JPH0771634B2 - Exhaust gas purifying catalyst and its manufacturing method - Google Patents
Exhaust gas purifying catalyst and its manufacturing methodInfo
- Publication number
- JPH0771634B2 JPH0771634B2 JP60266145A JP26614585A JPH0771634B2 JP H0771634 B2 JPH0771634 B2 JP H0771634B2 JP 60266145 A JP60266145 A JP 60266145A JP 26614585 A JP26614585 A JP 26614585A JP H0771634 B2 JPH0771634 B2 JP H0771634B2
- Authority
- JP
- Japan
- Prior art keywords
- refractory
- inorganic powder
- range
- silica
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000843 powder Substances 0.000 claims description 50
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 39
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 33
- 239000012784 inorganic fiber Substances 0.000 claims description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- 239000000919 ceramic Substances 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000006262 metallic foam Substances 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229920000620 organic polymer Polymers 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 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 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 239000002657 fibrous material Substances 0.000 claims 1
- 239000010419 fine particle Substances 0.000 description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 28
- 229910052799 carbon Inorganic materials 0.000 description 28
- 239000000835 fiber Substances 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005192 partition Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
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- 238000009825 accumulation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 244000215068 Acacia senegal Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- SEOYGHAMTIOETD-UHFFFAOYSA-N O[N+]([O-])=O.[O-][N+](=O)[Pt][N+]([O-])=O Chemical compound O[N+]([O-])=O.[O-][N+](=O)[Pt][N+]([O-])=O SEOYGHAMTIOETD-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts 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
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- 229920001577 copolymer Polymers 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].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.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
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- OHZZTXYKLXZFSZ-UHFFFAOYSA-I manganese(3+) 5,10,15-tris(1-methylpyridin-1-ium-4-yl)-20-(1-methylpyridin-4-ylidene)porphyrin-22-ide pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mn+3].C1=CN(C)C=CC1=C1C(C=C2)=NC2=C(C=2C=C[N+](C)=CC=2)C([N-]2)=CC=C2C(C=2C=C[N+](C)=CC=2)=C(C=C2)N=C2C(C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 OHZZTXYKLXZFSZ-UHFFFAOYSA-I 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- 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
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
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- 230000036962 time dependent Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- -1 wire mesh Substances 0.000 description 1
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、デイーゼルエンジン排ガスあるいは可燃性炭
素微粒子を含有する産業排ガスの浄化用触媒およびその
製法に関するものである。近年、デイーゼルエンジン排
ガス中の炭素系微粒子状物質（主として固体状炭素微粒
子、硫酸塩など硫黄系微粒子、そして液状ないし、固体
状の高分子量炭化水素微粒子などよりなる）が環境衛生
上問題化する傾向にある。これら微粒子はその粒子径が
ほとんど１ミクロン以下であり大気中に浮遊しやすく吸
収により人体内に取り込まれやすいためである。したが
つてこれら微粒子のデイーゼルエンジンなどからの排出
規制を厳しくしていく方向で検討が進められている。The present invention relates to a catalyst for purifying diesel engine exhaust gas or industrial exhaust gas containing combustible carbon fine particles and a method for producing the same. In recent years, carbonaceous particulate matter (mainly consisting of solid carbon particulates, sulfur particulates such as sulfates, and liquid or solid high molecular weight hydrocarbon particulates) in diesel engine exhaust gas has become a problem for environmental hygiene. It is in. This is because these fine particles have a particle diameter of almost 1 micron or less and are easily suspended in the atmosphere and easily absorbed into the human body by absorption. Therefore, studies are underway in the direction of tightening regulations on the emission of these fine particles from diesel engines and the like.
ところで、これら微粒子の除去方法としては、大別して
以下の２つの方法がある。１つは耐熱性ガスフイルター
（セラミツクフオーム、ワイヤーメツシュ、金属発泡
体、ウオールフロータイプのセラミツクハニカムなど）
を用いて排気ガスを過して微粒子を捕捉し、圧損が上
昇すればバーナーなどで蓄積した微粒子を燃焼せしめて
フイルターを再生する方法と、他なこの耐熱性ガスフイ
ルター構造を持つ担体に触媒物質を担持させ過操作と
ともに、燃焼処理も行なわせて上記燃焼再生の頻度を少
なくするとか、再生の必要のないほどに触媒の燃焼活性
を高める方法である。By the way, methods for removing these fine particles are roughly classified into the following two methods. One is a heat resistant gas filter (ceramic foam, wire mesh, metal foam, wall flow type ceramic honeycomb, etc.)
The exhaust gas is used to capture particulates, and if the pressure loss increases, the particulates accumulated by a burner are burned to regenerate the filter, and another carrier with this heat-resistant gas filter structure is used as a catalyst material. Is carried out and the combustion process is carried out together with the over-operation to reduce the frequency of the combustion regeneration, or the combustion activity of the catalyst is increased to the extent that regeneration is unnecessary.
前者の場合、微粒子の除去効果を高めれば高めるほど圧
損上昇が早く再生頻度も多くなり煩瑣であり、経済的に
も著しく不利となるであろう。それにくらべ後者の方法
は、デイーゼルエンジン排気ガスの排出条件（ガス組成
および温度）において、触媒活性を有効に維持しうる触
媒物質が採用されるならばはるかに優れた方法と考えら
れる。In the case of the former, the higher the effect of removing fine particles, the faster the pressure loss rises, the more frequently the regeneration is performed, which is troublesome, and the economy will be significantly disadvantageous. On the other hand, the latter method is considered to be far superior if a catalytic substance capable of effectively maintaining the catalytic activity is adopted under the emission conditions (gas composition and temperature) of the diesel engine exhaust gas.
しかし、デイーゼルエンジンの排気ガス温度はガソリン
エンジンの場合と比較して格段に低く、通常のエンジン
の走行条件下でえられる温度内で蓄積した微粒子を良好
に着火燃焼させる性能を有する上記排ガス浄化触媒が要
求されるにもかかわらず、今迄この条件に適合する触媒
は提案されていないのが現状である。However, the exhaust gas temperature of the diesel engine is much lower than that of the gasoline engine, and the exhaust gas purifying catalyst having the ability to satisfactorily ignite and burn the particulates accumulated within the temperature obtained under normal engine running conditions. In spite of the requirement, the present situation is that no catalyst which meets this condition has been proposed so far.
従来より、炭素系微粒子の捕捉効果を高める目的で以下
の如き種々の提案がなされている。Conventionally, the following various proposals have been made for the purpose of enhancing the capturing effect of carbon-based fine particles.
三次元網状構造の多孔性セラミツク体と耐熱性を有する
繊維との混合物より成り、その繊維が前記多孔性セラミ
ツク体の骨格ならびにその空隙に絡んでいることを特徴
としている構造体（特開昭57−84747号公報）、 種々の三次元構造体の骨格表面に、不規則な配列状態の
突起を多数設けたことを特徴とする排気ガス浄化用構造
物（特開昭57−99314号公報、特開昭57−99315号公報、
特開昭57−162650号公報、特開昭58−14921号公報な
ど）、 貫通孔を有する構造体の貫通孔内壁に針状比５〜1000で
かつ直径とBET比表面積の積が、２〔μｍ・m2/g〕以上
である耐熱性無機質繊維を接着せしめてなる構造体（特
開昭59−142820号公報）、 セラミツクフイルタにおいて、セラミツクフイルタの担
体表面上に繊維径0.1〜１μｍおよび繊維長10〜200μｍ
の繊維状無機物質を0.5〜70重量％含むセラミツク被覆
層を形成させることを特徴とする微粒子捕集用セラミツ
クフイルタ（特開昭60−106514号公報）。A structure comprising a mixture of a porous ceramic body having a three-dimensional network structure and a fiber having heat resistance, wherein the fiber is entangled in the skeleton of the porous ceramic body and its voids (JP-A-57). -84747), an exhaust gas purifying structure characterized in that a large number of protrusions in an irregular array are provided on the skeleton surface of various three-dimensional structures (Japanese Patent Laid-Open No. 57-99314). JP-A-57-99315,
JP-A-57-162650, JP-A-58-14921, etc.), a structure having a through hole has an acicular ratio of 5 to 1000 on the inner wall of the through hole, and the product of the diameter and the BET specific surface area is 2 [ μm · m 2 / g] or more, a structure formed by adhering heat-resistant inorganic fibers (Japanese Patent Application Laid-Open No. 59-142820), in a ceramic filter, a fiber diameter of 0.1 to 1 μm and a fiber on the carrier surface of the ceramic filter. Length 10-200 μm
A ceramic filter for collecting fine particles, which comprises forming a ceramic coating layer containing 0.5 to 70% by weight of the fibrous inorganic substance (JP-A-60-106514).
