurry was washed 3 times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., and mortar ground to obtain a Rh-supported yttria-stabilized zirconia product powder having a YSZ surface precipitated film formed. (The fourth step). The film weight of the surface precipitated film (YSZ) was 1 g with respect to 30 g of yttria-stabilized zirconia (YSZ) which is a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out. As in FIG. 2, no growth of particles was observed and a chart showing almost no deterioration was obtained. The
（発明例１４）
３００ｇのヘプチルアミンに基材粒子として３０ｇのイットリア安定化ジルコニア（ＹＳＺ）（新日本電工株式会社製、商品名ＴＺ−８Ｙ、比表面積；１０ｍ２／ｇ）を加え、超音波で３０分解砕し、イットリア安定化ジルコニア分散液を得た。その後、そのイットリア安定化ジルコニア分散液に３．１６ｇの酢酸Ｐｄを加え、窒素フロー下、１２０℃で２０分加熱することによって酢酸Ｐｄを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１４０℃で５分加熱することによって、イットリア安定化ジルコニア（ＹＳＺ）にパラジウム（Ｐｄ）を担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してイットリア安定化ジルコニアにパラジウム（Ｐｄ）を担持した基材粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながら硝酸Ｃｅ溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末（ＹＳＺ）粒子の表面にＣｅＯ２の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、ＣｅＯ２表面沈殿膜を形成したＰｄ担持イットリア安定化ジルコニア製品粉末を得た（第四工程）。表面沈殿膜（ＣｅＯ２）は、基材粒子であるイットリア安定化ジルコニア（ＹＳＺ）３０ｇに対する膜質量は１ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention Example 14 )
Add 30 g of yttria stabilized zirconia (YSZ) (trade name: TZ-8 Y, specific surface area: 10 m 2 / g, made by Shin Nippon Denko Co., Ltd.) as a substrate particle to 300 g of heptylamine and decompose 30 by ultrasonic wave Yttria stabilized zirconia dispersion was obtained. Thereafter, 3.16 g of Pd acetate was added to the yttria-stabilized zirconia dispersion, and Pd acetate was dissolved by heating at 120 ° C. for 20 minutes under nitrogen flow to obtain a complexing reaction liquid (first step) . Next, the complexation reaction solution was irradiated with microwaves and heated at 140 ° C. for 5 minutes to obtain a slurry in which palladium (Pd) is supported on yttria stabilized zirconia (YSZ) (second step).
The slurry was separated and allowed to stand, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours in a vacuum drier maintained at 60 ° C. to separate palladium (Pd) into yttria stabilized zirconia. A supported base powder was obtained (third step).
Water is added to the obtained base powder to make a slurry of 150 ml, and a Ce nitrate solution is added while stirring, pH is adjusted to 9 with aqueous ammonia, and CeO 2 is added to the surface of base powder (YSZ) particles. The surface sediment was allowed to settle. The obtained slurry is washed 3 times using 2% aqueous ammonia, dried at 120 ° C., calcined at 700 ° C., and mortar ground to obtain a Pd-supported yttria-stabilized zirconia product powder in which a CeO 2 surface precipitated film is formed. (4th step). The film weight of the surface precipitated film (CeO 2 ) was 1 g based on 30 g of the yttria stabilized zirconia (YSZ) as the substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out. As in FIG. 2, no growth of particles was observed and a chart showing almost no deterioration was obtained. The
（発明例１５）
３００ｇのオレイルアミンに基材粒子として３０ｇのアルミナ（Ａｌ２Ｏ３）（新日本電工株式会社製、商品名ＡＫＰ−Ｇ１５、比表面積；１４８ｍ２／ｇ）を加え、超音波で３０分解砕し、アルミナ分散液を得た。その後、そのアルミナ分散液に３．９８ｇの塩化白金酸を加え、窒素フロー下、１２０℃で２０分加熱することによって塩化白金酸を溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して２３５℃で５分加熱することによって、アルミナに白金を担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してアルミナに白金を担持した基材粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながら塩化Ｙ溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面にＹ２Ｏ３の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、Ｙ２Ｏ３表面沈殿膜を形成したＰｔ担持アルミナ製品粉末を得た（第四工程）。表面沈殿膜（Ｙ２Ｏ３）は、基材粒子であるアルミナ（Ａｌ２Ｏ３）３０ｇに対する膜質量は０．４ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention Example 15 )
30 g of alumina (Al 2 O 3 ) (manufactured by Shin Nippon Electric Co., Ltd., trade name AKP-G15, specific surface area: 148 m 2 / g) is added as a substrate particle to 300 g of oleylamine, and it is decomposed and broken by ultrasonic 30. An alumina dispersion was obtained. Thereafter, 3.98 g of chloroplatinic acid was added to the alumina dispersion, and the chloroplatinic acid was dissolved by heating at 120 ° C. for 20 minutes under nitrogen flow to obtain a complexing reaction solution (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 235 ° C. for 5 minutes to obtain a slurry in which platinum is supported on alumina (second step).
