JP6087362B2 - Platinum-based oxidation catalyst and exhaust gas purification method using the same - Google Patents
Platinum-based oxidation catalyst and exhaust gas purification method using the same Download PDFInfo
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- JP6087362B2 JP6087362B2 JP2014538249A JP2014538249A JP6087362B2 JP 6087362 B2 JP6087362 B2 JP 6087362B2 JP 2014538249 A JP2014538249 A JP 2014538249A JP 2014538249 A JP2014538249 A JP 2014538249A JP 6087362 B2 JP6087362 B2 JP 6087362B2
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- platinum
- oxidation catalyst
- oxide
- exhaust gas
- catalyst
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims description 237
- 239000003054 catalyst Substances 0.000 title claims description 124
- 229910052697 platinum Inorganic materials 0.000 title claims description 94
- 238000007254 oxidation reaction Methods 0.000 title claims description 63
- 230000003647 oxidation Effects 0.000 title claims description 61
- 238000000034 method Methods 0.000 title claims description 22
- 238000000746 purification Methods 0.000 title claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 90
- 239000002245 particle Substances 0.000 claims description 75
- 239000007789 gas Substances 0.000 claims description 68
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 55
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 55
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 36
- 239000011593 sulfur Substances 0.000 claims description 36
- 229910052717 sulfur Inorganic materials 0.000 claims description 36
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 36
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 31
- 239000010457 zeolite Substances 0.000 claims description 27
- 229910044991 metal oxide Inorganic materials 0.000 claims description 26
- 150000004706 metal oxides Chemical class 0.000 claims description 26
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 26
- 239000010937 tungsten Substances 0.000 claims description 26
- 229910052721 tungsten Inorganic materials 0.000 claims description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 25
- 239000011148 porous material Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- 238000002485 combustion reaction Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052815 sulfur oxide Inorganic materials 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 239000004071 soot Substances 0.000 claims description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 6
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 3
- 208000005374 Poisoning Diseases 0.000 description 31
- 231100000572 poisoning Toxicity 0.000 description 29
- 230000000607 poisoning effect Effects 0.000 description 29
- 239000000463 material Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 16
- 229910000510 noble metal Inorganic materials 0.000 description 16
- 230000010718 Oxidation Activity Effects 0.000 description 14
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910003446 platinum oxide Inorganic materials 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 4
- 150000003057 platinum Chemical class 0.000 description 4
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 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 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- -1 hydrocarbons Chemical class 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RBAKORNXYLGSJB-UHFFFAOYSA-N azane;platinum(2+);dinitrate Chemical compound N.N.N.N.[Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RBAKORNXYLGSJB-UHFFFAOYSA-N 0.000 description 2
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- NDBYXKQCPYUOMI-UHFFFAOYSA-N platinum(4+) Chemical compound [Pt+4] NDBYXKQCPYUOMI-UHFFFAOYSA-N 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 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 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000011733 molybdenum Substances 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
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical group [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- ZONODCCBXBRQEZ-UHFFFAOYSA-N platinum tungsten Chemical compound [W].[Pt] ZONODCCBXBRQEZ-UHFFFAOYSA-N 0.000 description 1
- JTAFSELAEYLDJR-UHFFFAOYSA-J platinum(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Pt+4] JTAFSELAEYLDJR-UHFFFAOYSA-J 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Description
本発明は、白金系酸化触媒、及びそれを用いた排気ガス浄化方法に関し、より詳しくは、希薄燃焼機関から排出される硫黄酸化物を含む排気ガスに含まれる炭化水素（ＨＣ）、一酸化炭素（ＣＯ）、窒素酸化物（ＮＯｘ）、煤などの微粒子成分の内、特に炭化水素を酸化浄化する能力に長ける白金系酸化触媒、及びそれを用いた排気ガス浄化方法に関する。 The present invention relates to a platinum-based oxidation catalyst and an exhaust gas purification method using the same, and more particularly, hydrocarbons (HC) and carbon monoxide contained in exhaust gas containing sulfur oxides emitted from a lean combustion engine. The present invention relates to a platinum-based oxidation catalyst having a high ability to oxidize and purify hydrocarbons among particulate components such as (CO), nitrogen oxide (NOx) and soot, and an exhaust gas purification method using the same.
ボイラー、ガスタービン、リーンバーン型ガソリンエンジン、ディーゼルエンジン等の希薄燃焼機関から排出される排気ガスには、燃料や燃焼空気に由来した様々な有害物質が含まれる。このような有害物質としては炭化水素（ＨＣ）、可溶性有機成分（Ｓｏｌｕｂｌｅ Ｏｒｇａｎｉｃ Ｆｒａｃｔｉｏｎ：ＳＯＦともいう）、煤（Ｓｏｏｔ）、一酸化炭素（ＣＯ）、窒素酸化物（ＮＯｘ）などがあり、これら有害成分の排出量に関する規制は年々強化されている。それら有害成分の浄化方法としては、加熱された排気ガスを触媒に接触させて浄化する方法が実用化されている。 Exhaust gas emitted from lean combustion engines such as boilers, gas turbines, lean burn gasoline engines, and diesel engines contains various harmful substances derived from fuel and combustion air. Such harmful substances include hydrocarbons (HC), soluble organic fraction (also called SOF), soot, carbon monoxide (CO), nitrogen oxides (NOx), and the like. Regulations on component emissions are getting stronger year by year. As a method for purifying these harmful components, a method for purifying heated exhaust gas by bringing it into contact with a catalyst has been put into practical use.
この様な人体や環境に悪影響を及ぼす排気ガス中の有害成分の排出量を削減する試みは主に欧米、日本などを中心に主導的に行われ、これらの有害物質の排出基準を満たすため、触媒の改良の他、使用される軽油等の燃料中の触媒被毒物質である硫黄（Ｓ）の量も削減されている。
その一方で、アフリカ、中南米、中東、ロシアを含む北アジア、中国、インドを含む南アジア、中央アジア、東南アジアなどにおいては低硫黄化が進んでいる国や地域もあるものの、規制自体が緩く、使用される軽油等の燃料中の硫黄についても精製度の低い物が使用されている。
触媒性能を阻害する要因としては、一般には高温下に長時間晒されることによる貴金属のシンタリング（粒子成長）が挙げられるが、硫黄やリン、炭化水素等の被毒成分による貴金属、貴金属担持母材及び助触媒成分への被毒なども活性低下の要因になっている。
欧米、日本などでは、燃料中の硫黄の量が削減されているため、主に貴金属のシンタリングが触媒性能を阻害する要因となっているが、燃料中の硫黄の量が多いその他の国々においては、硫黄などの被毒物質による貴金属成分への被毒が触媒性能低下の主因といえ、大きな問題となっている。
このため、燃料中の硫黄の量が多い条件下であっても有害物質を高効率で浄化できる触媒が求められている。Attempts to reduce emissions of harmful components in exhaust gases that adversely affect the human body and the environment are mainly conducted mainly in Europe, the United States, and Japan. In order to meet the emission standards for these harmful substances, In addition to catalyst improvements, the amount of sulfur (S), which is a catalyst poisoning substance in fuels such as light oil used, has also been reduced.
On the other hand, there are countries and regions where sulfur reduction is progressing in North Asia including Africa, Central and South America, the Middle East, Russia, South Asia including China and India, Central Asia, Southeast Asia, etc., but regulations themselves are loose. As for sulfur in fuels such as light oil used, those having a low degree of purification are used.
As a factor that hinders catalyst performance, there is generally sintering of noble metals (particle growth) due to exposure to high temperatures for a long time. However, noble metals and noble metal support mothers due to poisoning components such as sulfur, phosphorus and hydrocarbons. Poisoning of materials and promoter components has also been a factor in reducing activity.
In Europe, the United States, Japan, etc., the amount of sulfur in the fuel has been reduced, so precious metal sintering is a factor that hinders catalyst performance, but in other countries where the amount of sulfur in the fuel is high However, poisoning of noble metal components by poisoning substances such as sulfur is a major problem because it is the main cause of catalyst performance deterioration.
Therefore, there is a need for a catalyst that can purify harmful substances with high efficiency even under conditions where the amount of sulfur in the fuel is large.
硫黄酸化物が排気ガス中に共存する条件で、酸化触媒によるＨＣ及びＣＯの酸化機能の低下を抑制する手段が、今までに幾つかの触媒で試みられた。
その一つとして、チタニアとゼオライトとを含有する担体と、該担体に担持された貴金属とを有してなる排ガス浄化用酸化物触媒であって、該ゼオライトの含有量が該触媒に対して３５〜５０重量％である酸化触媒が提案されている。具体的には、さらにチタニアの含有量が触媒全体に対して３５〜６０重量％となり、ゼオライトがＺＳＭ−５タイプのゼオライトおよび／またはβタイプのゼオライトであり、貴金属が白金で、０．３〜６．０重量％となるようにしている（特許文献１参照）。A number of catalysts have been tried so far to suppress the deterioration of the oxidation function of HC and CO by the oxidation catalyst under the condition that sulfur oxides coexist in the exhaust gas.
One of them is an exhaust gas-purifying oxide catalyst comprising a carrier containing titania and zeolite, and a noble metal supported on the carrier, the content of the zeolite being 35 with respect to the catalyst. An oxidation catalyst of ˜50% by weight has been proposed. Specifically, the titania content is 35 to 60% by weight based on the whole catalyst, the zeolite is a ZSM-5 type zeolite and / or a β type zeolite, the noble metal is platinum, It is set to 6.0% by weight (see Patent Document 1).
また、（Ａ）白金および／またはパラジウムならびにタングステン、アンチモン、モリブデン、ニッケル、バナジウム、マンガン、鉄、ビスマス、コバルト、亜鉛およびアルカリ土類金属よりなる群から選ばれた少なくとも１種の金属の触媒活性酸化物を第１の耐火性無機酸化物粉末（ａ）に担持してなる白金および／またはパラジウム担持耐火性無機酸化物粉末および（Ｂ）第二の耐火性無機酸化物粉末（ｂ）よりなる触媒組成物を三次元構造体に被覆してなり、該白金および／またはパラジウムが前記第１の耐火性無機酸化物粉末（ａ）に対して５〜５０重量％の範囲にあることを特徴とするディーゼルエンジン用排ガス浄化用触媒が提案されており、ここで、耐硫黄特性を有する三酸化タングステンを粉末状で付与する触媒調製法が適用されている（特許文献２参照）。
しかし、これらの触媒でも十分な耐硫黄性は得られておらず、さらなる触媒の改良が求められている。(A) catalytic activity of platinum and / or palladium and at least one metal selected from the group consisting of tungsten, antimony, molybdenum, nickel, vanadium, manganese, iron, bismuth, cobalt, zinc and alkaline earth metals Platinum and / or palladium-supported refractory inorganic oxide powder formed by supporting an oxide on the first refractory inorganic oxide powder (a) and (B) a second refractory inorganic oxide powder (b) A catalyst composition is coated on a three-dimensional structure, and the platinum and / or palladium is in the range of 5 to 50% by weight with respect to the first refractory inorganic oxide powder (a). A catalyst for purifying exhaust gas for diesel engines has been proposed. Here, a catalyst preparation method in which tungsten trioxide having sulfur resistance is imparted in powder form is suitable. Are (see Patent Document 2).
