JP2006159134A - Catalyst for clarifying exhaust gas and its production method - Google Patents
Catalyst for clarifying exhaust gas and its production method Download PDFInfo
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- JP2006159134A JP2006159134A JP2004356908A JP2004356908A JP2006159134A JP 2006159134 A JP2006159134 A JP 2006159134A JP 2004356908 A JP2004356908 A JP 2004356908A JP 2004356908 A JP2004356908 A JP 2004356908A JP 2006159134 A JP2006159134 A JP 2006159134A
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- metal oxide
- exhaust gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 133
- 239000002245 particle Substances 0.000 claims abstract description 133
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 131
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 27
- 239000011164 primary particle Substances 0.000 claims abstract description 21
- 238000010298 pulverizing process Methods 0.000 claims abstract description 20
- 239000002612 dispersion medium Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims description 74
- 238000000746 purification Methods 0.000 claims description 48
- 238000010304 firing Methods 0.000 claims description 27
- 239000000839 emulsion Substances 0.000 claims description 22
- 229910000510 noble metal Inorganic materials 0.000 claims description 22
- 239000011325 microbead Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000009841 combustion method Methods 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 50
- 239000002609 medium Substances 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 86
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 31
- 229910052751 metal Inorganic materials 0.000 description 22
- 239000002184 metal Substances 0.000 description 22
- 239000007921 spray Substances 0.000 description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
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- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000001308 synthesis method Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- -1 zirconium ions Chemical class 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 239000010419 fine particle Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000003832 Lantana Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002078 nanoshell Substances 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- 239000010412 oxide-supported catalyst Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 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
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- QKYBEKAEVQPNIN-UHFFFAOYSA-N barium(2+);oxido(oxo)alumane Chemical compound [Ba+2].[O-][Al]=O.[O-][Al]=O QKYBEKAEVQPNIN-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006172 buffering agent Substances 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
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 229910021432 inorganic complex Chemical class 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 239000000047 product Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000005507 spraying Methods 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 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
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
本発明は排ガス浄化用触媒及びその製造方法に関し、詳しくは、排ガス中のHC、NOx、COx等を浄化するための排ガス浄化用触媒並びにその排ガス浄化用触媒を製造するための方法に関する。 The present invention relates to an exhaust gas purifying catalyst and a method for producing the same, and more particularly to an exhaust gas purifying catalyst for purifying HC, NO x , CO x and the like in the exhaust gas and a method for producing the exhaust gas purifying catalyst.
近年、人間を取り巻く環境に存在し得る成分であって人体に影響を及ぼす可能性のある有害ガスの存在が問題視されるようになってきており、例えば排ガス中の有害成分であるHC、NOx、COx等をより確実に浄化することが可能な排ガス浄化用触媒の開発が望まれている。 In recent years, the presence of harmful gases that can exist in the environment surrounding humans and can affect the human body has been regarded as a problem. For example, HC and NO that are harmful components in exhaust gas. Development of an exhaust gas purifying catalyst capable of more reliably purifying x , CO x and the like is desired.
このような背景の下で、排ガスを浄化するための各種の触媒が開発されており、例えば特開平9−155192号公報(特許文献1)には、助触媒と、担体上に担持された貴金属とからなる排ガス浄化用触媒であって、助触媒がセリウム酸化物とジルコニウム酸化物とが互いに固溶した酸化物固溶体を含む粒子であり、該粒子中のセリウム酸化物に対するジルコニウム酸化物の固溶度が50%以上で且つ該粒子を構成する結晶子の平均径が100nm以下であることを特徴とする排ガス浄化用触媒が開示されている。しかしながら、特許文献1に記載されている排ガス浄化用触媒は、焼成して得た複合酸化物助触媒粉末と担体粉末とを混合することによって得ており、このような複合酸化物助触媒粉末及び担体粉末はサブミクロンから数ミクロンの粒径を有する2次凝集体を形成しているため、助触媒の偏在等によって浄化性能の向上に限界があった。 Under such a background, various catalysts for purifying exhaust gas have been developed. For example, Japanese Patent Application Laid-Open No. 9-155192 (Patent Document 1) discloses a promoter and a noble metal supported on a carrier. The co-catalyst is a particle containing an oxide solid solution in which cerium oxide and zirconium oxide are in solid solution with each other, and the solid solution of zirconium oxide in the cerium oxide in the particle An exhaust gas purifying catalyst is disclosed in which the degree is 50% or more and the average diameter of crystallites constituting the particles is 100 nm or less. However, the exhaust gas purifying catalyst described in Patent Document 1 is obtained by mixing a composite oxide promoter powder obtained by firing and a carrier powder. Since the carrier powder forms a secondary aggregate having a particle size of submicron to several microns, there is a limit to improvement in purification performance due to uneven distribution of the promoter.
また、特開平10−202101号公報(特許文献2)には、セリウム、アルミニウム及びジルコニウムの各イオンを含む混合溶液に、アルカリ性溶液と過酸化水素水とを添加して複合酸化物の前駆体が分散した懸濁液を形成し、該懸濁液に比表面積の大きな担体を添加して混合物とし、該混合物を焼成して形成されたことを特徴とする複合酸化物担持触媒担体が開示されている。しかしながら、特許文献2に記載されている複合酸化物担持触媒担体にあっては、複合酸化物助触媒と担体とをナノレベルオーダーで均質混合できる点で優れているものの、複合酸化物助触媒の機能を発揮させるために必要な焼成工程における焼成温度が低いと反応及び固溶が十分に進行せず、逆に焼成温度が高いと粒成長や複合酸化物助触媒成分と担体成分との反応が発生してしまい、いずれにせよ触媒性能の向上に限界があった。 Japanese Patent Laid-Open No. 10-202101 (Patent Document 2) discloses a composite oxide precursor obtained by adding an alkaline solution and hydrogen peroxide water to a mixed solution containing cerium, aluminum, and zirconium ions. Disclosed is a composite oxide-supported catalyst support formed by forming a dispersed suspension, adding a support having a large specific surface area to the suspension to form a mixture, and firing the mixture. Yes. However, the composite oxide-supported catalyst carrier described in Patent Document 2 is excellent in that the composite oxide promoter and the carrier can be homogeneously mixed on the nano-level order. If the firing temperature is low in the firing step necessary to exert the function, the reaction and solid solution will not proceed sufficiently. Conversely, if the firing temperature is high, the grain growth and the reaction between the composite oxide promoter component and the support component will occur. In any case, there was a limit to improving the catalyst performance.
さらに、特開2002−1120号公報(特許文献3)には、中空状酸化物粉末と中実状酸化物粉末を含む担体と、該担体に担持された触媒活性を有する金属又は金属酸化物とよりなることを特徴とする排ガス浄化用触媒が開示されている。しかしながら、特許文献3に記載されている排ガス浄化用触媒は、中空状酸化物粉末と中実状酸化物粉末とを乾式混合法や湿式混合法で混合する方法や、ゾルゲル法や沈殿法によって中空状酸化物粉末の表面に中実状酸化物粒子を析出させる方法によって得ており、前者の方法では中空状酸化物粉末及び中実状酸化物粉末がサブミクロンから数ミクロンの粒径を有する2次凝集体を形成しているため、浄化性能の向上に限界があった。また、後者の方法では、中実状酸化物粉末に複合酸化物助触媒としての機能を発揮させるために必要な焼成工程における焼成温度が低いと反応及び固溶が十分に進行せず、逆に焼成温度が高いと粒成長や複合酸化物助触媒成分と担体成分との反応が発生してしまい、いずれにせよ浄化性能の向上に限界があった。 Furthermore, Japanese Patent Application Laid-Open No. 2002-1120 (Patent Document 3) includes a carrier containing hollow oxide powder and solid oxide powder, and a metal or metal oxide having catalytic activity carried on the carrier. An exhaust gas purifying catalyst is disclosed. However, the exhaust gas-purifying catalyst described in Patent Document 3 is hollow by a method of mixing a hollow oxide powder and a solid oxide powder by a dry mixing method or a wet mixing method, a sol-gel method or a precipitation method. The solid oxide particles are obtained by depositing solid oxide particles on the surface of the oxide powder. In the former method, the hollow oxide powder and the secondary oxide in which the solid oxide powder has a particle size of submicron to several microns are obtained. As a result, there was a limit to improving the purification performance. In the latter method, if the firing temperature in the firing step necessary for the solid oxide powder to function as a composite oxide promoter is low, the reaction and solid solution do not proceed sufficiently, and on the contrary, firing is performed. When the temperature is high, grain growth and reaction between the composite oxide promoter component and the carrier component occur, and in any case, there is a limit to improvement in purification performance.
排ガス中の有害成分に対する規制が益々強化される昨今の状況下にあって、このような有害成分をより確実に浄化することが可能な排ガス浄化用触媒に要求される触媒性能は厳しくなる一方であり、より浄化性能が高く且つ高温耐久性に優れた排ガス浄化用触媒の開発が望まれている。
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、浄化性能が十分に高く且つ高温耐久性に優れた排ガス浄化用触媒を製造することができる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, and an object of the present invention is to provide a method capable of producing an exhaust gas purification catalyst having sufficiently high purification performance and excellent high-temperature durability. To do.
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、高温焼成によって均質化した複合金属酸化物凝集体を高度に粉砕して得た複合金属酸化物からなるコロイド粒子のゾルを特定の金属酸化物担体の表面に供給して担持せしめることにより、上記目的が達成されることを見出し、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 developed a colloidal particle sol composed of a composite metal oxide obtained by highly pulverizing a composite metal oxide aggregate homogenized by high-temperature firing. The inventors have found that the above object can be achieved by supplying and supporting a specific metal oxide support on the surface, and have completed the present invention.