また白金族金属を炭素系微粒子燃焼用触媒として使用し
ている例としては、ロジウム7.5％／白金合金とか、Pt/
Pd＝50/50の混合物とか、酸化タンタルまたは酸化セリ
ウム上に担持したパラジウムあるいはパラジウムと75重
量％以下の白金からなる合金等が、SOF（soluble organ
ic fraction）に対して効果があることが提案されてい
る（特開昭55−24597号公報）。Examples of using platinum group metal as a catalyst for burning carbon-based fine particles include rhodium 7.5% / platinum alloy, Pt /
A mixture of Pd = 50/50, palladium supported on tantalum oxide or cerium oxide, or an alloy composed of palladium and 75% by weight or less of platinum, etc.
ic fraction) has been proposed to be effective (JP-A-55-24597).
その他、貴金属、クロムおよびこれらのものの触媒的に
活性な化合物からなる群から選ばれた少なくとも１種の
担持された材料および第１遷移系列の元素、銀、ハフニ
ウムおよびこれらのものの触媒的に活性な化合物から成
る群から選ばれた少くとも１種のバルク材料の、触媒的
に有効な量の混合物から成り、担持された該材料が多孔
性耐火無機酸化物に担持されていることから成る組成物
（特開昭57−24640号公報）、 バナジウムまたはバナジウム化合物にアンチモン、アル
カリ金属、モリブデン、白金、ランタンなどを組合わせ
た炭素系微粒子浄化用触媒（特開昭58−174236号公
報）、 銅または銅化合物にモリブデンまたはバナジウムを組合
わせ、さらに白金、ロジウムなども組合わせてなる炭素
系微粒子浄化用触媒（特開昭59−82944号公報）、 白金を担持して700〜1000℃で熱処理してサルフエート
の生成能を抑制した炭素系微粒子浄化用触媒（特開昭59
−36543号公報）、 パラジウムとロジウム、ルテニウム、ニツケル、亜鉛お
よびチタニウムの少なくとも１種とを組合わせてなる炭
素系微粒子浄化用触媒（特開昭59−80330号公報）等の
提案がなされている。In addition, at least one supported material selected from the group consisting of noble metals, chromium and catalytically active compounds of these, and elements of the first transition series, silver, hafnium and catalytically active compounds of these. A composition comprising a catalytically effective amount of a mixture of at least one bulk material selected from the group consisting of compounds, the supported material being supported on a porous refractory inorganic oxide. (JP-A-57-24640), a catalyst for purifying carbon-based fine particles in which vanadium or a vanadium compound is combined with antimony, alkali metal, molybdenum, platinum, lanthanum (JP-A-58-174236), copper or A catalyst for purifying carbon-based fine particles, which is formed by combining molybdenum or vanadium with a copper compound, and also by combining platinum, rhodium, etc. (JP-A-59-82944). Platinum supported to 700 to 1000 ° C. in heat treated by suppressing the generation capacity of Sarufueto carbon-based particles purifying catalyst (JP 59
-36543), a catalyst for purifying carbon-based fine particles, which is a combination of palladium and at least one of rhodium, ruthenium, nickel, zinc, and titanium (Japanese Patent Laid-Open No. 59-80330), and the like have been proposed. .
しかしながら、本発明者らは、白金族元素を炭素系微粒
子の燃焼用触媒として使用する場合、これらに開示され
ている触媒では、白金族元素の有する炭素系微粒子の低
温着火性を充分に引き出すことは困難であることを見い
出した。However, when the platinum group element is used as a catalyst for burning carbon-based fine particles, the inventors of the present invention can sufficiently bring out the low-temperature ignitability of the carbon-based fine particles of the platinum-group element with the catalysts disclosed therein. Found difficult.
すなわち、白金族元素の有する炭素系微粒子の低温着火
性を引き出すには、排ガスのガス接触面あるいは接触部
において、層状に蓄積する炭素系微粒子に対して、接触
効率を高めるように、接触担持層を突起状に担持せしめ
る必要があり、さらにその形状に機械的強度を与えるこ
とにより、かくして低温着火性能を有する実用的触媒を
提案しうることを見い出したものである。That is, in order to bring out the low-temperature ignitability of the carbon-based fine particles having the platinum group element, the contact-supporting layer is formed so as to increase the contact efficiency with respect to the carbon-based fine particles accumulated in layers on the gas contact surface or contact portion of the exhaust gas. It has been found that a practical catalyst having low-temperature ignitability can be proposed by supporting the particles in the form of protrusions and further imparting mechanical strength to the shape.
本発明者らは、ここに特にデイーゼルエンジンからの排
ガス中に含まれる炭素系微粒子を、より低温から燃焼さ
せうる触媒およびその調製法を提案する。The inventors of the present invention propose a catalyst capable of burning carbon-based fine particles contained in exhaust gas from a diesel engine from a lower temperature, and a method for preparing the same.
本発明にかかる触媒は以下の如き点で高い評価が与えら
れる。上述のようにデイーゼルエンジンからの排ガス温
度は、ガソリン車に比べて格段に低く市中走行時排ガス
温度は、マニホールド出口でも450℃に達しないことか
ら、300℃以下でも炭素系微粒子の燃焼性能が良好な触
媒が要求される。The catalyst according to the present invention is highly evaluated in the following points. As described above, the exhaust gas temperature from the diesel engine is much lower than that of a gasoline vehicle, and the exhaust gas temperature during city driving does not reach 450 ° C even at the manifold outlet. Good catalysts are required.
しかし従来提案されている白金族を含有する触媒は三次
元構造体のガス接触部に微細粒子で層状に触媒成分が担
持されているか、あるいは骨材の内部細孔内壁面に担持
されていて、捕捉された炭素系微粒子との接触効率が悪
く、白金族を含有する触媒活性物質から充分な燃焼性能
を引き出せていないのが現状である。However, conventionally proposed catalysts containing a platinum group, the catalyst component is supported in a layer in fine particles in the gas contact portion of the three-dimensional structure, or is supported on the inner pore inner wall surface of the aggregate, The present situation is that the efficiency of contact with the captured carbon-based fine particles is poor, and sufficient combustion performance cannot be derived from the catalytically active substance containing the platinum group.
従つて、本発明者らは、炭素系微粒子がガス接触部壁面
あるいはガス接触部に層状に蓄積することに注目し、該
蓄積層に触媒活性成分の粗粒状物を突起状に担持させ、
触媒と炭素系微粒子の接触効率を上げることにより著し
く、触媒性能を高めることを見い出し本発明の完成した
ものである。Therefore, the present inventors have noticed that the carbon-based fine particles are accumulated in the gas contact portion wall surface or the gas contact portion in a layered manner, and the coarse particles of the catalytically active component are supported in a protrusion shape in the accumulation layer,
The inventors have found that the catalytic performance is remarkably enhanced by increasing the contact efficiency between the catalyst and the carbon-based fine particles, and the present invention has been completed.
本発明は以下の如く特定される。 The present invention is specified as follows.
（１）耐火性三次元構造体のガス接触面あるいはガス接
触部に、粒子径が５〜300μｍである耐火性無機質粉末
と該無機質粉末の平均粒子径の1/300〜1/5の範囲の平均
直径および1/10〜20の範囲の平均長さを有する耐火性無
機質繊維とを、該無機質粉末と該無機質繊維との重量比
が1:0.7〜1:0.07の範囲で、該無機質粉末と該無機質繊
維とを突起状に形成し、該突起状に形成されてなる耐火
性無機質粉末に、白金、ロジウム、パラジウムよりなる
白金族元素の少くとも１種を含有してなる触媒活性物質
を担持せしめてなることを特徴とする排ガス浄化用触
媒。(1) On the gas contact surface or the gas contact portion of the refractory three-dimensional structure, a refractory inorganic powder having a particle diameter of 5 to 300 μm and a range of 1/300 to 1/5 of the average particle diameter of the inorganic powder A refractory inorganic fiber having an average diameter and an average length in the range of 1/10 to 20, the weight ratio of the inorganic powder and the inorganic fiber in the range of 1: 0.7 to 1: 0.07, the inorganic powder and The inorganic fiber is formed in a protrusion shape, and the refractory inorganic powder formed in the protrusion shape carries a catalytically active substance containing at least one platinum group element consisting of platinum, rhodium and palladium. An exhaust gas-purifying catalyst characterized by being used at most.