However, sufficient sulfur resistance is not obtained even with these catalysts, and further improvement of the catalyst is demanded.
本発明の目的は、上記従来の課題に鑑み、希薄燃焼機関から排出される硫黄酸化物を含む排気ガスに含まれる有害物質（ＨＣ、ＣＯ、ＮＯｘ、煤など）の内、特に炭化水素を酸化浄化する能力に長けた白金系酸化触媒、及びそれを用いた排気ガス浄化方法を提供することにある。 An object of the present invention is to oxidize hydrocarbons, particularly hydrocarbons, among harmful substances (HC, CO, NOx, soot, etc.) contained in exhaust gas containing sulfur oxides emitted from a lean combustion engine in view of the above conventional problems. It is an object of the present invention to provide a platinum-based oxidation catalyst having excellent purifying ability and an exhaust gas purifying method using the same.
本発明者らは、上記従来の課題を解決するために鋭意研究を重ね、ディーゼルエンジン等の希薄燃焼機関から排出される硫黄酸化物を含む排気ガス中の有害成分である炭化水素（ＨＣ）、一酸化炭素（ＣＯ）、窒素酸化物（ＮＯｘ）、煤などを酸化する白金系排気ガス浄化用触媒において、金属酸化物上に担持された白金（Ｐｔ）粒子の近傍に適切に担持されたタングステン酸化物の微粒子が白金への硫黄酸化物の被毒を抑制し、また温度上昇時の硫黄脱離を促進する役割を果たし、高濃度の硫黄酸化物を含む排気ガスに長時間晒されても硫黄酸化物の白金への被毒が抑制されるため、特にＨＣを酸化する能力の低下が抑制されることを見出して、本発明を完成するに至った。 In order to solve the above-mentioned conventional problems, the present inventors have repeated intensive research, and hydrocarbons (HC), which are harmful components in exhaust gas containing sulfur oxides emitted from lean combustion engines such as diesel engines, In a platinum-based exhaust gas purifying catalyst that oxidizes carbon monoxide (CO), nitrogen oxide (NOx), soot, etc., tungsten appropriately supported in the vicinity of platinum (Pt) particles supported on the metal oxide Oxide particulates play a role in suppressing sulfur oxide poisoning to platinum and promoting sulfur desorption when the temperature rises, and even if exposed to exhaust gas containing high concentration of sulfur oxide for a long time. Since the poisoning of sulfur oxides to platinum is suppressed, it has been found that particularly a decrease in the ability to oxidize HC is suppressed, and the present invention has been completed.
即ち、本発明の第１の発明によれば、希薄燃焼機関のディーゼルエンジンから排出される炭化水素（ＨＣ）、一酸化炭素（ＣＯ）、窒素酸化物（ＮＯｘ）、煤などの微粒子成分、および硫黄酸化物を含む排気ガス中から、炭化水素を酸化浄化する白金系酸化触媒において、
一体構造型担体の表面に、少なくとも白金（Ｐｔ）及びタングステン酸化物が担持された金属酸化物（Ａ）と、ゼオライト（Ｂ）とを含む触媒組成物が被覆され、前記金属酸化物（Ａ）は、シリカ、アルミナ、酸化ネオジム、酸化プラセオジム、または酸化バリウムから選ばれる１種以上を含む耐熱チタニアであって、該耐熱チタニアのＢＥＴ比表面積値が３０〜３００ｍ ２ ／ｇ、かつ細孔径が３０〜３００ｎｍであり、
しかも前記白金（Ｐｔ）粒子の近傍に、凝集粒子径が３００ｎｍ以下のタングステン酸化物粒子が存在することを特徴とする白金系酸化触媒が提供される。
That is, according to the first invention of the present invention, particulate components such as hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx), soot and the like discharged from a diesel engine of a lean combustion engine, and In platinum-based oxidation catalysts that oxidize and purify hydrocarbons from exhaust gas containing sulfur oxides,
The surface of the monolithic structure-type support is coated with a catalyst composition containing at least platinum (Pt) and a tungsten oxide-supported metal oxide (A) and zeolite (B), and the metal oxide (A). Is a heat-resistant titania containing one or more selected from silica, alumina, neodymium oxide, praseodymium oxide, or barium oxide, and the heat-resistant titania has a BET specific surface area value of 30 to 300 m 2 / g and a pore diameter of 30. ~ 300nm,
In addition , a platinum-based oxidation catalyst is provided in which tungsten oxide particles having an aggregate particle diameter of 300 nm or less are present in the vicinity of the platinum (Pt) particles.
また、本発明の第２の発明によれば、第１の発明において、白金（Ｐｔ）及びタングステン酸化物の担持量が、タングステン酸化物を三酸化タングステン（ＷＯ３）換算したモル比率で、１：０．３〜５．０であることを特徴とする白金系酸化触媒が提供される。
また、本発明の第３の発明によれば、第１の発明において、触媒組成物の被覆量が、一体構造型担体の容量当り、２０〜１７０ｇ／Ｌであることを特徴とする白金系酸化触媒が提供される。
また、本発明の第４の発明によれば、第１の発明において、白金（Ｐｔ）の含有量が、一体構造型担体の容量当り、０．５〜５ｇ／Ｌであることを特徴とする白金系酸化触媒が提供される。
また、本発明の第５の発明によれば、第１の発明において、金属酸化物（Ａ）の含有量が、一体構造型担体の容量当り、１０〜１６０ｇ／Ｌであることを特徴とする白金系酸化触媒が提供される。
また、本発明の第６の発明によれば、第１の発明において、ゼオライト（Ｂ）が、β型ゼオライト、又はＭＦＩ型のゼオライトから選ばれる１種以上であることを特徴とする白金系酸化触媒が提供される。
また、本発明の第７の発明によれば、第１の発明において、ゼオライト（Ｂ）の含有量が、一体構造型担体の容量当り、５〜６０ｇ／Ｌであることを特徴とする白金系酸化触媒が提供される。
According to the second invention of the present invention, in the first invention, the supported amount of platinum (Pt) and tungsten oxide is 1 in terms of a molar ratio obtained by converting tungsten oxide into tungsten trioxide (WO 3 ). A platinum-based oxidation catalyst is provided that is 0.3 to 5.0.
According to a third aspect of the present invention, there is provided a platinum-based oxidation according to the first aspect, wherein the coating amount of the catalyst composition is 20 to 170 g / L per volume of the monolithic support. A catalyst is provided.
According to the fourth invention of the present invention, in the first invention, the platinum (Pt) content is 0.5 to 5 g / L per volume of the monolithic structure type carrier. A platinum-based oxidation catalyst is provided.
According to a fifth aspect of the present invention, in the first aspect, the content of the metal oxide (A) is 10 to 160 g / L per volume of the monolithic structure type carrier. A platinum-based oxidation catalyst is provided.
According to a sixth aspect of the present invention, the platinum-based oxidation according to the first aspect, wherein the zeolite (B) is at least one selected from β-type zeolite and MFI-type zeolite. A catalyst is provided.
Further, according to the seventh invention of the present invention, in the first invention, the content of zeolite (B) is 5 to 60 g / L per volume of the monolithic structure type carrier. An oxidation catalyst is provided.
さらに、本発明の第８の発明によれば、第１〜第７のいずれかの発明の白金系酸化触媒を希薄内燃機関の排気ガス流路に配置し、これに排気ガスを流通させることを特徴とする排気ガス浄化方法が提供される。
また、本発明の第９の発明によれば、第８の発明において、希薄内燃機関は、ディーゼルエンジンであることを特徴とする排気ガス浄化方法が提供される。
また、本発明の第１０の発明によれば、第８の発明において、希薄内燃機関は、硫黄の量が５０ｐｐｍ以上の燃料を使用することを特徴とする排気ガス浄化方法が提供される。
Further, according to the eighth invention of the present invention, the platinum-based oxidation catalyst of any one of the first to seventh inventions is disposed in the exhaust gas flow path of the lean internal combustion engine, and the exhaust gas is circulated through the catalyst. A featured exhaust gas purification method is provided.
According to a ninth aspect of the present invention, there is provided the exhaust gas purification method according to the eighth aspect, wherein the lean internal combustion engine is a diesel engine.
According to a tenth aspect of the present invention, there is provided the exhaust gas purification method according to the eighth aspect , wherein the lean internal combustion engine uses a fuel having a sulfur amount of 50 ppm or more.
本発明の白金系酸化触媒は、特に炭化水素（ＨＣ）の酸化浄化活性に優れ、ディーゼルエンジンなどの希薄燃焼機関から排出される有害成分（ＨＣ、ＣＯなど）に対して高い酸化浄化性能を発揮する。
さらに、本発明の白金系酸化触媒は、耐硫黄性に優れるため、高価な白金の使用量が少なくて済むので低コストで触媒を製造する事ができ、排気ガス浄化装置を安価で安定的に生産し供給することができる。The platinum-based oxidation catalyst of the present invention is particularly excellent in hydrocarbon (HC) oxidation purification activity and exhibits high oxidation purification performance against harmful components (HC, CO, etc.) emitted from lean combustion engines such as diesel engines. To do.
Furthermore, since the platinum-based oxidation catalyst of the present invention is excellent in sulfur resistance, the amount of expensive platinum used can be reduced, so that the catalyst can be produced at low cost, and the exhaust gas purifying apparatus can be manufactured stably at low cost. Can be produced and supplied.
以下、白金粒子が酸化タングステン粒子とともに金属酸化物上に担持された白金系酸化触媒組成物を含む本発明の白金系酸化触媒、及びそれを用いた排気ガス浄化方法について詳細に説明する。なお、ディーゼル自動車用途における実施形態を中心に述べるが、本発明は自動車用途に限定されるものではなく、発電など様々な電力源に使用されるディーゼルエンジンンにも有効であることはいうまでもない。 Hereinafter, the platinum-based oxidation catalyst of the present invention including a platinum-based oxidation catalyst composition in which platinum particles are supported on a metal oxide together with tungsten oxide particles, and an exhaust gas purification method using the same will be described in detail. In addition, although described centering on embodiment in a diesel vehicle use, it cannot be overemphasized that this invention is not limited to a vehicle use, but is effective also for the diesel engine used for various electric power sources, such as an electric power generation. Absent.