すなわち、本発明の第一の排ガス浄化用触媒の製造方法は、高温焼成によって均質化した複合金属酸化物凝集体を粉砕して得た平均粒径が20nm以下である複合金属酸化物からなるコロイド粒子が分散媒中に均一分散しているゾルを、金属種の気相状態からの凝縮酸化によって合成されたナノ一次粒子鎖状凝集体からなり且つ前記コロイド粒子の平均粒径より大きい中心細孔直径を有している金属酸化物担体の表面に供給した後、前記ゾルを乾燥せしめて前記金属酸化物担体に前記コロイド粒子が担持されてなる排ガス浄化用触媒を得ることを特徴とする方法である。 That is, the first method for producing an exhaust gas purifying catalyst of the present invention is a colloid comprising a composite metal oxide having an average particle size of 20 nm or less obtained by pulverizing a composite metal oxide aggregate homogenized by high-temperature firing. A sol in which particles are uniformly dispersed in a dispersion medium is composed of nano-primary particle chain aggregates synthesized by condensation oxidation from a gas phase state of a metal species and has a central pore larger than the average particle size of the colloidal particles. After supplying to the surface of the metal oxide support having a diameter, the sol is dried to obtain an exhaust gas purifying catalyst in which the colloidal particles are supported on the metal oxide support. is there.
また、本発明の第二の排ガス浄化用触媒の製造方法は、高温焼成によって均質化した複合金属酸化物凝集体を粉砕して得た平均粒径が20nm以下である複合金属酸化物からなるコロイド粒子が分散媒中に分散しているゾルを、エマルジョン燃焼法によって合成された中空酸化物粉末からなり且つ前記コロイド粒子の平均粒径より大きい中心細孔直径を有している金属酸化物担体の表面に供給した後、前記ゾルを乾燥せしめて前記金属酸化物担体に前記コロイド粒子が担持されてなる排ガス浄化用触媒を得ることを特徴とする方法である。 Further, the second method for producing an exhaust gas purifying catalyst of the present invention is a colloid comprising a composite metal oxide having an average particle size of 20 nm or less obtained by pulverizing a composite metal oxide aggregate homogenized by high-temperature firing. A sol in which particles are dispersed in a dispersion medium is made of a hollow oxide powder synthesized by an emulsion combustion method and has a central pore diameter larger than the average particle diameter of the colloidal particles. After supplying to the surface, the sol is dried to obtain an exhaust gas purifying catalyst in which the colloidal particles are supported on the metal oxide carrier.
上記本発明の第一及び第二の排ガス浄化用触媒の製造方法においては、前記ゾルが、前記複合金属酸化物凝集体を直径100μm以下のマイクロビーズを用いて粉砕して得たものであることが好ましい。 In the first and second exhaust gas purification catalyst production methods of the present invention, the sol is obtained by pulverizing the composite metal oxide aggregate using microbeads having a diameter of 100 μm or less. Is preferred.
また、上記本発明の第一及び第二の排ガス浄化用触媒の製造方法は、前記金属酸化物担体及び/又は前記コロイド粒子の表面に貴金属を担持せしめる担持工程を更に含んでいることが好ましい。 The first and second exhaust gas purifying catalyst production methods of the present invention preferably further include a loading step of loading a noble metal on the surface of the metal oxide support and / or the colloidal particles.
本発明の第一の排ガス浄化用触媒は、高温焼成によって均質化した複合金属酸化物凝集体を粉砕して得た平均粒径が20nm以下である複合金属酸化物からなるコロイド粒子が分散媒中に均一分散しているゾルを、金属種の気相状態からの凝縮酸化によって合成されたナノ一次粒子鎖状凝集体からなり且つ前記コロイド粒子の平均粒径より大きい中心細孔直径を有している金属酸化物担体の表面に供給した後、前記ゾルを乾燥せしめることによって前記金属酸化物担体に前記コロイド粒子が担持されていることを特徴とするものである。 In the first exhaust gas purifying catalyst of the present invention, colloidal particles composed of a composite metal oxide having an average particle diameter of 20 nm or less obtained by pulverizing a composite metal oxide aggregate homogenized by high-temperature firing are contained in a dispersion medium. The sol is uniformly dispersed in a nano-primary particle chain aggregate synthesized by condensation oxidation from a gas phase state of a metal species and has a central pore diameter larger than the average particle diameter of the colloidal particles. The colloidal particles are supported on the metal oxide carrier by drying the sol after being supplied to the surface of the metal oxide carrier.
また、本発明の第二の排ガス浄化用触媒は、高温焼成によって均質化した複合金属酸化物凝集体を粉砕して得た平均粒径が20nm以下である複合金属酸化物からなるコロイド粒子が分散媒中に分散しているゾルを、エマルジョン燃焼法によって合成された中空酸化物粉末からなり且つ前記コロイド粒子の平均粒径より大きい中心細孔直径を有している金属酸化物担体の表面に供給した後、前記ゾルを乾燥せしめることによって前記金属酸化物担体に前記コロイド粒子が担持されていることを特徴とするものである。 Further, the second exhaust gas purifying catalyst of the present invention has dispersed colloidal particles composed of a composite metal oxide having an average particle size of 20 nm or less obtained by pulverizing a composite metal oxide aggregate homogenized by high-temperature firing. A sol dispersed in a medium is supplied to the surface of a metal oxide support made of a hollow oxide powder synthesized by an emulsion combustion method and having a central pore diameter larger than the average particle diameter of the colloidal particles. Then, the colloidal particles are supported on the metal oxide carrier by drying the sol.
上記本発明の第一及び第二の排ガス浄化用触媒においては、前記ゾルが、前記複合金属酸化物凝集体を直径100μm以下のマイクロビーズを用いて粉砕して得たものであることが好ましい。 In the first and second exhaust gas purifying catalysts of the present invention, the sol is preferably obtained by pulverizing the composite metal oxide aggregate using microbeads having a diameter of 100 μm or less.
また、上記本発明の第一及び第二の排ガス浄化用触媒においては、前記金属酸化物担体及び/又は前記コロイド粒子の表面に貴金属が更に担持されていることが好ましい。 In the first and second exhaust gas purifying catalysts of the present invention, it is preferable that a noble metal is further supported on the surface of the metal oxide support and / or the colloidal particles.
なお、本発明によって浄化性能が十分に高く且つ高温耐久性に優れた排ガス浄化用触媒が得られるようにな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、先ず、金属酸化物担体に担持される複合金属酸化物の触媒や助触媒としての機能は、その均質性に依存する。本発明にかかる複合金属酸化物は、高温焼成によって均質化された複合金属酸化物凝集体を粉砕して得られているため、従来のゾルゲル法や沈殿法によって得られる複合金属酸化物より均質性に優れており、その機能が最大限に発揮される。また、従来のように金属酸化物担体に担持される複合金属酸化物が凝集していると、担体の一部にしか複合金属酸化物粒子が被覆されないため、触媒や助触媒として機能すべき複合金属酸化物が有効利用されない。それに対して、本発明においては、平均粒径が20nm以下である複合金属酸化物からなるコロイド粒子が、凝集のない分散状態(ゾル状態)で多孔質又は中空状の金属酸化物担体の表面に供給されるため、触媒や助触媒として機能すべき複合金属酸化物のコロイド粒子が担体上に均質に被覆され、触媒や助触媒として有効利用される。さらに、従来のように複合金属酸化物が凝集して担体の細孔径より大きくなってしまっていると、複合金属酸化物粒子は担体の細孔内に入ることができないため、結果的に担体の2次凝集体表面にゾル粒子が凝集してしまい、均質な被覆状態にはならない。それに対して、本発明においては、担体の中心細孔直径が複合金属酸化物からなるコロイド粒子の粒径よりも大きいため、コロイド粒子の均質な被覆が細孔内にも形成され、しかもコロイド粒子が相互に接触しにくいため、その粒成長も十分に抑制される。したがって、本発明においては、複合金属酸化物からなるコロイド粒子の触媒や助触媒としての機能の向上と、その被覆の均質性による有効利用との相乗効果により、浄化性能が十分に高く且つ高温耐久性に優れた排ガス浄化用触媒が得られるようになると本発明者らは推察する。 The reason why an exhaust gas purification catalyst having sufficiently high purification performance and excellent high-temperature durability can be obtained by the present invention is not necessarily clear, but the present inventors speculate as follows. That is, first, the function of the composite metal oxide supported on the metal oxide support as a catalyst or a cocatalyst depends on its homogeneity. Since the composite metal oxide according to the present invention is obtained by pulverizing a composite metal oxide aggregate homogenized by high-temperature firing, it is more homogeneous than a composite metal oxide obtained by a conventional sol-gel method or precipitation method. It is excellent in its function. In addition, when the composite metal oxide supported on the metal oxide support is agglomerated as in the prior art, the composite metal oxide particles are only coated on a part of the support, so that the composite that should function as a catalyst or a co-catalyst is used. Metal oxide is not effectively used. On the other hand, in the present invention, colloidal particles made of a composite metal oxide having an average particle diameter of 20 nm or less are dispersed on the surface of a porous or hollow metal oxide carrier in a dispersed state (sol state) without aggregation. Since it is supplied, colloidal particles of a composite metal oxide that should function as a catalyst or a cocatalyst are uniformly coated on the support and are effectively used as a catalyst or a cocatalyst. Furthermore, if the composite metal oxide is agglomerated and becomes larger than the pore diameter of the support as in the conventional case, the composite metal oxide particles cannot enter the pores of the support. The sol particles are aggregated on the surface of the secondary agglomerate, and the uniform coating state is not obtained. On the other hand, in the present invention, since the center pore diameter of the support is larger than the particle size of the colloidal particles made of the composite metal oxide, a uniform coating of the colloidal particles is also formed in the pores. Since they are difficult to contact each other, the grain growth is sufficiently suppressed. Therefore, in the present invention, the purification performance is sufficiently high and the durability at high temperature is improved by the synergistic effect of the improvement of the function as a catalyst or co-catalyst of the colloidal particles composed of the composite metal oxide and the effective use due to the homogeneity of the coating. The present inventors speculate that an exhaust gas purifying catalyst having excellent properties can be obtained.