（２）耐火性三次元構造体が、セラミックフォーム、セ
ラミックハニカム、ウォールフロータイプのハニカムモ
ノリス、メタルハニカムまたは金属発泡体であることを
特徴とする上記（１）記載の触媒。(2) The catalyst according to (1) above, wherein the refractory three-dimensional structure is a ceramic foam, a ceramic honeycomb, a wall flow type honeycomb monolith, a metal honeycomb, or a metal foam.
（３）耐火性無機質粉末が、活性アルミナ、シリカ、チ
タニア、ジルコニア、シリカ−アルミナ、アルミナ−ジ
ルコニア、アルミナ−チタニア、シリカ−チタニア、シ
リカ−ジルコニア、チタニア−ジルコニアおよびゼオラ
イトよりなる群から選ばれた少くとも１種であり、かつ
その粒子径が５〜300μｍの範囲に実質的に分布してな
ることを特徴とする上記（１）記載の触媒。(3) The refractory inorganic powder is selected from the group consisting of activated alumina, silica, titania, zirconia, silica-alumina, alumina-zirconia, alumina-titania, silica-titania, silica-zirconia, titania-zirconia and zeolite. The catalyst according to (1) above, wherein the catalyst is at least one kind and has a particle size substantially distributed in a range of 5 to 300 μm.
（４）耐火性三次元構造体のガス接触面あるいはガス接
触部に、粒子径が５〜300μｍである耐火性無機質粉末
と該無機質粉末の平均粒子径の1/300〜1/5の範囲の平均
直径および1/10〜20の範囲の平均長さを有する耐火性無
機質繊維とを、該無機質粉末と該無機質繊維との重量比
が1:0.7〜1:0.07の範囲で、該無機質粉末と該無機質繊
維とを突起状に形成し、該突起状に形成されてなる耐火
性無機質粉末に、白金、ロジウム、パラジウムよりなる
白金族元素の少くとも１種と、鉄、コバルト、ニッケ
ル、モリブデン、タングステン、ニオブ、リン、鉛、亜
鉛、錫、銅、マンガン、セリウム、ランタン、銀、バリ
ウム、マグネシウム、カルシウム、ストロンチウムより
なるアルカリ土類金属、カリウム、ナトリウム、セシウ
ム、ルビジウムよりなるアルカリ金属よりなる群から選
ばれた少くとも１種を含有してなる触媒活性物質を担持
せしめてなることを特徴とする排ガス浄化用触媒。(4) The refractory inorganic powder having a particle diameter of 5 to 300 μm and the range of 1/300 to 1/5 of the average particle diameter of the inorganic powder on the gas contact surface or the gas contact portion of the refractory three-dimensional structure. A refractory inorganic fiber having an average diameter and an average length in the range of 1/10 to 20, the weight ratio of the inorganic powder and the inorganic fiber in the range of 1: 0.7 to 1: 0.07, the inorganic powder and The inorganic fibers are formed in a protrusion shape, and the refractory inorganic powder formed in the protrusion shape includes at least one platinum group element consisting of platinum, rhodium and palladium, and iron, cobalt, nickel and molybdenum, Alkaline earth metal consisting of tungsten, niobium, phosphorus, lead, zinc, tin, copper, manganese, cerium, lanthanum, silver, barium, magnesium, calcium and strontium, alkali consisting of potassium, sodium, cesium and rubidium Exhaust gas purifying catalyst, characterized by comprising brought carrying a catalyst active substance comprising a least one member selected from the group consisting of the genus.
（５）耐火性三次元構造体が、セラミックフォーム、セ
ラミックハニカム、ウォールフロータイプのハニカムモ
ノリス、メタルハニカムまたは金属発泡体であることを
特徴とする上記（４）記載の触媒。(5) The catalyst according to (4) above, wherein the refractory three-dimensional structure is a ceramic foam, a ceramic honeycomb, a wall flow type honeycomb monolith, a metal honeycomb or a metal foam.
（６）耐火性無機質粉末が、活性アルミナ、シリカ、チ
タニア、ジルコニア、シリカ−アルミナ、アルミナ−ジ
ルコニア、アルミナ−チタニア、シリカ−チタニア、シ
リカ−ジルコニア、チタニア−ジルコニアおよびゼオラ
イトよりなる群から選ばれた少くとも１種であり、かつ
その粒子径が５〜300μｍの範囲に実質的に分布してな
ることを特徴とする上記（４）記載の触媒。(6) The refractory inorganic powder is selected from the group consisting of activated alumina, silica, titania, zirconia, silica-alumina, alumina-zirconia, alumina-titania, silica-titania, silica-zirconia, titania-zirconia and zeolite. The catalyst according to (4) above, which is at least one kind and has a particle diameter substantially distributed in a range of 5 to 300 μm.
（７）触媒活性物質を担持せしめた粒子径が５〜300μ
ｍである耐火性無機質粉末と、該耐火性無機質粉末の平
均粒子径の1/300〜1/5の範囲の平均直径および1/10〜20
の範囲の平均長さを有する耐火性無機質繊維状物質と
を、該無機質粉末と該無機質繊維との重量比が1:0.7〜
1:0.07の範囲で混合し、かつアルミナゾル、チタニアゾ
ル、ジルコニアゾル、シリカゾル、可溶性ベーマイト、
可溶性有機高分子化合物よりなる群から選ばれた少くと
も１種の分散剤とともに水性スラリー化し、えられたス
ラリーを用いて耐火性三次元構造体のガス接触面あるい
はガス接触部に、該無機質粉末と該無機質繊維とを突起
状に担持せしめることを特徴とする排ガス浄化用触媒の
製法。(7) Particle size supporting catalytically active substance is 5-300μ
m of the refractory inorganic powder, and an average diameter in the range of 1/300 to 1/5 and 1/10 to 20 of the average particle diameter of the refractory inorganic powder.
A refractory inorganic fibrous substance having an average length in the range of, the weight ratio of the inorganic powder and the inorganic fiber is 1: 0.7 ~
Mixing in the range of 1: 0.07, and alumina sol, titania sol, zirconia sol, silica sol, soluble boehmite,
The inorganic powder is made into an aqueous slurry together with at least one dispersant selected from the group consisting of soluble organic polymer compounds, and the obtained slurry is used on the gas contact surface or the gas contact portion of the refractory three-dimensional structure. A method for producing an exhaust gas-purifying catalyst, characterized in that and the inorganic fibers are supported in a protrusion shape.
（８）耐火性三次元構造体が、セラミックフォーム、セ
ラミックハニカム、ウォールフロータイプのハニカムモ
ノリス、メタルハニカムまたは金属発泡体であることを
特徴とする上記（７）記載の製法。(8) The method according to (7) above, wherein the fire-resistant three-dimensional structure is a ceramic foam, a ceramic honeycomb, a wall-flow type honeycomb monolith, a metal honeycomb, or a metal foam.
炭素系微粒子は三次元構造体のガス接触部に層状に蓄積
し、例えば、ウオールフロータイプのハニカム（ガス流
れ方向に、多数の流通管よりなり該流通管は交互に、入
口部が開口し、出口部で閉塞されている流通管と、入口
部が閉塞され出口部で開口されている流通管とから構成
され、その流通管壁がガスフイルター機構を有する多孔
性隔壁で構成されているセラミツクモノリスハニカム）
の隔壁には多数の細孔が存在し、この細孔を通してガス
が通過する際、炭素系微粒子は過されるが細孔の平均
径が炭素系微粒子の直径よりもかなり大きいにもかかわ
らず炭素系微粒子は、細孔入口側壁面にブリツジを形成
し、ガス入口側隔壁面に層状に累積する。仮に白金族元
素含有触媒がこの隔壁面あるいは隔壁細孔内骨材上に、
突起を形成することなく層状に担持されている場合は、
該炭素系微粒子の蓄積物に対する触媒活性成分の接触効
率は悪く好ましい触媒作用は見られない。The carbon-based fine particles are accumulated in a layer form in the gas contact portion of the three-dimensional structure, for example, a wall flow type honeycomb (in the gas flow direction, the plurality of flow pipes are alternately formed, the flow pipes are alternately opened, and the inlet portion is opened, A ceramic monolith composed of a flow pipe closed at the outlet and a flow pipe closed at the inlet and opened at the outlet, the flow pipe wall being formed of a porous partition wall having a gas filter mechanism. Honeycomb)
There are many pores in the partition walls, and when the gas passes through these pores, the carbon-based fine particles are passed through, but the average diameter of the pores is much larger than the diameter of the carbon-based fine particles. The fine particles form a bridging on the side wall surface of the pore inlet and accumulate in layers on the side wall surface of the gas inlet side. If the platinum group element-containing catalyst is present on the partition wall surface or on the aggregate in the partition wall pores,
When it is supported in layers without forming protrusions,
The contact efficiency of the catalytically active component with the accumulation of the carbon-based fine particles is poor and no preferable catalytic action is observed.
