JP2008178811A - Aqueous solution of composite particle precursor and method for manufacturing composite particle using the same - Google Patents
Aqueous solution of composite particle precursor and method for manufacturing composite particle using the same Download PDFInfo
- Publication number
- JP2008178811A JP2008178811A JP2007014662A JP2007014662A JP2008178811A JP 2008178811 A JP2008178811 A JP 2008178811A JP 2007014662 A JP2007014662 A JP 2007014662A JP 2007014662 A JP2007014662 A JP 2007014662A JP 2008178811 A JP2008178811 A JP 2008178811A
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- Prior art keywords
- compound
- aqueous solution
- acid
- composite particle
- particle precursor
- Prior art date
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- Granted
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- 239000011246 composite particle Substances 0.000 title claims abstract description 141
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 113
- 239000002243 precursor Substances 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 238000000034 method Methods 0.000 title description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 171
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- 239000010948 rhodium Substances 0.000 claims abstract description 12
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 9
- 239000010931 gold Substances 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 229910052788 barium Inorganic materials 0.000 claims description 23
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 235000015165 citric acid Nutrition 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- -1 malonic acid ester Chemical class 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 claims description 3
- KJTLQQUUPVSXIM-ZCFIWIBFSA-N (R)-mevalonic acid Chemical compound OCC[C@](O)(C)CC(O)=O KJTLQQUUPVSXIM-ZCFIWIBFSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims description 3
- KJTLQQUUPVSXIM-UHFFFAOYSA-N DL-mevalonic acid Natural products OCCC(O)(C)CC(O)=O KJTLQQUUPVSXIM-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229940091181 aconitic acid Drugs 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 175
- 239000003054 catalyst Substances 0.000 description 104
- 230000000052 comparative effect Effects 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000000746 purification Methods 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 9
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- MSYNCHLYGJCFFY-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;titanium(4+) Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O MSYNCHLYGJCFFY-UHFFFAOYSA-B 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 101150058765 BACE1 gene Proteins 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- 150000002823 nitrates Chemical class 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- 238000010521 absorption reaction Methods 0.000 description 2
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- DLNAGPYXDXKSDK-UHFFFAOYSA-K cerium(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ce+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O DLNAGPYXDXKSDK-UHFFFAOYSA-K 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 230000003247 decreasing effect Effects 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
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- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
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- 239000002253 acid Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
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- 239000002738 chelating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
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- 229910021480 group 4 element Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
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- 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、複合粒子前駆体水溶液並びにそれを用いた複合粒子の製造方法に関する。 The present invention relates to a composite particle precursor aqueous solution and a method for producing composite particles using the same.
従来から、自動車等の排ガスに含まれる有害な窒素酸化物（ＮＯｘ）を浄化するために、ＮＯｘの吸蔵及び／又は還元が可能な複合粒子が、排ガス浄化触媒（ＮＯｘ吸蔵還元型触媒）の材料として利用されてきた。そして、より高い活性を示す複合粒子を製造するために、種々の方法や前駆体水溶液等が研究されてきた。 Conventionally, in order to purify harmful nitrogen oxides (NOx) contained in exhaust gas of automobiles, etc., composite particles capable of storing and / or reducing NOx have been used as materials for exhaust gas purification catalysts (NOx storage reduction type catalysts). Has been used as. And in order to manufacture the composite particle which shows higher activity, various methods, precursor aqueous solution, etc. have been studied.
このような複合粒子の製造方法としては、例えば、特開２０００−２７９８２４号公報（特許文献１）において、キレート化剤により白金、ロジウム、イリジウム、ルテニウム、パラジウム、銀、金、オスミウム、レニウムのいずれか１種又は２種以上の触媒金属をキレート結合させて得られる複合金属コロイドを用い、担体に複合金属を担持し、その後、アルカリ金属、アルカリ土類金属及び希土類のいずれかに属する元素の化合物の１種又は２種以上を含む水溶液を用いて、アルカリ金属、アルカリ土類金属及び希土類のいずれかに属する元素の１種又は２種以上を担持する複合粒子の製造方法が開示されている。しかしながら、特許文献１に記載のような複合粒子の製造方法においては、前記水溶液中にセリウムをイオンの状態で混合するために酢酸セリウムを用いた場合には、酢酸セリウムの水に対する溶解度が水１００ｇに対して２０ｇと低いため、高濃度で含有させることができなかった（東京化学同人「化学大辞典」参照）。そのため、セリウムの担持量の高い触媒を製造する場合に前記水溶液を用いると担持工程やコストが増加するという問題があった。 As a method for producing such composite particles, for example, in JP-A-2000-279824 (Patent Document 1), any of platinum, rhodium, iridium, ruthenium, palladium, silver, gold, osmium, and rhenium is used with a chelating agent. Or a compound of an element belonging to any one of alkali metal, alkaline earth metal, and rare earth, using a composite metal colloid obtained by chelating a single or two or more types of catalyst metals and supporting the composite metal on a carrier A method for producing composite particles carrying one or more elements belonging to any one of alkali metals, alkaline earth metals and rare earths using an aqueous solution containing one or more of these is disclosed. However, in the method for producing composite particles as described in Patent Document 1, when cerium acetate is used to mix cerium in an ionic state in the aqueous solution, the solubility of cerium acetate in water is 100 g of water. Therefore, it could not be contained at a high concentration (see Tokyo Kagaku Doujin “Chemical Dictionary”). For this reason, when the above aqueous solution is used in the production of a catalyst having a high cerium loading, there is a problem in that the loading process and cost increase.
また、複合粒子を製造する際に用いる複合粒子前駆体水溶液としては、例えば、特開２００５−６０１４７号公報（特許文献２）において、アルカリ金属，アルカリ土類金属及び希土類元素から選ばれる少なくとも一種の元素を含む第１化合物と、第３族元素、第４族元素及び遷移金属から選ばれる少なくとも一種の元素を含む第２化合物と、多座配位子を有する第３化合物と、過酸化水素と、が水に溶解してなる複合粒子水溶液が開示されている。しかしながら、特許文献２に記載の複合粒子水溶液においては、水溶液中にＮＯｘの酸化還元成分である白金等が含有されておらず、前記酸化還元成分が担持された触媒を製造する場合には、前記複合粒子水溶液を担体に担持させる工程の他に酸化還元成分を担体に担持させる工程が別途必要となるため、効率よく触媒を製造することができなかった。また、このような触媒の製造方法を採用した場合においては、得られる触媒においてアルカリ成分等の近傍に必ずしも前記酸化還元成分が存在しなかった。そのため、このような複合粒子水溶液を用いて得られる触媒においては、ＮＯｘ浄化能が必ずしも十分なものではなかった。
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、水溶液中に複合粒子の前駆体である金属元素を高濃度で且つ安定した状態で含有させることができ、十分に高いＮＯｘ浄化能を有し且つ十分に微細化された複合粒子を効率よく製造することが可能な複合粒子前駆体水溶液及びそれを用いた複合粒子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-described problems of the prior art. A metal element that is a precursor of composite particles can be contained in an aqueous solution at a high concentration and in a stable state, and the NOx is sufficiently high. It is an object of the present invention to provide a composite particle precursor aqueous solution capable of efficiently producing composite particles having a purifying ability and sufficiently refined, and a method for producing composite particles using the same.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、アルカリ金属及びアルカリ土類金属からなる群から選択される少なくとも１種の金属元素を含有する第１の化合物と、チタン、アルミニウム及び希土類金属からなる群から選択される少なくとも１種の金属元素を含有する第２の化合物とを用いて複合粒子を製造する際に用いる複合粒子前駆体水溶液に、前記第１及び第２の化合物とともに、多座配位子を有する第３の化合物と、白金、ロジウム、パラジウム、金、銀、銅、コバルト、鉄、マンガン及びニッケルからなる群から選択される少なくとも１種の金属元素を含有する第４の化合物と、アンモニアとを含有させることにより、得られる複合粒子前駆体水溶液中に前記第１、第２及び第４の化合物を高濃度且つ安定した状態で含有させることができ、これを利用することで、十分に高いＮＯｘ浄化能を有し且つ十分に微細化された複合粒子を効率よく得ることが可能となることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that a first compound containing at least one metal element selected from the group consisting of alkali metals and alkaline earth metals, titanium, In the composite particle precursor aqueous solution used when producing composite particles using a second compound containing at least one metal element selected from the group consisting of aluminum and rare earth metals, the first and second A compound containing a third compound having a polydentate ligand and at least one metal element selected from the group consisting of platinum, rhodium, palladium, gold, silver, copper, cobalt, iron, manganese and nickel The first compound, the second compound and the fourth compound are in a high concentration and stable state in the resulting composite particle precursor aqueous solution by containing the fourth compound and ammonia. In order to complete the present invention, it is found that by using this, composite particles having sufficiently high NOx purification ability and sufficiently fine particles can be obtained efficiently. It came.
すなわち、本発明の複合粒子前駆体水溶液は、アルカリ金属及びアルカリ土類金属からなる群から選択される少なくとも１種の金属元素を含有する第１の化合物と、
チタン、アルミニウム、ジルコニウム及び希土類金属からなる群から選択される少なくとも１種の金属元素を含有する第２の化合物と、
多座配位子を有する第３の化合物と、
白金、ロジウム、パラジウム、金、銀、銅、コバルト、鉄、マンガン及びニッケルからなる群から選択される少なくとも１種の金属元素を含有する第４の化合物と、
アンモニアと、
を含むことを特徴とするものである。
That is, the aqueous composite particle precursor solution of the present invention includes a first compound containing at least one metal element selected from the group consisting of alkali metals and alkaline earth metals,
A second compound containing at least one metal element selected from the group consisting of titanium, aluminum, zirconium and rare earth metals;
A third compound having a multidentate ligand;
A fourth compound containing at least one metal element selected from the group consisting of platinum, rhodium, palladium, gold, silver, copper, cobalt, iron, manganese and nickel;
With ammonia,
It is characterized by including.
上記本発明にかかる第１の化合物としては、バリウムを含有する化合物であることが好ましい。 The first compound according to the present invention is preferably a compound containing barium.
また、上記本発明にかかる第２の化合物としては、チタン、アルミニウム、セリウム及びジルコニウムからなる群から選択される少なくとも１種の金属元素を含有する化合物であることが好ましい。 Further, the second compound according to the present invention is preferably a compound containing at least one metal element selected from the group consisting of titanium, aluminum, cerium and zirconium.
