JPWO2017212944A1 - Exhaust gas purification catalyst - Google Patents
Exhaust gas purification catalystInfo
- Publication number
- JPWO2017212944A1 JPWO2017212944A1 JP2017528862A JP2017528862A JPWO2017212944A1 JP WO2017212944 A1 JPWO2017212944 A1 JP WO2017212944A1 JP 2017528862 A JP2017528862 A JP 2017528862A JP 2017528862 A JP2017528862 A JP 2017528862A JP WO2017212944 A1 JPWO2017212944 A1 JP WO2017212944A1
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- cual
- gas purification
- purification catalyst
- peak area
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000000746 purification Methods 0.000 title claims abstract description 41
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 42
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 23
- 229910018565 CuAl Inorganic materials 0.000 claims description 54
- 239000007789 gas Substances 0.000 claims description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 239000010949 copper Substances 0.000 description 64
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 62
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 40
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010304 firing Methods 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical group 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- -1 and in particular Chemical compound 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 238000012937 correction 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
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000011214 refractory ceramic Substances 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/227—Measuring photoelectric effect, e.g. photoelectron emission microscopy [PEEM]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
アルミナ粒子の表面にＣｕ元素が存在してなる構成を備えた排気ガス浄化触媒に関し、優れた触媒活性を発揮し、三元触媒として有効に使用することができる、新たな排気ガス浄化触媒を提供せんとする。アルミナ粒子の表面にＣｕ元素が存在してなる構成を備えた排気ガス浄化触媒であって、Ｘ線光電子分光法（XPS：X-ray Photoelectron Spectroscopy）で測定される、Ｃｕ２ｐ及びＡｌ２ｐの各ピーク面積の合計面積を１００％としたとき、Ｃｕ２ｐのピーク面積の割合が７〜２８％であることを特徴とする排気ガス浄化触媒を提案する。Provided a new exhaust gas purification catalyst that exhibits excellent catalytic activity and can be used effectively as a three-way catalyst, with regard to an exhaust gas purification catalyst having a structure in which Cu element is present on the surface of alumina particles I'm sorry. An exhaust gas purifying catalyst having a structure in which Cu element is present on the surface of alumina particles, each peak area of Cu2p and Al2p measured by X-ray photoelectron spectroscopy (XPS) An exhaust gas purifying catalyst is proposed in which the ratio of the peak area of Cu2p is 7 to 28% when the total area is 100%.
Description
本発明は、内燃機関から排出される排気ガスを浄化するために用いることができる排気ガス浄化触媒に関する。 The present invention relates to an exhaust gas purification catalyst that can be used to purify exhaust gas discharged from an internal combustion engine.
ガソリンを燃料とする自動車の排気ガス中には、炭化水素（ＨＣ）、一酸化炭素（ＣＯ）、窒素酸化物（ＮＯx）等の有害成分が含まれる。前記炭化水素（ＨＣ）に関しては酸化させて水と二酸化炭素とに転化させて、又、前記一酸化炭素（ＣＯ）に関しては酸化させて二酸化炭素に転化させて、又、前記窒素酸化物（ＮＯx）に関しては還元させて窒素に転化させて、それぞれの有害成分を触媒で浄化する必要がある。
このような排気ガスを処理するための触媒（以下「排気ガス浄化触媒」と称する）として、ＣＯ、ＨＣ及びＮＯｘを酸化還元することができる三元触媒（Three way catalysts：ＴＷＣ）が用いられている。当該三元触媒は、排気パイプのエンジンとマフラーの中間位置にコンバーターの形態で取付けられるのが一般的である。The exhaust gas of automobiles that use gasoline as fuel contains harmful components such as hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NO x ). The hydrocarbon (HC) is oxidized and converted to water and carbon dioxide, the carbon monoxide (CO) is oxidized and converted to carbon dioxide, and the nitrogen oxide (NO) Regarding x ), it is necessary to reduce it and convert it to nitrogen, and to purify each harmful component with a catalyst.
As a catalyst for treating such exhaust gas (hereinafter referred to as “exhaust gas purification catalyst”), a three-way catalyst (TWC) capable of oxidizing and reducing CO, HC and NO x is used. ing. The three-way catalyst is generally attached in the form of a converter at an intermediate position between the exhaust pipe engine and the muffler.