１．白金系酸化触媒組成物
本発明の白金系酸化触媒組成物（以下、触媒組成物ともいう）は、白金（Ｐｔ）とタングステン酸化物を金属酸化物上に担持し、白金粒子の近傍に凝集粒子径が３００ｎｍ以下のタングステン酸化物粒子が存在し、ゼオライトを含有している。白金とタングステン酸化物の担持量の比率は、タングステン酸化物を三酸化タングステン（ＷＯ３）に換算したモル比で、１：０．３〜５．０が好ましい。1. Platinum-Based Oxidation Catalyst Composition The platinum-based oxidation catalyst composition of the present invention (hereinafter also referred to as catalyst composition) carries platinum (Pt) and tungsten oxide on a metal oxide, and aggregates particles in the vicinity of the platinum particles. Tungsten oxide particles having a diameter of 300 nm or less exist and contain zeolite. The ratio of the supported amount of platinum and tungsten oxide is preferably a molar ratio of tungsten oxide converted to tungsten trioxide (WO 3 ), and is preferably 1: 0.3 to 5.0.
（１）金属酸化物
上記貴金属成分や助触媒成分は、金属酸化物（母材とも言う）に担持され、必要に応じ他の触媒成分と混合し、触媒組成物として構造型担体に被覆される。このように貴金属成分や助触媒成分を担持する母材の金属酸化物としては、排気ガス浄化用触媒の分野で公知の触媒材料が使用できる。このような無機材料は、耐熱性が高く、その比表面積値が大きいことで貴金属成分を安定に高分散できる多孔質の物が好ましい。
本発明では、金属酸化物として、チタニア、シリカ、シリカ−アルミナ、セリア、セリア−ジルコニアなどを例示できる。一般にチタニア系母材は、固体酸性が強いが故に硫黄が付着しにくい母材として知られ、一方、アルミナ系母材は、チタニアと比較して固体酸性が弱いが故に硫黄が吸着しやすい母材としてよく知られている。そのため、排気ガス中に硫黄酸化物が含まれている場合、母材としてはチタニアをはじめ硫黄が付着しにくい固体酸性の強い金属酸化物が一般に使用され、アルミナの様な硫黄が付着しやすい固体酸性の弱い金属酸化物はあまり使用されていない。
しかし、本発明では、白金（Ｐｔ）とタングステン酸化物が金属酸化物上に担持され、白金粒子の近傍に凝集粒子径が３００ｎｍ以下のタングステン酸化物粒子が存在していれば、硫黄酸化物を含む排気ガスに曝される触媒の母材として、一般的なチタニア系母材だけでなく、当該条件では使用に不向きとされるアルミナ系母材も使用することができる。
(1) Metal oxide The noble metal component and the promoter component are supported on a metal oxide (also referred to as a base material), mixed with other catalyst components as necessary, and coated on a structural support as a catalyst composition. . As the metal oxide of the base material supporting the noble metal component and the promoter component, a catalyst material known in the field of exhaust gas purification catalyst can be used. Such an inorganic material is preferably a porous material having high heat resistance and having a large specific surface area, which can stably and highly disperse the noble metal component.
In the present invention, titania, silica, silica-alumina, ceria, ceria-zirconia and the like can be exemplified as the metal oxide. In general, titania-based matrix is known as a matrix that is hard to adhere to sulfur due to its strong solid acidity, while alumina-based matrix is a matrix that is easy to adsorb sulfur because of its weak solid acidity compared to titania. Well known as. Therefore, when the exhaust gas contains sulfur oxides, titania and other metal oxides with strong solid acidity that are hard to adhere to sulfur are generally used as the base material, and solids such as alumina that are easily attached with sulfur. Less acidic metal oxides are used less frequently.
However, in the present invention, platinum (Pt) and tungsten oxide are supported on a metal oxide, and if tungsten oxide particles having an aggregate particle diameter of 300 nm or less are present in the vicinity of the platinum particles, sulfur oxides are added. As a base material of the catalyst exposed to the exhaust gas contained, not only a general titania base material but also an alumina base material which is unsuitable for use under the conditions can be used.
（１−１）チタニア（ＴｉＯ２）
本発明において、触媒材料の一つとして使用しうるチタニアは、多孔質無機酸化物の一種であり、貴金属であるＰｔを高分散に担持する母材として機能する。また、固体酸性が強いため、硫黄がほとんど吸着しないことがよく知られている。結晶構造としては、アナタース型の他、ルチル型、ブルカイト型が挙げられ、Ｐｔの活性点を増やすため、ＢＥＴ比表面積の大きいアナタース型が特に好ましい。さらに、チタニアは、単独で使用してもよいが、雰囲気温度の上昇とともにＢＥＴ比表面積が低下するため、シリカ、アルミナ、酸化ネオジム、酸化プラセオジム、酸化バリウム等を少量加えて、耐熱性を向上させたチタニア系複合酸化物を使用することが望ましい。
(1-1) Titania (TiO 2 )
In the present invention, titania that can be used as one of the catalyst materials is a kind of porous inorganic oxide, and functions as a base material that supports Pt, which is a noble metal, in a highly dispersed state. Further, it is well known that sulfur is hardly adsorbed due to its strong solid acidity. Examples of the crystal structure include an anatase type, a rutile type and a brookite type, and an anatase type having a large BET specific surface area is particularly preferable in order to increase the active site of Pt. In addition, titania may be used alone, but since the BET specific surface area decreases as the ambient temperature increases, a small amount of silica, alumina, neodymium oxide, praseodymium oxide, barium oxide, etc. is added to improve heat resistance. It is desirable to use a titania-based composite oxide.
本発明において、チタニア又はチタニア系複合酸化物のＢＥＴ比表面積値（ＢＥＴ法による、以下同様）は、３０〜３００ｍ２／ｇが好ましく、５０〜２００ｍ２／ｇがより好ましい。ＢＥＴ比表面積が３０ｍ２／ｇ以下の場合、貴金属や助触媒などの分散性が悪化するので好ましくない。一方、３００ｍ２／ｇ以上になると、粒子内の細孔径が小さくなり過ぎて、細孔内でのガスの拡散が遅くなるので好ましくない。In the present invention, BET specific surface area of the titania or titania-based composite oxide (by the BET method, hereinafter the same) is preferably 30~300m 2 / g, 50~200m 2 / g is more preferable. When the BET specific surface area is 30 m 2 / g or less, the dispersibility of noble metals, promoters and the like deteriorates, which is not preferable. On the other hand, if it is 300 m 2 / g or more, the pore diameter in the particles becomes too small, and gas diffusion in the pores becomes slow, which is not preferable.
また、チタニア又はチタニア系複合酸化物の粒子内の細孔径は、３０〜３００ｎｍが好ましく、１００〜２５０ｎｍがより好ましい。細孔径が３０ｎｍ未満では硫黄などの被毒成分による細孔の閉塞等の恐れもあり、３００ｎｍを超えるとＢＥＴ比表面積が低下するため、貴金属や助触媒などの分散性が悪化するので好ましくない。 Moreover, 30-300 nm is preferable and, as for the pore diameter in the particle | grains of titania or a titania type complex oxide, 100-250 nm is more preferable. If the pore diameter is less than 30 nm, there is a risk of pore clogging due to poisoning components such as sulfur.
チタニア又はチタニア系複合酸化物の平均粒径は、０．３〜５０μｍであることが好ましく、０．５〜３０μｍであることがより好ましい。０．３μｍ未満では粒子−粒子間の空隙が小さくなり過ぎて、空隙間のガスの拡散が遅くなるので好ましくなく、５０μｍを超えると粒子の中心部までのガスの拡散が遅くなり、粒子の中心部が有効に活用されないので好ましくない。 The average particle size of titania or titania-based composite oxide is preferably 0.3 to 50 μm, and more preferably 0.5 to 30 μm. If it is less than 0.3 μm, the particle-particle gap is too small, and gas diffusion between the gaps is slow, which is not preferable. If it exceeds 50 μm, gas diffusion to the center of the particle is delayed, and the center of the particle This is not preferable because the part is not used effectively.
（１−２）アルミナ（Ａｌ２Ｏ３）
本発明において、触媒材料の一つとして使用しうるアルミナは、排気ガス浄化用触媒の金属酸化物として一般に使用されている。アルミナの結晶構造としては、γ−アルミナ、β−アルミナ、δ−アルミナ、η−アルミナ、θ−アルミナが挙げられ、Ｐｔの活性点を増やすため、ＢＥＴ比表面積の大きいγ−アルミナが特に好ましい。また、γ−アルミナにランタン、ジルコニア、セリアなどを添加することが好ましい。特に、ランタンが添加されたγ−アルミナは、耐熱性に優れ、白金成分やパラジウム成分等の貴金属成分を担持させた場合、高温時にも高い触媒活性を維持することが可能である（特開２００４−２９０８２７号公報）。(1-2) Alumina (Al 2 O 3 )
In the present invention, alumina that can be used as one of the catalyst materials is generally used as a metal oxide of an exhaust gas purification catalyst. Examples of the crystal structure of alumina include γ-alumina, β-alumina, δ-alumina, η-alumina, and θ-alumina. In order to increase the active site of Pt, γ-alumina having a large BET specific surface area is particularly preferable. Moreover, it is preferable to add lanthanum, zirconia, ceria, etc. to γ-alumina. In particular, γ-alumina to which lanthanum is added has excellent heat resistance, and when a noble metal component such as a platinum component or a palladium component is supported, high catalytic activity can be maintained even at high temperatures (Japanese Patent Laid-Open No. 2004-2004). -290827).
本発明において、アルミナのＢＥＴ比表面積は、８０〜２５０ｍ２／ｇであることが好ましく、更に、１００〜２００ｍ２／ｇがより好ましい。アルミナのＢＥＴ比表面積値が２５０ｍ２／ｇより大きいと相対的に細孔径が小さくなるので、ガスの拡散の悪化や細孔の閉塞が懸念される。一方、ＢＥＴ比表面積が８０ｍ２／ｇより小さいと貴金属や助触媒の分散性の悪化が懸念される。In the present invention, BET specific surface area of the alumina is preferably 80~250m 2 / g, further, 100 to 200 m 2 / g is more preferable. When the BET specific surface area value of alumina is larger than 250 m 2 / g, the pore diameter becomes relatively small, and there is a concern about deterioration of gas diffusion and pore clogging. On the other hand, when the BET specific surface area is less than 80 m 2 / g, there is a concern that the dispersibility of the noble metal or the promoter may be deteriorated.