The slurry was separated and allowed to stand, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to support platinum powder on alumina. Obtained (third step).
Water is added to the obtained base powder to make a slurry of 150 ml, and a Y chloride solution is added while stirring, pH is adjusted to 9 with aqueous ammonia, and the surface of Y 2 O 3 on the surface of base powder particles Sedimented film was allowed to settle. The obtained slurry was washed 3 times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., and mortar ground to obtain a Pt-supporting alumina product powder having a Y 2 O 3 surface precipitated film formed. (The fourth step). The film weight of the surface precipitated film (Y 2 O 3 ) was 0.4 g with respect to 30 g of alumina (Al 2 O 3 ) as the substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out, as in FIG. The
（発明例１６）
３００ｇのドデシルアミンに基材粒子として３０ｇのアルミナ（Ａｌ２Ｏ３）（新日本電工株式会社製、商品名ＡＫＰ−Ｇ１５、比表面積；１４８ｍ２／ｇ）を加え、超音波で３０分解砕し、アルミナ分散液を得た。その後、そのアルミナ分散液に３．９８ｇの塩化ロジウムを加え、窒素フロー下、１２０℃で２０分加熱することによって塩化ロジウムを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して２３５℃で５分加熱することによって、アルミナにロジウム（Ｒｈ）を担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してアルミナにロジウム（Ｒｈ）を担持した基材粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながら塩化Ｌａ溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面にＬａ２Ｏ３の表面沈殿膜を沈殿させた。得られたスラリーを、2％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、Ｌａ２Ｏ３表面沈殿膜を形成したＲｈ担持アルミナ製品粉末を得た（第四工程）。表面沈殿膜（Ｌａ２Ｏ３）は、基材粒子であるアルミナ（Ａｌ２Ｏ３）３０ｇに対する膜質量は０．４ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
Invention 16
30 g of alumina (Al 2 O 3 ) (manufactured by Shin Nippon Electric Co., Ltd., trade name AKP-G15, specific surface area: 148 m 2 / g) is added as a substrate particle to 300 g of dodecylamine, and the powder is broken by ultrasonication 30 Alumina dispersion was obtained. Thereafter, 3.98 g of rhodium chloride was added to the alumina dispersion, and the rhodium chloride was dissolved by heating at 120 ° C. for 20 minutes under a nitrogen flow to obtain a complexation reaction solution (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 235 ° C. for 5 minutes to obtain a slurry in which rhodium (Rh) is supported on alumina (second step).
The slurry was allowed to stand and separated, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to load rhodium (Rh) on alumina. Material powder was obtained (third step).