さらに、上記本発明にかかる第２の化合物としては、セリウムを含有する化合物であることがより好ましく、酢酸セリウムであることが更に好ましい。 Furthermore, the second compound according to the present invention is more preferably a compound containing cerium, and further preferably cerium acetate.
また、上記本発明にかかる第２の化合物としては、チタンを含有する化合物であることがより好ましい。 In addition, the second compound according to the present invention is more preferably a compound containing titanium.
さらに、上記本発明の第３の化合物としては、クエン酸、シュウ酸、コハク酸、マレイン酸、リンゴ酸、アジピン酸、酒石酸、マロン酸、フマル酸、アコニット酸、グルタル酸、エチレンジアミン四酢酸、乳酸、グリコール酸、グリセリン酸、サリチル酸、メバロン酸、エチレンジアミン、アセト酢酸エチル、マロン酸エステル、グリコール及びピナコールからなる群から選択される少なくとも１種であることが好ましく、クエン酸であることがより好ましい。 Further, the third compound of the present invention includes citric acid, oxalic acid, succinic acid, maleic acid, malic acid, adipic acid, tartaric acid, malonic acid, fumaric acid, aconitic acid, glutaric acid, ethylenediaminetetraacetic acid, lactic acid. , Glycolic acid, glyceric acid, salicylic acid, mevalonic acid, ethylenediamine, ethyl acetoacetate, malonic acid ester, glycol and pinacol are preferred, and citric acid is more preferred.
また、上記本発明にかかる前記第４の化合物としては、パラジウムを含有する化合物であることが好ましく、酢酸パラジウムであることがより好ましい。 In addition, the fourth compound according to the present invention is preferably a compound containing palladium, more preferably palladium acetate.
また、上記本発明の複合粒子前駆体水溶液においては、前記第３の化合物の含有量が、前記第２の化合物中に含有される金属元素の含有量に対してモル換算で２倍以上であることが好ましい。 Moreover, in the composite particle precursor aqueous solution of the present invention, the content of the third compound is twice or more in terms of molar relative to the content of the metal element contained in the second compound. It is preferable.
さらに、上記本発明の複合粒子前駆体水溶液においては、前記第４の化合物の含有量が、０．００１〜０．５ｍｏｌ／Ｌであることが好ましい。 Furthermore, in the composite particle precursor aqueous solution of the present invention, the content of the fourth compound is preferably 0.001 to 0.5 mol / L.
また、上記本発明の複合粒子前駆体水溶液においては、前記アンモニアの含有量が、前記第３の化合物の含有量に対してモル換算で２倍以上であることが好ましい。 In the composite particle precursor aqueous solution of the present invention, it is preferable that the ammonia content is twice or more in terms of mole relative to the content of the third compound.
さらに、上記本発明の複合粒子前駆体水溶液においては、前記アンモニアの含有量が、０．４ｍｏｌ／Ｌ以上であることが好ましい。 Furthermore, in the composite particle precursor aqueous solution of the present invention, the ammonia content is preferably 0.4 mol / L or more.
また、本発明の複合粒子の製造方法は、上記本発明の複合粒子前駆体水溶液を焼成して複合粒子を得ることを特徴とする方法である。 The method for producing composite particles of the present invention is a method characterized in that the composite particle precursor aqueous solution of the present invention is fired to obtain composite particles.
なお、本発明の複合粒子前駆体水溶液及び複合粒子の製造方法によって、上記目的が達成される理由は必ずしも定かではないが、本発明者らは以下のように推察する。すなわち、本発明の複合粒子前駆体水溶液においては、前記第１及び第２の化合物とともに、多座配位子を有する第３の化合物と、白金、ロジウム、パラジウム、金、銀、銅、コバルト、鉄、マンガン及びニッケルからなる群から選択される少なくとも１種の金属元素を含有する第４の化合物と、アンモニアとが含有されている。そのため、前記水溶液においては、前記第１の化合物と前記第２の化合物と前記第４の化合物とが前記多座配位子を介して互いに相互作用し、近接した状態で保持される。従って、このような水溶液中においては、前記第１の化合物に由来するアルカリ成分と、前記第４の化合物に由来するＮＯｘ還元成分（酸化還元成分）とが近接した状態で保持される。また、本発明の複合粒子前駆体水溶液においては、アンモニアが含有されていることから、前記第１の化合物と前記第２の化合物と前記第４の化合物と前記多座配位子とが含有されている水溶液に沈殿が生じることなく、前記第１の化合物と前記第２の化合物と前記第４の化合物とが高濃度で且つ安定した状態で保持される。また、本発明の複合粒子前駆体水溶液を焼成すると、配位子として存在する嵩高い多座配位子が酸化分解され、各成分が十分に微細化された状態で複合化される。さらに、このようにして得られた複合粒子においては、第１の化合物に由来するバリウム等の塩基性成分と、第４の化合物に由来するパラジウム等のＮＯｘ酸化還元成分とが、セリウム酸化物やチタン酸化物を介して近接化された状態で存在するため、ＮＯｘ吸蔵還元に必要な酸化−吸蔵−還元のサイクルを高効率で進行させることができ、十分に高いＮＯｘ浄化能を発揮できるものと本発明者らは推察する。 The reason why the above object is achieved by the composite particle precursor aqueous solution and the composite particle manufacturing method of the present invention is not necessarily clear, but the present inventors speculate as follows. That is, in the composite particle precursor aqueous solution of the present invention, together with the first and second compounds, a third compound having a polydentate ligand, platinum, rhodium, palladium, gold, silver, copper, cobalt, A fourth compound containing at least one metal element selected from the group consisting of iron, manganese, and nickel, and ammonia are contained. Therefore, in the aqueous solution, the first compound, the second compound, and the fourth compound interact with each other through the multidentate ligand and are held in close proximity. Therefore, in such an aqueous solution, the alkali component derived from the first compound and the NOx reducing component (oxidation-reducing component) derived from the fourth compound are held in close proximity. In addition, since the composite particle precursor aqueous solution of the present invention contains ammonia, the first compound, the second compound, the fourth compound, and the multidentate ligand are contained. The first compound, the second compound, and the fourth compound are maintained at a high concentration and in a stable state without causing precipitation in the aqueous solution. In addition, when the composite particle precursor aqueous solution of the present invention is baked, the bulky multidentate ligand present as a ligand is oxidized and decomposed, and each component is composited in a sufficiently refined state. Further, in the composite particles obtained in this way, a basic component such as barium derived from the first compound and a NOx redox component such as palladium derived from the fourth compound are cerium oxide or Because it exists in a state of being close to each other through titanium oxide, the oxidation-occlusion-reduction cycle necessary for NOx occlusion reduction can be advanced with high efficiency, and a sufficiently high NOx purification ability can be exhibited. The present inventors speculate.
本発明によれば、水溶液中に複合粒子の前駆体である金属元素を高濃度で且つ安定した状態で含有させることができ、十分に高いＮＯｘ浄化能を有し且つ十分に微細化された複合粒子を効率よく製造することを可能とする複合粒子前駆体水溶液及びそれを用いた複合粒子の製造方法を提供することが可能となる。 According to the present invention, a metal element that is a precursor of composite particles can be contained in an aqueous solution at a high concentration and in a stable state, and has a sufficiently high NOx purification ability and a sufficiently refined composite. It becomes possible to provide a composite particle precursor aqueous solution capable of efficiently producing particles and a method for producing composite particles using the same.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
先ず、本発明の複合粒子前駆体水溶液について説明する。すなわち、本発明の複合粒子前駆体水溶液は、アルカリ金属及びアルカリ土類金属からなる群から選択される少なくとも１種の金属元素を含有する第１の化合物と、
チタン、アルミニウム、ジルコニウム及び希土類金属からなる群から選択される少なくとも１種の金属元素を含有する第２の化合物と、
多座配位子を有する第３の化合物と、
白金、ロジウム、パラジウム、金、銀、銅、コバルト、鉄、マンガン及びニッケルからなる群から選択される少なくとも１種の金属元素を含有する第４の化合物と、
アンモニアと、
を含むことを特徴とするものである。
First, the composite particle precursor aqueous solution of the present invention will be described. That is, the aqueous composite particle precursor solution of the present invention includes a first compound containing at least one metal element selected from the group consisting of alkali metals and alkaline earth metals,
A second compound containing at least one metal element selected from the group consisting of titanium, aluminum, zirconium and rare earth metals;
A third compound having a multidentate ligand;
A fourth compound containing at least one metal element selected from the group consisting of platinum, rhodium, palladium, gold, silver, copper, cobalt, iron, manganese and nickel;
With ammonia,
It is characterized by including.
第１の化合物が含有するアルカリ金属としてはリチウム、ナトリウム、カリウム、セシウム等が挙げられる。また、第１の化合物が含有するアルカリ土類金属としてはバリウム、マグネシウム、カルシウム、ストロンチウム等が挙げられる。また、第１の化合物としては、アルカリ金属又は前記アルカリ土類金属の水酸化物、酢酸塩、炭酸塩、硝酸塩等が挙げられる。このような第１の化合物としては、高い塩基性を有し、酸化物を形成させた際に十分に高いＮＯｘ吸蔵能を発揮できるという観点から、バリウムを含有する化合物（硝酸バリウム、酢酸バリウム等）を用いることが好ましい。なお、このような第１の化合物は、１種を単独で、あるいは２種以上を混合して用いてもよい。 Examples of the alkali metal contained in the first compound include lithium, sodium, potassium, and cesium. Examples of the alkaline earth metal contained in the first compound include barium, magnesium, calcium, and strontium. Examples of the first compound include alkali metal or alkaline earth metal hydroxides, acetates, carbonates, nitrates, and the like. As such a first compound, a compound containing barium (barium nitrate, barium acetate, etc.) has a high basicity and can exhibit a sufficiently high NOx occlusion ability when an oxide is formed. ) Is preferably used. In addition, you may use such 1st compound individually by 1 type or in mixture of 2 or more types.