また、アルミナは細孔径（モード径、以下同じ）が８〜５０ｎｍであることが好ましく、更に、１０〜４０ｎｍであることがより好ましく、１２〜３０ｎｍがさらに好ましい。アルミナの細孔径が８ｎｍより小さいと細孔内でのガスの拡散が遅くなる上、煤などにより細孔が閉塞される恐れがある。一方、細孔径が５０ｎｍより大きいと相対的にＢＥＴ比表面積が小さくなり、貴金属や助触媒などの分散性が悪化するので好ましくない。アルミナの平均粒径は、０．３〜５０μｍであることが好ましく、０．５〜３０μｍであることがより好ましい。０．３μｍ未満では粒子−粒子間の空隙が小さくなり過ぎて、空隙間のガスの拡散が遅くなるので好ましくなく、５０μｍを超えると粒子の中心部までのガスの拡散が遅くなり、粒子の中心部が有効に活用されないので好ましくない。 Alumina preferably has a pore diameter (mode diameter, hereinafter the same) of 8 to 50 nm, more preferably 10 to 40 nm, and further preferably 12 to 30 nm. If the pore diameter of alumina is smaller than 8 nm, the diffusion of gas in the pores will be slow and the pores may be blocked by soot or the like. On the other hand, if the pore diameter is larger than 50 nm, the BET specific surface area becomes relatively small, and the dispersibility of noble metals, promoters and the like deteriorates. The average particle diameter of alumina is preferably 0.3 to 50 μm, and more preferably 0.5 to 30 μm. If it is less than 0.3 μm, the particle-particle gap is too small, and gas diffusion between the gaps is slow, which is not preferable. If it exceeds 50 μm, gas diffusion to the center of the particle is delayed, and the center of the particle This is not preferable because the part is not used effectively.
アルミナの耐久性を向上させるため、さらにバリウム、マグネシウムなどのアルカリ土類、セリウム、ランタン、ネオジム、プラセオジムなどの希土類元素などを付与してもよい。添加量はアルミナの高ＢＥＴ比表面積の大幅な低減を避けるためにも３０重量％以下が好ましい。
なお、前記シリカ、ジルコニアなどの物性についても、チタニアやアルミナに準じて選定することができる。In order to improve the durability of alumina, an alkaline earth such as barium or magnesium, or a rare earth element such as cerium, lanthanum, neodymium, or praseodymium may be added. The addition amount is preferably 30% by weight or less in order to avoid a significant reduction in the high BET specific surface area of alumina.
The physical properties of silica, zirconia, etc. can also be selected according to titania and alumina.
（２）白金（Ｐｔ）
本発明においては、触媒成分の一つとして使用する貴金属元素の白金は、活性金属として機能する。
白金は、上記金属酸化物に担持されるが、その際に使用する出発塩としては、水酸化白金(ＩＶ)酸のエタノールアミン溶液、テトラアンミン白金（ＩＩ）酢酸塩、テトラアンミン白金（ＩＩ）炭酸塩、テトラアンミン白金（ＩＩ）硝酸塩、水酸化白金(ＩＶ)酸の硝酸溶液、硝酸白金、ジニトロジアンミン白金硝酸、塩化白金（ＩＶ）酸などが好ましい。特に、焼成後に塩素、硫化物などの残渣が残らない水酸化白金(ＩＶ)酸のエタノールアミン溶液、テトラアンミン白金（ＩＩ）酢酸塩、テトラアンミン白金（ＩＩ）炭酸塩、テトラアンミン白金（ＩＩ）硝酸塩、水酸化白金(ＩＶ)酸の硝酸溶液、硝酸白金、ジニトロジアンミン白金硝酸の使用が好ましい。
金属酸化物上への白金の担持量は、特に制限はないが、０．５〜５ｇ／Ｌが好ましく、０．５〜３ｇ／Ｌがより好ましい。白金の量が０．５ｇ／Ｌより少ないと酸化活性が乏しく、５ｇ／Ｌより多いと、酸化活性に対して価格が高くなり好ましくない。(2) Platinum (Pt)
In the present invention, the noble metal element platinum used as one of the catalyst components functions as an active metal.
Platinum is supported on the metal oxide, and the starting salt used in this case includes ethanolamine solution of platinum (IV) hydroxide, tetraammineplatinum (II) acetate, tetraammineplatinum (II) carbonate. , Tetraammineplatinum (II) nitrate, nitric acid solution of platinum hydroxide (IV) acid, platinum nitrate, dinitrodiammine platinum nitrate, platinum chloride (IV) acid and the like are preferable. In particular, platinumamine (IV) acid ethanolamine solution, tetraammineplatinum (II) acetate, tetraammineplatinum (II) carbonate, tetraammineplatinum (II) nitrate, water that does not leave residues such as chlorine and sulfide after firing. Preference is given to using a nitric acid solution of platinum (IV) oxide, platinum nitrate, dinitrodiammine platinum nitrate.
The amount of platinum supported on the metal oxide is not particularly limited, but is preferably 0.5 to 5 g / L, and more preferably 0.5 to 3 g / L. When the amount of platinum is less than 0.5 g / L, the oxidation activity is poor, and when it is more than 5 g / L, the price is high with respect to the oxidation activity, which is not preferable.
（３）タングステン酸化物
本発明において、触媒材料の一つとして使用するタングステン酸化物は、三酸化タングステン（ＷＯ３）、または三酸化タングステン（ＷＯ３）および二酸化タングステン（ＷＯ２）から成る。混合物である場合、ＷＯ３とＷＯ２の混合比率は特に制限されない。
タングステン酸化物は、固体酸性が強く、硫黄がほとんど吸着しないことから助触媒として機能する。(3) Tungsten oxide In the present invention, the tungsten oxide used as one of the catalyst materials comprises tungsten trioxide (WO 3 ), or tungsten trioxide (WO 3 ) and tungsten dioxide (WO 2 ). In the case of a mixture, the mixing ratio of WO 3 and WO 2 is not particularly limited.
Tungsten oxide functions as a promoter because it has a strong solid acidity and hardly adsorbs sulfur.
硫黄の吸着性という面においてタングステン酸化物は、チタニアと同様の性質を有する一方、タングステン酸化物は、酸化チタンに比べ密度が２〜３倍ほど高い（ＷＯ３で７．１６ｇ／ｃｍ３、ＷＯ２で１２．１ｇ／ｃｍ３、ＴｉＯ２はアナタース型で３．９０ｇ／ｃｍ３、ルチル型が４．２７ｇ／ｃｍ３である）。そのため、タングステン酸化物はチタニアに比べＢＥＴ比表面積は低くなり、貴金属の担体としては、分散性に問題があるものの熱によるシンタリングの影響を受けにくい。Tungsten oxide in terms of the adsorption of the sulfur, while having properties similar to titania, tungsten oxide, higher 2-3 times density compared with titanium oxide (WO 3 at 7.16 g / cm 3, WO 2 in 12.1 g / cm 3, TiO 2 is 3.90 g / cm 3 in anatase, rutile is 4.27g / cm 3). Therefore, tungsten oxide has a lower BET specific surface area than titania, and as a noble metal support, although it has a problem in dispersibility, it is hardly affected by sintering due to heat.
金属酸化物上にタングステン酸化物を微粒子として担持しかつ高分散させるため、出発塩としては、液状、ゾル状のものが好ましい。液状のものとしては、メタタングステン酸アンモニウム、リンタングステン酸、メタタングステン酸ナトリウム等が好ましい。特に、焼成後に塩素、硫化物等の残渣が残らないメタタングテン酸アンモニウムの使用が好ましい。また、ゾル状のものとしては二酸化タングステンゾル、三酸化タングステンゾルが好ましい。 Since the tungsten oxide is supported on the metal oxide as fine particles and is highly dispersed, the starting salt is preferably in a liquid or sol form. As the liquid, ammonium metatungstate, phosphotungstic acid, sodium metatungstate and the like are preferable. In particular, it is preferable to use ammonium metatungstate that does not leave residues such as chlorine and sulfide after firing. Moreover, as a sol form, a tungsten dioxide sol and a tungsten trioxide sol are preferable.
タングステン酸化物の粒子径は、凝集粒子の状態で３００ｎｍ以下でなければならない。粒子径は、２００ｎｍ以下がより好ましく、１００ｎｍ以下がさらに好ましく、５０ｎｍ以下が特に好ましい。なお、凝集粒子とは一次粒子が１個以上数個から数十個固まった状態を指し、二次粒子径とも呼称する。タングステン酸化物の凝集粒子径が３００ｎｍを越えると１個当りの粒子径が大きくなり過ぎて、タングステン酸化物の分散性が悪化し、白金の近傍にタングステン酸化物が存在する割合が減少するため、白金粒子への硫黄の被毒を抑制する効果が低下するので好ましくない。なお、一次粒子が１個の大きさ、すなわちタングステン酸化物結晶子の大きさは、後述するＳＴＥＭ／ＥＤＸでは確認できないほど小さく、１ｎｍ以下（０．５ｎｍ程度）である。 The particle diameter of tungsten oxide must be 300 nm or less in the state of aggregated particles. The particle diameter is more preferably 200 nm or less, further preferably 100 nm or less, and particularly preferably 50 nm or less. Aggregated particles refer to a state in which one or more primary particles are solidified to several to several tens, and are also referred to as secondary particle diameters. When the aggregate particle diameter of tungsten oxide exceeds 300 nm, the particle diameter per particle becomes too large, the dispersibility of tungsten oxide deteriorates, and the proportion of tungsten oxide existing in the vicinity of platinum decreases. Since the effect which suppresses the poisoning of the sulfur to platinum particle falls, it is not preferable. The size of one primary particle, that is, the size of the tungsten oxide crystallite is so small that it cannot be confirmed by STEM / EDX described later, and is 1 nm or less (about 0.5 nm).
金属酸化物上へのタングステン酸化物の担持量は、特に制限されないが、三酸化タングステン（ＷＯ３）換算で０．１５〜１５ｇ／Ｌが好ましく、０．２〜１０ｇ／Ｌがより好ましい。タングステン酸化物の量が三酸化タングステン（ＷＯ３）換算で０．１５ｇ／Ｌより少ないと硫黄による被毒を抑制する効果が乏しく、１５ｇ／Ｌより多いと白金粒子自体を被覆する恐れがある上、価格の面でも好ましくない。
また、白金粒子と近接させて担持する必要があるため、白金とタングステン酸化物の担持量の比率は、タングステン酸化物を三酸化タングステン（ＷＯ３）にモル換算して、１：０．３〜５．０であることが好ましく、１：０．３〜３．０がより好ましく、１：０．５〜２．０が特に好ましい。白金とタングステン酸化物の担持量の比率が０．３未満であると、タングステン酸化物の絶対量が不足して硫黄による白金の被毒を抑え難くなるので好ましくない。一方、５．０を超えるとタングステン酸化物が白金の表面を被覆したり母材の細孔を閉塞させたりし、触媒活性を抑制するので好ましくない。The amount of tungsten oxide supported on the metal oxide is not particularly limited, but is preferably 0.15 to 15 g / L, more preferably 0.2 to 10 g / L in terms of tungsten trioxide (WO 3 ). If the amount of tungsten oxide is less than 0.15 g / L in terms of tungsten trioxide (WO 3 ), the effect of suppressing poisoning by sulfur is poor, and if it exceeds 15 g / L, platinum particles themselves may be coated. It is not preferable in terms of price.