Water is added to the obtained base powder to make a slurry of 150 ml, La chloride solution is added while stirring, pH is adjusted to 9 with aqueous ammonia, and the surface of La 2 O 3 on the surface of base powder particles. Sedimented film was allowed to settle. The obtained slurry was washed three times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., and mortar-grounded to obtain a Rh-supporting alumina product powder in which a La 2 O 3 surface precipitation film was formed. (The fourth step). The surface precipitated film (La 2 O 3 ) had a film weight of 0.4 g with respect to 30 g of alumina (Al 2 O 3 ) which is a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out. As in FIG. 2, no growth of particles was observed and a chart showing almost no deterioration was obtained. The
（発明例１７）
３００ｇのオクチルアミンに基材粒子として３０ｇのアルミナ（Ａｌ２Ｏ３）（新日本電工株式会社製、商品名ＡＫＰ−Ｇ１５、比表面積；１４８ｍ２／ｇ）を加え、超音波で３０分解砕し、アルミナ分散液を得た。その後、そのアルミナ分散液に３．１６ｇの酢酸Ｐｄを加え、窒素フロー下、１２０℃で２０分加熱することによって酢酸Ｐｄを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１４０℃で５分加熱することによって、アルミナにＰｄを担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してアルミナにパラジウム（Ｐｄ）担持した基材粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながら塩化Ａｌ溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面にＡｌ２Ｏ３の表面沈殿膜を沈殿させた。得られたスラリーを、２％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行い、Ｙ２Ｏ３表面沈殿膜を形成したＰｄ担持アルミナ製品粉末を得た（第四工程）。表面沈殿膜（Ａｌ２Ｏ３）は、基材粒子であるアルミナ（Ａｌ２Ｏ３）３０ｇに対する膜質量は６ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
( Invention Example 17 )
30 g of alumina (Al 2 O 3 ) (manufactured by Shin Nippon Electric Co., Ltd., trade name AKP-G15, specific surface area: 148 m 2 / g) is added as a substrate particle to 300 g of octylamine, and it is decomposed by ultrasonication 30 Alumina dispersion was obtained. Thereafter, 3.16 g of Pd acetate was added to the alumina dispersion, and Pd acetate was dissolved by heating at 120 ° C. for 20 minutes under nitrogen flow to obtain a complexing reaction liquid (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 140 ° C. for 5 minutes to obtain a slurry in which Pd is supported on alumina (second step).
The slurry was allowed to stand and separated, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours with a vacuum drier maintained at 60 ° C. to support palladium (Pd) supported on alumina A powder was obtained (third step).
Water is added to the obtained base powder to make a slurry of 150 ml, an Al chloride solution is added while stirring, pH is adjusted to 9 with aqueous ammonia, and the surface of Al 2 O 3 on the surface of base powder particles. Sedimented film was allowed to settle. The obtained slurry was washed 3 times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., and mortar ground to obtain a Pd-loaded alumina product powder having a Y 2 O 3 surface precipitated film formed. (The fourth step). The surface precipitated film (Al 2 O 3 ) had a film weight of 6 g with respect to 30 g of alumina (Al 2 O 3 ) which is a substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out, as in FIG. The
（発明例１８）
３００ｇのオレイルアミンに基材粒子として３０ｇのアルミナ（Ａｌ２Ｏ３）（新日本電工株式会社製、商品名ＡＫＰ−Ｇ１５、比表面積；１４８ｍ２／ｇ）を加え、超音波で３０分解砕し、アルミナ分散液を得た。その後、そのアルミナ分散液に３．２４ｇの硝酸Ｐｄを加え、窒素フロー下、１２０℃で２０分加熱することによって硝酸Ｐｄを溶解させて錯化反応液を得た（第一工程）。次いで、その錯化反応液に、マイクロ波を照射して１４０℃で５分加熱することによって、アルミナにパラジウム（Ｐｄ）を担持したスラリーを得た（第二工程）。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してアルミナにパラジウム（Ｐｄ）を担持した基材粉末を得た（第三工程）。
得られた基材粉末に対して、水を加え１５０ｍｌのスラリーとし、撹拌しながらケイ酸Ｎａ溶液を添加し、アンモニア水でｐＨを９に調整、基材粉末粒子の表面にＳｉＯ２の表面沈殿膜を沈殿させた。得られたスラリーを、2％アンモニア水を用いて３回洗浄した後、１２０℃乾燥、７００℃焼成、乳鉢粉砕を行いＳｉＯ２表面沈殿膜を形成したＰｄ担持アルミナ製品粉末を得た（第四工程）。表面沈殿膜（ＳｉＯ２）は、基材粒子であるアルミナ（Ａｌ２Ｏ３）３０ｇに対する膜質量は６ｇであった。
得られた製品粉末に対して空気中１１５０℃で５時間の耐熱劣化加速試験を行い、ＸＲＤ測定を行ったところ図２と同様に粒子の成長が無く、ほとんど劣化が見られないチャートが得られた。
Invention Example 18
30 g of alumina (Al 2 O 3 ) (manufactured by Shin Nippon Electric Co., Ltd., trade name AKP-G15, specific surface area: 148 m 2 / g) is added as a substrate particle to 300 g of oleylamine, and it is decomposed and broken by ultrasonic 30. An alumina dispersion was obtained. Thereafter, 3.24 g of Pd nitrate was added to the alumina dispersion, and Pd nitrate was dissolved by heating at 120 ° C. for 20 minutes under a nitrogen flow to obtain a complexing reaction liquid (first step). Next, the complexation reaction solution was irradiated with microwaves and heated at 140 ° C. for 5 minutes to obtain a slurry in which palladium (Pd) is supported on alumina (second step).