また、第２の化合物が含有する希土類金属としては、スカンジウム、イットリウム、ランタン、セリウム、プラセオジウム、ネオジム等が挙げられる。また、第２の化合物としては、チタン、アルミニウム、ジルコニウム及び希土類金属の水酸化物、酢酸塩、炭酸塩、硝酸塩等が挙げられる。このような第２の化合物としては、酸化物を形成させた際に比較的高比表面積を有するという観点から、チタン、アルミニウム、セリウム及びジルコニウムからなる群から選択される少なくとも１種の金属元素を含有する化合物が好ましい。 Examples of the rare earth metal contained in the second compound include scandium, yttrium, lanthanum, cerium, praseodymium, and neodymium. Examples of the second compound include titanium, aluminum, zirconium and rare earth metal hydroxides, acetates, carbonates, nitrates, and the like. As such a second compound, at least one metal element selected from the group consisting of titanium, aluminum, cerium and zirconium is used from the viewpoint of having a relatively high specific surface area when an oxide is formed. Compounds containing are preferred.
また、第２の化合物としては、第１の化合物と第４の化合物とを分散性よく複合化させるという観点からは、セリウムを含有する化合物（酢酸セリウム、硝酸セリウム等）がより好ましく、酢酸セリウムが更に好ましい。 The second compound is more preferably a compound containing cerium (cerium acetate, cerium nitrate, etc.) from the viewpoint of complexing the first compound and the fourth compound with good dispersibility, and cerium acetate. Is more preferable.
さらに、第２の化合物としては、第１の化合物と第４の化合物とを分散性よく複合化させるという観点からは、チタンを含有する化合物（酢酸チタン、硝酸チタン等）がより好ましい。なお、このような第２の化合物は、１種を単独で、あるいは２種以上を混合して用いてもよい。 Furthermore, as the second compound, a compound containing titanium (such as titanium acetate or titanium nitrate) is more preferable from the viewpoint of complexing the first compound and the fourth compound with good dispersibility. In addition, you may use such a 2nd compound individually by 1 type or in mixture of 2 or more types.
第３の化合物が有する多座配位子とは、２個以上の配位基で配位し得るものをいう。このような第３の化合物としては、クエン酸、シュウ酸等の多価カルボン酸類、グリコール、ピナコール等のジオール類、エチレンジアミン等のジアミン類、アセト酢酸エチル等の２つのカルボニル基を有するエステル類等が挙げられる。このような第３の化合物としては、クエン酸、シュウ酸、コハク酸、マレイン酸、リンゴ酸、アジピン酸、酒石酸、マロン酸、フマル酸、アコニット酸、グルタル酸、エチレンジアミン四酢酸、乳酸、グリコール酸、グリセリン酸、サリチル酸、メバロン酸、エチレンジアミン、アセト酢酸エチル、マロン酸エステル、グリコール及びピナコールが好ましく、中でも、ヒドロキシ基を併せ持つカルボン酸であるという観点から、クエン酸、乳酸、リンゴ酸、酒石酸、グリコール酸、サリチル酸がより好ましく、嵩高く、より微細化された複合粒子を製造できるという観点から、クエン酸が特に好ましい。なお、このような第３の化合物は、１種を単独で、あるいは２種以上を混合して用いてもよい。 The multidentate ligand that the third compound has is a ligand that can coordinate with two or more coordination groups. Examples of the third compound include polyvalent carboxylic acids such as citric acid and oxalic acid, diols such as glycol and pinacol, diamines such as ethylenediamine, and esters having two carbonyl groups such as ethyl acetoacetate. Is mentioned. Such third compounds include citric acid, oxalic acid, succinic acid, maleic acid, malic acid, adipic acid, tartaric acid, malonic acid, fumaric acid, aconitic acid, glutaric acid, ethylenediaminetetraacetic acid, lactic acid, glycolic acid. , Glyceric acid, salicylic acid, mevalonic acid, ethylenediamine, ethyl acetoacetate, malonic acid ester, glycol and pinacol are preferred, and among them, citric acid, lactic acid, malic acid, tartaric acid, glycol from the viewpoint of being a carboxylic acid having a hydroxy group. Acid and salicylic acid are more preferable, and citric acid is particularly preferable from the viewpoint that bulky and finer composite particles can be produced. In addition, you may use such 3rd compound individually by 1 type or in mixture of 2 or more types.
また、第４の化合物は、白金、ロジウム、パラジウム、金、銀、銅、コバルト、鉄、マンガン及びニッケルからなる群から選択される少なくとも１種の金属元素を含有する化合物である。このような第４の化合物としては、白金、ロジウム、パラジウム、金、銀、銅、コバルト、鉄、マンガン及びニッケルの水酸化物、酢酸塩、炭酸塩、硝酸塩等が挙げられる。このような第４の化合物としては、第２の化合物と溶液中にて複合化合物を形成し易く、焼成分解後に酸化還元性能を有するという観点から、パラジウムを含有する化合物（硝酸パラジウム、酢酸パラジウム等）が好ましく、酢酸パラジウムがより好ましい。なお、このような第４の化合物は、１種を単独で、あるいは２種以上を混合して用いてもよい。 The fourth compound is a compound containing at least one metal element selected from the group consisting of platinum, rhodium, palladium, gold, silver, copper, cobalt, iron, manganese, and nickel. Examples of the fourth compound include platinum, rhodium, palladium, gold, silver, copper, cobalt, iron, manganese and nickel hydroxides, acetates, carbonates and nitrates. As such a fourth compound, a compound containing palladium (palladium nitrate, palladium acetate, etc.) from the viewpoint of easily forming a composite compound in solution with the second compound and having redox performance after calcination decomposition. ) Is preferred, and palladium acetate is more preferred. In addition, you may use such 4th compound individually by 1 type or in mixture of 2 or more types.
また、本発明において、第１の化合物と、第２の化合物と、第３の化合物と、第４の化合物と、前記アンモニアとを含有させる溶媒は、水（好ましくはイオン交換水及び蒸留水等の純水）である。 In the present invention, the solvent containing the first compound, the second compound, the third compound, the fourth compound, and the ammonia is water (preferably ion-exchanged water, distilled water, or the like). Of pure water).
また、本発明の複合粒子前駆体水溶液における第１の化合物の前記金属元素の含有量としては、０．０５ｍｏｌ／Ｌ以上であることが好ましく、０．２ｍｏｌ／Ｌ〜２．０ｍｏｌ／Ｌであることがより好ましい。また、第２の化合物の前記金属元素の含有量としては、０．０５ｍｏｌ／Ｌ以上であることが好ましく、０．２ｍｏｌ／Ｌ〜１．０ｍｏｌ／Ｌであることがより好ましい。このような第１及び第２の化合物の含有量が前記下限未満では、第１及び第２の化合物の濃度が低すぎて製造効率が低下する傾向にあり、他方、前記上限を超えると、第１及び第２の化合物の濃度が高くなりすぎて焼成した際に均一に反応が起こらず、複合粒子を均一に製造できなくなる傾向にある。 Further, the content of the metal element of the first compound in the composite particle precursor aqueous solution of the present invention is preferably 0.05 mol / L or more, and is 0.2 mol / L to 2.0 mol / L. It is more preferable. Moreover, as content of the said metal element of a 2nd compound, it is preferable that it is 0.05 mol / L or more, and it is more preferable that it is 0.2 mol / L-1.0 mol / L. When the content of the first and second compounds is less than the lower limit, the concentrations of the first and second compounds tend to be too low and the production efficiency tends to decrease. When the concentration of the first and second compounds becomes too high, the reaction does not occur uniformly when baked, and the composite particles tend not to be produced uniformly.
さらに、第２の化合物の金属元素の含有量としては、第１の化合物の金属元素の含有量に対してモル換算で０．２〜５倍となるようにすることが好ましい。このような割合で第１の化合物と第２の化合物とを含有させることで、得られる複合粒子に、より高度なＮＯｘ吸蔵能を発揮させることが可能となる。また、第２の化合物の金属元素の含有量が第１の化合物の金属元素の含有量に対してモル比で０．２倍未満では、第１の化合物の単独相が多くなって、得られる複合粒子の割合が低下し、効果が小さくなる傾向にあり、他方、５倍を超えると、第２の化合物の単独相が多くなり、同様に得られる複合粒子の割合が低下する傾向にある。 Further, the content of the metal element of the second compound is preferably 0.2 to 5 times in terms of mole relative to the content of the metal element of the first compound. By including the first compound and the second compound at such a ratio, it is possible to cause the obtained composite particles to exhibit a higher level of NOx storage ability. In addition, when the content of the metal element of the second compound is less than 0.2 times in molar ratio with respect to the content of the metal element of the first compound, the single phase of the first compound is increased and obtained. The proportion of the composite particles tends to decrease and the effect tends to be small. On the other hand, when the ratio exceeds five times, the single phase of the second compound increases, and the proportion of the composite particles obtained similarly tends to decrease.
また、第３の化合物の含有量としては、０．１５ｍｏｌ／Ｌ以上であることが好ましく、０．７ｍｏｌ／Ｌ〜２．０ｍｏｌ／Ｌであることがより好ましい。このような第３の化合物の含有量が前記下限未満では、第１の化合物、第２の化合物及び第４の化合物に対する多座配位子の含有量が少なくなるため、水溶液中において、第１の化合物、第２の化合物及び第４の化合物を近接した状態で保持することが困難となる傾向にあり、他方、前記上限を超えると、第１の化合物、第２の化合物及び第４の化合物の濃度が低下することで担持効率が低下する傾向にある。 In addition, the content of the third compound is preferably 0.15 mol / L or more, and more preferably 0.7 mol / L to 2.0 mol / L. When the content of the third compound is less than the lower limit, the content of the polydentate ligand with respect to the first compound, the second compound, and the fourth compound is decreased. When the above upper limit is exceeded, the first compound, the second compound, and the fourth compound tend to be difficult to keep in close proximity to each other. The carrier efficiency tends to decrease due to a decrease in the concentration of the catalyst.
また、このような第３の化合物の含有量としては、前記第２の化合物中に含有される金属元素の含有量に対してモル換算で２倍以上（より好ましくは２．５〜１０倍）であることが好ましい。第３の化合物の含有量が前記第２の化合物中に含有される金属元素の含有量に対してモル換算で２倍未満であると、水溶液中において第１の化合物、第２の化合物及び第４の化合物の錯体の形成が困難となり、第１の化合物、第２の化合物及び第４の化合物を近接した状態で保持することが困難となり、複合粒子の製造が困難となる傾向にある。 Moreover, as content of such a 3rd compound, it is 2 times or more (more preferably 2.5 to 10 times) in molar conversion with respect to content of the metal element contained in a said 2nd compound. It is preferable that When the content of the third compound is less than twice the molar content of the metal element contained in the second compound, the first compound, the second compound, and the second compound in the aqueous solution It becomes difficult to form a complex of the compound No. 4, and it becomes difficult to hold the first compound, the second compound and the fourth compound in close proximity, and it tends to be difficult to produce composite particles.