従つて、本発明においては、三次元構造体のガス接触部
に白金族元素含有の触媒組成物を突起状に担持せしめ接
触効率を高め炭素系微粒子の燃焼効率を著しく向上させ
たことを特徴としている。Therefore, in the present invention, the gas contact portion of the three-dimensional structure is characterized by supporting the platinum group element-containing catalyst composition in the form of protrusions to improve the contact efficiency and significantly improve the combustion efficiency of the carbon-based fine particles. There is.
三次元構造体としては、セラミツクフオーム、セラミツ
クハニカム、フオールフロータイプのハニカムモノリ
ス、メタルハニカム、金属発泡体等が好適に用いられ
る。As the three-dimensional structure, ceramic foam, ceramic honeycomb, for flow type honeycomb monolith, metal honeycomb, metal foam or the like is preferably used.
白金族元素などの触媒成分を担持する耐火性無機質粉体
としては、活性アルミナ、シリカ、チタニア、ジルコニ
ア、シリカ−アルミナ、アルミナ−ジルコニア、アルミ
ナ−チタニア、シリカ−チタニア、シリカ−ジルコニ
ア、チタニア−ジルコニア、ゼオライト等が好適であ
る。Examples of the refractory inorganic powder carrying a catalyst component such as a platinum group element include activated alumina, silica, titania, zirconia, silica-alumina, alumina-zirconia, alumina-titania, silica-titania, silica-zirconia, titania-zirconia. , Zeolite and the like are preferable.
無機質繊維としては、ガラス繊維、アルミナ繊維、シリ
カ繊維、窒化硅素（Si3N4）、シリコンカーバイド（Si
C）、チタン酸カリウム、ロツクウール、ジルコニア、
チタンカーバイド、鉄、ニツケル、タングステン、イン
酸カルシウム等の無機ファイバーあるいはウイスカーが
好適に用いられる。しかも、耐火性無機質粉体は粒子径
５〜300μｍに分布しているのが好ましく、また無機質
繊維は、耐火性無機質粉体の平均粒子径に対して1/300
〜1/5、好ましくは1/200〜1/7の直径でかつ1/10〜20、
好ましくは1/5〜15の繊維長さのものが好ましく、耐火
性無機質粉体の重量比に対して1:0.7〜1:0.07の比であ
る。Inorganic fibers include glass fibers, alumina fibers, silica fibers, silicon nitride (Si 3 N 4 ), silicon carbide (Si
C), potassium titanate, rock wool, zirconia,
Inorganic fibers such as titanium carbide, iron, nickel, tungsten, calcium innate or whiskers are preferably used. In addition, the refractory inorganic powder is preferably distributed in a particle size of 5 to 300 μm, and the inorganic fiber is 1/300 of the average particle size of the refractory inorganic powder.
~ 1/5, preferably 1 / 200-1 / 7 diameter and 1 / 10-20,
The fiber length of 1/5 to 15 is preferable, and the ratio is 1: 0.7 to 1: 0.07 with respect to the weight ratio of the refractory inorganic powder.
無機質繊維の線径および長さは、用いる耐火性無機質粉
体の平均粒子径と相関性が強く、線径は平均粒子径の1/
300〜1/5が好ましく、この範囲以外のものは、線径が細
すぎる場合は粒子に単にからまつてしまつたり、あるい
は太すぎる場合は突起状担持を阻害してしまつたりして
好ましくない。The wire diameter and length of the inorganic fiber have a strong correlation with the average particle diameter of the refractory inorganic powder used, and the wire diameter is 1 / of the average particle diameter.
300 to 1/5 is preferable, and those other than this range are preferable because if the wire diameter is too thin, the particles are simply entangled, or if they are too thick, they hinder the protrusion-like support. Absent.
繊維の長さも、平均粒子径と相関しており、1/10〜20の
ものが好ましく、この範囲以外のものは、短かすぎる場
合は単に粒子のい空隙を埋めるだけであり、また長すぎ
る場合は粒子との分散が悪くなり、繊維だけの塊りを形
成して好ましくない。The length of the fiber also correlates with the average particle diameter, preferably 1/10 to 20. Other than this range, if the length is too short, it simply fills the voids without particles, and is also too long. In this case, the dispersion with the particles becomes poor and lumps of only fibers are formed, which is not preferable.
無機質粉体あるいは触媒活性成分を含有する無機質粉体
の粒子径は５〜300μｍが好ましく、５μｍ以下の場合
は生成する突起が小さく、ほとんど炭素系微粒子との接
触効率を高める効果は見い出されなかつた。300μｍよ
り大きい場合は突起の形成が困難であり、かつ生成する
突起の接触面積が減り炭素系微粒子の燃焼性能をあまり
高めないことがわかつた。The particle size of the inorganic powder or the inorganic powder containing the catalytically active component is preferably 5 to 300 μm, and when the particle size is 5 μm or less, the protrusions formed are small, and the effect of enhancing the contact efficiency with the carbon-based fine particles has not been found. . It has been found that when the thickness is larger than 300 μm, it is difficult to form the protrusions, and the contact area of the generated protrusions is reduced so that the combustion performance of the carbon-based fine particles is not so improved.
また、使用する無機質繊維の量は、無機質粉体の重量比
に対して1:0.7〜1:0.07の範囲が好ましく、1:0.7より多
く使用する場合には粒子による突起状を形成するのを妨
害することとなり、1:0.07より少ない場合は添加効果が
見られず、無機質繊維を用いない場合と同じ結果であつ
た。Further, the amount of the inorganic fiber used is preferably in the range of 1: 0.7 to 1: 0.07 with respect to the weight ratio of the inorganic powder, and when more than 1: 0.7 is used, it is necessary to form protrusions by particles. When it was less than 1: 0.07, the effect of addition was not observed, and the result was the same as when no inorganic fiber was used.
本発明にかかる触媒調製法は、特定されないが好ましい
ものとしては以下の方法が一例としてあげられる。The catalyst preparation method according to the present invention is not specified, but the following method is mentioned as a preferable example.
活性アルミナペレツトに触媒活性成分の水可溶性塩の水
溶液で含浸担持し、乾燥、焼成する。次いでハンマーミ
ル（例えば細川ミクロン社製、PULVERIXER）で粉枠し、
粉枠品を分級機（例えば細川ミクロン社製、MICRON SE
PARATOR,MS−Ｏ型）にて分級し、５μｍ〜300μｍの範
囲の粒径に実質的に分布する程度の耐火性無機質粗粒子
に白金元素などの触媒成分を担持した触媒活性物質担持
粉末をえる。An activated alumina pellet is impregnated and supported with an aqueous solution of a water-soluble salt of a catalytically active component, dried and calcined. Then, powder with a hammer mill (for example, PULVERIXER manufactured by Hosokawa Micron Co., Ltd.),
Classifying powder frame products (for example, MICRON SE manufactured by Hosokawa Micron Co., Ltd.
PARATOR, MS-O type) to obtain a catalytically active substance-supported powder in which a catalytic component such as platinum element is supported on refractory inorganic coarse particles having a particle size substantially in the range of 5 μm to 300 μm. .
次いでこの該粉状物を上記特定になる無機質繊維ととも
に、可溶性ベーマイト（例えばCONDEA社製、DISPURAL）
をアルミナ（Al2O3）換算で１〜20重量％含有する水溶
液に投入し撹拌する。分散剤としてのベーマイトの増粘
効果により撹拌中はもちろんのこと、撹拌を止めても粒
状活性物質は沈降せずに安定なスラリーがえられる。Then, this powdery substance is used together with the inorganic fiber to be specified above, soluble boehmite (for example, DISPURAL manufactured by CONDEA).