The slurry was allowed to stand and separated, and after removing the supernatant, the slurry was washed 3 times each with toluene and then dried for 6 hours with a vacuum dryer maintained at 60 ° C. to load palladium (Pd) supported on alumina. Material powder was obtained (third step).
Water is added to the obtained base powder to make a slurry of 150 ml, a sodium silicate solution is added while stirring, pH is adjusted to 9 with aqueous ammonia, surface precipitation of SiO 2 on the surface of base powder particles The membrane was allowed to settle. The obtained slurry was washed 3 times using 2% aqueous ammonia, then dried at 120 ° C., calcined at 700 ° C., mortar ground to obtain a Pd-loaded alumina product powder in which a SiO 2 surface precipitated film was formed (fourth) Process). The film weight of the surface precipitated film (SiO 2 ) was 6 g with respect to 30 g of alumina (Al 2 O 3 ) as the substrate particle.
The obtained product powder was subjected to an accelerated heat resistance deterioration test at 1150 ° C. for 5 hours in air, and XRD measurement was carried out. As in FIG. 2, no growth of particles was observed and a chart showing almost no deterioration was obtained. The
以上の実施例に述べたように、本発明によれば、これまで以上に過酷な使用環境下でも触媒金属の粒成長を抑制でき、触媒の高活性や高寿命等の性能を有する排ガス浄化用貴金属担持触媒が得られることが確認できた。 As described in the above examples, according to the present invention, it is possible to suppress the grain growth of the catalyst metal even in a more severe usage environment than before, and for exhaust gas purification having performance such as high activity and long life of the catalyst. It has been confirmed that a noble metal-supported catalyst can be obtained.
（参考１）
３００ｇのオレイルアミンに１．５ｇのＰｄに相当する酢酸パラジウム３．１６ｇを加え、窒素フロー下、オイルバスで１２０℃、２０分加熱することによって酢酸パラジウムを溶解させて錯化反応液を得た。次いで、その錯化反応液に、周波数２．４５ＧＨｚ、マイクロ波出力５００Ｗ、マルチモードの条件でマイクロ波を照射して１４０℃、５分加熱することによって、パラジウムナノ粒子スラリーを得た。
スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いてそれぞれ３回洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥してパラジウムナノ粒子粉末を得た。
得られたパラジウムナノ粒子のＳＥＭ（Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ、走査電子顕微鏡）写真を図３に示した。図３より、平均粒径１０ｎｍ以下の球形の略均一な粒子が形成されていることがわかった。
( Reference 1 )
3.16 g of palladium acetate corresponding to 1.5 g of Pd was added to 300 g of oleylamine, and palladium acetate was dissolved by heating at 120 ° C. for 20 minutes in an oil bath under nitrogen flow to obtain a complexed reaction solution. Then, the complexation reaction solution was irradiated with microwaves under the conditions of a frequency of 2.45 GHz, a microwave output of 500 W and a multi-mode, and heated at 140 ° C. for 5 minutes to obtain a palladium nanoparticle slurry.
The slurry was allowed to stand and separated, and after removing the supernatant, each was washed three times with toluene and then dried for 6 hours in a vacuum dryer maintained at 60 ° C. to obtain palladium nanoparticle powder.
The SEM (Scanning Electron Microscope) photograph of the obtained palladium nanoparticles is shown in FIG. From FIG. 3, it was found that spherical substantially uniform particles having an average particle diameter of 10 nm or less were formed.
本発明の製造方法によって得られた排ガス浄化用貴金属担持触媒は、耐久性に優れ、排ガス浄化システムに好適に使用できる。 The noble metal-supported catalyst for exhaust gas purification obtained by the production method of the present invention is excellent in durability and can be suitably used for an exhaust gas purification system.
Claims (5)
Priority Applications (1)
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| JP2003013105A (en) * | 2001-06-29 | 2003-01-15 | Toagosei Co Ltd | Method for manufacturing carrier with metal fine particles |
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