また、第４の化合物の前記金属元素の含有量としては、０．００１ｍｏｌ／Ｌ〜０．５ｍｏｌ／Ｌであることがより好ましく、０．０５ｍｏｌ／Ｌ〜０．１ｍｏｌ／Ｌであることがより好ましい。このような第４の化合物の前記金属元素の含有量が前記下限未満では、複合粒子を製造した際に、得られる複合粒子のＮＯの酸化性能やＮＯｘ還元性能が低下する傾向にあり、他方、前記上限を超えると、複合粒子の形成が困難となったり、コストが上昇する傾向にある。 Further, the content of the metal element in the fourth compound is more preferably 0.001 mol / L to 0.5 mol / L, and more preferably 0.05 mol / L to 0.1 mol / L. preferable. When the content of the metal element in the fourth compound is less than the lower limit, when the composite particles are produced, the NO oxidation performance and NOx reduction performance of the resulting composite particles tend to be reduced, When the upper limit is exceeded, formation of composite particles tends to be difficult, and costs tend to increase.
さらに、第４の化合物の金属元素の含有量としては、第１の化合物の金属元素の含有量に対してモル換算で０．００１〜０．５倍（より好ましくは０．００５〜０．２倍）となるようにすることが好ましい。このような割合で第１の化合物と第４の化合物とを含有させることで、得られる複合粒子に、より高度なＮＯｘ浄化性能を発揮させることが可能となる。また、第４の化合物の金属元素の含有量が第１の化合物の金属元素の含有量に対してモル比で０．００１倍未満では、第４の化合物の割合が低くなり、得られる複合体粒子のＮＯｘ還元性能が低下する傾向にあり、他方、０．５倍を超えると、複合粒子の形成が困難となったり、コストが上昇する傾向にある。 Furthermore, the content of the metal element of the fourth compound is 0.001 to 0.5 times (more preferably 0.005 to 0.2) in terms of moles relative to the content of the metal element of the first compound. Times). By containing the first compound and the fourth compound at such a ratio, it is possible to cause the obtained composite particles to exhibit a higher degree of NOx purification performance. In addition, when the content of the metal element of the fourth compound is less than 0.001 times in terms of molar ratio with respect to the content of the metal element of the first compound, the ratio of the fourth compound is low, and the resulting composite is obtained. On the other hand, when the NOx reduction performance of the particles tends to decrease, when it exceeds 0.5 times, formation of composite particles tends to be difficult or costs tend to increase.
また、前記アンモニアの含有量としては、０．４ｍｏｌ／Ｌ以上であることが好ましく、２．０ｍｏｌ／Ｌ〜１０ｍｏｌ／Ｌであることが更に好ましい。このようなアンモニアの含有量が前記下限未満では、得られる水溶液に沈殿が生じる傾向にあり、他方、前記上限を超えると、第１の化合物及び第２の化合物の濃度が低下することで担持効率が低下する傾向にある。 In addition, the ammonia content is preferably 0.4 mol / L or more, and more preferably 2.0 mol / L to 10 mol / L. When the ammonia content is less than the lower limit, precipitation tends to occur in the resulting aqueous solution. On the other hand, when the upper limit is exceeded, the concentration of the first compound and the second compound is decreased, thereby supporting efficiency. Tend to decrease.
さらに、前記アンモニアの含有量としては、前記第３の化合物の含有量に対してモル換算で２倍以上（より好ましくは２．８〜５倍）であることが好ましい。アンモニアの含有量が前記第３の化合物の含有量に対してモル換算で２倍未満では、第１の化合物、第２の化合物及び第４の化合物を安定した状態で含有させることが困難となり、沈殿が生じ易くなる傾向にある。 Furthermore, the ammonia content is preferably 2 times or more (more preferably 2.8 to 5 times) in terms of mole relative to the content of the third compound. If the ammonia content is less than twice the molar content of the third compound, it becomes difficult to contain the first compound, the second compound and the fourth compound in a stable state, Precipitation tends to occur easily.
また、本発明の複合粒子前駆体水溶液を製造するための方法としては、第１の化合物と、第２の化合物と、第３の化合物と、第４の化合物と、アンモニアとを水に溶解させることが可能な方法であればよく、特に制限されない。このような本発明の複合粒子前駆体水溶液を製造するための好適な方法としては、例えば、第３の化合物を水に溶解させた後に第２の化合物を添加して沈殿物を生じせしめ、その後、アンモニアを添加して、前記沈殿物を再度溶解させた後、この溶液に、第１の化合物を更に加えて撹拌し、沈殿物を生じせしめた後に再度溶解させ、更に、第４の化合物の粉末を添加し撹拌して溶解させて複合粒子前駆体水溶液を製造する方法が挙げられる。 Moreover, as a method for producing the composite particle precursor aqueous solution of the present invention, the first compound, the second compound, the third compound, the fourth compound, and ammonia are dissolved in water. The method is not particularly limited as long as it is possible. As a suitable method for producing such a composite particle precursor aqueous solution of the present invention, for example, the third compound is dissolved in water, and then the second compound is added to form a precipitate, and then Then, ammonia was added to dissolve the precipitate again, and then the first compound was further added to the solution and stirred. After the precipitate was formed, the precipitate was dissolved again. A method of producing a composite particle precursor aqueous solution by adding powder and stirring to dissolve is mentioned.
以上、本発明の複合粒子前駆体水溶液について説明したが、以下において、本発明の複合粒子の製造方法について説明する。 Although the composite particle precursor aqueous solution of the present invention has been described above, the method for producing the composite particles of the present invention will be described below.
本発明の複合粒子の製造方法は、上記本発明の複合粒子前駆体水溶液を焼成して複合粒子を製造する方法である。 The method for producing composite particles of the present invention is a method for producing composite particles by firing the composite particle precursor aqueous solution of the present invention.
このような焼成の条件は、特に制限されないが、例えば、大気中において、３００℃〜６００℃の温度範囲で加熱することが好ましく、３００℃〜５００℃の温度条件で加熱することがより好ましい。また、加熱時間としては、加熱温度によって異なるものであるため一概には言えないが、１〜３時間程度とすることができる。 Such firing conditions are not particularly limited, but for example, heating in the air is preferably performed in a temperature range of 300 ° C. to 600 ° C., and more preferably heating is performed in a temperature condition of 300 ° C. to 500 ° C. Further, the heating time varies depending on the heating temperature and cannot be generally described, but it can be set to about 1 to 3 hours.
このような焼成条件で上記本発明の複合粒子前駆体水溶液を焼成することで複合粒子を製造することができる。そして、複合粒子の製造に用いられる上記本発明の複合粒子前駆体水溶液においては、前記第１の化合物と前記第２の化合物と前記第４の化合物とが近接した状態で保持されているため、焼成して得られる複合粒子は十分に微細化されたものとなるとともに、ＮＯｘの吸蔵サイトと、ＮＯの酸化及びＮＯｘの還元を行う酸化還元サイトとが近接した状態となる。そのため、得られる複合粒子においては、十分に高いＮＯｘ吸蔵性能とＮＯｘ還元性能とを発揮でき、これにＮＯｘを接触させることによって十分な量のＮＯｘを効率よく吸蔵還元することができる。従って、このようにして得られる複合粒子は排ガス浄化触媒の材料として好適に用いることができる。例えば、前記複合粒子をバリウムとセリウムとパラジウムとの複合粒子とした場合においては、前記複合粒子を自動車等の排ガスと接触させた場合に、空燃比リーン状態において排ガス中のＮＯをパラジウムが酸化するとともに排ガス中のＮＯｘをバリウムがＢａ（ＮＯ3）2として吸蔵し、空燃比リッチ状態においてパラジウムによりＮＯｘを還元して排ガスを効率よく浄化できる。また、このような複合粒子は、硫黄被毒耐久性にも優れている。従って、自動車等の排ガスのような酸化硫黄を含有するガスを浄化するために前記複合粒子を用いた場合には、硫黄被毒回復性に優れ、長期にわたって十分に高いＮＯｘ還元性能を発揮することができる。なお、このような複合粒子の形状は特に制限されず、粉末状、ペレット状等の形状としてもよい。また、上記本発明の複合粒子前駆体水溶液を担体に担持させた後、焼成して、複合粒子を担体に担持させてもよい。この場合においては、担体上において前記複合粒子が十分に微細化され、前記複合粒子が担体に十分に分散された状態で担持される。 The composite particles can be produced by firing the composite particle precursor aqueous solution of the present invention under such firing conditions. And in the composite particle precursor aqueous solution of the present invention used for the production of composite particles, the first compound, the second compound and the fourth compound are held in close proximity, The composite particles obtained by firing become sufficiently fine, and the NOx storage site and the oxidation-reduction site that oxidizes NO and reduces NOx are in close proximity. Therefore, the obtained composite particles can exhibit sufficiently high NOx occlusion performance and NOx reduction performance, and a sufficient amount of NOx can be efficiently occluded and reduced by bringing NOx into contact therewith. Therefore, the composite particles obtained in this way can be suitably used as a material for an exhaust gas purification catalyst. For example, when the composite particle is a composite particle of barium, cerium, and palladium, when the composite particle is brought into contact with exhaust gas of an automobile or the like, palladium oxidizes NO in the exhaust gas in an air-fuel ratio lean state. At the same time, NOx in the exhaust gas is occluded as barium Ba (NO 3 ) 2 , and NOx can be reduced with palladium in an air-fuel rich state to efficiently purify the exhaust gas. Such composite particles are also excellent in sulfur poisoning durability. Therefore, when the composite particles are used to purify sulfur oxide-containing gas such as exhaust gas from automobiles, etc., it is excellent in sulfur poisoning recovery and exhibits sufficiently high NOx reduction performance over a long period of time. Can do. The shape of such composite particles is not particularly limited, and may be a powder shape, a pellet shape, or the like. Alternatively, the composite particle precursor aqueous solution of the present invention may be supported on a carrier and then fired to support the composite particles on the carrier. In this case, the composite particles are sufficiently miniaturized on the carrier, and the composite particles are supported in a sufficiently dispersed state on the carrier.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.