Moreover, since it is necessary to carry | support in close proximity to platinum particle, the ratio of the carrying amount of platinum and tungsten oxide is 1: 0.3- in terms of molar conversion of tungsten oxide to tungsten trioxide (WO 3 ). 5.0 is preferable, 1: 0.3 to 3.0 is more preferable, and 1: 0.5 to 2.0 is particularly preferable. If the ratio of the supported amount of platinum and tungsten oxide is less than 0.3, the absolute amount of tungsten oxide is insufficient, and it is difficult to suppress poisoning of platinum by sulfur. On the other hand, if it exceeds 5.0, tungsten oxide coats the surface of platinum or closes the pores of the base material and suppresses the catalytic activity.
（４）ゼオライト
本発明において、触媒材料として使用するゼオライトは、チタニアと同等かそれ以上に固体酸性が強く、硫黄がほとんど吸着しないものである。
ゼオライトとしては、例えば三次元の細孔構造を有するβ型、ＭＦＩ型のゼオライトをはじめ、Ａ、Ｘ、Ｙ、ＭＯＲ、ＣＨＡ、ＳＡＰＯなどのゼオライトまたはゼオライト様物質が使用できるが、ディーゼル排ガス中の炭化水素を捕捉するという機能を考慮するとβ型ゼオライト、又はＭＦＩ型のゼオライトがより好ましい。
ゼオライトとしては高表面積でかつ耐熱性のあるものが好ましい。より優れた耐熱性を得るには、ゼオライトのＳｉＯ２／Ａｌ２Ｏ３のモル比は、１０〜３００が好ましく、１５〜１００がより好ましい。また、ゼオライトのＢＥＴ比表面積は３００〜１０００ｍ２／ｇが好ましく、４００〜９００ｍ２／ｇがより好ましい。(4) Zeolite In the present invention, the zeolite used as the catalyst material has a solid acidity equivalent to or higher than that of titania and hardly adsorbs sulfur.
As the zeolite, for example, β-type and MFI-type zeolites having a three-dimensional pore structure, zeolites such as A, X, Y, MOR, CHA, and SAPO or zeolite-like substances can be used. In view of the function of capturing hydrocarbons, β-type zeolite or MFI-type zeolite is more preferable.
Zeolite having a high surface area and heat resistance is preferred. In order to obtain better heat resistance, the SiO 2 / Al 2 O 3 molar ratio of the zeolite is preferably 10 to 300, more preferably 15 to 100. Further, BET specific surface area of the zeolite is preferably 300~1000m 2 / g, 400~900m 2 / g is more preferable.
２．白金系酸化触媒
本発明の上記触媒組成物は、そのままで用いることができるが、本発明では、一体構造型触媒などの各種担体表面に被覆された構造型触媒として用いることが望ましい。2. Platinum-based oxidation catalyst The catalyst composition of the present invention can be used as it is, but in the present invention, it is preferably used as a structural catalyst coated on the surface of various supports such as a monolithic catalyst.
（一体構造型触媒）
本発明の白金系酸化触媒（排気ガス浄化用触媒、あるいは単に酸化触媒ともいう）において、担体の形状は、特に限定されるものではなく、角柱状、円筒状、球状、ハニカム状、シート状などの構造型担体から選択可能である。構造型担体のサイズは、特に制限されないが、角柱状、円筒状、球状のいずれかであれば、例えば数ミリから数センチの直径（長さ）のものが使用できる。中でも、ハニカム状のハニカム構造担体の使用が好ましい。(Integrated structure type catalyst)
In the platinum-based oxidation catalyst of the present invention (exhaust gas purification catalyst or simply referred to as an oxidation catalyst), the shape of the carrier is not particularly limited, and is a prismatic shape, a cylindrical shape, a spherical shape, a honeycomb shape, a sheet shape, and the like. It is possible to select from the following structural type carriers. The size of the structure-type carrier is not particularly limited, and a structural carrier having a diameter (length) of several millimeters to several centimeters can be used as long as it is any of a prismatic shape, a cylindrical shape, and a spherical shape. Among these, the use of a honeycomb-shaped honeycomb structure carrier is preferable.
（ハニカム構造担体）
ハニカム構造担体とは、コージェライト、シリコンカーバイド、窒化珪素等のセラミックや、ステンレス等の金属からなるもので、その構造は構造型担体中の全体に渡って伸びている平行な多数の微細な気体流路を有するもので一体構造型担体ともいわれる。このうち材質としてはコージェライトが耐久性、コストの理由で好ましい。
また、このようなハニカム構造担体としては、さらに開口部の孔数についても処理すべき排気ガスの種類、ガス流量、圧力損失あるいは除去効率などを考慮して適正な孔数が決められるが、そのセル密度は１００〜９００セル／ｉｎｃｈ２（１５５ｋ〜１４００ｋ／ｍ２）であることが好ましく、２００〜６００セル／ｉｎｃｈ２（３１０ｋ〜９３０ｋ／ｍ２）である事がより好ましい。セル密度が９００セル／ｉｎｃｈ２（１４００ｋ／ｍ２）を超えると、付着したＰＭで目詰まりが発生しやすく、１００セル／ｉｎｃｈ２（３１０ｋ／ｍ２）未満では幾何学的表面積が小さくなるため、触媒の有効使用率が低下してしまう。なお、セル密度とは、ハニカム構造担体を気体流路に対して直角に切断した際の断面における単位面積あたりのセル数のことである。
また、ハニカム構造担体には、気体流路が連通しているフロースルー型構造体と、気体流路の一部端面が目封じされ、かつ気体流路の壁面を通して気体が流通可能になっているウォールフロー型構造体とが広く知られている。フロースルー型構造体であれば空気抵抗が少なく、排気ガスの圧力損失が少ない。また、ウォールフロー型構造体であれば、排気ガス中に含まれる粒子状成分を濾し取ることが可能である。本発明の白金系酸化触媒は、そのどちらの構造体にも用いる事ができる。(Honeycomb structure carrier)
A honeycomb structure carrier is made of a ceramic such as cordierite, silicon carbide, silicon nitride, or a metal such as stainless steel, and the structure is a large number of parallel fine gases extending throughout the structure type carrier. It has a flow path and is also called a monolithic structure type carrier. Of these, cordierite is preferred as the material because of durability and cost.
Further, for such a honeycomb structure carrier, an appropriate number of holes can be determined in consideration of the type of exhaust gas to be processed, gas flow rate, pressure loss or removal efficiency, etc. The cell density is preferably 100 to 900 cells / inch 2 (155 k to 1400 k / m 2 ), and more preferably 200 to 600 cells / inch 2 (310 k to 930 k / m 2 ). When the cell density exceeds 900 cells / inch 2 (1400k / m 2 ), clogging tends to occur in the deposited PM, 100 cells / inch 2 (310k / m 2 ) for the geometric surface area is small at less than The effective usage rate of the catalyst will decrease. The cell density is the number of cells per unit area in a cross section when the honeycomb structure carrier is cut at right angles to the gas flow path.
In addition, the honeycomb structure carrier has a flow-through structure in which the gas flow path communicates with a part of the end face of the gas flow path, and gas can flow through the wall surface of the gas flow path. A wall flow structure is widely known. The flow-through structure has low air resistance and low exhaust gas pressure loss. Moreover, if it is a wall flow type structure, it is possible to filter out the particulate component contained in exhaust gas. The platinum-based oxidation catalyst of the present invention can be used for either structure.
（層構成）
本発明の白金系酸化触媒は、前記触媒組成物をハニカム構造担体に一層以上被覆したものである。層構成は、一層でもよいが、排気ガス規制の強化を受け、二層以上とすることが好ましい。(Layer structure)
The platinum-based oxidation catalyst of the present invention is obtained by coating one or more honeycomb structure carriers with the catalyst composition. The layer structure may be a single layer, but it is preferable to have two or more layers in response to stricter exhaust gas regulations.
（触媒調製法）
（１）触媒組成物の調製方法
本発明で用いる白金系酸化触媒組成物を調製するため、例えば、以下のような方法により、白金及びタングステン酸化物を金属酸化物に担持することができる。(Catalyst preparation method)
(1) Preparation Method of Catalyst Composition In order to prepare the platinum-based oxidation catalyst composition used in the present invention, for example, platinum and tungsten oxide can be supported on a metal oxide by the following method.
（プロセス１：同時担持）
出発原料として、おのおの先に述べた水溶性の白金塩と水溶性のタングステンを含有する原料を、特定量用意し、混合・攪拌して、水溶液とする。その際、白金塩水溶液とタングステン含有水溶液の性質（酸性・アルカリ性）が異なると、両方が凝集して沈殿物を生じる恐れがある為、白金及びタングステンを含有する水溶液の性質は酸性同士又はアルカリ性同士で統一する必要がある。(Process 1: Simultaneous loading)
As starting materials, specific amounts of the raw materials containing the water-soluble platinum salt and water-soluble tungsten described above are prepared, mixed and stirred to obtain an aqueous solution. At that time, if the properties (acidic / alkaline) of the platinum salt aqueous solution and the tungsten-containing aqueous solution are different, both may aggregate and produce a precipitate. Therefore, the aqueous solution containing platinum and tungsten is acidic or alkaline. Need to be unified.
（プロセス２：逐次担持）
出発原料である白金塩、タングステン含有原料を特定量用意し、混合せずに逐次担持する。出発原料は白金塩、タングステン含有原料とも水溶性であれば、水溶液の性質は酸性、中性、アルカリ性のいずれであっても問題ない。担持の順番については白金、タングステンの順であっても、その逆の、タングステン、白金の順でも可能であるが、タングステン、白金の順の場合、後から担持する白金が剥き出しになって硫黄酸化物により被毒されてしまう恐れがある。そこで高価な白金をできるだけ有効に活用するためには、白金、タングステンの順が好ましい。
なお、プロセス１、２については、触媒に使用可能な白金量、原材料代を含む製造コスト、要求される浄化性能などにより適宜使い分けることができるが、白金粒子のより近傍に酸化タングステン粒子を存在させるには、プロセス１の同時担持の方が好ましい。(Process 2: Sequential loading)
Prepare specific amounts of platinum salt and tungsten-containing materials as starting materials, and carry them sequentially without mixing. If the starting material is a water-soluble platinum salt and tungsten-containing material, there is no problem even if the nature of the aqueous solution is acidic, neutral or alkaline. The order of loading can be in the order of platinum and tungsten, or vice versa, but in the order of tungsten and platinum, but in the order of tungsten and platinum, the platinum that is loaded later becomes exposed and sulfur oxidation occurs. There is a risk of being poisoned by things. Therefore, in order to utilize expensive platinum as effectively as possible, the order of platinum and tungsten is preferable.