本発明によれば、浄化性能が十分に高く且つ高温耐久性に優れた排ガス浄化用触媒を効率良く且つ確実に製造することが可能となる。 According to the present invention, it is possible to efficiently and reliably manufacture an exhaust gas purification catalyst having sufficiently high purification performance and excellent high-temperature durability.
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、本発明において後述する金属酸化物担体の表面に供給するゾルについて説明する。すなわち、本発明にかかるゾルは、高温焼成によって均質化した複合金属酸化物凝集体を粉砕して得た平均粒径が20nm以下である複合金属酸化物からなるコロイド粒子が分散媒中に均一分散している分散液(懸濁液)である。 First, the sol supplied to the surface of the metal oxide support described later in the present invention will be described. That is, in the sol according to the present invention, colloidal particles made of a composite metal oxide having an average particle diameter of 20 nm or less obtained by pulverizing a composite metal oxide aggregate homogenized by high-temperature firing are uniformly dispersed in a dispersion medium. It is a dispersion liquid (suspension).
本発明において用いられる複合金属酸化物としては、アルミナ、ジルコニア、チタニア、シリカ、酸化鉄、希土類元素酸化物、アルカリ金属酸化物、アルカリ土類金属酸化物及び貴金属酸化物からなる群から選択される2種以上の複合金属酸化物が好ましい。希土類元素酸化物としては、セリウム、ランタン、ネオジム、イットリウム、プラセオジム等の酸化物が挙げられ、アルカリ金属酸化物としては、リチウム、ナトリウム、カリウム、セシウム等の酸化物が挙げられ、アルカリ土類金属酸化物としては、バリウム、ストロンチウム、カルシウム、マグネシウム等の酸化物が挙げられ、貴金属酸化物としては、白金、ロジウム、パラジウム、イリジウム等の酸化物が挙げられる。 The composite metal oxide used in the present invention is selected from the group consisting of alumina, zirconia, titania, silica, iron oxide, rare earth element oxide, alkali metal oxide, alkaline earth metal oxide, and noble metal oxide. Two or more mixed metal oxides are preferred. Examples of rare earth element oxides include oxides such as cerium, lanthanum, neodymium, yttrium, and praseodymium. Examples of alkali metal oxides include oxides such as lithium, sodium, potassium, and cesium, and alkaline earth metals. Examples of the oxide include oxides such as barium, strontium, calcium, and magnesium, and examples of the noble metal oxide include oxides such as platinum, rhodium, palladium, and iridium.
このような本発明において用いられる複合金属酸化物としては、得られる複合金属酸化物粒子が排ガス浄化用触媒としてより有効に機能するという観点から、アルミナ、ジルコニア、チタニア、シリカ、酸化鉄、セリア、ランタナ、ネオジア、イットリア、酸化バリウム、酸化リチウム及び酸化カリウムからなる群から選択される2種以上の複合金属酸化物が好ましく、中でも、アルミナ、ジルコニア、チタニア、セリア及びシリカからなる群から選択される少なくとも一種を含有する複合金属酸化物であることが特に好ましい。 As such a composite metal oxide used in the present invention, alumina, zirconia, titania, silica, iron oxide, ceria, from the viewpoint that the obtained composite metal oxide particles function more effectively as an exhaust gas purification catalyst. Two or more kinds of complex metal oxides selected from the group consisting of lantana, neodia, yttria, barium oxide, lithium oxide and potassium oxide are preferred, and among them, selected from the group consisting of alumina, zirconia, titania, ceria and silica. A composite metal oxide containing at least one kind is particularly preferable.
また、本発明において用いられる2種以上の金属酸化物の組み合わせとしては、特に制限されないが、得られる複合金属酸化物粒子が排ガス浄化用触媒としてより有効に機能するという観点から、セリア/ジルコニア固溶体のような酸素吸放出剤、チタン酸バリウム、バリウムアルミネートのようなNOx吸着剤を含む複合酸化物、パラジウム系ペロブスカイトのような貴金属を含む複合酸化物等が挙げられる。 Further, the combination of two or more metal oxides used in the present invention is not particularly limited, but from the viewpoint that the obtained composite metal oxide particles function more effectively as an exhaust gas purification catalyst, the ceria / zirconia solid solution. And a composite oxide containing a NOx adsorbent such as barium titanate and barium aluminate, and a composite oxide containing a noble metal such as palladium perovskite.
なお、このような各種の複合金属酸化物における金属酸化物の組成比は特に制限されず、その用途等に応じて適宜調整される。 In addition, the composition ratio of the metal oxide in such various composite metal oxides is not particularly limited, and is appropriately adjusted according to the use and the like.
本発明においては、上記の複合金属酸化物からなり且つ高温焼成によって均質化した複合金属酸化物凝集体を粉砕することによって、平均粒径が20nm以下である複合金属酸化物からなるコロイド粒子を得る。 In the present invention, colloidal particles made of a composite metal oxide having an average particle size of 20 nm or less are obtained by pulverizing the composite metal oxide aggregate made of the above composite metal oxide and homogenized by high-temperature firing. .
このような高温焼成によって均質化した複合金属酸化物凝集体を得る具体的な方法は特に制限されないが、例えば、酸化して前述の複合金属酸化物となる2種以上の金属の塩を含有する溶液を高速攪拌しながらアルカリ性物質を添加することにより前駆体沈殿物を得た後、得られた前駆体沈殿物を高温焼成することにより均質化された複合金属酸化物凝集体が得られる。 A specific method for obtaining a composite metal oxide aggregate homogenized by such high-temperature firing is not particularly limited, and includes, for example, a salt of two or more metals that are oxidized to form the composite metal oxide. After obtaining a precursor precipitate by adding an alkaline substance while stirring the solution at high speed, a homogenized composite metal oxide aggregate is obtained by firing the obtained precursor precipitate at a high temperature.
このような金属の塩としては、前記の金属の硝酸塩、酢酸塩、塩化物、硫酸塩、亜硫酸塩、無機錯塩(例えば、硝酸アルミニウム、オキシ硝酸ジルコニウム、硝酸セリウム、酢酸ジルコニウム、オキシ硫酸ジルコニウム、四塩化チタン、シュウ酸チタニルアンモニウム、硫酸チタニル、硝酸イットリウム)等の水溶性の塩が好適に用いられる。また、金属塩溶液を調製するための溶媒としては、特に制限されず、水、アルコール等の各種溶媒が挙げられる。さらに、アルカリ性物質としては、アンモニア、水酸化ナトリウム、水酸化カリウム等が挙げられるが、焼成時に容易に分離できるアンモニアが特に好ましい。 Examples of such metal salts include nitrates, acetates, chlorides, sulfates, sulfites, and inorganic complex salts (for example, aluminum nitrate, zirconium oxynitrate, cerium nitrate, zirconium acetate, zirconium oxysulfate, four Water-soluble salts such as titanium chloride, titanyl ammonium oxalate, titanyl sulfate, yttrium nitrate) are preferably used. Moreover, it does not restrict | limit especially as a solvent for preparing a metal salt solution, Various solvents, such as water and alcohol, are mentioned. Furthermore, examples of the alkaline substance include ammonia, sodium hydroxide, potassium hydroxide, and the like, and ammonia that can be easily separated during firing is particularly preferable.
また、前駆体沈殿物を高温焼成する際における焼成条件としては、特に制限されないが、酸化雰囲気(例えば、空気)中において400〜1000℃程度の温度で10〜600分程度焼成するという条件が好ましい。 In addition, the firing conditions for firing the precursor precipitate at a high temperature are not particularly limited, but a condition of firing at a temperature of about 400 to 1000 ° C. for about 10 to 600 minutes in an oxidizing atmosphere (for example, air) is preferable. .
このような本発明で用いる複合金属酸化物凝集体は、直径20nm以下(より好ましくは2〜10nm)の一次粒子(結晶子)の凝集体であることが必要である。一次粒子の直径が20nmを超えていると、粉砕しても平均粒径が20nm以下のコロイド粒子を得ることができず、結果として浄化性能及び高温耐久性に十分に優れた排ガス浄化用触媒が得られない。なお、複合金属酸化物の二次凝集体の平均粒径は特に制限されないが、200nm以下であることが好ましい。 Such a composite metal oxide aggregate used in the present invention needs to be an aggregate of primary particles (crystallites) having a diameter of 20 nm or less (more preferably 2 to 10 nm). If the diameter of the primary particles exceeds 20 nm, colloidal particles having an average particle size of 20 nm or less cannot be obtained even when pulverized, and as a result, an exhaust gas purifying catalyst having sufficiently excellent purification performance and high-temperature durability is obtained. I can't get it. The average particle size of the secondary aggregate of the composite metal oxide is not particularly limited, but is preferably 200 nm or less.