［複合粒子前駆体水溶液の調製］
（合成例１）
先ず、クエン酸１．５ｍｏｌをイオン交換水４５０ｍＬに溶解させ、得られた溶液を７５℃に加熱した。次に、前記溶液にチタンイソプロポキシド０．３ｍｏｌを加えて溶解させた後、室温まで冷却し、チタンクエン酸錯体水溶液（０．６４ｍｏｌ／Ｌ）を調製した。その後、前記チタンクエン酸錯体水溶液５５ｍＬに２８質量％ＮＨ３水溶液を３０ｍＬ加え、更に２．１４ｍｏｌ／Ｌ酢酸バリウム水溶液１６ｍＬを加えた後、攪拌し、バリウム（Ｂａ）とチタン（Ｔｉ）を含有するＢａＴｉ水溶液を調製した。
[Preparation of aqueous composite particle precursor solution]
(Synthesis Example 1)
First, 1.5 mol of citric acid was dissolved in 450 mL of ion exchange water, and the resulting solution was heated to 75 ° C. Next, after adding 0.3 mol of titanium isopropoxide to the solution and dissolving, it was cooled to room temperature to prepare a titanium citrate complex aqueous solution (0.64 mol / L). Thereafter, 30 mL of 28 mass% NH 3 aqueous solution was added to 55 mL of the titanium citrate complex aqueous solution, and further 16 mL of 2.14 mol / L barium acetate aqueous solution was added, followed by stirring to contain barium (Ba) and titanium (Ti). A BaTi aqueous solution was prepared.
（合成例２）
先ず、クエン酸０．９ｍｏｌをイオン交換水１６５ｍＬに溶解させ、得られた溶液を８０℃に加熱した。次に、前記溶液に酢酸セリウム０．３ｍｏｌを加え、攪拌し、沈殿を生成させた後、２８質量％ＮＨ３水溶液を１７０ｍＬ滴下し、沈殿を再溶解させ、室温まで冷却してセリウムクエン酸錯体水溶液（０．５７ｍｏｌ／Ｌ）を調製した。次いで、前記セリウムクエン酸錯体水溶液５４ｍＬに２．１６ｍｏｌ／Ｌ酢酸バリウム水溶液１６ｍＬを加え、攪拌し、沈殿を生成した後、再溶解させて、バリウムとセリウム（Ｃｅ）を含有するＢａＣｅ水溶液を調製した。
(Synthesis Example 2)
First, 0.9 mol of citric acid was dissolved in 165 mL of ion exchange water, and the resulting solution was heated to 80 ° C. Next, after adding 0.3 mol of cerium acetate to the solution and stirring to form a precipitate, 170 mL of 28 mass% NH 3 aqueous solution was dropped, the precipitate was redissolved, cooled to room temperature, and cooled to cerium citrate complex. An aqueous solution (0.57 mol / L) was prepared. Next, 16 mL of a 2.16 mol / L barium acetate aqueous solution was added to 54 mL of the cerium citrate complex aqueous solution, stirred, a precipitate was formed, and then redissolved to prepare a BaCe aqueous solution containing barium and cerium (Ce). .
（実施例１）
合成例１で得られたＢａＴｉ水溶液１０．１ｍＬに酢酸パラジウム粉末０．１９ｇを添加し、攪拌して溶解させて、バリウムとチタンとパラジウム（Ｐｄ）とを含有する複合粒子前駆体水溶液を調製した。
(Example 1)
0.19 g of palladium acetate powder was added to 10.1 mL of BaTi aqueous solution obtained in Synthesis Example 1, and dissolved by stirring to prepare a composite particle precursor aqueous solution containing barium, titanium, and palladium (Pd). .
（実施例２）
合成例２で得られたＢａＣｅ水溶液７．８ｍＬに酢酸パラジウム粉末０．１９ｇを添加し、攪拌して溶解させて、バリウムとセリウムとパラジウムとを含有する複合粒子前駆体水溶液を調製した。
(Example 2)
To 7.8 mL of the BaCe aqueous solution obtained in Synthesis Example 2, 0.19 g of palladium acetate powder was added and dissolved by stirring to prepare a composite particle precursor aqueous solution containing barium, cerium, and palladium.
（実施例３）
合成例１で得られたＢａＴｉ水溶液１０．１ｍＬに酢酸ロジウム粉末０．１９ｇを添加し、攪拌して溶解させて、バリウムとチタンとパラジウムとを含有する複合粒子前駆体水溶液を調製した。
(Example 3)
Rhodium acetate powder (0.19 g) was added to 10.1 mL of the BaTi aqueous solution obtained in Synthesis Example 1, and dissolved by stirring to prepare a composite particle precursor aqueous solution containing barium, titanium, and palladium.
（実施例４）
合成例１で得られたＢａＴｉ水溶液１０．１ｍＬに酢酸銀粉末０．１９ｇを添加し、攪拌して溶解させて、バリウムとチタンと銀とを含有する複合粒子前駆体水溶液を調製した。
Example 4
Silver acetate powder 0.19 g was added to 10.1 mL of BaTi aqueous solution obtained in Synthesis Example 1, and dissolved by stirring to prepare a composite particle precursor aqueous solution containing barium, titanium, and silver.
（比較例１）
先ず、クエン酸１．５ｍｏｌをイオン交換水４５０ｍＬに溶解させ、得られた溶液を７５℃に加熱した。次に、前記溶液にチタンイソプロポキシド０．３ｍｏｌを加え、溶解させた後、室温まで冷却し、チタンクエン酸錯体水溶液（０．６４ｍｏｌ／Ｌ）を調製した。次いで、前記チタンクエン酸錯体水溶液５５ｍＬに２．１４ｍｏｌ／Ｌ酢酸バリウム水溶液１６ｍＬと、酢酸パラジウム粉末０．１９ｇとを添加し、攪拌してバリウムとチタンとパラジウムとを含有する水溶液の調製を試みた。しかしながら、前記チタンクエン酸錯体水溶液に酢酸パラジウムが溶解せず、また、約５時間後には沈殿が生成され、バリウムとチタンとパラジウムとを含有する複合粒子製造用の水溶液を得ることができなかった。
(Comparative Example 1)
First, 1.5 mol of citric acid was dissolved in 450 mL of ion exchange water, and the resulting solution was heated to 75 ° C. Next, 0.3 mol of titanium isopropoxide was added to the solution and dissolved, and then cooled to room temperature to prepare a titanium citrate complex aqueous solution (0.64 mol / L). Subsequently, 16 mL of 2.14 mol / L barium acetate aqueous solution and 0.19 g of palladium acetate powder were added to 55 mL of the titanium citrate complex aqueous solution and stirred to prepare an aqueous solution containing barium, titanium, and palladium. . However, palladium acetate did not dissolve in the titanium citrate complex aqueous solution, and a precipitate was formed after about 5 hours, and an aqueous solution for producing composite particles containing barium, titanium, and palladium could not be obtained. .
（比較例２）
クエン酸０．９ｍｏｌをイオン交換水１６５ｍＬに溶解させ、得られた溶液を８０℃に加熱した。次に、前記溶液に酢酸セリウム０．３ｍｏｌを加え、攪拌すると沈殿生成した。次いで、前記溶液５４ｍＬに２．１６ｍｏｌ／Ｌ酢酸バリウム水溶液１６ｍＬ、酢酸パラジウム粉末０．１９ｇを添加し、攪拌してバリウムとセリウムとパラジウムとを含有する複合粒子製造用の水溶液の調製を試みたが、溶解せず、複合粒子製造用の水溶液を得ることはできなかった。
(Comparative Example 2)
0.9 mol of citric acid was dissolved in 165 mL of ion exchange water, and the resulting solution was heated to 80 ° C. Next, 0.3 mol of cerium acetate was added to the solution and stirred to form a precipitate. Next, 2.16 mol / L of barium acetate aqueous solution 16 mL and palladium acetate powder 0.19 g were added to 54 mL of the above solution and stirred to prepare an aqueous solution for producing composite particles containing barium, cerium and palladium. The aqueous solution for producing composite particles could not be obtained.
（比較例３）
１６質量％四塩化チタン水溶液４１ｇと、２．１６ｍｏｌ／Ｌ酢酸バリウム水溶液１６ｍＬと、酢酸パラジウム粉末０．１９ｇとを攪拌し、バリウムとチタンとパラジウムとを含有する複合粒子製造用の水溶液の調製を試みたが、溶解せず、複合粒子製造用の水溶液を得ることはできなかった。また、このような混合液に２８質量％ＮＨ３水を添加しても、複合粒子製造用の水溶液を得ることはできなかった。
(Comparative Example 3)
Preparation of an aqueous solution for producing composite particles containing barium, titanium, and palladium by stirring 41 g of 16 mass% titanium tetrachloride aqueous solution, 16 mL of 2.16 mol / L barium acetate aqueous solution, and 0.19 g of palladium acetate powder Although it tried, it did not melt | dissolve and the aqueous solution for composite particle manufacture was not able to be obtained. Further, even when 28% by mass NH 3 water was added to such a mixed solution, an aqueous solution for producing composite particles could not be obtained.
（比較例４）
酢酸セリウム（和光純薬工業）０．３ｍｏｌをイオン交換水３０３ｍＬに溶解させ、この溶液に２．１４ｍｏｌ／Ｌ酢酸バリウム水溶液１３９ｍＬを加えた溶液を得た。その後、前記溶液に２８質量％ＮＨ３水１００ｍＬを加えたところ、沈殿が生成してしまい、複合粒子製造用の水溶液を得ることはできなかった。
(Comparative Example 4)
Cerium acetate (Wako Pure Chemical Industries) 0.3 mol was dissolved in ion-exchanged water 303 mL, and a solution was obtained by adding 139 mL of a 2.14 mol / L barium acetate aqueous solution to this solution. Thereafter, when 100 mL of 28% by mass NH 3 water was added to the solution, a precipitate was formed, and an aqueous solution for producing composite particles could not be obtained.