Processes 1 and 2 can be appropriately selected depending on the amount of platinum that can be used for the catalyst, the manufacturing cost including the raw material cost, the required purification performance, etc., but the tungsten oxide particles are present closer to the platinum particles. For this, simultaneous loading of process 1 is preferable.
（２）一体構造型触媒の調製方法
本発明の白金系酸化触媒を調製するには、前記触媒組成物と、必要に応じてバインダーなどを水系媒体と共に混合してスラリー状混合物にしてから、一体構造型担体へ塗工して、乾燥、焼成する。
すなわち、まず、触媒組成物と水系媒体、及び必要に応じてバインダーを所定の比率で混合してスラリー状混合物を得る。本発明においては、水系媒体は、スラリー中で触媒組成物が均一に分散できる量を用いれば良い。
この際、必要に応じてｐＨ調整のための酸、塩基を配合したり、粘性の調整やスラリー分散性向上のための界面活性剤、分散用樹脂等を配合する事ができる。スラリーの混合方法としては、ボールミルなどによる粉砕混合が適用可能であるが、他の粉砕、もしくは混合方法を適用しても良い。(2) Preparation Method of Monolithic Catalyst To prepare the platinum-based oxidation catalyst of the present invention, the catalyst composition and, if necessary, a binder are mixed with an aqueous medium to form a slurry mixture, and then integrated. It is applied to a structural carrier, dried and fired.
That is, first, a catalyst composition, an aqueous medium, and a binder as necessary are mixed at a predetermined ratio to obtain a slurry mixture. In the present invention, the aqueous medium may be used in such an amount that the catalyst composition can be uniformly dispersed in the slurry.
At this time, if necessary, an acid or a base for adjusting the pH, a surfactant for adjusting the viscosity or improving the slurry dispersibility, a dispersing resin or the like can be added. As a mixing method of the slurry, pulverization and mixing by a ball mill or the like can be applied, but other pulverization or mixing methods may be applied.
次に、一体構造型担体へスラリー状混合物を塗工する。塗工方法は、特に限定されないが、ウォッシュコート法が好ましい。
塗工した後、乾燥、焼成を行う事により触媒組成物が担持された一体構造型触媒が得られる。なお、乾燥温度は、７０〜２００℃が好ましく、８０〜１５０℃がより好ましい。また、焼成温度は、３００〜７００℃が好ましく、４００〜６００℃がより好ましい。加熱手段については、電気炉やガス炉等の公知の加熱手段によって行う事ができる。Next, the slurry-like mixture is applied to the monolithic structure type carrier. The coating method is not particularly limited, but a wash coat method is preferable.
After coating, drying and firing are performed to obtain a monolithic structure type catalyst carrying the catalyst composition. In addition, 70-200 degreeC is preferable and, as for drying temperature, 80-150 degreeC is more preferable. Moreover, 300-700 degreeC is preferable and, as for baking temperature, 400-600 degreeC is more preferable. About a heating means, it can carry out by well-known heating means, such as an electric furnace and a gas furnace.
以下に実施例及び比較例を示し、本発明の特徴を一層明確にするが、本発明は、これら実施例の態様に限定されるものではない。 Examples and Comparative Examples are shown below to further clarify the features of the present invention, but the present invention is not limited to the embodiments.
（１）粒子径分布測定
ＳＨＩＭＡＤＺＵ社製ナノ粒子径分布測定装置ＳＡＬＤ−７１００を用いて、レーザー散乱法により各種粉末原料の粒度分布を測定した。平均細孔径としては、メディアン径（Ｄ５０）を採用した。(1) Particle size distribution measurement The particle size distribution of various powder raw materials was measured by a laser scattering method using a nano particle size distribution measuring device SALD-7100 manufactured by SHIMADZU. The median diameter (D50) was adopted as the average pore diameter.
（２）粒子径測定（タングステン酸化物）
メタタングステン酸アンモニウム又はリンタングステン酸を出発原料とする酸化タングステンの粒子径は、走査透過型電子顕微鏡（ＳＴＥＭ：Ｓｃａｎｎｉｎｇ Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ：MＤ−２０００ 株式会社日立ハイテクノロジーズ社製）、およびエネルギー分散型Ｘ線分光装置（ＥＤＸ：Ｅｎｅｒｇｙ Ｄｉｓｐｅｒｓｉｖｅ Ｘ−ｒａｙ Ｓｐｅｃｔｒｏｓｃｏｐｙ：ＶＥＮＴＡＧＥ １．４ Ｔｈｅｒｍｏ ＮＯＲＡＮ社製）で測定した。(2) Particle size measurement (tungsten oxide)
The particle diameter of tungsten oxide starting from ammonium metatungstate or phosphotungstic acid is determined by scanning transmission electron microscope (STEM: Scanning Transmission Electron Microscope: MD-2000, manufactured by Hitachi High-Technologies Corporation), and energy dispersive X It was measured with a line spectrometer (EDX: Energy Dispersive X-ray Spectroscopy: VENTAGE 1.4 Thermo NORAN).
（３）細孔分布測定
各種粉末原料０．３ｇを乾燥後、Ｔｈｅｒｍｏ社製ＰＡＳＣＡＬ１４０−４４０を用いて、Ｈｇ圧入法により、各原料の細孔分布を測定した。細孔径としては、モード径を採用した。(3) Pore distribution measurement After drying 0.3 g of various powder raw materials, the pore distribution of each raw material was measured by Hg press-in method using PASCAL 140-440 manufactured by Thermo. The mode diameter was adopted as the pore diameter.
（４）Ｓ被毒処理
実施例及び比較例で用いる触媒コア（直径２４ｍｍ×長さ６６ｍｍ、容積３０ｍＬ）は、まず電気炉内に入れ、空気雰囲気下、６５０℃、２０時間の熱処理を行った。その熱処理後の各触媒コアをサンプルホルダーに入れ、管状炉内で、触媒床温度を２５０℃又は３５０℃に設定し、表１に示す２，０００ｐｐｍのＳＯ２を含むガスに２時間曝すことでＳ被毒処理を行った。(4) S poisoning treatment The catalyst core (diameter 24 mm × length 66 mm, volume 30 mL) used in the examples and comparative examples was first placed in an electric furnace and heat-treated at 650 ° C. for 20 hours in an air atmosphere. . Each catalyst core after the heat treatment is placed in a sample holder, the catalyst bed temperature is set to 250 ° C. or 350 ° C. in a tubular furnace, and exposed to a gas containing 2,000 ppm SO 2 shown in Table 1 for 2 hours. S poisoning treatment was performed.
（５）モデルガス評価
Ｓ被毒処理後の各触媒コアをサンプルホルダーに入れ、モデルガス評価装置にセットした後、表２に示す反応ガスを流して触媒性能試験を行った。ＨＣ（具体的にはＣ３Ｈ６：Ｃ３Ｈ８＝８０：２０）の酸化反応の結果を図１〜２に、ＣＯの酸化反応の結果を図３〜４に示す。
なお、各有害成分の酸化性能の定義は以下の通りである。
ＨＣのＴ５０（℃）：ＨＣが酸化されてＨＣ濃度が５０％まで減少した時の触媒床温度。
ＣＯのＴ５０（℃）：ＣＯが酸化されてＣＯ濃度が５０％まで減少した時の触媒床温度。(5) Model gas evaluation Each catalyst core after the S poisoning treatment was put in a sample holder and set in a model gas evaluation apparatus, and then a reaction gas shown in Table 2 was flowed to conduct a catalyst performance test. The results of the oxidation reaction of HC (specifically C 3 H 6 : C 3 H 8 = 80: 20) are shown in FIGS. 1-2, and the results of the oxidation reaction of CO are shown in FIGS.
In addition, the definition of the oxidation performance of each harmful component is as follows.
HC T50 (° C.): catalyst bed temperature when HC is oxidized and HC concentration is reduced to 50%.
CO T50 (° C.): The catalyst bed temperature when CO is oxidized and the CO concentration is reduced to 50%.
（実施例１）
白金（Ｐｔ）換算で１．７６５ｇの水酸化白金(ＩＶ)酸のエタノールアミン溶液と三酸化タングステン（ＷＯ３）換算で２．１ｇのメタタングステン酸アンモニウムを秤量後、純水２０ｍＬに均一に溶解して白金とメタタングステン酸アンモニウムの両方を含む水溶液を調製し、ＢＥＴ比表面積９２ｍ２／ｇ、平均細孔径（メディアン径）１７５ｎｍ、平均粒径（Ｄ５０）２．５μｍのアナタース型耐熱チタニア（ＴｉＯ２：９０％、ＳｉＯ２：６％、Ａｌ２Ｏ３：４％）８０ｇに含浸担持した。この含水物を空気中５００℃で１時間焼成を行うことで、２．１重量％白金−２．５重量％三酸化タングステン担持チタニア系複合酸化物を得た。白金と酸化タングステンの担持量は、ＷＯ３換算でモル比率が１／１であった。
次に、当該白金−タングステン酸化物担持チタニア系複合酸化物８３．８６５ｇと、β型ゼオライト｛ＳＡＲ＝２４、ＢＥＴ比表面積＝７００ｍ２／ｇ、平均粒径（Ｄ５０）７．２μｍ｝３０ｇ、シリカゾル（シリカ換算で３ｇ）と水を加えて、ボールミルポット内で所定の粒度まで混合・粉砕することにより、スラリーを得た。
このスラリーを４００ｃｅｌｌ／ｉｎｃｈ２（６２０ｋ／ｍ３）、６ｍｉｌ（０．１５ｍｍ）のコーディエライト製ハニカムコア（２４ｍｍφ×６６ｍｍＬ、３０ｍＬ）にコーティングし、余分のスラリーをエアーガンで飛ばして乾燥した後、５００℃で１時間焼成することにより、実施例１の排気ガス浄化用触媒［Ｐｔ＝１．７６５ｇ／Ｌ、ＷＯ３（換算）＝２．１ｇ／Ｌ、ＷＯ３（換算）／Ｐｔ＝１／１（モル比）、チタニア系母材、触媒重量＝１１６．８６５ｇ／Ｌ］を得た。
前記のとおり、白金とタングステンの出発原料を均一溶液にした後、母材に担持させたので、タングステン酸化物粒子がＰｔの近傍に存在するといえる。タングステン酸化物の粒子径は、凝集粒子の状態で５ｎｍ以下であった（この数値は、ＳＴＥＭ及びＥＤＸの測定でのタングステン酸化物粒子の検出限界値以下である）。
その後、得られた酸化触媒を空気雰囲気下、６５０℃、２０時間電気炉内で焼成後、２５０℃又は３５０℃で２時間、２，０００ｐｐｍのＳＯ２を含むガスに２時間曝すことでＳ被毒処理を行った。そして、モデルガスによるＨＣおよびＣＯの各酸化活性を測定し、その結果を図１〜４に示した。Example 1
1.765 g of platinum hydroxide (IV) acid ethanolamine solution in terms of platinum (Pt) and 2.1 g of ammonium metatungstate in terms of tungsten trioxide (WO 3 ) were weighed and dissolved uniformly in 20 mL of pure water. An aqueous solution containing both platinum and ammonium metatungstate was prepared, and anatase heat-resistant titania (TiO 2) having a BET specific surface area of 92 m 2 / g, an average pore diameter (median diameter) of 175 nm, and an average particle diameter (D50) of 2.5 μm. (2 : 90%, SiO 2 : 6%, Al 2 O 3 : 4%) 80 g). The hydrated product was calcined in air at 500 ° C. for 1 hour to obtain a 2.1 wt% platinum-2.5 wt% tungsten trioxide-supported titania-based composite oxide. The molar amount of platinum and tungsten oxide supported was 1/1 in terms of WO 3 .