本発明において、複合金属酸化物凝集体を粉砕し、平均粒径が20nm以下である複合金属酸化物からなるコロイド粒子が分散媒中に均一分散しているゾルを得る方法は特に限定されず、公知の粉砕方法、分級方法、分散方法等が適宜用いられるが、直径100μm以下(特に好ましくは30〜50μm)のマイクロビーズを用いて複合金属酸化物凝集体を粉砕し、分散媒中に分散せしめる方法が特に好ましい。このように特定のマイクロビーズを用いて本発明にかかるゾルを得ると、複合金属酸化物からなるコロイド粒子がナノレベルで均一に混合され、極めて均一なゾルが得られる傾向にある。このようなマイクロビーズの直径が100μmを超えていると、平均粒径が20nm以下であるコロイド粒子、更にはナノレベルの均一混合状態が達成されず、結果として浄化性能及び高温耐久性に十分に優れた排ガス浄化用触媒が得られにくくなる傾向にある。また、このようなマイクロビーズの直径は、複合金属酸化物の二次凝集体の平均粒径の250〜1000倍のものが好ましい。マイクロビーズの直径が前記下限未満では分散の効率が低下する傾向にあり、他方、前記上限を超えると平均粒径が20nm以下であるコロイド粒子が得られにくくなる傾向にある。なお、マイクロビーズの材質は特に制限されず、例えばジルコニア、ガラス等が挙げられる。 In the present invention, the method of pulverizing the composite metal oxide aggregate and obtaining a sol in which colloidal particles composed of the composite metal oxide having an average particle diameter of 20 nm or less are uniformly dispersed in the dispersion medium is not particularly limited. Known pulverization methods, classification methods, dispersion methods, and the like are used as appropriate, but the composite metal oxide aggregates are pulverized using microbeads having a diameter of 100 μm or less (particularly preferably 30 to 50 μm) and dispersed in a dispersion medium. The method is particularly preferred. As described above, when a sol according to the present invention is obtained using specific microbeads, colloidal particles made of a composite metal oxide are uniformly mixed at the nano level and there is a tendency to obtain a very uniform sol. When the diameter of such microbeads exceeds 100 μm, colloidal particles having an average particle diameter of 20 nm or less, and furthermore, a nano-level uniform mixing state cannot be achieved, resulting in sufficient purification performance and high-temperature durability. It tends to be difficult to obtain an excellent exhaust gas purifying catalyst. The diameter of such microbeads is preferably 250 to 1000 times the average particle size of the secondary aggregate of the composite metal oxide. If the diameter of the microbead is less than the lower limit, the dispersion efficiency tends to decrease. On the other hand, if the microbead exceeds the upper limit, colloidal particles having an average particle diameter of 20 nm or less tend not to be obtained. The material of the microbead is not particularly limited, and examples thereof include zirconia and glass.
また、本発明において用いる分散媒は、前記複合金属酸化物からなるコロイド粒子を分散させることができる液体であればよく、特に制限されないが、水、アルコール等が好適に用いられる。また、かかる分散媒に他の成分を添加する必要は特にないが、酢酸等の酸、アンモニア等の塩基、緩衝剤等を適宜添加して分散媒のpHを調整してもよい。 The dispersion medium used in the present invention is not particularly limited as long as it is a liquid that can disperse the colloidal particles made of the composite metal oxide, and water, alcohol, and the like are preferably used. Further, it is not particularly necessary to add other components to the dispersion medium, but the pH of the dispersion medium may be adjusted by appropriately adding an acid such as acetic acid, a base such as ammonia, a buffering agent, or the like.
さらに、本発明にかかるゾルにおける複合金属酸化物からなるコロイド粒子の含有量(固形分濃度)は特に制限されず、後述する金属酸化物担体の表面に担持せしめるコロイド粒子の量等に応じて適宜調整されるが、0.1〜50質量%程度であることが好ましい。 Further, the content (solid content concentration) of the colloidal particles composed of the composite metal oxide in the sol according to the present invention is not particularly limited, and is appropriately determined according to the amount of colloidal particles supported on the surface of the metal oxide carrier described later. Although adjusted, it is preferable that it is about 0.1-50 mass%.
次に、本発明において担体として用いられる金属酸化物担体について説明する。すなわち、本発明においては、
(i)金属種の気相状態からの凝縮酸化によって合成されたナノ一次粒子鎖状凝集体からなり且つ前記コロイド粒子の平均粒径より大きい中心細孔直径を有している金属酸化物担体(多孔質金属酸化物担体)、或いは、
(ii)エマルジョン燃焼法によって合成された中空酸化物粉末からなり且つ前記コロイド粒子の平均粒径より大きい中心細孔直径を有している金属酸化物担体(中空金属酸化物担体)、
を担体として用いる。
Next, the metal oxide support used as the support in the present invention will be described. That is, in the present invention,
(i) A metal oxide support comprising a nano-primary particle chain aggregate synthesized by condensation oxidation from a gas phase state of a metal species and having a central pore diameter larger than the average particle diameter of the colloid particles ( Porous metal oxide support), or
(ii) a metal oxide support (hollow metal oxide support) comprising a hollow oxide powder synthesized by an emulsion combustion method and having a central pore diameter larger than the average particle diameter of the colloidal particles,
Is used as a carrier.
このような金属酸化物担体を構成する金属酸化物としては、アルミナ、ジルコニア、チタニア、シリカ、酸化鉄、希土類元素酸化物、アルカリ金属酸化物及びアルカリ土類金属酸化物からなる群から選択される1種以上の金属酸化物が好ましく、排ガス浄化用触媒の担体としてより有効に機能するという観点から、アルミナ、ジルコニア、チタニア、シリカ、酸化鉄、セリア、ランタナ、ネオジア、イットリア、酸化バリウム、酸化リチウム及び酸化カリウムからなる群から選択される1種以上の金属酸化物がより好ましく、中でも、アルミナ、ジルコニア、チタニア、セリア及びシリカからなる群から選択される単純酸化物、或いはそれらと希土類元素酸化物、アルカリ金属酸化物又はアルカリ土類金属酸化物との複合金属酸化物が特に好ましい。さらに、高比表面積と高耐熱性との双方がより高水準に達成される傾向にあることから、金属酸化物担体を構成する金属酸化物としては、アルミナ、希土類元素添加アルミナ、アルカリ金属添加アルミナ、アルカリ土類金属添加アルミナが特に好ましい。 The metal oxide constituting such a metal oxide support is selected from the group consisting of alumina, zirconia, titania, silica, iron oxide, rare earth element oxide, alkali metal oxide, and alkaline earth metal oxide. One or more metal oxides are preferable, and from the viewpoint of more effectively functioning as a support for an exhaust gas purification catalyst, alumina, zirconia, titania, silica, iron oxide, ceria, lantana, neodia, yttria, barium oxide, lithium oxide And one or more metal oxides selected from the group consisting of potassium oxide, more preferably, simple oxides selected from the group consisting of alumina, zirconia, titania, ceria, and silica, or rare earth element oxides thereof. Particularly preferred are composite metal oxides with alkali metal oxides or alkaline earth metal oxides. Arbitrariness. Furthermore, since both high specific surface area and high heat resistance tend to be achieved at a higher level, the metal oxides constituting the metal oxide support include alumina, rare earth element-added alumina, alkali metal-added alumina. Alkaline earth metal-added alumina is particularly preferred.
また、本発明において用いられる金属酸化物担体はいずれも、前記コロイド粒子の平均粒径より大きい中心細孔直径を有していることが必要であり、前記コロイド粒子の平均粒径の2倍以上の中心細孔直径を有していることがより好ましい。このように担体の中心細孔直径がコロイド粒子の粒径よりも大きいと、コロイド粒子の均質な被覆が細孔内にも形成され、しかも触媒内におけるガスの拡散性も良好となることから、複合金属酸化物からなるコロイド粒子の触媒や助触媒としての機能の向上と、その被覆の均質性による有効利用との相乗効果により、得られる排ガス浄化用触媒の浄化性能が十分に高くなる。このような金属酸化物担体は、細孔容量が大きく、0.5cc/g以上の細孔容量を有していることがより好ましい。 In addition, any metal oxide support used in the present invention needs to have a central pore diameter larger than the average particle diameter of the colloidal particles, and is at least twice the average particle diameter of the colloidal particles. More preferably, it has a central pore diameter of When the center pore diameter of the support is larger than the particle size of the colloidal particles, a uniform coating of colloidal particles is formed in the pores, and the gas diffusibility in the catalyst is also improved. Due to the synergistic effect of the improvement of the function of the colloidal particles made of the composite metal oxide as a catalyst or cocatalyst and the effective use due to the homogeneity of the coating, the purification performance of the resulting exhaust gas purification catalyst is sufficiently high. Such a metal oxide support has a large pore volume, and more preferably has a pore volume of 0.5 cc / g or more.