［複合粒子が担持された触媒の調製］
（調製例１：触媒担体の製造）
直径３０ｍｍ×長さ５０ｍｍＬの六角セルコージェライトモノリス基材に、アルミナ１００ｇ、チタニア−ジルコニア複合酸化物１００ｇ及びロジウム０．５ｇを担持したジルコニア５０ｇと、セリア−ジルコニア複合酸化物２０ｇとを含む担体を、前記モノリス基材１Ｌあたりの担持量が２７０ｇ／Ｌとなるようにしてコートし、触媒担体を調製した。
[Preparation of catalyst carrying composite particles]
(Preparation Example 1: Production of catalyst carrier)
A carrier comprising 100 g of alumina, 100 g of titania-zirconia composite oxide and 50 g of zirconia supporting 0.5 g of rhodium, and 20 g of ceria-zirconia composite oxide on a hexagonal cell cordierite monolith substrate having a diameter of 30 mm and a length of 50 mmL. The catalyst carrier was prepared by coating so that the supported amount per liter of the monolith substrate was 270 g / L.
（調製例２：触媒担体の製造）
直径３０ｍｍ×長さ５０ｍｍＬの六角セルコージェライトモノリス基材に、アルミナを、前記モノリス基材１Ｌあたりの担持量が２００ｇ／Ｌとなるようにしてコートし、触媒担体を調製した。
(Preparation Example 2: Production of catalyst carrier)
A catalyst carrier was prepared by coating a hexagonal cell cordierite monolith substrate having a diameter of 30 mm and a length of 50 mmL with an alumina coating amount of 200 g / L per 1 L of the monolith substrate.
（実施例５）
調製例１で得られた触媒担体にジニトロジアンミンＰｔ硝酸溶液を、担体１ＬあたりのＰｔの担持量が１．５ｇ／Ｌとなるようにして吸着担持させた後、大気中、３００℃の温度条件で３時間焼成して、Ｐｔ担持触媒を調製した。
(Example 5)
After the dinitrodiammine Pt nitric acid solution was adsorbed and supported on the catalyst support obtained in Preparation Example 1 so that the supported amount of Pt per 1 L of the support was 1.5 g / L, the temperature condition in the atmosphere was 300 ° C. Was calcined for 3 hours to prepare a Pt-supported catalyst.
次いで、前記Ｐｔ担持触媒に対して、実施例１で得られた複合粒子前駆体水溶液を、触媒１Ｌあたり各金属元素の担持量がそれぞれＢａ：０．２ｍｏｌ／Ｌ、Ｔｉ：０．２ｍｏｌ／Ｌ、Ｐｄ：０．５ｇ／Ｌとなるようにして吸水含浸させて担持し、大気中、３００℃の温度条件で３時間焼成することにより、前記Ｐｔ担持触媒上に複合粒子を製造し、ＮＯｘ吸蔵還元型触媒を調製した。 Next, with respect to the Pt-supported catalyst, the amount of each metal element supported per 1 L of the composite particle precursor aqueous solution obtained in Example 1 is Ba: 0.2 mol / L, Ti: 0.2 mol / L. , Pd: 0.5 g / L, impregnated with water and supported, and calcined in the atmosphere at 300 ° C. for 3 hours to produce composite particles on the Pt-supported catalyst. A reduced catalyst was prepared.
（実施例６）
実施例１で得られた複合粒子前駆体水溶液に代えて実施例２で得られた複合粒子前駆体水溶液を用いた以外は実施例５と同様にして、Ｐｔ担持触媒上に複合粒子を製造し、ＮＯｘ吸蔵還元型触媒を調製した。
(Example 6)
A composite particle was produced on a Pt-supported catalyst in the same manner as in Example 5 except that the composite particle precursor aqueous solution obtained in Example 2 was used instead of the composite particle precursor aqueous solution obtained in Example 1. A NOx occlusion reduction catalyst was prepared.
（実施例７）
調製例１で得られた触媒担体に代えて調製例２で得られた触媒担体を用いた以外は実施例５と同様にして、Ｐｔ担持触媒上に複合粒子を製造し、ＮＯｘ吸蔵還元型触媒を調製した。
(Example 7)
A composite particle was produced on a Pt-supported catalyst in the same manner as in Example 5 except that the catalyst carrier obtained in Preparation Example 2 was used instead of the catalyst carrier obtained in Preparation Example 1, and a NOx occlusion reduction type catalyst was produced. Was prepared.
（比較例５）
調製例１で得られた触媒担体に、ジニトロジアンミンＰｔ硝酸溶液及び硝酸パラジウム溶液を用いて、前記触媒担体１ＬあたりのＰｔとＰｄの担持量がそれぞれＰｔ１．５ｇ／Ｌ、Ｐｄ０．５ｇ／ＬとなるようにしてＰｔとＰｄとを選択吸着担持した後、大気中、３００℃の温度条件で３時間焼成し、ＰｔＰｄ担持触媒を調製した。
(Comparative Example 5)
Using the dinitrodiammine Pt nitric acid solution and the palladium nitrate solution as the catalyst carrier obtained in Preparation Example 1, the supported amounts of Pt and Pd per liter of the catalyst carrier were Pt 1.5 g / L and Pd 0.5 g / L, respectively. In this way, Pt and Pd were selectively adsorbed and supported, and then calcined in the atmosphere at 300 ° C. for 3 hours to prepare a PtPd-supported catalyst.
次に、ＰｔＰｄ担持触媒に２．１４ｍｏｌ／Ｌ酢酸バリウム水溶液を、触媒１ＬあたりのＢａの担持量が０．２ｍｏｌ／Ｌとなるようにして吸水含浸させることにより担持し、大気中、３００℃の温度条件で３時間焼成し、比較のためのＮＯｘ吸蔵還元型触媒を調製した。 Next, a PtPd-supported catalyst was supported by impregnating a 2.14 mol / L barium acetate aqueous solution with water absorption so that the supported amount of Ba per liter of the catalyst was 0.2 mol / L. The NOx occlusion reduction type catalyst for comparison was prepared by calcining for 3 hours under temperature conditions.
（比較例６）
実施例１で得られた複合粒子前駆体水溶液に代えて合成例１で得られたＢａＴｉ水溶液を用い、更にＰｔの担持量を触媒１Ｌあたり２ｇ／Ｌとした以外は実施例５と同様にして、比較のためのＮＯｘ吸蔵還元型触媒を調製した。
(Comparative Example 6)
The same procedure as in Example 5 was conducted except that the BaTi aqueous solution obtained in Synthesis Example 1 was used in place of the composite particle precursor aqueous solution obtained in Example 1, and the amount of Pt supported was 2 g / L per liter of catalyst. A NOx occlusion reduction catalyst for comparison was prepared.
（比較例７）
実施例２で得られた複合粒子前駆体水溶液に代えて合成例２で得られたＢａＣｅ水溶液を用い、更にＰｔの担持量を触媒１Ｌあたり２ｇ／Ｌとした以外は実施例６と同様にして、比較のためのＮＯｘ吸蔵還元型触媒を調製した。
(Comparative Example 7)
The same procedure as in Example 6 was performed except that the BaCe aqueous solution obtained in Synthesis Example 2 was used in place of the composite particle precursor aqueous solution obtained in Example 2 and the amount of Pt supported was 2 g / L per liter of catalyst. A NOx occlusion reduction catalyst for comparison was prepared.
（比較例８）
調製例１で得られた触媒担体に代えて調製例２で得られた触媒担体を用いた以外は比較例５と同様にして、比較のためのＮＯｘ吸蔵還元型触媒を調製した。
(Comparative Example 8)
A NOx occlusion reduction catalyst for comparison was prepared in the same manner as in Comparative Example 5 except that the catalyst carrier obtained in Preparation Example 2 was used instead of the catalyst carrier obtained in Preparation Example 1.
（実施例８）
調製例２で得られた触媒担体に、実施例１で得られた複合粒子前駆体水溶液を、担体１Ｌあたりの各金属元素の担持量がそれぞれＢａ：０．２ｍｏｌ／Ｌ、Ｔｉ：０．２ｍｏｌ／Ｌ、Ｐｄ：０．５ｇ／Ｌとなるようにして吸水含浸させて担持し、大気中、３００℃の温度条件で３時間焼成することにより、担体上に複合粒子を製造し、ＮＯｘ吸蔵還元型触媒を調製した。
(Example 8)
The catalyst carrier obtained in Preparation Example 2 is mixed with the composite particle precursor aqueous solution obtained in Example 1, and the supported amount of each metal element per liter of the carrier is Ba: 0.2 mol / L, Ti: 0.2 mol, respectively. / L, Pd: impregnated with water so as to be 0.5 g / L, supported, and calcined in the atmosphere at a temperature of 300 ° C. for 3 hours to produce composite particles on the carrier. A type catalyst was prepared.
（実施例９）
調製例２で得られた触媒担体に、実施例２で得られた複合粒子前駆体水溶液を、担体１Ｌあたりの各金属元素の担持量がそれぞれＢａ：０．２ｍｏｌ／Ｌ、Ｃｅ：０．２ｍｏｌ／Ｌ、Ｐｄ：０．５ｇ／Ｌとなるようにして吸水含浸させて担持し、大気中、３００℃の温度条件で３時間焼成することにより、担体上に複合粒子を製造し、ＮＯｘ吸蔵還元型触媒を調製した。
Example 9
The catalyst carrier obtained in Preparation Example 2 is mixed with the composite particle precursor aqueous solution obtained in Example 2, and the supported amount of each metal element per liter of the carrier is Ba: 0.2 mol / L, Ce: 0.2 mol, respectively. / L, Pd: impregnated with water so as to be 0.5 g / L, supported, and calcined in the atmosphere at a temperature of 300 ° C. for 3 hours to produce composite particles on the carrier. A type catalyst was prepared.
（比較例９）
先ず、調製例２で得られた触媒担体に、硝酸パラジウム溶液を用いて、担体１ＬあたりのＰｄの担持量が０．５ｇ／ＬとなるようにしてＰｄを選択吸着担持し、大気中、３００℃の温度条件で３時間焼成して、Ｐｄ担持触媒を調製した。次いで、Ｐｄ担持触媒に２．１４ｍｏｌ／Ｌ酢酸バリウム水溶液を、触媒１ＬあたりＢａの担持量が０．２ｍｏｌ／Ｌとなるようにして吸水含浸させて担持し、大気中、３００℃の温度条件で３時間焼成することにより、比較のためのＮＯｘ吸蔵還元型触媒を調製した。
(Comparative Example 9)
First, Pd is selectively adsorbed and supported on the catalyst support obtained in Preparation Example 2 using a palladium nitrate solution so that the amount of Pd supported per liter of support is 0.5 g / L. The Pd-supported catalyst was prepared by calcination for 3 hours under the temperature condition of ° C. Next, a 2.14 mol / L barium acetate aqueous solution is supported on the Pd supported catalyst by impregnating with water so that the supported amount of Ba is 0.2 mol / L per liter of the catalyst. By burning for 3 hours, a NOx occlusion reduction type catalyst for comparison was prepared.