Next, 83.865 g of the platinum-tungsten oxide-supported titania composite oxide, β-type zeolite {SAR = 24, BET specific surface area = 700 m 2 / g, average particle size (D50) 7.2 μm} 30 g, silica sol (3 g in terms of silica) and water were added and mixed and pulverized to a predetermined particle size in a ball mill pot to obtain a slurry.
This slurry was coated on 400 cell / inch 2 (620 k / m 3 ), 6 mil (0.15 mm) cordierite honeycomb core (24 mmφ × 66 mmL, 30 mL), and the excess slurry was dried with an air gun. By firing at 500 ° C. for 1 hour, the exhaust gas purifying catalyst of Example 1 [Pt = 1.765 g / L, WO 3 (converted) = 2.1 g / L, WO 3 (converted) / Pt = 1 / 1 (molar ratio), titania-based matrix, catalyst weight = 116.865 g / L].
As described above, since the starting materials of platinum and tungsten are made into a uniform solution and then supported on the base material, it can be said that the tungsten oxide particles are present in the vicinity of Pt. The particle diameter of the tungsten oxide was 5 nm or less in the state of aggregated particles (this value is below the detection limit value of the tungsten oxide particles in the STEM and EDX measurements).
Thereafter, the obtained oxidation catalyst was calcined in an electric furnace at 650 ° C. for 20 hours in an air atmosphere, and then exposed to a gas containing 2,000 ppm of SO 2 for 2 hours at 250 ° C. or 350 ° C. for 2 hours. Poison treatment was performed. And each oxidation activity of HC and CO by model gas was measured, and the result was shown in FIGS.
（実施例２）
メタタングステン酸アンモニウムの代わりに、リンタングステン酸を三酸化タングステン（ＷＯ３）換算で２．１ｇを用いた他は実施例１と同様にして、実施例２の排気ガス浄化用触媒［Ｐｔ＝１．７６５ｇ／Ｌ、ＷＯ３（換算）＝２．１ｇ／Ｌ、ＷＯ３（換算）／Ｐｔ＝１／１（モル比率）、チタニア系母材、触媒重量＝１１６．８６５ｇ／Ｌ］を得た。タングステン酸化物の粒子径は、凝集粒子の状態で５ｎｍ以下であった。
前記のとおり、白金とタングステンの出発原料を均一溶液にした後、母材に担持させたので、タングステン酸化物粒子がＰｔの近傍に存在するといえる。タングステン酸化物の粒子径は、凝集粒子の状態で５ｎｍ以下であった（この数値は、ＳＴＥＭ及びＥＤＸの測定でのタングステン酸化物粒子の検出限界値以下である）。
その後、得られた酸化触媒を実施例１に記載の条件でＳ被毒処理を行い、引き続き、モデルガスによるＨＣおよびＣＯの各酸化活性を測定し、その結果を図１〜４に示した。(Example 2)
Exhaust gas purifying catalyst of Example 2 [Pt = 1] in the same manner as in Example 1 except that 2.1 g of phosphotungstic acid in terms of tungsten trioxide (WO 3 ) was used instead of ammonium metatungstate. .765 g / L, WO 3 (converted) = 2.1 g / L, WO 3 (converted) / Pt = 1/1 (molar ratio), titania-based matrix, catalyst weight = 116.865 g / L]. . The particle diameter of the tungsten oxide was 5 nm or less in the state of aggregated particles.
As described above, since the starting materials of platinum and tungsten are made into a uniform solution and then supported on the base material, it can be said that the tungsten oxide particles are present in the vicinity of Pt. The particle diameter of the tungsten oxide was 5 nm or less in the state of aggregated particles (this value is below the detection limit value of the tungsten oxide particles in the STEM and EDX measurements).
Thereafter, the obtained oxidation catalyst was subjected to S poisoning treatment under the conditions described in Example 1, and subsequently, the HC and CO oxidation activities by the model gas were measured. The results are shown in FIGS.
（比較例１）
メタタングステン酸アンモニウムを加えなかった他は実施例１の触媒調製法と同様にして、比較例１の排気ガス浄化用触媒［Ｐｔ＝１．７６５ｇ／Ｌ、チタニア系母材、触媒重量＝１１４．７６５ｇ／Ｌ］を得た。
その後、得られた酸化触媒を実施例１に記載の条件でＳ被毒処理を行い、引き続き、モデルガスによるＨＣおよびＣＯの各酸化活性を測定し、その結果を図１〜４に示した。(Comparative Example 1)
Except for not adding ammonium metatungstate, the exhaust gas purifying catalyst of Comparative Example 1 [Pt = 1.765 g / L, titania-based base material, catalyst weight = 114. 765 g / L].
Thereafter, the obtained oxidation catalyst was subjected to S poisoning treatment under the conditions described in Example 1, and subsequently, the HC and CO oxidation activities by the model gas were measured. The results are shown in FIGS.
（比較例２）
ＢＥＴ比表面積９２ｍ２／ｇ、平均細孔径１７５ｎｍ、平均粒径（Ｄ５０）２．５μｍのアナタース型耐熱チタニア（ＴｉＯ２：９０％、ＳｉＯ２：６％、Ａｌ２Ｏ３：４％）８０ｇと平均粒径（Ｄ５０）３．５μｍの無水タングステン酸（ＷＯ３）２．１ｇを撹拌機でよく混合した。次に、白金（Ｐｔ）換算で１．７６ｇの水酸化白金(ＩＶ)酸のエタノールアミン溶液を秤量後、純水１０ｍＬに溶解して白金（ＩＶ）酸のエタノールアミン水溶液を調製し、その混合物に含浸担持したこの含水物を空気中５００℃、１時間の焼成を行うことで、２．１重量％白金−２．５重量％三酸化タングステン担持チタニア系複合酸化物を得た。ＷＯ３／Ｐｔのモル比は１／１であった。
これ以外は実施例１の触媒調製法と同様にして、比較例２の排気ガス浄化用触媒［Ｐｔ＝１．７６５ｇ／Ｌ、ＷＯ３＝２．１ｇ／Ｌ、ＷＯ３／Ｐｔ＝１／１（モル比）、触媒重量＝１１６．８６５ｇ／Ｌ］を得た。三酸化タングステンの粒子径は、粉砕後の微粒子の状態で１．１μｍであった。三酸化タングステンの粒子径が、白金（Ｐｔ）粒子の粒径５〜１０ｎｍに対して１００倍以上も大きいので、ほとんどのＰｔ粒子は三酸化タングステン粒子の近傍に存在しないことになる。
その後、得られた酸化触媒を実施例１に記載の条件でＳ被毒処理を行い、引き続き、モデルガスによるＨＣおよびＣＯの各酸化活性を測定し、その結果を図１〜４に示した。(Comparative Example 2)
Anatase type heat resistant titania (TiO 2 : 90%, SiO 2 : 6%, Al 2 O 3 : 4%) having a BET specific surface area of 92 m 2 / g, an average pore diameter of 175 nm, and an average particle diameter (D50) of 2.5 μm 2.1 g of tungstic anhydride (WO 3 ) having an average particle diameter (D50) of 3.5 μm was mixed well with a stirrer. Next, 1.76 g of platinum (IV) acid ethanolamine solution in terms of platinum (Pt) was weighed and then dissolved in 10 mL of pure water to prepare an ethanolamine aqueous solution of platinum (IV) acid. The hydrated product impregnated and supported was calcined at 500 ° C. for 1 hour in air to obtain a 2.1 wt% platinum-2.5 wt% tungsten trioxide supported titania composite oxide. The molar ratio of WO 3 / Pt was 1/1.
Otherwise in the same manner as the catalyst preparation of Example 1, a catalyst for purifying exhaust gases of Comparative Example 2 [Pt = 1.765g / L, WO 3 = 2.1g / L, WO 3 / Pt = 1/1 (Molar ratio), catalyst weight = 116.865 g / L]. The particle diameter of tungsten trioxide was 1.1 μm in the state of fine particles after pulverization. Since the particle diameter of tungsten trioxide is more than 100 times larger than the particle diameter of platinum (Pt) particles of 5 to 10 nm, most Pt particles are not present in the vicinity of the tungsten trioxide particles.
Thereafter, the obtained oxidation catalyst was subjected to S poisoning treatment under the conditions described in Example 1, and subsequently, the HC and CO oxidation activities by the model gas were measured. The results are shown in FIGS.
（実施例３）
アナタース型チタニア（ＴｉＯ２：９０％、ＳｉＯ２：６％、Ａｌ２Ｏ３：４％）の代わりに、ＢＥＴ比表面積１５０ｍ２／ｇ、平均細孔径１５ｎｍ、平均粒径（Ｄ５０）３０μｍのγ−アルミナを同量用いた他は実施例１と同様にして、実施例３の排気ガス浄化用触媒［Ｐｔ＝１．７６ｇ／Ｌ、ＷＯ３（換算）＝２．１ｇ／Ｌ、ＷＯ３（換算）／Ｐｔ＝１／１（モル比）、アルミナ系母材、触媒重量＝１１６．８６５ｇ／Ｌ］を得た。
タングステン酸化物の粒子径は、凝集粒子の状態で５ｎｍ以下であった。前記のとおり、白金とタングステンの出発原料を均一溶液にした後、母材に担持させたので、タングステン酸化物粒子がＰｔの近傍に存在するといえる。タングステン酸化物の粒子径は、凝集粒子の状態で５ｎｍ以下であった（この数値は、ＳＴＥＭ及びＥＤＸの測定でのタングステン酸化物粒子の検出限界値以下である）。
その後、得られた酸化触媒を実施例１に記載の条件でＳ被毒処理を行い、引き続き、モデルガスによるＨＣおよびＣＯの各酸化活性を測定し、その結果を図１〜４に示した。なお、この実施例３は、参考例である。
(Example 3)
Instead of anatase type titania (TiO 2 : 90%, SiO 2 : 6%, Al 2 O 3 : 4%), a BET specific surface area of 150 m 2 / g, an average pore diameter of 15 nm, and an average particle diameter (D50) of 30 μm -Exhaust gas purifying catalyst of Example 3 [Pt = 1.76 g / L, WO 3 (converted) = 2.1 g / L, WO 3 ( Conversion) / Pt = 1/1 (molar ratio), alumina base material, catalyst weight = 116.865 g / L].