Is added to an aqueous solution containing 1 to 20% by weight in terms of alumina (Al 2 O 3 ) and stirred. Due to the thickening effect of boehmite as a dispersant, a stable slurry can be obtained not only during stirring but also when the stirring is stopped, the granular active substance does not sediment.
該ミラリーを用いて三次元構造体に担持し、余分なスラ
リーを取除くことにより、構造体内部壁面あるいは骨格
表面に凹凸の大きい突起状の触媒被覆層を形成すること
ができる。次いで乾燥し、200〜800℃とくに300〜700℃
の温度で焼成する。By supporting the three-dimensional structure using the millary and removing the excess slurry, it is possible to form a protruding catalyst coating layer having large irregularities on the inner wall surface of the structure or the skeleton surface. Then dry and 200-800 ℃, especially 300-700 ℃
Bake at the temperature of.
この調製方法において粗粒状触媒活性成分をスラリー化
する際、粗粒子が沈降しないように増粘効果を有するア
ルミナ、チタニア、ジルコニア、シリカなどのゾルや可
溶性ベーマイト、可溶性有機高分子化合物よりなる群か
ら選ばれた少なくとも１種の分散剤とともに水性スラリ
ー化せしめて使用しうるが、該可溶性有機高分子化合物
としては、ポリアクリル酸ナトリウム、ポリアクリル酸
アンモニウム、アクリル酸−マレイン酸共重合体のナト
リウム塩またはアンモニウム塩、ポリエチレンオキサイ
ド、ポリビニルアルコール、カルボキシメチルセルロー
ス、メチルセルロース、ヒドロキシエチルセルロース、
でんぷん、アラビアゴム、グアーガム、にかわ等が好適
に用いられる。When slurrying the coarse-particle catalytically active component in this preparation method, alumina having a thickening effect so that coarse particles do not settle, titania, zirconia, sol such as silica and soluble boehmite, from the group consisting of soluble organic polymer compounds It may be used in the form of an aqueous slurry together with at least one selected dispersant, and the soluble organic polymer compound may be sodium polyacrylate, ammonium polyacrylate, sodium salt of acrylic acid-maleic acid copolymer. Or ammonium salt, polyethylene oxide, polyvinyl alcohol, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose,
Starch, gum arabic, guar gum, glue and the like are preferably used.
また触媒コート層をさらに多孔性にするためにスラリー
中にポリエチレングリコールなどの可溶性有機高分子化
合物を添加して焼成により除去する方法を併用しても良
い。In order to make the catalyst coat layer more porous, a method of adding a soluble organic polymer compound such as polyethylene glycol to the slurry and removing it by firing may be used in combination.
その他、本発明に好適な調製法としては、あらかじめ耐
熱性無機物質の粒状物（上記と同じ分級した粒度のも
の）を三次元構造体に担持しておき、触媒活性成分の水
溶液あるいは有機溶媒可溶性塩の溶液を含浸担持して触
媒化しても良い。In addition, as a preparation method suitable for the present invention, a granular material of a heat-resistant inorganic substance (having the same classified particle size as above) is previously loaded on a three-dimensional structure, and an aqueous solution of a catalytically active component or an organic solvent soluble A salt solution may be impregnated and supported for catalysis.
本発明にかかる触媒においては、触媒活性成分を含む全
担持量はとくに限定されるものではないは、三次元構造
体１あたり10〜200g、好ましくは20〜150gの範囲であ
る。In the catalyst according to the present invention, the total supported amount including the catalytically active component is not particularly limited, but is in the range of 10 to 200 g, preferably 20 to 150 g per one-dimensional structure 1.
耐火性無機質粉体としては、三次元構造体１あたり５
〜150g、好ましくは10〜120gの範囲であり、無機質繊維
は、耐火性無機質粉体の重量に対して1:0.7〜1:0.07の
比で用いる。As a refractory inorganic powder, 5 per 3D structure 1
It is in the range of up to 150 g, preferably 10 to 120 g, and the inorganic fibers are used in a ratio of 1: 0.7 to 1: 0.07 with respect to the weight of the refractory inorganic powder.
触媒活性成分は、酸化物あるいは金属として三次元構造
体１あたり0.01〜70g、好ましくは0.05〜50gの範囲で
ある。The amount of the catalytically active component as an oxide or a metal is 0.01 to 70 g, preferably 0.05 to 50 g per one-dimensional structure 1.
〔作 用〕 炭素系微粒子の燃焼反応は、固体−固体の反応であり、
触媒活性物質と炭素系微粒子の接触効率が非常に重要な
要因である。[Operation] The combustion reaction of carbon-based fine particles is a solid-solid reaction,
The contact efficiency between the catalytically active substance and the carbon-based fine particles is a very important factor.
本発明はこの点に鑑み、触媒活性成分と耐火性無機質粉
体と無機質繊維とからなる好適な大きさの突起状触媒を
付着せしめ、炭素系微粒子との接触効率を高めることに
より燃焼効率を著しく向上させたことを特徴としてい
る。In view of this point, the present invention attaches a protrusion-shaped catalyst of a suitable size consisting of a catalytically active component, a refractory inorganic powder, and an inorganic fiber, and significantly increases the combustion efficiency by increasing the contact efficiency with the carbon-based fine particles. It is characterized by improving.
該突起状触媒中の無機質繊維の作用効果は炭素系微粒子
のブリツジ化を防止し、触媒活性成分との接触効率を更
に高める作用をするものと思われ、無機質繊維を用いな
い場合よりも更に低温で炭素系微粒子が燃焼することを
見い出し本発明を完成したのである。The action effect of the inorganic fibers in the protrusion-shaped catalyst is considered to prevent bridging of the carbon-based fine particles and further increase the contact efficiency with the catalytically active component, which is lower than that when no inorganic fibers are used. Then, they found that the carbon-based fine particles burned and completed the present invention.
以下本発明の実施例と比較例とを示し、本発明を具体的
に説明する。Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples of the present invention.
実施例１ 市販の活性アルミナペレツト（３〜5mmφ表面積150m2/
g）2kgを量りとり、Ptとして15g含有するジニトロジア
ンミン白金の硝酸溶液と、ロジウム（Rh）として1.67g
含有する硝酸ロジウム水溶液の混合溶液1.4に浸漬担
持し、150℃で３時間乾燥し500℃で２時間焼成した。Example 1 Commercially available activated alumina pellets (3-5 mmφ surface area 150 m 2 /
g) Weigh out 2 kg, nitric acid solution of dinitrodiammine platinum containing 15 g as Pt, and 1.67 g as rhodium (Rh)
It was dipped and supported in a mixed solution 1.4 of the aqueous rhodium nitrate solution contained therein, dried at 150 ° C. for 3 hours, and calcined at 500 ° C. for 2 hours.
該焼成ペレットを、ハンマーミルで粉枠し、分級装置で
５μｍ以下の粒径のものをカットし、また300μｍ以上
の程度のものは飾を用いて取り除いた。以上の操作によ
り、平均粒子径78μｍのPt:Rh担持した粉末触媒をえ
た。あらかじめ可溶性ベーマイト100g（Al2O3換算75g）
を、溶解させてえた水溶液に該分級粉末触媒1kgを分散
させ安定したスラリー２をえた。The fired pellets were framed with a hammer mill, and those having a particle size of 5 μm or less were cut by a classifier, and those having a particle size of 300 μm or more were removed using a decoration. By the above operation, a Pt: Rh-supported powder catalyst having an average particle diameter of 78 μm was obtained. 100g of soluble boehmite (75g of Al 2 O 3 equivalent)
1 kg of the classified powder catalyst was dispersed in an aqueous solution obtained by dissolving to obtain a stable slurry 2.
該スラリーに、市販のシリコンカーバイドウイスカー
（線径1.7μｍ、長さ80μｍ）100gを撹拌させながら分
散させた。100 g of commercially available silicon carbide whiskers (wire diameter 1.7 μm, length 80 μm) were dispersed in the slurry while stirring.
このスラリーの粘度は91cps（室温）であつた。The viscosity of this slurry was 91 cps (room temperature).