このような三元触媒としては、高い比表面積を有する耐火性酸化物多孔質体、例えば高い比表面積を有するアルミナ多孔質体に、白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）等の貴金属を担持し、これを基材、例えば耐火性セラミック又は金属製ハニカム構造で出来ているモノリス型（monolithic）基材に担持したり、或いは、耐火性粒子に担持したりしたものが知られている。 As such a three-way catalyst, a refractory oxide porous body having a high specific surface area, such as an alumina porous body having a high specific surface area, platinum (Pt), palladium (Pd), rhodium (Rh), etc. It is known to carry a noble metal and carry it on a substrate, for example a monolithic substrate made of a refractory ceramic or metal honeycomb structure, or on a refractory particle. Yes.
しかし、白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）等の貴金属は、とても高価であるため、排気ガス浄化触媒の開発においては、貴金属元素の使用量を削減することが求められている。 However, since noble metals such as platinum (Pt), palladium (Pd), and rhodium (Rh) are very expensive, it is required to reduce the amount of noble metal elements used in the development of exhaust gas purification catalysts. .
そこで、これら貴金属に代えて、例えば遷移金属である銅（Ｃｕ）を活性成分として触媒担体（アルミナ、ゼオライトなど）に担持させた触媒が提案されている（例えば特許文献１参照）。 Therefore, instead of these noble metals, for example, a catalyst in which copper (Cu), which is a transition metal, is supported on a catalyst carrier (alumina, zeolite, etc.) as an active component has been proposed (for example, see Patent Document 1).
また、特許文献２は、Ｃｕを含有する化合物と、アルミナとを混合して混合物を調製し、前記混合物を、８５０℃以上１２００℃未満で熱処理することにより得られる排気ガス浄化触媒を開示している。 Patent Document 2 discloses an exhaust gas purification catalyst obtained by mixing a compound containing Cu and alumina to prepare a mixture, and heat-treating the mixture at 850 ° C. or more and less than 1200 ° C. Yes.
特許文献３は、希土類元素が添加されたスピネル結晶構造を有するＣｕＡｌ2Ｏ4を含む触媒であって、前記希土類元素がランタノイドであり、前記ＣｕＡｌ2Ｏ4の表面にＣｕＯが担持された状態で存在しており、Ｃｕ−Ｋα線によるＸ線回折パターンにおいて、ＣｕＯ及びＣｕＡｌ2Ｏ4に帰属する回折ピークを有し、且つα−Ａｌ2Ｏ3に帰属する回折ピークを有さないことを特徴とする触媒を開示している。
この特許文献３には、アルミナへＣｕを担持させて、ＣｕＡｌ２Ｏ４の生成させる温度で焼成することにより（［００３０］）、ＣｕＯがＣｕＡｌ２Ｏ４の表面に担持された状態で存在することになるから、ＣｕＯによる触媒活性を確保しながら、ＣｕＡｌ２Ｏ４の助長作用を利用することができる旨が記載されている（［０００９］）。Patent Document 3 is a catalyst containing CuAl 2 O 4 having a spinel crystal structure to which a rare earth element is added, wherein the rare earth element is a lanthanoid, and CuO is supported on the surface of the CuAl 2 O 4. It exists and has a diffraction peak attributed to CuO and CuAl 2 O 4 in an X-ray diffraction pattern by Cu-Kα ray, and does not have a diffraction peak attributed to α-Al 2 O 3. The catalyst is disclosed.
In this Patent Document 3, CuO is present in a state of being supported on the surface of CuAl 2 O 4 by supporting Cu on alumina and firing at a temperature at which CuAl 2 O 4 is formed ([0030]). Therefore, it is described that the promoting action of CuAl 2 O 4 can be utilized while ensuring the catalytic activity by CuO ([0009]).
本発明者は、触媒活性成分としての銅（Ｃｕ）に着目し、アルミナ粒子の表面にＣｕ元素が存在してなる構成を備えた排気ガス浄化触媒について研究を行ったところ、Ｃｕの担持量を高めても、期待した程には触媒活性が高まらないことを見出した。さらにこの原因について研究を進めたところ、ＣｕＡｌ２Ｏ４の生成によって、Ｃｕの触媒活性が阻害されていることが分かってきた。The present inventor paid attention to copper (Cu) as a catalytic active component and conducted research on an exhaust gas purification catalyst having a structure in which Cu element is present on the surface of alumina particles. It has been found that the catalytic activity does not increase as expected even if it is increased. Further studies on this cause have revealed that the catalytic activity of Cu is inhibited by the formation of CuAl 2 O 4 .