The particle diameter of the tungsten oxide was 5 nm or less in the state of aggregated particles. As described above, since the starting materials of platinum and tungsten are made into a uniform solution and then supported on the base material, it can be said that the tungsten oxide particles are present in the vicinity of Pt. The particle diameter of the tungsten oxide was 5 nm or less in the state of aggregated particles (this value is below the detection limit value of the tungsten oxide particles in the STEM and EDX measurements).
Thereafter, the obtained oxidation catalyst was subjected to S poisoning treatment under the conditions described in Example 1, and subsequently, the HC and CO oxidation activities by the model gas were measured. The results are shown in FIGS. This Example 3 is a reference example.
（比較例３）
メタタングステン酸アンモニウムを加えなかった他は実施例３（参考例）の触媒調製法と同様にして、比較例３の排気ガス浄化用触媒［Ｐｔ＝１．７６５ｇ／Ｌ、アルミナ系母材、触媒重量＝１１４．７６５ｇ／Ｌ］を得た。
その後、得られた酸化触媒を実施例１に記載の条件でＳ被毒処理を行い、引き続き、モデルガスによるＨＣおよびＣＯの各酸化活性を測定し、その結果を図１〜４に示した。
(Comparative Example 3)
Except that ammonium metatungstate was not added, the exhaust gas purifying catalyst of Comparative Example 3 [Pt = 1.765 g / L, alumina base material, catalyst in the same manner as the catalyst preparation method of Example 3 (Reference Example) Weight = 114.765 g / L].
Thereafter, the obtained oxidation catalyst was subjected to S poisoning treatment under the conditions described in Example 1, and subsequently, the HC and CO oxidation activities by the model gas were measured. The results are shown in FIGS.
「評価」
図１〜４に示した結果から、次のことが分かる。すなわち、メタタングステン酸アンモニウム、リンタングステン酸といった水溶性のタングステンを原料とし、白金とタングステン酸化物の母材としてチタニア系複合酸化物である耐熱チタニアを使用して調製された実施例１及び２の白金系酸化触媒は、水溶性のタングステンを添加しなかった比較例１に比べ、Ｓ被毒処理後のＨＣ酸化活性が向上し、Ｓ被毒処理温度が２５０℃、３５０℃の両方の領域とも、ＨＣ酸化の着火性能向上が顕著である。一方、不溶性のタングステンを原料として調製された比較例２の触媒では、三酸化タングステン（ＷＯ３）の粒子径は１．１μｍであり、タングステン無添加の比較例１に比べ、Ｓ被毒処理温度が２５０℃、３５０℃の両方の領域において、いずれもＨＣ酸化の着火性能が悪化した。これらの結果は、本発明によれば、水溶性のタングステンを原料とすることで白金の近傍に凝集粒子径が３００ｎｍ以下のタングステン酸化物の微粒子が形成されることで白金のＳ被毒が抑制され、それによりＨＣ酸化の着火性能が向上することを示唆している。
同様の現象は白金とタングステン酸化物の母材を耐熱チタニアからγ−アルミナに置き換えても認められ、実施例３（参考例）と比較例３の比較から、白金の近傍に凝集粒子径が３００ｎｍ以下のタングステン酸化物の微粒子が形成されることで白金のＳ被毒が抑制され、それによりＳ被毒温度によらず、ＨＣ酸化の着火性能が向上している。
"Evaluation"
The following can be understood from the results shown in FIGS. That is, in Examples 1 and 2 prepared using water-soluble tungsten such as ammonium metatungstate and phosphotungstic acid as a raw material, and heat-resistant titania, which is a titania-based composite oxide, as a base material of platinum and tungsten oxide. Compared with Comparative Example 1 in which water-soluble tungsten was not added, the platinum-based oxidation catalyst improved the HC oxidation activity after the S poisoning treatment, and the S poisoning treatment temperatures were both 250 ° C. and 350 ° C. The ignition performance improvement of HC oxidation is remarkable. On the other hand, in the catalyst of Comparative Example 2 prepared using insoluble tungsten as a raw material, the particle size of tungsten trioxide (WO 3 ) is 1.1 μm, and compared with Comparative Example 1 without addition of tungsten, the S poisoning treatment temperature. However, in both the 250 ° C. and 350 ° C. regions, the ignition performance of HC oxidation deteriorated. These results show that, according to the present invention, by using water-soluble tungsten as a raw material, tungsten oxide fine particles having an aggregate particle diameter of 300 nm or less are formed in the vicinity of platinum, thereby suppressing S poisoning of platinum. This suggests that the ignition performance of HC oxidation is improved.
The same phenomenon is observed even when the base material of platinum and tungsten oxide is replaced with γ-alumina from heat-resistant titania. From the comparison between Example 3 (Reference Example) and Comparative Example 3, the aggregated particle diameter is 300 nm in the vicinity of platinum. Formation of the following tungsten oxide fine particles suppresses S-poisoning of platinum, thereby improving the ignition performance of HC oxidation regardless of the S-poisoning temperature.
これに対し、ＣＯ酸化の着火性能においては、水溶性のタングステンを原料として使用した実施例１及び２はタングステン無添加の比較例１に比べ、着火性能が向上する場合もある一方で、逆に性能が悪化する場合も見られ、ＨＣ酸化の場合と異なり、微小なタングステン酸化物による性能向上は明確には得られていない。同様な現象は不溶性のタングステンを原料とする比較例２でも見られ、タングステン無添加の比較例１に比べ、Ｓ被毒処理の温度により着火性能が向上する場合だけでなく、逆に悪化する場合が見られ、効果が安定しなかった。
一方、白金とタングステン酸化物を担持する母材を耐熱チタニアからγ−アルミナに置き換えると、実施例３（参考例）と比較例３の比較により、Ｓ被毒後のＣＯの着火性能はＨＣの時に比べ促進効果自体は小さいものの、微小なタングステン酸化物による性能向上が明らかに確認できた。
すなわち、本発明の様に、白金の近傍に凝集粒子径が３００ｎｍ以下のタングステン酸化物が存在することにより、それらを担持する母材として、耐硫黄性の高いチタニア系金属酸化物だけでなく、耐硫黄性に乏しいアルミナ系金属酸化物を用いた場合でも優れた耐硫黄性が発揮されることが明らかである。
以上により、本発明では、白金粒子を耐硫黄性に乏しいアルミナ系金属酸化物に担持しても触媒性能上の効果はあるが、耐硫黄性の高いチタニア系金属酸化物に担持して用いると、さらに顕著な作用効果が得られることが分かる。
On the other hand, in terms of the ignition performance of CO oxidation, Examples 1 and 2 using water-soluble tungsten as a raw material may improve the ignition performance compared to Comparative Example 1 without addition of tungsten. In some cases, the performance deteriorates, and unlike the case of HC oxidation, the performance improvement by the minute tungsten oxide is not clearly obtained. The same phenomenon can be seen in Comparative Example 2 using insoluble tungsten as a raw material. Compared with Comparative Example 1 without addition of tungsten, not only the ignition performance is improved by the temperature of the S poisoning process, but also the deterioration is caused. Was seen and the effect was not stable.
On the other hand, when the base material supporting platinum and tungsten oxide is replaced with γ-alumina from heat-resistant titania, the comparison of Example 3 (Reference Example) and Comparative Example 3 shows that the ignition performance of CO after S poisoning is HC. Although the accelerating effect itself is small compared to the case, the performance improvement by the minute tungsten oxide was clearly confirmed.
That is, as in the present invention, the presence of tungsten oxide having an aggregate particle diameter of 300 nm or less in the vicinity of platinum, as a base material for supporting them, not only titania-based metal oxides with high sulfur resistance, It is clear that excellent sulfur resistance is exhibited even when an alumina-based metal oxide having poor sulfur resistance is used.
As described above, in the present invention, even when platinum particles are supported on an alumina-based metal oxide having poor sulfur resistance, there is an effect on the catalyst performance, but when supported on a titania-based metal oxide having high sulfur resistance, It can be seen that a further remarkable effect can be obtained.
本発明の白金系酸化触媒は、希薄燃焼により発生する炭化水素及び一酸化炭素の酸化除去技術、例えばディーゼル自動車用途をはじめ、ガソリン自動車、船舶等の移動体用途や、発電機等の定置用途などに使用可能である。 The platinum-based oxidation catalyst of the present invention is a technique for oxidizing and removing hydrocarbons and carbon monoxide generated by lean combustion, for example, diesel vehicles, mobile vehicles such as automobiles and ships, stationary applications such as generators, etc. Can be used.
Claims (10)
一体構造型担体の表面に、少なくとも白金（Ｐｔ）及びタングステン酸化物が担持された金属酸化物（Ａ）と、ゼオライト（Ｂ）とを含む触媒組成物が被覆され、前記金属酸化物（Ａ）は、シリカ、アルミナ、酸化ネオジム、酸化プラセオジム、または酸化バリウムから選ばれる１種以上を含む耐熱チタニアであって、該耐熱チタニアのＢＥＴ比表面積値が３０〜３００ｍ ２ ／ｇ、かつ細孔径が３０〜３００ｎｍであり、
しかも前記白金（Ｐｔ）粒子の近傍に、凝集粒子径が３００ｎｍ以下のタングステン酸化物粒子が存在することを特徴とする白金系酸化触媒。 Hydrocarbons from hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx), soot and other particulate components emitted from lean-burn diesel engines , and exhaust gases containing sulfur oxides In platinum-based oxidation catalyst for oxidation purification,
The surface of the monolithic structure-type support is coated with a catalyst composition containing at least platinum (Pt) and a tungsten oxide-supported metal oxide (A) and zeolite (B), and the metal oxide (A). Is a heat-resistant titania containing one or more selected from silica, alumina, neodymium oxide, praseodymium oxide, or barium oxide, and the heat-resistant titania has a BET specific surface area value of 30 to 300 m 2 / g and a pore diameter of 30. ~ 300nm,
In addition , a platinum-based oxidation catalyst characterized in that tungsten oxide particles having an aggregate particle diameter of 300 nm or less are present in the vicinity of the platinum (Pt) particles.
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| CN110721706B (en) * | 2019-10-30 | 2023-03-28 | 中国石油化工股份有限公司 | Oxidation catalyst for purifying CO and preparation method and application thereof |
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