担体として、市販のオープンハニカムモノリス（材質：
コージエライト）5.66インチ径×6.0インチ長さ、300セ
ル／平行インチ、壁厚６ミルのものを用いた。A commercially available open honeycomb monolith (material:
Cordierite) 5.66 inch diameter × 6.0 inch length, 300 cells / parallel inch, and wall thickness 6 mil were used.
該担体をスラリーに浸漬し引上げて余分なスラリーをエ
アーブローで取り除いた。ついで150℃で３時間乾燥し
空気中500℃で２時間焼成し完成触媒をえた。The carrier was immersed in the slurry and pulled up to remove excess slurry by air blow. Then, it was dried at 150 ° C. for 3 hours and calcined in air at 500 ° C. for 2 hours to obtain a finished catalyst.
出来上りの各成分の担持量はAl2O3120g/−担体、Pt0.
9g/−担体、Rh0.1g/−担体、シリコンカーバイドウ
イスカー12g/−担体であつた。The loading amount of each component of the finished product is Al 2 O 3 120 g / − carrier, Pt 0.
The carrier was 9 g / -carrier, Rh 0.1 g / -carrier, and silicon carbide whiskers 12 g / -carrier.
実施例２ 市販のシリカ−アルミナ（アルミナ13％）ペレツト（３
〜5mmφ、表面積230m2/g）1kgに白金（Pt）として20g含
有するジニトロジアンミン白金の硝酸溶液の水溶液750m
lに浸漬担持し、150℃で３時間乾燥し、500℃で２時間
焼成し、次いで硝酸鉛〔Pb（NO3）２〕371gを溶解した
水溶液150mlに含浸した。150℃で３時間乾燥し、500℃
で２時間焼成した。該焼成ペレットを、パンマーミルで
粉枠し、分級装置で５μｍ以下の粒径のものをカット
し、また300μｍ以上の程度のものは飾を用いて取り除
いた。以上の操作により、平均粒径82μｍの触媒含有粉
末触媒をえた。あらかじめシリカゾル（スノーテツクス
−Ｏ、日産化学製）をSiO2換算で15g含有する水溶液に
該分級粉末触媒150gを分散させ、次に市販のガラス繊維
（線径13μｍ、長さ200μｍ）の10gを投入して撹拌しな
がら分散させ、安定したスラリー520mlをえた。担体と
して、市販のウォールフロータイプのハニカムモノリス
（材質：コージェライト）5.66インチ径×6.0インチ長
さ、100セル／平方インチ、壁厚17ミル、隔壁の有する
平均細孔径は28μｍのものを用いた。該担体のガス入口
部から上記スラリー520mlを注ぎ、余分なスラリーを反
対側からの空気ブローで取り除いた。ついで150℃で３
時間乾燥し、空気中500℃で２時間焼成し、完成触媒を
えた。出来上りの各成分の担持量は、シリカ−アルミナ
40g/−担体、PbO10g/−担体、Pt1.0g/−担体、ガ
ラス繊維3.3g/−担体であつた。Example 2 Commercially available silica-alumina (13% alumina) pellets (3
～5Mmfai, an aqueous solution of diammine dinitro platinum nitric acid solution 20g contained in the surface area of 230m 2 / g) 1kg of platinum (Pt) 750 meters
It was immersed in 1 l, dried at 150 ° C. for 3 hours, calcined at 500 ° C. for 2 hours, and then impregnated with 150 ml of an aqueous solution in which 371 g of lead nitrate [Pb (NO 3 ) 2 ] was dissolved. Dry at 150 ℃ for 3 hours, 500 ℃
It was baked for 2 hours. The fired pellets were powder-framed with a Panmer mill, and those having a particle size of 5 μm or less were cut by a classifier, and those having a particle size of 300 μm or more were removed using a decoration. By the above operation, a catalyst-containing powder catalyst having an average particle size of 82 μm was obtained. In advance, 150 g of the classified powder catalyst was dispersed in an aqueous solution containing 15 g of silica sol (Snowtex-O, manufactured by Nissan Kagaku) in terms of SiO 2 , and then 10 g of commercially available glass fiber (diameter 13 μm, length 200 μm) was added. And dispersed with stirring to give 520 ml of a stable slurry. As the carrier, a commercially available wall-flow type honeycomb monolith (material: cordierite) 5.66 inch diameter × 6.0 inch length, 100 cells / square inch, wall thickness 17 mil, and partition walls having an average pore diameter of 28 μm were used. . 520 ml of the above slurry was poured from the gas inlet of the carrier, and excess slurry was removed by air blowing from the opposite side. Then at 150 ℃ 3
It was dried for an hour and calcined in air at 500 ° C. for 2 hours to obtain a finished catalyst. The amount of each finished component loaded is silica-alumina.
The carrier was 40 g / -carrier, PbO 10 g / -carrier, Pt 1.0 g / -carrier, and glass fiber 3.3 g / -carrier.
実施例３ 実施例１において、担体としてオープンハニカムモノリ
スのかわりに、市販のセラミツクフオーム（嵩密度0.35
g/cm3、空孔率87.5％、容積1.7）を用いる以外は全て
同じ方法で触媒を調製した。出来上りの各成分の担持量
はAl2O3120g/−担体、Pt0.9g/−担体、Ph0.1g/−
担体、シリコンカーバイドウイスカー12g/−担体であ
つた。Example 3 In Example 1, instead of the open honeycomb monolith as the carrier, a commercially available ceramic foam (bulk density 0.35) was used.
A catalyst was prepared by the same method except using g / cm 3 , porosity 87.5%, and volume 1.7). The loading amount of each component of the finished product is Al 2 O 3 120 g / − carrier, Pt 0.9 g / − carrier, Ph 0.1 g / −
The carrier was silicon carbide whiskers 12 g / -carrier.
実施例４ 実施例１〜３におけると同じ方法で、下記表１に示す触
媒組成の触媒をえた。Example 4 A catalyst having a catalyst composition shown in Table 1 below was obtained by the same method as in Examples 1 to 3.
ここでモリブデンはパラモリブデン酸アンモニウム、リ
ンはリン酸二水素アンモニウム、タングステンはパラタ
ングステン酸アンモン、ニオブは五塩化ニオブ、他はす
べて硝酸塩を用いた。Here, molybdenum was ammonium paramolybdate, phosphorus was ammonium dihydrogen phosphate, tungsten was ammonium paratungstate, niobium was pentachloride, and the others were nitrates.
比較例１ 市販の活性アルミナペレット（３〜5mmφ、表面積150m2
/g）1kgを量りとり、白金（Pt）として20g含有するジニ
トロジアンミン白金の硝酸溶液の水溶液750mlに浸漬担
持し、150℃で３時間乾燥し、500℃で２時間焼成した。
このようにして調製したPt担持アルミナペレツトを粉枠
し、その後湿式ミルで通常のウオツシユコートを行なう
程度まで湿式粉枠し平均粒子径0.9μｍとしたスラリー
を調製し520mlのスラリーをえた。該スラリーに市販の
アルミナ繊維（線径９μｍ、長さ900μｍ）10gを撹拌し
ながら投入し分散させた。他はすべて同じ方法で触媒を
調製しAl2O350g/−担体、Pt1.0g/−担体、アルミナ
繊維3.3g/−担体の完成触媒をえた。 Comparative Example 1 Commercially available activated alumina pellets (3-5 mmφ, surface area 150 m 2
1 g was weighed and immersed in 750 ml of an aqueous solution of nitric acid solution of dinitrodiammine platinum containing 20 g of platinum (Pt), dipped and supported, dried at 150 ° C. for 3 hours, and calcined at 500 ° C. for 2 hours.
The Pt-supported alumina pellets thus prepared were powder-framed, and then wet-milled to the extent that ordinary wash coating was performed with a wet mill to prepare a slurry having an average particle size of 0.9 μm, and 520 ml of slurry was obtained. 10 g of a commercially available alumina fiber (wire diameter 9 μm, length 900 μm) was added to the slurry while stirring and dispersed. A catalyst was prepared in the same manner except that Al 2 O 3 50 g / -support, Pt 1.0 g / -support and alumina fiber 3.3 g / -support were completed.
比較例２ 実施例１において、シリコンカーバイドウイスカーを用
いない以外はすべて同じ方法で触媒を調製し、Al2O3120
g/−担体、Pt0.9g/−担体、Rh0.1g/−担体の完成
触媒をえた。Comparative Example 2 A catalyst was prepared in the same manner as in Example 1 except that silicon carbide whiskers were not used, and Al 2 O 3 120
The finished catalyst of g / -support, Pt0.9g / -support and Rh0.1g / -support was obtained.