かかる知見に基づき、本発明者は、アルミナ粒子の表面にＣｕ元素が存在してなる構成を備えた排気ガス浄化触媒に関し、優れた触媒活性を発揮し、三元触媒として有効に使用することができる、新たな排気ガス浄化触媒を提供せんとするものである。 Based on such knowledge, the present inventor relates to an exhaust gas purification catalyst having a structure in which Cu elements are present on the surface of alumina particles, and exhibits excellent catalytic activity and can be used effectively as a three-way catalyst. It is intended to provide a new exhaust gas purification catalyst that can be produced.
かかる課題解決のため、本発明は、アルミナ粒子の表面にＣｕ元素が存在してなる構成を備えた排気ガス浄化触媒であって、Ｘ線光電子分光法（XPS：X-ray Photoelectron Spectroscopy）で測定される、Ｃｕの２ｐ軌道（Ｃｕ２ｐ）及びＡｌの２ｐ軌道（Ａｌ２ｐ）の結合エネルギーに対応する各ピークの合計面積を１００％としたとき、Ｃｕ２ｐのピーク面積の割合（「Ｃｕ被覆率」とも称する）が７〜２８％であることを特徴とする排気ガス浄化触媒を提案する。 In order to solve this problem, the present invention is an exhaust gas purification catalyst having a structure in which Cu element is present on the surface of alumina particles, and is measured by X-ray photoelectron spectroscopy (XPS). When the total area of each peak corresponding to the binding energy of Cu 2p orbit (Cu2p) and Al 2p orbit (Al2p) is 100%, the ratio of the peak area of Cu2p (also referred to as “Cu coverage”) ) Is 7 to 28%, an exhaust gas purification catalyst is proposed.
本発明が提案する排気ガス浄化触媒によれば、触媒活性成分として貴金属を担持しなくても、優れた触媒活性を発揮し、三元触媒として有効に使用することができる。 According to the exhaust gas purification catalyst proposed by the present invention, even if no noble metal is supported as a catalytic active component, it exhibits excellent catalytic activity and can be used effectively as a three-way catalyst.
次に、実施の形態例に基づいて本発明を説明する。但し、本発明が次に説明する実施形態に限定されるものではない。 Next, the present invention will be described based on an embodiment. However, the present invention is not limited to the embodiment described below.
＜本排気ガス浄化触媒＞
本発明の実施形態の一例に係る排気ガス浄化触媒（「本排気ガス浄化触媒」と称する）は、アルミナ粒子の表面にＣｕ元素が存在してなる構成を備えた排気ガス浄化触媒である。<Exhaust gas purification catalyst>
An exhaust gas purification catalyst (referred to as “the present exhaust gas purification catalyst”) according to an example of an embodiment of the present invention is an exhaust gas purification catalyst having a configuration in which Cu elements are present on the surface of alumina particles.
（アルミナ粒子）
上記アルミナ粒子は、Ａｌ2Ｏ3からなる粒子でもよいし、Ａｌ2Ｏ3のほかに他の成分を含有する粒子でもよい。(Alumina particles)
The alumina particles may be particles of Al 2 O 3, it may be particles containing in addition to the other components of the Al 2 O 3.
上記アルミナ粒子が含有し得るＡｌ2Ｏ3以外の上記「他の成分」としては、例えばランタノイドや、バリウム（Ｂａ）の酸化物を挙げることができる。
該ランタノイドとしては、例えばランタン（Ｌａ），セリウム（Ｃｅ），プラセオジム（Ｐｒ），ネオジム（Ｎｄ），プロメチウム（Ｐｍ），サマリウム（Ｓｍ），ユーロピウム（Ｅｕ），ガドリニウム（Ｇｄ），テルビウム（Ｔｂ），ジスプロジウム（Ｄｙ），ホルミウム（Ｈｏ），エルビウム（Ｅｒ），ツリウム（Ｔｍ），イッテルビウム（Ｙｂ），ルテチウム（Ｌｕ）から選ばれる一種または二種以上を挙げることができる。Examples of the “other components” other than Al 2 O 3 that can be contained in the alumina particles include lanthanoids and barium (Ba) oxides.