（実施例１０）
調製例１で得られた触媒担体に、ジニトロジアンミンＰｔ硝酸溶液を用いて、触媒１ＬあたりのＰｔの担持量が１．５ｇ／ＬとなるようにしてＰｔを選択吸着担持し、大気中、３００℃の温度条件で３時間焼成し、Ｐｔ担持触媒を調製した。
(Example 10)
Using the dinitrodiammine Pt nitric acid solution on the catalyst support obtained in Preparation Example 1, Pt was selectively adsorbed and supported so that the amount of Pt supported per liter of the catalyst was 1.5 g / L. The Pt-supported catalyst was prepared by calcination for 3 hours under the temperature condition of ° C.
次に、前記Ｐｔ担持触媒に、実施例３で得られた複合粒子前駆体水溶液を、触媒１Ｌあたりの各金属元素の担持量がそれぞれＢａ：０．２ｍｏｌ／Ｌ、Ｔｉ：０．２ｍｏｌ／Ｌ、Ｒｈ：０．５ｇ／Ｌとなるようにして吸水含浸させて担持し、大気中、３００℃で３時間、焼成することにより、前記Ｐｔ担持触媒上に複合粒子を製造し、ＮＯｘ吸蔵還元型触媒を調製した。 Next, on the Pt-supported catalyst, the composite particle precursor aqueous solution obtained in Example 3 was used, and the supported amount of each metal element per 1 L of the catalyst was Ba: 0.2 mol / L, Ti: 0.2 mol / L, respectively. , Rh: 0.5 g / L of water absorption impregnated and supported, and calcined in the atmosphere at 300 ° C. for 3 hours to produce composite particles on the Pt-supported catalyst. A catalyst was prepared.
（実施例１１）
調製例１で得られた触媒担体に、ジニトロジアンミンＰｔ硝酸溶液を用いて、担体１ＬあたりのＰｔの担持量が１．５ｇ／ＬとなるようにしてＰｔを選択吸着担持し、大気中、３００℃の温度条件で３時間焼成し、Ｐｔ担持触媒を調製した。
(Example 11)
Using the dinitrodiammine Pt nitric acid solution on the catalyst support obtained in Preparation Example 1, Pt was selectively adsorbed and supported so that the amount of Pt supported per liter of support was 1.5 g / L. The Pt-supported catalyst was prepared by calcination for 3 hours under the temperature condition of ° C.
次に、前記Ｐｔ担持触媒に、実施例４で得られた複合粒子前駆体水溶液を、触媒１Ｌあたりの各金属元素の担持量がそれぞれＢａ：０．２ｍｏｌ／Ｌ、Ｔｉ：０．２ｍｏｌ／Ｌ、Ａｇ：１０ｇ／Ｌとなるようにして吸水含浸させて担持し、大気中、３００℃で３時間、焼成することにより、前記Ｐｔ担持触媒上に複合粒子を製造し、ＮＯｘ吸蔵還元型触媒を調製した。 Next, on the Pt-supported catalyst, the composite particle precursor aqueous solution obtained in Example 4 is used, and the supported amount of each metal element per 1 L of the catalyst is Ba: 0.2 mol / L, Ti: 0.2 mol / L, respectively. , Ag: 10 g / L, impregnated with water and supported, and calcined in the atmosphere at 300 ° C. for 3 hours to produce composite particles on the Pt-supported catalyst. Prepared.
なお、実施例５〜１１及び比較例５〜９で得られたＮＯｘ吸蔵還元型触媒の構成及びＮＯｘ還元成分の添加方法をまとめて表１に示す。 In addition, the structure of the NOx occlusion reduction type catalyst obtained in Examples 5-11 and Comparative Examples 5-9 and the addition method of the NOx reducing component are shown together in Table 1.
＜ＮＯｘ吸蔵還元型触媒の性能の評価＞
［耐久試験］
実施例５〜６及び８〜１１で得られたＮＯｘ吸蔵還元型触媒並びに比較例５〜９で得られた比較のためのＮＯｘ吸蔵還元型触媒を用い、各触媒に対して、それぞれ７５０℃の温度条件下において、表２に示す組成のリーンガス及びリッチガスをリーン／リッチ＝１１０秒／１０秒の間隔で変動させながら５時間流通させた。
<Evaluation of NOx storage reduction catalyst performance>
[An endurance test]
Using the NOx occlusion reduction type catalysts obtained in Examples 5 to 6 and 8 to 11 and the NOx occlusion reduction type catalyst for comparison obtained in Comparative Examples 5 to 9, each catalyst had a temperature of 750 ° C. Under the temperature condition, the lean gas and the rich gas having the composition shown in Table 2 were circulated for 5 hours while changing at an interval of lean / rich = 110 seconds / 10 seconds.
［ＮＯｘ浄化試験］
耐久試験後の実施例５〜６及び８〜１１で得られたＮＯｘ吸蔵還元型触媒並びに比較例５〜９で得られた比較のためのＮＯｘ吸蔵還元型触媒を用い、各触媒に対して、４００℃の温度条件下において、表３に示す組成のリッチガス及びリーンガスをリーン／リッチ＝１２０秒／３秒の間隔で変動させながら流通させ、ＮＯｘ浄化率を測定した。なお、空間速度（ＳＶ）はすべて５１４００ｈ−１とした。
[NOx purification test]
Using the NOx occlusion reduction type catalysts obtained in Examples 5-6 and 8-11 after the durability test and the NOx occlusion reduction type catalyst for comparison obtained in Comparative Examples 5-9, for each catalyst, Under a temperature condition of 400 ° C., a rich gas and a lean gas having the composition shown in Table 3 were allowed to flow while varying at intervals of lean / rich = 120 seconds / 3 seconds, and the NOx purification rate was measured. All space velocities (SV) were set to 51400 h −1 .
このようなＮＯｘ浄化試験の結果を表４及び表５に示す。なお、表４にはＰｔを担持したＮＯｘ吸蔵還元型触媒（実施例５、６、１０、１１及び比較例５、６、７）を用いた場合のＮＯｘ浄化率を示し、表５にはＰｔを担持していないＮＯｘ吸蔵還元型触媒（実施例８、９及び比較例９）を用いた場合のＮＯｘ浄化率を示す。 Tables 4 and 5 show the results of such NOx purification tests. Table 4 shows NOx purification rates in the case of using Pt-supported NOx storage reduction catalysts (Examples 5, 6, 10, 11 and Comparative Examples 5, 6, 7). Table 5 shows Pt. The NOx purification rate at the time of using the NOx occlusion reduction type catalyst (Examples 8 and 9 and comparative example 9) which does not carry NO is shown.
表４に示す結果からも明らかなように、実施例５〜６及び比較例５〜６で得られたＮＯｘ吸蔵還元型触媒を比較すると、同量のＰｄを担持しているにもかかわらず、実施例５〜６で得られたＮＯｘ吸蔵還元型触媒においては、ＮＯｘ浄化性能が向上することが確認された。このような結果から、本発明の複合粒子前駆体水溶液（実施例１又は２）を用いた場合には、予め担持させるＰｔの量を減少させることができることが確認され、ＰｔからＰｄへの置き換えによりコストを削減できることが分かった。また、同量のＰｔとＰｄとが担持された実施例５及び比較例５で得られたＮＯｘ吸蔵還元型触媒を比較すると、本発明の複合粒子前駆体水溶液（実施例１）を用いてＰｄを複合担持させた実施例５で得られたＮＯｘ吸蔵還元型触媒に優位性が認められた。 As is clear from the results shown in Table 4, when the NOx occlusion reduction type catalysts obtained in Examples 5-6 and Comparative Examples 5-6 were compared, although the same amount of Pd was supported, In the NOx occlusion reduction type catalysts obtained in Examples 5 to 6, it was confirmed that the NOx purification performance was improved. From these results, it was confirmed that when the composite particle precursor aqueous solution of the present invention (Example 1 or 2) was used, the amount of Pt supported in advance could be reduced, and the replacement from Pt to Pd was performed. It was found that the cost can be reduced. Further, when the NOx occlusion reduction type catalysts obtained in Example 5 and Comparative Example 5 in which the same amounts of Pt and Pd were supported were compared, Pd was obtained using the composite particle precursor aqueous solution (Example 1) of the present invention. The NOx occlusion reduction catalyst obtained in Example 5 in which the catalyst was supported in a composite manner was recognized to be superior.
さらに、表４に示す結果からも明らかなように、実施例１０〜１１及び比較例５〜６で得られたＮＯｘ吸蔵還元型触媒を比較すると、本発明の複合粒子前駆体水溶液（実施例３又は４）を用いて、Ｐｄ以外の成分であるＲｈやＡｇを複合粒子として担持した実施例１０〜１１で得られたＮＯｘ吸蔵還元型触媒の方が高いＮＯｘ浄化性能を示すことが確認された。 Further, as is clear from the results shown in Table 4, when the NOx occlusion reduction type catalysts obtained in Examples 10-11 and Comparative Examples 5-6 were compared, the composite particle precursor aqueous solution of the present invention (Example 3) Or 4), it was confirmed that the NOx occlusion reduction type catalysts obtained in Examples 10 to 11 in which Rh and Ag, which are components other than Pd, were supported as composite particles showed higher NOx purification performance. .
また、表５に示す結果からも明らかなように、実施例８〜９及び比較例９で得られたＮＯｘ吸蔵還元型触媒を比較すると、本発明の複合粒子前駆体水溶液（実施例１又は２）を用いてＰｄを複合粒子として担持したＮＯｘ吸蔵還元型触媒（実施例８〜９）の方が、高いＮＯｘ浄化性能を示すことが確認され、触媒中にＰｔを含まない場合においてもＮＯｘ浄化性能を発揮できることが確認された。 As is clear from the results shown in Table 5, when the NOx occlusion reduction type catalysts obtained in Examples 8 to 9 and Comparative Example 9 are compared, the composite particle precursor aqueous solution of the present invention (Example 1 or 2). NOx occlusion reduction catalysts (Examples 8 to 9) supporting Pd as composite particles using NO) are confirmed to exhibit higher NOx purification performance, and even when Pt is not included in the catalyst, NOx purification is achieved. It was confirmed that performance could be demonstrated.