比較例３ 実施例１においてPt,Rhを使用しない以外はすべて同じ
方法で触媒を調製し、Al2O3120g/−担体、シリコンカ
ーバイドウイスカー12g/−担体の完成触媒をえた。Comparative Example 3 A catalyst was prepared in the same manner as in Example 1 except that Pt and Rh were not used, and a finished catalyst of Al 2 O 3 120 g / -support and silicon carbide whiskers 12 g / -support was obtained.
比較例４ 実施例２において硝酸鉛〔Pb（NO3）２〕371g用いるか
わりに硝酸クロム〔Cr（NO3）３・9H2O〕を1316gを用い
る以外は同じ方法で触媒を調製し出来上りの各成分の担
持量はシリカ−アルミナ40g/−担体、Cr2O310g/−
担体、Pt1.0g/−担体、ガラス繊維3.3g/−担体であ
つた。Lead nitrate Comparative Example 4 Example 2 [Pb (NO 3) 2] 371g of chromium nitrate instead of using [Cr (NO 3) 3 · 9H 2 O ] except using 1316g is to prepare a catalyst in the same way the finished The amount of each component supported is silica-alumina 40 g / -carrier, Cr 2 O 3 10 g /-
The carrier was Pt 1.0 g / -carrier, and glass fiber 3.3 g / -carrier.
実施例６ 実施例１〜４、比較例１〜４でえられた触媒について、
排気量2300cc、４気筒デイーゼルエンジンを用いて、触
媒の評価試験を行なつた。エンジンの回転数2500rpm、
トルク4.0kg・ｍの条件で微粒子の捕捉約２時間を行な
い、次いでトルクを0.5kg・ｍ間隔で５分毎に上昇させ
て、触媒層の圧損変化を連続的に記録し、微粒子が触媒
上で排ガス温度上昇に伴ない、微粒子の蓄積による圧力
上昇と微粒子の燃焼による圧力降下とが等しくなる温度
（Te）と着火燃焼し、圧損が急激に降下する温度（Ti）
を求めた。また2500rpm、トルク4.0kg・ｍで微粒子を捕
捉する場合の圧損の経時変化を１時間あたりの圧損変化
量をチヤートから計算して△Ｐ（mmHg/Hr）の値を求め
た。また、2500rpm、トルク4.0kg・ｍの微粒子捕捉条件
下でダイリユーシヨントンネルを用いて、微粒子の触媒
入口および出口の微粒子の量を測定し、微粒子の浄化率
（％）を求めた。それらの結果を表２に示した。Example 6 Regarding the catalysts obtained in Examples 1 to 4 and Comparative Examples 1 to 4,
A catalyst evaluation test was performed using a 2300cc 4-cylinder diesel engine. Engine speed 2500rpm,
Fine particles are captured for about 2 hours under the condition of a torque of 4.0 kg · m, and then the torque is increased at intervals of 0.5 kg · m every 5 minutes to continuously record the pressure loss change of the catalyst layer, and the fine particles are on the catalyst. The temperature at which the pressure rise due to the accumulation of fine particles and the pressure drop due to the combustion of fine particles become equal with the exhaust gas temperature rise (Te) and the temperature at which ignition loss occurs and the pressure loss drops sharply (Ti)
I asked. Further, the time-dependent change in pressure loss when trapping fine particles at 2500 rpm and a torque of 4.0 kg · m was calculated from the amount of pressure loss change per hour from the chart to obtain the value of ΔP (mmHg / Hr). Further, the amount of fine particles at the catalyst inlet and outlet of the fine particles was measured using a dilution tunnel under the fine particle capturing conditions of 2500 rpm and a torque of 4.0 kg · m to obtain the fine particle purification rate (%). The results are shown in Table 2.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 23/58 Ａ 23/60 Ａ 23/62 Ａ 23/63 23/648 23/652 23/656 23/89 Ａ 27/185 Ａ Ｂ０１Ｊ 23/64 １０２ Ａ １０３ Ａ １０４ Ａ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication location B01J 23/58 A 23/60 A 23/62 A 23/63 23/648 23/652 23/656 23/89 A 27/185 A B01J 23/64 102 A 103 A 104 A
Claims (8)
ガス接触部に、粒子径が５〜300μｍである耐火性無機
質粉末と該無機質粉末の平均粒子径の1/300〜1/5の範囲
の平均直径および1/10〜20の範囲の平均長さを有する耐
火性無機質繊維とを、該無機質粉末と該無機質繊維との
重量比が1:0.7〜1:0.07の範囲で、該無機質粉末と該無
機質繊維とを突起状に形成し、該突起状に形成されてな
る耐火性無機質粉末に、白金、ロジウム、パラジウムよ
りなる白金族元素の少くとも１種を含有してなる触媒活
性物質を担持せしめてなることを特徴とする排ガス浄化
用触媒。1. A refractory inorganic powder having a particle diameter of 5 to 300 μm and 1/300 to 1/5 of the average particle diameter of the inorganic powder on the gas contact surface or the gas contact portion of the refractory three-dimensional structure. A refractory inorganic fiber having an average diameter in the range and an average length in the range of 1/10 to 20, the weight ratio of the inorganic powder and the inorganic fiber in the range of 1: 0.7 to 1: 0.07, the inorganic A catalytically active substance comprising a powder and the inorganic fiber formed in a projection shape, and the refractory inorganic powder formed in the projection shape containing at least one platinum group element consisting of platinum, rhodium and palladium. An exhaust gas purifying catalyst, characterized in that
ム、セラミックハニカム、ウォールフロータイプのハニ
カムモノリス、メタルハニカムまたは金属発泡体である
ことを特徴とする特許請求の範囲第（１）記載の触媒。2. The catalyst according to claim 1, wherein the refractory three-dimensional structure is ceramic foam, ceramic honeycomb, wall flow type honeycomb monolith, metal honeycomb or metal foam. .
カ、チタニア、ジルコニア、シリカーアルミナ、アルミ
ナージルコニア、アルミナーチタニア、シリカーチタニ
ア、シリカージルコニア、チタニアージルコニアおよび
ゼオライトよりなる群から選ばれた少くとも１種であ
り、かつその粒子径が５〜300μｍの範囲に実質的に分
布してなることを特徴とする特許請求の範囲（１）記載
の触媒。3. The refractory inorganic powder is selected from the group consisting of activated alumina, silica, titania, zirconia, silica-alumina, alumina-zirconia, alumina-titania, silica-titania, silica-zirconia, titania-zirconia and zeolite. The catalyst according to claim (1), characterized in that it is at least one kind and that its particle size is substantially distributed in the range of 5 to 300 μm.
ガス接触部に、粒子径が５〜300μｍである耐火性無機
質粉末と該無機質粉末の平均粒子径の1/300〜1/5の範囲
の平均直径および1/10〜20の範囲の平均長さを有する耐
火性無機質繊維とを、該無機質粉末と該無機質繊維との
重量比が1:0.7〜1:0.07の範囲で、該無機質粉末と該無
機質繊維とを突起状に形成し、該突起状に形成されてな
る耐火性無機質粉末に、白金、ロジウム、パラジウムよ
りなる白金族元素の少くとも１種と、鉄、コバルト、ニ
ッケル、モリブデン、タングステン、ニオブ、リン、
鉛、亜鉛、錫、銅、マンガン、セリウム、ランタン、
銀、バリウム、マグネシウム、カルシウム、ストロンチ
ウムよりなるアルカリ土類金属、カリウム、ナトリウ
ム、セシウム、ルビジウムよりなるアルカリ金属よりな
る群から選ばれた少くとも１種を含有してなる触媒活性
物質を担持せしめてなることを特徴とする排ガス浄化用
触媒。4. A refractory inorganic powder having a particle diameter of 5 to 300 μm and 1/300 to 1/5 of the average particle diameter of the inorganic powder on the gas contact surface or the gas contact portion of the refractory three-dimensional structure. A refractory inorganic fiber having an average diameter in the range and an average length in the range of 1/10 to 20, the weight ratio of the inorganic powder and the inorganic fiber in the range of 1: 0.7 to 1: 0.07, the inorganic A powder and the inorganic fiber are formed in a projection shape, and the refractory inorganic powder formed in the projection shape includes at least one platinum group element consisting of platinum, rhodium and palladium, and iron, cobalt and nickel, Molybdenum, tungsten, niobium, phosphorus,
Lead, zinc, tin, copper, manganese, cerium, lanthanum,
Support a catalytically active substance containing at least one selected from the group consisting of alkaline earth metals consisting of silver, barium, magnesium, calcium and strontium, and alkali metals consisting of potassium, sodium, cesium and rubidium. An exhaust gas purifying catalyst characterized by:
ム、セラミックハニカム、ウォールフロータイプのハニ
カムモノリス、メタルハニカムまたは金属発泡体である
ことを特徴とする特許請求の範囲第（４）記載の触媒。5. The catalyst according to claim 4, wherein the refractory three-dimensional structure is ceramic foam, ceramic honeycomb, wall flow type honeycomb monolith, metal honeycomb or metal foam. .