Examples of the lanthanoid include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), and terbium (Tb). , Dysprodium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).
上記「他の成分」の含有量に関しては、Ｃｕが当該「他の成分」と反応することでＣｕの分散性が低下して、触媒活性が低下してしまうのを防止する観点からすると、Ａｌ2Ｏ3に対して５質量％以下であるのが好ましく、特に３質量％以下であるのがより好ましい。他方、熱的安定性確保の観点からすると、当該「他の成分」の含有量は、Ａｌ2Ｏ3に対して０．５質量％以上であるのが好ましい。With respect to the content of the “other component”, from the viewpoint of preventing Cu from reacting with the “other component” to lower the dispersibility of Cu and reducing the catalytic activity, Al It is preferably 5% by mass or less with respect to 2 O 3 , and more preferably 3% by mass or less. On the other hand, from the viewpoint of ensuring thermal stability, the content of the “other components” is preferably 0.5% by mass or more with respect to Al 2 O 3 .
アルミナ粒子を構成するＡｌ2Ｏ3の結晶構造としては、δ−Ａｌ2Ｏ3、γ−Ａｌ2Ｏ3、θ−Ａｌ2Ｏ3及びα−Ａｌ2Ｏ3を挙げることができる。中でも、本排気ガス浄化触媒においては、耐熱性と比表面積のバランスの観点から、γ−Ａｌ2Ｏ3及びθ−Ａｌ2Ｏ3が好ましく、中でも耐熱性を維持したままＣｕの分散性を高くすることができる観点から、θ−Ａｌ2Ｏ3が特に好ましい。
なお、上記アルミナ粒子は、これら結晶構造の異なる２種類以上のＡｌ2Ｏ3が複数組み合わさったアルミナ粒子であってもよい。Examples of the crystal structure of Al 2 O 3 constituting the alumina particles include δ-Al 2 O 3 , γ-Al 2 O 3 , θ-Al 2 O 3 and α-Al 2 O 3 . Among these, in the present exhaust gas purification catalyst, γ-Al 2 O 3 and θ-Al 2 O 3 are preferable from the viewpoint of the balance between heat resistance and specific surface area, and among them, Cu dispersibility is high while maintaining heat resistance. From the viewpoint of being able to do, θ-Al 2 O 3 is particularly preferable.
The alumina particles may be alumina particles in which two or more types of Al 2 O 3 having different crystal structures are combined.
（平均粒子径）
アルミナ粒子の平均粒子径（Ｄ５０）は１μｍ〜６０μｍであるのが好ましい。
アルミナ粒子の平均粒子径（Ｄ５０）が１μｍ以上であれば、剥離強度を維持しつつ、耐熱性を維持できるから好ましい。他方、本アルミナの平均粒子径（Ｄ５０）が６０μｍ以下であれば、剥離強度を維持しつつガス接触性を高めることができるから好ましい。
かかる観点から、アルミナ粒子の平均粒子径（Ｄ５０）は１μｍ〜６０μｍであるのが好ましく、中でも３μｍより大きく或いは５０μｍ以下、その中でも特に５μｍ以上或いは４０μｍ以下であるのが好ましい。(Average particle size)
The average particle diameter (D50) of the alumina particles is preferably 1 μm to 60 μm.
An average particle diameter (D50) of alumina particles of 1 μm or more is preferable because heat resistance can be maintained while maintaining peel strength. On the other hand, if the average particle diameter (D50) of this alumina is 60 μm or less, it is preferable because the gas contact property can be enhanced while maintaining the peel strength.
From such a viewpoint, the average particle diameter (D50) of the alumina particles is preferably 1 μm to 60 μm, more preferably 3 μm or more and 50 μm or less, and particularly preferably 5 μm or more or 40 μm or less.
（Ｃｕ元素）
アルミナ粒子の表面に存在するＣｕ元素は、ＣｕＯｘ（０≦ｘ≦１）、ＣｕＡｌ２Ｏ４などの状態で存在している場合を包含する。
この際、当該ＣｕＡｌ２Ｏ４は、アルミナ粒子の表面において、Ｃｕ元素がアルミナに固溶した状態で存在すると推定され、当該ＣｕＯｘ（０≦ｘ≦１）は、アルミナ粒子表面に担持された状態で存在すると推定される。(Cu element)
The Cu element present on the surface of the alumina particles includes a case where Cu element is present in a state such as CuO x (0 ≦ x ≦ 1), CuAl 2 O 4 or the like.