このような本発明にかかる金属酸化物担体(i)(金属種の気相状態からの凝縮酸化によって合成されたナノ一次粒子鎖状凝集体からなる多孔質金属酸化物担体)を得る方法としては、例えば、T.Tani et al.,"Evolution of the Morphology of Zinc Oxide/Silica Particles Made by Spray Combustion", J.Am.Ceram.Soc.,vol.87,No.3,p.365-370,(2004)に記載されている気相合成法が好適に採用される。 As a method of obtaining such a metal oxide support (i) according to the present invention (a porous metal oxide support comprising nano-primary particle chain aggregates synthesized by condensation oxidation from a gas phase of a metal species), For example, T. Tani et al., “Evolution of the Morphology of Zinc Oxide / Silica Particles Made by Spray Combustion”, J. Am. Ceram. Soc., Vol. 87, No. 3, p. 365-370, The gas phase synthesis method described in (2004) is preferably employed.
このように金属種(金属微粒子、クラスタ等)の気相状態からの凝縮酸化によって多孔質金属酸化物を合成する気相合成法によれば、一般にナノサイズの一次粒子が鎖状に凝集した構造の二次粒子からなる多孔質金属酸化物粉末(ナノ一次粒子鎖状凝集体)となるので、共沈法等の湿式合成法で得られる金属酸化物粉末と比較すると、一次粒子どうしの接触面積が小さい。そのため、このようなナノ一次粒子鎖状凝集体においては粒成長が抑制され、比表面積の低下が十分に抑制される。さらに、このようなナノ一次粒子鎖状凝集体は、合成時に高温を経ているため、共沈法等の湿式合成法で得られる金属酸化物粉末より耐熱性にも優れている。 In this way, according to the gas phase synthesis method of synthesizing a porous metal oxide by condensation oxidation from a gas phase state of metal species (metal fine particles, clusters, etc.), a structure in which nano-sized primary particles are generally aggregated in a chain shape Because it becomes a porous metal oxide powder (nano primary particle chain aggregate) consisting of secondary particles, the contact area between primary particles compared to metal oxide powder obtained by a wet synthesis method such as coprecipitation method Is small. Therefore, in such nano primary particle chain aggregates, grain growth is suppressed, and a decrease in specific surface area is sufficiently suppressed. Furthermore, since such nano primary particle chain aggregates are subjected to a high temperature during synthesis, they are superior in heat resistance to metal oxide powders obtained by a wet synthesis method such as a coprecipitation method.
このような気相合成法としては、気相火炎法、噴霧火炎法、プラズマ法、レーザー法等が例示されるが、火炎を熱源としておりエネルギー効率のよい気相火炎法、噴霧火炎法が好ましく、中でも、金属元素を含む有機溶液を噴霧燃焼させる噴霧火炎法が好ましい。噴霧火炎法によれば、ガス原料を用いる気相火炎法に比べて原料選択の自由度が高く、また複数種の原料の混合も容易である。 Examples of such a gas phase synthesis method include a gas phase flame method, a spray flame method, a plasma method, and a laser method, but a gas phase flame method and a spray flame method that use a flame as a heat source and have high energy efficiency are preferable. Among them, the spray flame method in which an organic solution containing a metal element is spray-combusted is preferable. According to the spray flame method, the degree of freedom in selecting a raw material is higher than that in a gas phase flame method using a gas raw material, and mixing of a plurality of types of raw materials is easy.
気相合成法として噴霧火炎法を用いる場合、原料として、有機金属錯体、金属アルコキシド、金属塩化物、金属硫酸塩、金属酢酸塩、金属プロピオン酸塩等の有機溶媒に可溶な金属化合物を用いることができる。また、有機溶媒は特に制限されず、用いる原料の溶解性、合成条件等を考慮して、炭化水素、アルコール、アルデヒド、カルボン酸、エーテル、エステル等から選択して用いることができる。さらに、水、過酸化水素、アンモニア水等の無機溶媒を混合することも可能である。なお、溶媒中の原料濃度は、特に制限されないが、合成速度の観点から0.1モル/L以上であることが好ましい。 When the spray flame method is used as a gas phase synthesis method, a metal compound soluble in an organic solvent such as an organometallic complex, metal alkoxide, metal chloride, metal sulfate, metal acetate, or metal propionate is used as a raw material. be able to. The organic solvent is not particularly limited, and can be selected from hydrocarbons, alcohols, aldehydes, carboxylic acids, ethers, esters, and the like in consideration of solubility of raw materials used, synthesis conditions, and the like. Furthermore, it is also possible to mix inorganic solvents, such as water, hydrogen peroxide, and ammonia water. The raw material concentration in the solvent is not particularly limited, but is preferably 0.1 mol / L or more from the viewpoint of the synthesis rate.
このような噴霧火炎法による具体的な合成条件は特に制限されず、必要な合成速度、火炎温度等に応じて、溶液流量、噴霧ガス種、噴霧ガス流量、補助火炎用ガス種、補助火炎用ガス流量、燃焼補助ガス種、燃焼補助ガス流量等を適宜設定すればよい。 The specific synthesis conditions by such spray flame method are not particularly limited, and depending on the required synthesis rate, flame temperature, etc., the solution flow rate, spray gas type, spray gas flow rate, auxiliary flame gas type, auxiliary flame use The gas flow rate, combustion auxiliary gas type, combustion auxiliary gas flow rate, etc. may be set as appropriate.
また、本発明にかかる金属酸化物担体(ii)(エマルジョン燃焼法によって合成された中空酸化物粉末からなる中空金属酸化物担体)を得る方法としては、例えば、T.Tani et al.,"Morphology of Oxide Particles Made by the Emulsion Combustion Method", J.Am.Ceram.Soc.,vol.86,No.6,p.898-904,(2003)、特開2000−203810号公報、特開2002−1120号公報に記載されているエマルジョン燃焼法が好適に採用される。 In addition, as a method for obtaining the metal oxide support (ii) according to the present invention (hollow metal oxide support comprising a hollow oxide powder synthesized by an emulsion combustion method), for example, T. Tani et al., “Morphology of Oxide Particles Made by the Emulsion Combustion Method ", J. Am. Ceram. Soc., vol. 86, No. 6, p. 898-904, (2003), JP 2000-203810 A, JP 2002-2002. The emulsion combustion method described in Japanese Patent No. 1120 is preferably employed.
このような中空酸化物粉末は、合成時に高温を経ているため、共沈法等の湿式合成法で得られる金属酸化物粉末より耐熱性にも優れている。 Since such a hollow oxide powder undergoes a high temperature during synthesis, it is superior in heat resistance to a metal oxide powder obtained by a wet synthesis method such as a coprecipitation method.
このようなエマルジョン燃焼法においては、原料となる金属元素を含む水溶液又は水分散液が有機溶媒中に分散してなるW/O型エマルジョンを噴霧燃焼することにより中空酸化物粉末を製造することができる。 In such an emulsion combustion method, a hollow oxide powder can be produced by spray combustion of a W / O emulsion in which an aqueous solution or aqueous dispersion containing a metal element as a raw material is dispersed in an organic solvent. it can.
現時点ではこの原因は明らかではないが、表面酸化膜形成速度が大きいために、粒子収縮の小さい段階で粒子表面に表面酸化膜が形成され、結果として非常に肉薄の多孔質中空体となると推察される。 The cause of this is not clear at this time, but because the surface oxide film formation rate is high, it is presumed that a surface oxide film is formed on the particle surface at a stage of small particle shrinkage, resulting in a very thin porous hollow body. The
このようなW/O型エマルジョンの噴霧燃焼においては、上記のように一つの分散粒子径が一つの反応の場となるが、エマルジョン中の分散粒子径が100nmよりも小さいと表面酸化膜形成前に粒子が完全に収縮してしまい、中空状とはならないため、好ましくない。一方、分散粒子径が10μmよりも大きいと、反応場が大きくなりすぎて不均質になる可能性があり好ましくない。エマルジョン中の分散粒子径が100nm〜10μmの範囲であれば、製造される金属酸化物からなる中空状粒子の外径が20〜2000nmとなる。外径が20nmより小さいと中空部が存在しなくなり、2000nmを超える中空状粉末を上記方法で製造することは困難である。 In such spray combustion of a W / O type emulsion, one dispersed particle diameter becomes one reaction field as described above. If the dispersed particle diameter in the emulsion is smaller than 100 nm, the surface oxide film is not formed. Since the particles are completely shrunk and do not become hollow, it is not preferable. On the other hand, if the dispersed particle size is larger than 10 μm, the reaction field becomes too large and may become inhomogeneous, which is not preferable. When the dispersed particle diameter in the emulsion is in the range of 100 nm to 10 μm, the outer diameter of the hollow particles made of the metal oxide to be produced is 20 to 2000 nm. When the outer diameter is smaller than 20 nm, the hollow portion does not exist, and it is difficult to produce a hollow powder having a diameter exceeding 2000 nm by the above method.
また、噴霧燃焼時の燃焼温度は1000℃以下(より好ましくは700〜900℃)とすることが好ましい。燃焼温度が1000℃を超えると生成物の一部が粒成長して中空構造が破壊するおそれがあり、また比表面積が低下する傾向にあるので好ましくない。他方、燃焼温度が低すぎると、有機成分が完全に燃焼せず、炭素成分が残留し易くなる傾向にある。 Moreover, it is preferable that the combustion temperature at the time of spray combustion shall be 1000 degrees C or less (more preferably 700-900 degreeC). If the combustion temperature exceeds 1000 ° C., part of the product may grow and the hollow structure may be destroyed, and the specific surface area tends to decrease. On the other hand, if the combustion temperature is too low, the organic component does not completely burn and the carbon component tends to remain.