このような結果から、本発明の複合粒子前駆体水溶液を用いてＰｄ等の酸化還元成分（ＮＯｘ還元成分）を複合担持した場合には、酸化還元成分がＮＯｘ吸蔵成分に近接した状態で微細化されて担持されるため、十分に高いＮＯｘ浄化性能を示すものと推察される。 From these results, when the composite particle precursor aqueous solution of the present invention is used to carry a redox component (NOx reducing component) such as Pd in a composite manner, the redox component is refined in a state close to the NOx occlusion component. Therefore, it is presumed that sufficiently high NOx purification performance is exhibited.
［ＥＰＭＡ観察］
耐久試験後の実施例５及び比較例５で得られたＮＯｘ吸蔵還元型触媒のコート層断面におけるＰｄとＢａの分布状態を、Ｘ線マイクロアナライザ（ＥＰＭＡ）により調べた。得られた結果を図１〜４に示す。なお、図１は、実施例５で得られたＮＯｘ吸蔵還元型触媒のコート層中のＰｄの分布状態を示す電子像であり、図２は、実施例５で得られたＮＯｘ吸蔵還元型触媒のコート層中のＢａの分布状態を示す電子像である。また、図３は、比較例５で得られたＮＯｘ吸蔵還元型触媒のコート層中のＰｄの分布状態を示す電子像であり、図４は、比較例５で得られたＮＯｘ吸蔵還元型触媒のコート層中のＢａの分布状態を示す電子像である。
[EPMA observation]
The distribution state of Pd and Ba in the cross section of the coating layer of the NOx occlusion reduction catalyst obtained in Example 5 and Comparative Example 5 after the durability test was examined using an X-ray microanalyzer (EPMA). The obtained results are shown in FIGS. 1 is an electron image showing the distribution state of Pd in the coating layer of the NOx occlusion reduction catalyst obtained in Example 5, and FIG. 2 is an NOx occlusion reduction catalyst obtained in Example 5. It is an electronic image which shows the distribution state of Ba in the coat layer of. 3 is an electronic image showing the distribution state of Pd in the coating layer of the NOx occlusion reduction catalyst obtained in Comparative Example 5, and FIG. 4 is the NOx occlusion reduction catalyst obtained in Comparative Example 5. It is an electronic image which shows the distribution state of Ba in the coat layer of.
図１〜４に示す結果からも明らかなように、実施例５で得られたＮＯｘ吸蔵還元型触媒においては、コート層の全体にＰｄとＢａが均一に分布しているのに対して、比較例５で得られたＮＯｘ吸蔵還元型触媒においては、コート層中にＰｄとＢａが均一に分布していないことが確認された。このような結果から、実施例５で得られたＮＯｘ吸蔵還元型触媒においては、ＰｄとＢａとがより近接化した状態で担持されていることが確認された。 As is apparent from the results shown in FIGS. 1 to 4, in the NOx occlusion reduction type catalyst obtained in Example 5, Pd and Ba are uniformly distributed in the entire coating layer, but the comparison is made. In the NOx occlusion reduction type catalyst obtained in Example 5, it was confirmed that Pd and Ba were not uniformly distributed in the coat layer. From these results, it was confirmed that in the NOx occlusion reduction type catalyst obtained in Example 5, Pd and Ba were supported in a closer state.
［ＸＲＤ解析］
初期状態の実施例７及び比較例８で得られたＮＯｘ吸蔵還元型触媒中のコート層を掻きとって粉末を得た。その後、前記粉末に対してＸＲＤ解析することにより、各触媒に担持されたＢａ化合物の結晶構造を調査した。実施例７及び比較例８で得られたＮＯｘ吸蔵還元型触媒から掻きとった粉末のＸＲＤパターンを図５に示す。
[XRD analysis]
The coating layer in the NOx occlusion reduction catalyst obtained in Example 7 and Comparative Example 8 in the initial state was scraped to obtain a powder. Then, the crystal structure of the Ba compound supported on each catalyst was investigated by XRD analysis of the powder. FIG. 5 shows an XRD pattern of the powder scraped from the NOx occlusion reduction type catalyst obtained in Example 7 and Comparative Example 8.
図５に示す結果からも明らかなように、比較例８で得られたＮＯｘ吸蔵還元型触媒においては、約３０ｎｍのＢａＣＯ３に帰属される回折線が確認され、平均粒径が約３０ｎｍであると算出された。一方、実施例５で得られたＮＯｘ吸蔵還元型触媒においては、ＢａＣＯ３やＢａＴｉＯ３などＢａ由来の化合物の回折線は確認されず、Ｂａ化合物が微細な状態で存在することが確認された。 As is clear from the results shown in FIG. 5, in the NOx occlusion reduction type catalyst obtained in Comparative Example 8, a diffraction line attributed to BaCO 3 of about 30 nm was confirmed, and the average particle diameter was about 30 nm. And calculated. On the other hand, in the NOx occlusion reduction type catalyst obtained in Example 5, diffraction lines of Ba-derived compounds such as BaCO 3 and BaTiO 3 were not confirmed, and it was confirmed that the Ba compound was present in a fine state.
［透過電子顕微鏡（ＴＥＭ）による測定］
初期状態の実施例７で得られたＮＯｘ吸蔵還元型触媒から掻きとった前記粉末を透過電子顕微鏡（ＴＥＭ）により測定し、Ｂａ、Ｔｉ、Ｐｄの分散状態を調べた。得られた測定結果のうち、ＴＥＭ写真を図６に示し、図６に示すＴＥＭ写真中の○で囲った部分のＥＤＸ元素分析結果を示すグラフを図７に示す。
[Measurement by transmission electron microscope (TEM)]
The powder scraped from the NOx occlusion reduction catalyst obtained in Example 7 in the initial state was measured with a transmission electron microscope (TEM) to examine the dispersion state of Ba, Ti, and Pd. Among the obtained measurement results, a TEM photograph is shown in FIG. 6, and a graph showing an EDX elemental analysis result of a portion surrounded by a circle in the TEM photograph shown in FIG. 6 is shown in FIG.
図６又は図７に示す結果からも明らかなように、実施例７で得られたＮＯｘ吸蔵還元型触媒においては、アルミナ表面上にＢａ、Ｔｉ、Ｐｄが３０ｎｍ以内の範囲に共存分布していることが確認された。 As is clear from the results shown in FIG. 6 or FIG. 7, in the NOx occlusion reduction type catalyst obtained in Example 7, Ba, Ti, and Pd coexist on the alumina surface within the range of 30 nm or less. It was confirmed.
このような図１〜７に示す結果からも明らかなように、本発明の複合粒子前駆体水溶液を用いることで、３０ｎｍ以下の微細な状態で複合ＮＯｘ吸蔵成分とＰｄ等の酸化還元成分が近接化して担持されることが確認され、本発明の複合粒子前駆体水溶液によりＮＯｘ浄化性能が十分に高い触媒を効率よく製造できることが分かった。 As is clear from the results shown in FIGS. 1 to 7, by using the aqueous composite particle precursor solution of the present invention, the composite NOx storage component and the redox component such as Pd are close to each other in a fine state of 30 nm or less. It was confirmed that a catalyst having a sufficiently high NOx purification performance can be efficiently produced by the composite particle precursor aqueous solution of the present invention.
以上説明したように、本発明によれば、水溶液中に複合粒子の前駆体である金属元素を高濃度で且つ安定した状態で含有させることができ、十分に高いＮＯｘ浄化能を有し且つ十分に微細化された複合粒子を効率よく製造することが可能な複合粒子前駆体水溶液及びそれを用いた複合粒子の製造方法を提供することが可能となる。 As described above, according to the present invention, a metal element that is a precursor of composite particles can be contained in an aqueous solution in a high concentration and in a stable state, and has a sufficiently high NOx purification ability and sufficient. It is possible to provide a composite particle precursor aqueous solution capable of efficiently producing finely divided composite particles and a method for producing composite particles using the same.
したがって、本発明の複合粒子前駆体水溶液は、自動所用のＮＯｘ吸蔵型還元触媒を製造する際に用いる材料等として特に有用である。 Therefore, the composite particle precursor aqueous solution of the present invention is particularly useful as a material or the like used when producing a NOx occlusion-type reduction catalyst for automated use.
Claims (13)
チタン、アルミニウム、ジルコニウム及び希土類金属からなる群から選択される少なくとも１種の金属元素を含有する第２の化合物と、
多座配位子を有する第３の化合物と、
白金、ロジウム、パラジウム、金、銀、銅、コバルト、鉄、マンガン及びニッケルからなる群から選択される少なくとも１種の金属元素を含有する第４の化合物と、
アンモニアと、
を含むことを特徴とする複合粒子前駆体水溶液。 A first compound containing at least one metal element selected from the group consisting of alkali metals and alkaline earth metals;
A second compound containing at least one metal element selected from the group consisting of titanium, aluminum, zirconium and rare earth metals;
A third compound having a multidentate ligand;
A fourth compound containing at least one metal element selected from the group consisting of platinum, rhodium, palladium, gold, silver, copper, cobalt, iron, manganese and nickel;
With ammonia,
A composite particle precursor aqueous solution comprising:
Priority Applications (1)
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| JP2007014662A JP4811666B2 (en) | 2007-01-25 | 2007-01-25 | Composite particle precursor aqueous solution for producing NOx occlusion reduction type catalyst and method for producing NOx occlusion reduction type catalyst using the same |
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| WO2010147163A1 (en) * | 2009-06-16 | 2010-12-23 | 株式会社 キャタラー | Exhaust gas purifying catalyst, powder material, and method for producing exhaust gas purifying catalyst |
| JP2011000519A (en) * | 2009-06-17 | 2011-01-06 | Toyota Central R&D Labs Inc | Catalyst for purifying exhaust gas |
| WO2013128261A3 (en) * | 2012-03-02 | 2013-12-27 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas control apparatus, exhaust gas control method and exhaust gas purification catalyst |
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| WO2013128261A3 (en) * | 2012-03-02 | 2013-12-27 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas control apparatus, exhaust gas control method and exhaust gas purification catalyst |
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