At this time, the CuAl 2 O 4 is presumed to be present in a state where the Cu element is dissolved in the alumina on the surface of the alumina particles, and the CuO x (0 ≦ x ≦ 1) was supported on the surface of the alumina particles. Presumed to exist in the state.
本排気ガス浄化触媒においては、アルミナ粒子の表面に存在するＣｕ元素の存在割合に関し、Ｘ線光電子分光法（XPS：X-ray Photoelectron Spectroscopy）で測定される、Ｃｕの２ｐ軌道（「Ｃｕ２ｐ」とも称する）及びＡｌの２ｐ軌道（「Ａｌ２ｐ」とも称する）の結合エネルギーに対応する各ピークの合計面積を１００％としたとき、Ｃｕ２ｐのピーク面積の割合すなわちＣｕ被覆率は７〜２８％であることが好ましい。
この際、Ｘ線光電子分光法で測定される、Ｃｕ２ｐ及びＡｌ２ｐの各ピーク面積の合計面積に対するＣｕ２ｐのピーク面積の割合は、アルミナ粒子表面のＣｕ元素の存在割合を示していると言える。表面に露出しているＣｕが活性種として作用するから、Ｃｕ被覆率は大きいほどよいが、大きすぎるとシンタリングしてしまう。
かかる観点から、上記Ｃｕ被覆率は７〜２８％であるのが好ましく、中でもＣｕのシンタリングを防ぎ、ＮＯｘ浄化性能をより向上させる観点から２０％以下とすることがより好ましく、その中でも１８％以下、特に１５％以下であるのが好ましい。
なお、「アルミナ粒子の表面にＣｕ元素が存在」とは、例えばＣｕ元素がＣｕＡｌ２Ｏ４となっているように、アルミナに固溶した状態で存在する場合も含むし、またＣｕＯなどとしてアルミナ粒子表面に担持された状態で存在する場合も含む。
また、「担持」とは、Ｃｕなどの活性金属が、アルミナなどの無機多孔質材料と反応せずに固定化されている状態を指す。In this exhaust gas purification catalyst, the Cu 2p orbital (also referred to as “Cu2p”) is measured by X-ray photoelectron spectroscopy (XPS) with respect to the abundance ratio of the Cu element present on the surface of the alumina particles. And the total area of each peak corresponding to the binding energy of the Al 2p orbit (also referred to as “Al2p”) is 100%, the ratio of the peak area of Cu2p, that is, the Cu coverage is 7 to 28%. Is preferred.
At this time, it can be said that the ratio of the peak area of Cu2p to the total area of each peak area of Cu2p and Al2p measured by X-ray photoelectron spectroscopy indicates the presence ratio of Cu element on the surface of the alumina particles. Since Cu exposed on the surface acts as an active species, the higher the Cu coverage, the better. However, if it is too large, sintering will occur.
From this viewpoint, it is preferred the Cu coverage is 7-28%, inter alia to prevent sintering of Cu, NO is more preferably more from the viewpoint of improving than 20% of x purification performance, among which 18 % Or less, particularly preferably 15% or less.
Note that “the presence of Cu element on the surface of alumina particles” includes, for example, the case where Cu element is present in a solid solution state in alumina such as CuAl 2 O 4, and also includes alumina as CuO. Including the case where it is supported on the particle surface.
“Supported” refers to a state in which an active metal such as Cu is immobilized without reacting with an inorganic porous material such as alumina.
さらに本排気ガス浄化触媒は、Ｃｕ０〜１価及びＣｕ２価を含み、且つ、触媒に含まれるＣｕ２価量よりも、触媒に含まれるＣｕ０〜１価量の方が多い方が好ましい。Ｃｕ２価よりもＣｕ０〜１価の方が、よりメタルのＣｕに近いから触媒活性が高いからである。 Further, the present exhaust gas purification catalyst preferably contains Cu0 to 1 valence and Cu2 valence, and more Cu0 to 1 valence contained in the catalyst than Cu2 valence contained in the catalyst. This is because the catalytic activity is higher because Cu 0 to 1 valence is closer to Cu of metal than Cu valence.