このようなエマルジョン燃焼法において使用する金属元素の原料としては、金属硝酸塩、金属酢酸塩、金属硫酸塩、金属塩化物塩、錯塩等の水溶性の金属塩を用いることができる。そしてW/Oエマルジョンは、この金属塩の水溶液と有機溶媒とを分散剤を介して攪拌することで形成できる。使用する有機溶媒としては、ヘキサン、オクタン、ケロシン、ガソリン等、水溶液とW/Oエマルジョンを形成可能な有機溶媒であればよい。また、使用する分散剤の種類及び添加量は特に限定されず、カチオン性界面活性剤、アニオン性界面活性剤、ノニオン性界面活性剤のいずれでもよく、水溶液、有機溶媒の種類及び必要とするエマルジョンの分散粒子径に応じて、分散剤の種類及び添加量を変化させればよい。 As a raw material of the metal element used in such an emulsion combustion method, water-soluble metal salts such as metal nitrates, metal acetates, metal sulfates, metal chloride salts and complex salts can be used. And a W / O emulsion can be formed by stirring the aqueous solution of this metal salt and the organic solvent through a dispersing agent. The organic solvent to be used may be any organic solvent that can form a W / O emulsion with an aqueous solution, such as hexane, octane, kerosene, and gasoline. The type and amount of the dispersant used are not particularly limited, and any of a cationic surfactant, an anionic surfactant, and a nonionic surfactant may be used. The type and amount of the dispersing agent may be changed according to the dispersed particle size.
さらに、W/Oエマルジョンの噴霧燃焼雰囲気は特に限定されないが、酸素が充分でないと不完全燃焼によって有機溶媒中の炭素成分が残留し易くなる傾向にあるため、エマルジョン中の有機溶媒が完全燃焼できる程度の酸素(空気)を供給することが好ましい。 Further, the spray combustion atmosphere of the W / O emulsion is not particularly limited, but if there is not enough oxygen, the carbon component in the organic solvent tends to remain due to incomplete combustion, so that the organic solvent in the emulsion can be completely burned. It is preferable to supply a certain amount of oxygen (air).
本発明の排ガス浄化用触媒の製造方法においては、前述の複合金属酸化物からなるコロイド粒子が分散媒中に均一分散しているゾルを、上記多孔質又は中空状の金属酸化物担体の表面に供給した後、前記ゾルを乾燥せしめて本発明の排ガス浄化用触媒を得る。 In the method for producing an exhaust gas purifying catalyst of the present invention, a sol in which colloidal particles composed of the composite metal oxide are uniformly dispersed in a dispersion medium is applied to the surface of the porous or hollow metal oxide carrier. After the supply, the sol is dried to obtain the exhaust gas purifying catalyst of the present invention.
ここで金属酸化物担体の表面にゾルを供給する具体的な方法は特に制限されず、例えば、前記ゾルに担体を浸漬する方法や、前記ゾルをスプレー等により担体表面にコーティングする方法が好適に採用される。また、金属酸化物担体の表面に供給するゾルの量は特に制限されず、得られる排ガス浄化用触媒の要求性能等に応じて適宜調整されるが、金属酸化物担体100質量部に対して担持されるコロイド粒子の量が0.1〜50質量部程度であることが好ましい。コロイド粒子の担持量が前記下限未満では、コロイド粒子により得られる触媒活性が不十分となる傾向にあり、他方、前記上限を超えると、触媒活性が飽和すると共にコストが高騰する傾向にある。 Here, the specific method of supplying the sol to the surface of the metal oxide support is not particularly limited, and for example, a method of immersing the support in the sol or a method of coating the sol on the support surface by spraying or the like is preferable. Adopted. Further, the amount of sol supplied to the surface of the metal oxide support is not particularly limited, and is appropriately adjusted according to the required performance of the obtained exhaust gas purifying catalyst, but supported on 100 parts by mass of the metal oxide support. The amount of colloidal particles to be formed is preferably about 0.1 to 50 parts by mass. If the supported amount of colloidal particles is less than the lower limit, the catalytic activity obtained by the colloidal particles tends to be insufficient, while if the upper limit is exceeded, the catalytic activity is saturated and the cost tends to increase.
本発明において、金属酸化物担体の表面に供給されたゾルを乾燥させる乾燥処理の具体的な条件は特に制限されず、例えば、80〜200℃程度の温度で1〜24時間程度の時間をかけて乾燥せしめる常温又は加熱乾燥、液体窒素を用いて0°以下の温度に凍結させた後に減圧下で乾燥せしめる凍結乾燥といった手法が適宜採用される。 In the present invention, the specific conditions of the drying treatment for drying the sol supplied to the surface of the metal oxide support are not particularly limited, and for example, it takes about 1 to 24 hours at a temperature of about 80 to 200 ° C. A technique such as room temperature or heat drying for drying and freeze-drying by freezing to a temperature of 0 ° or less using liquid nitrogen and then drying under reduced pressure is appropriately employed.
また、本発明においては、上記の乾燥工程の後に焼成工程を含んでいてもよく、かかる焼成工程においては排ガス浄化用触媒を400〜1000℃程度の温度で1〜10時間程度の時間保持することが好ましい。このような焼成工程を採用することにより、担体の比表面積低下をより確実に抑制できる傾向にある。 Moreover, in this invention, the baking process may be included after said drying process, and in this baking process, the catalyst for exhaust gas purification is hold | maintained for about 1 to 10 hours at the temperature of about 400-1000 degreeC. Is preferred. By adopting such a firing step, a decrease in the specific surface area of the carrier tends to be more reliably suppressed.
さらに、本発明においては、前記金属酸化物担体及び/又は前記コロイド粒子の表面に貴金属(貴金属微粒子)を担持せしめることがより好ましい。かかる担持工程において用いられる貴金属は特に制限されず、Pt、Pd、Rh、Ru、Au、Ag、Os、Irからなる群から選択される少なくとも一種の貴金属が挙げられ、中でも触媒活性の観点からPt、Rh、Pd、Irが好ましく、Ptが特に好ましい。また、排ガス浄化用触媒に担持される貴金属の量も特に制限されないが、前記コロイド粒子が担持されている金属酸化物担体100質量部に対して担持される貴金属の量が0.1〜10質量部程度であることが好ましい。貴金属の量が上記下限未満では、貴金属により得られる触媒活性が不十分となる傾向にあり、他方、上記上限を超えると、貴金属による触媒活性が飽和すると共にコストが高騰する傾向にある。さらに、貴金属を担持せしめる具体的な方法も特に制限されず、例えば、前記コロイド粒子が担持された金属酸化物担体を貴金属塩の溶液に接触せしめ、更に必要に応じて還元処理及び/又は焼成処理を施すといった方法が適宜採用される。また、担持される貴金属微粒子の粒径も特に制限されないが、平均粒径が0.1〜10nm程度であることが一般的である。 Furthermore, in the present invention, it is more preferable to support a noble metal (noble metal fine particles) on the surface of the metal oxide support and / or the colloidal particles. The noble metal used in the supporting step is not particularly limited, and includes at least one noble metal selected from the group consisting of Pt, Pd, Rh, Ru, Au, Ag, Os, and Ir. , Rh, Pd and Ir are preferable, and Pt is particularly preferable. The amount of the noble metal supported on the exhaust gas purification catalyst is not particularly limited, but the amount of the noble metal supported on 100 parts by mass of the metal oxide support on which the colloidal particles are supported is 0.1 to 10 mass. It is preferable that it is about a part. When the amount of the noble metal is less than the above lower limit, the catalytic activity obtained by the noble metal tends to be insufficient, while when the amount exceeds the upper limit, the catalytic activity due to the noble metal is saturated and the cost tends to increase. Further, the specific method for supporting the noble metal is not particularly limited. For example, the metal oxide support on which the colloidal particles are supported is brought into contact with a solution of the noble metal salt, and further, reduction treatment and / or calcination treatment as necessary. The method of applying is suitably adopted. Further, the particle size of the noble metal fine particles supported is not particularly limited, but the average particle size is generally about 0.1 to 10 nm.
以上説明した本発明の方法によって得られる本発明の排ガス浄化用触媒においては、前述の金属酸化物担体の表面に前記複合金属酸化物からなるコロイド粒子(貴金属を担持させた場合は更に貴金属微粒子)がナノレベルの均一状態で担持されている。このような本発明の排ガス浄化用触媒は、粉末の状態で使用してもよいが、必要に応じて成形して使用してもよい。成形する手段はどのようなものでも良いが、押出成形、打錠成形、転動造粒、圧縮成形、CIP等が好ましい。また、その形状は使用箇所、方法に応じて決めることができ、例えば円柱状、破砕状、球状、ハニカム状、凹凸状、波板状等が挙げられる。 In the exhaust gas purifying catalyst of the present invention obtained by the method of the present invention described above, colloidal particles composed of the composite metal oxide on the surface of the metal oxide support (if noble metal is supported, further noble metal fine particles) Is supported in a nano-level uniform state. Such an exhaust gas purifying catalyst of the present invention may be used in a powder state, but may be molded and used as necessary. Any molding means may be used, but extrusion molding, tablet molding, rolling granulation, compression molding, CIP and the like are preferable. Moreover, the shape can be determined according to a use location and a method, for example, cylindrical shape, crushed shape, spherical shape, honeycomb shape, uneven shape, corrugated shape, etc. are mentioned.