カ、チタニア、ジルコニア、シリカーアルミナ、アルミ
ナージルコニア、アルミナーチタニア、シリカーチタニ
ア、シリカージルコニア、チタニアージルコニアおよび
ゼオライトよりなる群から選ばれた少くとも１種であ
り、かつその粒子径が５〜300μｍの範囲に実質的に分
布してなることを特徴とする特許請求の範囲（４）記載
の触媒。6. The refractory inorganic powder is selected from the group consisting of activated alumina, silica, titania, zirconia, silica-alumina, alumina-zirconia, alumina-titania, silica-titania, silica-zirconia, titania-zirconia and zeolite. The catalyst according to claim (4), characterized in that it is at least one kind and that its particle size is substantially distributed in the range of 5 to 300 μm.
300μｍである耐火性無機質粉末と、該耐火性無機質粉
末の平均粒子径の1/300〜1/5の範囲の平均直径および1/
10〜20の範囲の平均長さを有する耐火性無機質繊維状物
質とを、該無機質粉末と該無機質繊維との重量比が1:0.
7〜1:0.07の範囲で混合し、かつアルミナゾル、チタニ
アゾル、ジルコニアゾル、シリカゾル、可溶性ベーマイ
ト、可溶性有機高分子化合物よりなる群から選ばれた少
くとも１種の分散剤とともに水性スラリー化し、えられ
たスラリーを用いて耐火性三次元構造体のガス接触面あ
るいはガス接触部に、該無機質粉末と該無機質繊維とを
突起状に担持せしめることを特徴とする排ガス浄化用触
媒の製法。7. The particle size supporting the catalytically active substance is 5 to 5.
The refractory inorganic powder having a diameter of 300 μm, and the average diameter in the range of 1/300 to 1/5 of the average particle diameter of the refractory inorganic powder and 1 /
The refractory inorganic fibrous material having an average length in the range of 10 to 20, the weight ratio of the inorganic powder and the inorganic fiber is 1: 0.
Mixing in the range of 7 to 1: 0.07 and forming an aqueous slurry together with at least one dispersant selected from the group consisting of alumina sol, titania sol, zirconia sol, silica sol, soluble boehmite, and soluble organic polymer compound. A method for producing an exhaust gas-purifying catalyst, characterized in that the inorganic powder and the inorganic fibers are supported in the form of protrusions on the gas contact surface or the gas contact portion of the refractory three-dimensional structure using the slurry.
ム、セラミックハニカム、ウォールフロータイプのハニ
カムモノリス、メタルハニカムまたは金属発泡体である
ことを特徴とする特許請求の範囲第（７）記載の製法。8. The method according to claim 7, wherein the refractory three-dimensional structure is a ceramic foam, a ceramic honeycomb, a wall flow type honeycomb monolith, a metal honeycomb or a metal foam. .
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60266145A JPH0771634B2 (en) | 1985-11-28 | 1985-11-28 | Exhaust gas purifying catalyst and its manufacturing method |
| CA000512739A CA1260909A (en) | 1985-07-02 | 1986-06-30 | Exhaust gas cleaning catalyst and process for production thereof |
| EP86108950A EP0211233B1 (en) | 1985-07-02 | 1986-07-01 | Exhaust gas cleaning catalyst and process for production thereof |
| US06/880,827 US4749671A (en) | 1985-07-02 | 1986-07-01 | Exhaust gas cleaning catalyst and process for production thereof |
| DE8686108950T DE3666536D1 (en) | 1985-07-02 | 1986-07-01 | Exhaust gas cleaning catalyst and process for production thereof |
| AT86108950T ATE47533T1 (en) | 1985-07-02 | 1986-07-01 | EXHAUST GAS PURIFICATION CATALYST AND PROCESS OF PRODUCTION. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60266145A JPH0771634B2 (en) | 1985-11-28 | 1985-11-28 | Exhaust gas purifying catalyst and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62129146A JPS62129146A (en) | 1987-06-11 |
| JPH0771634B2 true JPH0771634B2 (en) | 1995-08-02 |
Family
ID=17426929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60266145A Expired - Lifetime JPH0771634B2 (en) | 1985-07-02 | 1985-11-28 | Exhaust gas purifying catalyst and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0771634B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008512234A (en) * | 2004-09-13 | 2008-04-24 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニー | Catalyst support substrate coated with a washcoat comprising fibrous material |
| JP2008188511A (en) * | 2007-02-02 | 2008-08-21 | Matsushita Electric Ind Co Ltd | Exhaust gas cleaning filter and its manufacturing method |
| WO2011115352A1 (en) * | 2010-03-17 | 2011-09-22 | Korea Institute Of Science And Technology | Unshaped refractory composition added with alumina sol binder |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH067920B2 (en) * | 1987-03-31 | 1994-02-02 | 株式会社リケン | Exhaust gas purification material and exhaust gas purification method |
| JP2577757B2 (en) * | 1987-10-22 | 1997-02-05 | 株式会社日本触媒 | Diesel exhaust gas purification catalyst |
| JPH01159029A (en) * | 1987-12-16 | 1989-06-22 | Toyota Motor Corp | Exhaust gas purification apparatus of diesel engines |
| JPH04250848A (en) * | 1990-12-27 | 1992-09-07 | Toyota Motor Corp | Catalyst to decrease diesel particulate |
| JP3093119B2 (en) * | 1994-11-15 | 2000-10-03 | 日揮化学株式会社 | Method for producing honeycomb structured catalyst for exhaust gas purification |
| JPH09206598A (en) * | 1996-02-07 | 1997-08-12 | Matsushita Electric Ind Co Ltd | Catalyst and its production |
| JP3897483B2 (en) * | 1999-03-31 | 2007-03-22 | トヨタ自動車株式会社 | Exhaust gas purification catalyst, method for producing the same, and exhaust gas purification method |
| JP4246412B2 (en) * | 2001-07-05 | 2009-04-02 | 株式会社日本触媒 | Exhaust gas treatment catalyst and exhaust gas purification method using the same |
| JP4826207B2 (en) * | 2005-10-28 | 2011-11-30 | 日産自動車株式会社 | Exhaust gas purification catalyst and method for producing exhaust gas purification catalyst |
| JP5130632B2 (en) * | 2006-02-28 | 2013-01-30 | 日産自動車株式会社 | Exhaust gas purification catalyst and method for producing the same |
| WO2008096413A1 (en) * | 2007-02-06 | 2008-08-14 | Ibiden Co., Ltd. | Honeycomb structure |
| JP5888150B2 (en) * | 2012-06-29 | 2016-03-16 | トヨタ自動車株式会社 | Exhaust gas purification catalyst and method for producing the same |
| JP5825221B2 (en) * | 2012-08-08 | 2015-12-02 | トヨタ自動車株式会社 | Exhaust gas purification catalyst and method for producing the same |
-
1985
- 1985-11-28 JP JP60266145A patent/JPH0771634B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008512234A (en) * | 2004-09-13 | 2008-04-24 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニー | Catalyst support substrate coated with a washcoat comprising fibrous material |
| JP2008188511A (en) * | 2007-02-02 | 2008-08-21 | Matsushita Electric Ind Co Ltd | Exhaust gas cleaning filter and its manufacturing method |
| WO2011115352A1 (en) * | 2010-03-17 | 2011-09-22 | Korea Institute Of Science And Technology | Unshaped refractory composition added with alumina sol binder |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62129146A (en) | 1987-06-11 |
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