さらに、本発明の排ガス浄化用触媒の具体的な使用方法は特に制限されず、処理対象となる有害成分を含む気体と触媒とをバッチ式或いは連続的に接触させることによって有害成分の浄化が達成される。なお、処理対象となる有害成分としては、特に制限されないが、排ガス中のNOx、CO、HC、SOx等が挙げられる。 Furthermore, the specific method of using the exhaust gas purifying catalyst of the present invention is not particularly limited, and purification of harmful components is achieved by bringing the gas containing the harmful components to be treated into contact with the catalyst batchwise or continuously. Is done. As the harmful components to be processed is not particularly limited, NO x in the exhaust gas, CO, HC, SO x and the like.
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.
(実施例1)
硝酸セリウム水溶液(Ce濃度:1.0mol/L)とオキシ硝酸ジルコニル水溶液(Zr濃度:1.0mol/L)とを金属イオンモル比がCe:Zr=50:50になるように混合した。得られた混合溶液にセリウムイオンの1.1モル倍のH2O2を含有するH2O2水溶液を添加し、十分に攪拌した。その後、混合溶液にアンモニア水を加え(添加量:中和当量の1.1倍)、前駆体沈殿を得た。得られた前駆体沈殿を遠心分離し、110℃に12時間保持して乾燥した後、大気中で400℃に3時間保持して仮焼成し、更に700℃に5時間保持して焼成してセリア(CeO2)−ジルコニア(ZrO2)固溶体(Ce/Zr=50/50(モル比)、以後「CZ」という)からなる複合金属酸化物凝集体を得た。得られた複合金属酸化物凝集体(CZ凝集体)の1次粒子の平均粒径は8nm、2次凝集体の平均粒径は200nmであった。
Example 1
An aqueous cerium nitrate solution (Ce concentration: 1.0 mol / L) and an aqueous zirconyl oxynitrate solution (Zr concentration: 1.0 mol / L) were mixed so that the metal ion molar ratio was Ce: Zr = 50: 50. A H 2 O 2 aqueous solution containing H 2 O 2 1.1 mol times as much as cerium ions was added to the obtained mixed solution and sufficiently stirred. Thereafter, aqueous ammonia was added to the mixed solution (addition amount: 1.1 times the neutralization equivalent) to obtain a precursor precipitate. The obtained precursor precipitate is centrifuged, dried at 110 ° C. for 12 hours, dried, held at 400 ° C. for 3 hours in the atmosphere, and calcined, and further held at 700 ° C. for 5 hours and calcined. A composite metal oxide aggregate composed of ceria (CeO 2 ) -zirconia (ZrO 2 ) solid solution (Ce / Zr = 50/50 (molar ratio), hereinafter referred to as “CZ”) was obtained. The average particle diameter of the primary particles of the obtained composite metal oxide aggregate (CZ aggregate) was 8 nm, and the average particle diameter of the secondary aggregate was 200 nm.
次に、得られたCZ凝集体を、直径50μmのジルコニア製マイクロビーズ及び寿工業株式会社製「ウルトラアペックスミル」を用いて水溶液中で120分間粉砕及び混合して分散させ、平均粒径が15nmの均質なCZコロイド粒子が均一分散しているCZゾル溶液を得た。 Next, the obtained CZ aggregate was dispersed by pulverizing and mixing for 120 minutes in an aqueous solution using zirconia microbeads having a diameter of 50 μm and “Ultra Apex Mill” manufactured by Kotobuki Industries Co., Ltd. A CZ sol solution in which homogeneous CZ colloidal particles were uniformly dispersed was obtained.
また、金属酸化物担体として、以下のようにして噴霧火炎法により合成したアルミナのナノ一次粒子鎖状凝集体を用いた。すなわち、アルミニウムアルコキシドのアルコール溶液(Al濃度:0.5mol/L)を2流体ノズルを用いて噴霧し、ノズル周囲に配置したメタン/酸素予混合火炎のバーナーで着火し、溶液の噴霧火炎を形成した。その結果、噴霧火炎中での気相反応により、アルミナからなるナノ一次粒子鎖状凝集体が生成された。得られたナノ一次粒子鎖状凝集体(アルミナ多孔質担体)の1次粒子の平均粒径は20nm、2次凝集体の平均粒径は300nm、中心細孔直径は30nmであった。 Further, as the metal oxide support, an alumina nano primary particle chain aggregate synthesized by a spray flame method as follows was used. That is, an alcohol solution of aluminum alkoxide (Al concentration: 0.5 mol / L) is sprayed using a two-fluid nozzle and ignited with a methane / oxygen premixed flame burner arranged around the nozzle to form a spray flame of the solution did. As a result, nano primary particle chain aggregates made of alumina were generated by a gas phase reaction in a spray flame. The average primary particle size of the obtained nano primary particle chain aggregate (alumina porous carrier) was 20 nm, the average particle size of the secondary aggregate was 300 nm, and the central pore diameter was 30 nm.
次いで、前記で得られたCZゾル溶液(濃度:固形分10wt%)中に噴霧火炎法で合成したアルミナ多孔質担体を加え、十分に湿式混合せしめた。次に、得られたスラリーを蒸発乾固させ、表面にCZコロイド粒子が均一に担持されているアルミナ多孔質担体を得た。CZコロイド粒子の担持量は、アルミナ多孔質担体100質量部に対して10質量部であった。 Subsequently, the alumina porous carrier synthesized by the spray flame method was added to the CZ sol solution (concentration: solid content 10 wt%) obtained above, and sufficiently wet mixed. Next, the obtained slurry was evaporated to dryness to obtain an alumina porous carrier having CZ colloid particles uniformly supported on the surface. The supported amount of CZ colloidal particles was 10 parts by mass with respect to 100 parts by mass of the alumina porous carrier.
続いて、CZコロイド粒子が担持されているアルミナ多孔質担体を白金ジニトロジアンミン水溶液(Pt濃度:5.0wt%)に含浸せしめた後、得られたスラリーを蒸発乾固させ、更に大気中で300℃に3時間保持して焼成して白金及びCZコロイド粒子が担持されているアルミナ多孔質担体からなる触媒粉末を得た。白金の担持量は、CZコロイド粒子が担持されているアルミナ多孔質担体100質量部に対して1質量部であった。得られた触媒粉末を金型プレス(1トン/cm2)で圧粉成形し、粉砕して直径0.5〜1mmのペレット状の排ガス浄化用触媒を得た。 Subsequently, after impregnating an alumina porous carrier carrying CZ colloidal particles with an aqueous platinum dinitrodiammine solution (Pt concentration: 5.0 wt%), the resulting slurry was evaporated to dryness, and further 300 atmospheres in the atmosphere. A catalyst powder comprising an alumina porous carrier on which platinum and CZ colloidal particles were supported was obtained by baking at 3 ° C. for 3 hours. The amount of platinum supported was 1 part by mass with respect to 100 parts by mass of the alumina porous carrier on which CZ colloidal particles were supported. The obtained catalyst powder was compacted by a mold press (1 ton / cm 2 ) and pulverized to obtain a pellet-shaped exhaust gas purification catalyst having a diameter of 0.5 to 1 mm.
(実施例2)
金属酸化物担体として、以下のようにしてエマルジョン燃焼法により合成した中空アルミナ粉末を用いるようにした以外は、実施例1と同様にしてペレット状の排ガス浄化用触媒を得た。すなわち、硝酸アルミニウム水溶液(濃度:1mol/L)と、界面活性剤(第一工業製薬社製、ソルゲン90)入りのケロシン(濃度:5wt%)とを65:35(体積比)の割合で混合し、高速攪拌してW/O型エマルジョンを得た。そしてこのようにして得られたW/O型エマルジョンを2流体ノズルを用いて噴霧し、ノズル周囲に配置したメタン/酸素予混合火炎のバーナーで着火し、溶液の噴霧火炎を形成した。その結果、燃焼熱によってW/O型エマルジョンの個々の水滴中で溶媒蒸発及び酸化反応が発生し、アルミナからなる殻厚10nmの中空アルミナ粉末(ナノシェル中空アルミナ)が生成された。このようにして得られたナノシェル中空アルミナ(アルミナ多孔質担体)の1次粒子の平均粒径は300nm、2次凝集体の平均粒径は6μm、中心細孔直径は100nmであった。
(Example 2)
A pellet-shaped exhaust gas purification catalyst was obtained in the same manner as in Example 1 except that the hollow alumina powder synthesized by the emulsion combustion method as described below was used as the metal oxide support. That is, an aluminum nitrate aqueous solution (concentration: 1 mol / L) and kerosene (concentration: 5 wt%) containing a surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Sorgen 90) are mixed at a ratio of 65:35 (volume ratio). The mixture was stirred at a high speed to obtain a W / O type emulsion. The W / O type emulsion thus obtained was sprayed using a two-fluid nozzle and ignited with a methane / oxygen premixed flame burner arranged around the nozzle to form a spray flame of the solution. As a result, solvent evaporation and oxidation reaction occurred in the individual water droplets of the W / O emulsion by the heat of combustion, and a hollow alumina powder (nanoshell hollow alumina) having a shell thickness of 10 nm made of alumina was produced. The average particle size of the primary particles of the nanoshell hollow alumina (alumina porous support) thus obtained was 300 nm, the average particle size of the secondary aggregate was 6 μm, and the center pore diameter was 100 nm.
(比較例1)
マイクロビーズを用いた分散処理を行わず、実施例1において得られたCZ凝集体をそのまま噴霧火炎法で合成したアルミナ多孔質担体と湿式混合せしめるようにした以外は、実施例1と同様にしてペレット状の排ガス浄化用触媒を得た。
(Comparative Example 1)
The same procedure as in Example 1 was conducted, except that the CZ aggregate obtained in Example 1 was wet-mixed with the alumina porous carrier synthesized by the spray flame method without performing the dispersion treatment using microbeads. A pellet-shaped exhaust gas purification catalyst was obtained.
(比較例2)
金属酸化物担体として、硝酸アルミニウム水溶液(Al濃度:1.0mol/L)からの沈殿反応によって合成した高比表面積アルミナ多孔体(1次粒子の平均粒径:6nm、2次凝集体の平均粒径:1μm、中心細孔直径:8nm)を用いるようにした以外は実施例1と同様にしてペレット状の排ガス浄化用触媒を得た。
(Comparative Example 2)
High specific surface area alumina porous material (average particle size of primary particles: 6 nm, average particle size of secondary aggregate) synthesized by precipitation reaction from aqueous aluminum nitrate solution (Al concentration: 1.0 mol / L) as metal oxide support Exhaust gas purification catalyst in the form of pellets was obtained in the same manner as in Example 1 except that the diameter was 1 μm and the center pore diameter was 8 nm.
(比較例3)
硝酸セリウム及びオキシ硝酸ジルコニウムを含有する水溶液(Ce濃度:1.0mol/L、Zr濃度:1.0mol/L)に、噴霧火炎法で合成したアルミナ多孔質担体を加え(添加量:水溶液から生成するセリア/ジルコニアの量の10倍質量)、十分に湿式混合せしめるようにした以外は実施例1と同様にしてペレット状の排ガス浄化用触媒を得た。
(Comparative Example 3)
Alumina porous carrier synthesized by spray flame method is added to an aqueous solution containing cerium nitrate and zirconium oxynitrate (Ce concentration: 1.0 mol / L, Zr concentration: 1.0 mol / L) (addition amount: generated from the aqueous solution) Exhaust gas purification catalyst in the form of pellets was obtained in the same manner as in Example 1 except that the mixture was sufficiently wet-mixed.
<高温耐久性試験及び触媒活性試験>
実施例1〜2及び比較例1〜3で得られたペレット状の排ガス浄化用触媒に対して、ペレット触媒耐久試験装置を用いて以下のようにして高温耐久性試験及び触媒活性試験を行った。
<High temperature durability test and catalytic activity test>
The pellet-shaped exhaust gas purification catalyst obtained in Examples 1-2 and Comparative Examples 1-3 was subjected to a high-temperature durability test and a catalytic activity test as follows using a pellet catalyst durability test apparatus. .
すなわち、先ず、表1に示す組成を有するリッチガスとリーンガスを全流量が350ml/minとなるように5分間隔で交互に流した雰囲気中で、実施例1〜2及び比較例1〜3で得られた各ペレット状の排ガス浄化用触媒1.5gを1000℃に5時間保持した。 That is, first, in an atmosphere in which rich gas and lean gas having the composition shown in Table 1 were alternately flowed at intervals of 5 minutes so that the total flow rate was 350 ml / min, obtained in Examples 1-2 and Comparative Examples 1-3. Each pellet-shaped exhaust gas purifying catalyst 1.5 g was held at 1000 ° C. for 5 hours.
次に、かかる高温耐久性試験後のペレット状の排気ガス浄化性能を、ペレット触媒耐久試験装置を用いてダイナミックストイキ昇温試験により以下のようにして評価した。すなわち、表2に示す組成を有するリッチガスとリーンガスを全流量が7000ml/minとなるように1秒間隔で交互に流した雰囲気中で、実施例1〜2及び比較例1〜3で得られた各ペレット状の排ガス浄化用触媒1.5gを12℃/minの昇温速度で加熱していき、各温度(入りガス温度)におけるHC、CO及びNOxに対する浄化率を連続的に測定した。 Next, the pellet-like exhaust gas purification performance after the high temperature durability test was evaluated by a dynamic stoichiometric temperature increase test using a pellet catalyst durability test apparatus as follows. That is, it was obtained in Examples 1-2 and Comparative Examples 1-3 in an atmosphere in which rich gas and lean gas having the composition shown in Table 2 were alternately flowed at intervals of 1 second so that the total flow rate was 7000 ml / min. Each pellet-shaped exhaust gas purification catalyst 1.5 g was heated at a rate of temperature increase of 12 ° C./min, and the purification rates for HC, CO, and NOx at each temperature (inlet gas temperature) were continuously measured.
測定時のSVは約200,000h−1とし、各有害成分(HC、CO、NOx)が80%浄化される温度(80%浄化温度)を算出した。なお、自動車用排ガス浄化用触媒の実使用条件においては、排気ガス流速が早いことから排気ガスの触媒内部への拡散が律速になる場合があり、本試験においては拡散律速領域での触媒性能に相当する80%浄化温度を評価指標として用いた。 SV at the time of measurement was about 200,000 h −1, and the temperature at which each harmful component (HC, CO, NO x ) was purified by 80% (80% purification temperature) was calculated. It should be noted that in the actual usage conditions of the exhaust gas purification catalyst for automobiles, the exhaust gas flow rate is fast, so the diffusion of the exhaust gas inside the catalyst may be rate-limiting, and in this test the catalyst performance in the diffusion rate-limiting region is affected. The corresponding 80% purification temperature was used as an evaluation index.
表3に、高温耐久性試験後の各排ガス浄化用触媒のC3H6(HC)に対する80%浄化温度を示す。また、高温耐久性試験後の各排ガス浄化用触媒は、CO及びNOxに関しても定性的に同様の浄化性能を示した。 Table 3 shows the 80% purification temperature for C 3 H 6 (HC) of each exhaust gas purification catalyst after the high-temperature durability test. Each exhaust gas purifying catalyst after the high temperature durability test showed qualitatively similar purification performance with regard CO and NO x.
表3に示した結果から明らかな通り、本発明の方法によって得られた本発明の排ガス浄化用触媒(実施例1〜2)によって達成された80%浄化温度は、比較例1〜3で得られた触媒の80%浄化温度よりも低く、高温耐久性に優れた高性能の浄化性能を有していることが確認された。 As is apparent from the results shown in Table 3, the 80% purification temperature achieved by the exhaust gas purification catalyst of the present invention (Examples 1 and 2) obtained by the method of the present invention was obtained in Comparative Examples 1 to 3. It was confirmed that the obtained catalyst had a high-performance purification performance that was lower than the 80% purification temperature of the catalyst and had excellent high-temperature durability.
一方、CZ凝集体をゾル化することなくアルミナ多孔質担体に担持せしめた比較例1で得られた触媒においては、CZ粒子が凝集して不均質に担持されており、CZによる触媒活性が有効に活用されていないことが確認された。 On the other hand, in the catalyst obtained in Comparative Example 1 in which CZ aggregates were supported on an alumina porous support without solification, CZ particles were aggregated and supported inhomogeneously, and the catalytic activity by CZ was effective. It was confirmed that it was not used for
また、比較例2で得られた触媒においては、アルミナ多孔質担体の細孔径が小さいためにCZコロイド粒子が細孔内部まで入ることができず、CZ粒子が凝集して不均質に担持されており、CZによる触媒活性が有効に活用されていないことが確認された。 Further, in the catalyst obtained in Comparative Example 2, since the pore diameter of the alumina porous carrier is small, the CZ colloid particles cannot enter the inside of the pores, and the CZ particles are aggregated and supported inhomogeneously. It was confirmed that the catalytic activity by CZ was not effectively utilized.
さらに、比較例3で得られた触媒においては、CZを金属塩の状態でアルミナ多孔質担体に担持せしめているためある程度均質ではあるが、反応及び固溶が不十分で組成が不均質なため、CZによる本来の触媒機能が十分には発現されていないことが確認された。 Furthermore, the catalyst obtained in Comparative Example 3 is homogeneous to some extent because CZ is supported on the alumina porous support in the form of a metal salt, but because the reaction and solid solution are insufficient and the composition is inhomogeneous. It was confirmed that the original catalytic function by CZ was not fully expressed.
以上説明したように、本発明によれば、浄化性能が十分に高く且つ高温耐久性に優れた排ガス浄化用触媒を効率良く且つ確実に製造することが可能となる。したがって、本発明の方法は、浄化性能及び高温耐久性に優れた排ガス浄化用触媒の製造方法として非常に有用である。 As described above, according to the present invention, it is possible to efficiently and reliably manufacture an exhaust gas purification catalyst having sufficiently high purification performance and excellent high-temperature durability. Therefore, the method of the present invention is very useful as a method for producing an exhaust gas purification catalyst having excellent purification performance and high temperature durability.
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JP2009233580A (en) * | 2008-03-27 | 2009-10-15 | Mazda Motor Corp | Catalyst for cleaning exhaust gas and its manufacturing method |
JP2010012397A (en) * | 2008-07-02 | 2010-01-21 | Mazda Motor Corp | Catalytic material for cleaning exhaust gas, method for producing the same, and catalyst for cleaning exhaust gas |
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JP2009233580A (en) * | 2008-03-27 | 2009-10-15 | Mazda Motor Corp | Catalyst for cleaning exhaust gas and its manufacturing method |
JP2010012397A (en) * | 2008-07-02 | 2010-01-21 | Mazda Motor Corp | Catalytic material for cleaning exhaust gas, method for producing the same, and catalyst for cleaning exhaust gas |
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