かかる観点から、前記Ｃｕの２ｐ軌道の結合エネルギーをＸ線光電子分光法（XPS：X-ray Photoelectron Spectroscopy）で測定して得られる、９２５ｅＶ〜９４０ｅＶのピーク面積（Ｃｕ０〜２価に相当）に対する、９２５ｅＶ〜９３５ｅＶのピーク面積（Ｃｕ０〜１価に相当：Ｃｕ１価ピークのショルダー部分に、Ｃｕ０価ピークが重複して観測されるため、このショルダー部分を含めてＣｕ０〜１価ピークとする）の比率（「Ｃｕ０〜１価の面積率」とも称する）は５０％以上であるのが好ましい。 From this point of view, with respect to the peak area of 925 eV to 940 eV (corresponding to Cu 0 to 2 valence) obtained by measuring the binding energy of the Cu 2p orbit by X-ray photoelectron spectroscopy (XPS), Ratio of peak area of 925 eV to 935 eV (corresponding to Cu 0 to 1 valence: Cu 0 valence peak is observed overlapping with the shoulder portion of Cu 1 valence peak, and this shoulder portion is included as Cu 0 to 1 valence peak) (Also referred to as “Cu 0 to monovalent area ratio”) is preferably 50% or more.
この際、９２５ｅＶ〜９４０ｅＶのピーク面積は０〜２価のＣｕの含有量と相関し、９２５ｅＶ〜９３５ｅＶのピーク面積は０〜１価のＣｕの含有量に相関するから、当該「Ｃｕ０〜１価の面積率」が５０％以上であるのが好ましいということは、Ｃｕ０〜１価（Ｃｕ、Ｃｕ２Ｏなど）及びＣｕ２価（ＣｕＯ、ＣｕＡｌ２Ｏ４など）の中で、Ｃｕ０〜１価の存在割合が高い方が好ましいことを意味している。Ｃｕ２価よりもＣｕ０〜１価の方が触媒活性が高いため、Ｃｕ０〜１価の存在割合を高めることで、本排気ガス浄化触媒の触媒活性を高めることができる。
かかる観点から、当該Ｃｕ０〜１価の面積率は、５５％以上であるのがより好ましく、中でも６０％以上であるのがさらに好ましい。
後述するように、窒素雰囲気下で焼成することにより、Ｃｕ２価よりもＣｕ０〜１価の存在比率を高めることができる。但し、かかる方法に限定するものではなく、水素や一酸化炭素などの還元雰囲気でも構わない。At this time, the peak area of 925 eV to 940 eV correlates with the content of 0 to 2 valent Cu, and the peak area of 925 eV to 935 eV correlates with the content of 0 to 1 valent Cu. It is preferable that the “area ratio” is 50% or more, among Cu 0 to 1 valence (Cu, Cu 2 O, etc.) and Cu 2 valence (CuO, CuAl 2 O 4 etc.). This means that a higher abundance ratio is preferable. Since the catalytic activity of Cu0 to monovalent is higher than that of Cu2, the catalytic activity of the exhaust gas purification catalyst can be increased by increasing the ratio of Cu0 to monovalent.
From this viewpoint, the Cu0 to monovalent area ratio is more preferably 55% or more, and particularly preferably 60% or more.
As will be described later, by firing in a nitrogen atmosphere, the abundance ratio of Cu 0 to 1 valence can be increased rather than Cu 2 valence. However, the method is not limited to this method, and a reducing atmosphere such as hydrogen or carbon monoxide may be used.
また、本排気ガス浄化触媒は、ＣｕＯｘ（０≦ｘ≦１）及びＣｕＡｌ２Ｏ４を含み、Ｈ２による昇温反応法（Ｈ２−ＴＰＲ）により得られる水素消費ピークにおける前記ＣｕＯｘ及びＣｕＡｌ２Ｏ４のピーク面積において、ＣｕＯｘ及びＣｕＡｌ２Ｏ４のピーク面積に対するＣｕＡｌ２Ｏ４のピーク面積率（（ＣｕＡｌ２Ｏ４／（ＣｕＯｘ+ＣｕＡｌ２Ｏ４））×１００）が５０％以下であるのが好ましい。Further, the exhaust gas purifying catalyst, CuO x (0 ≦ x ≦ 1) and CuAl 2 O 4 wherein the warm reaction method by H 2 (H 2 -TPR) the CuO x and in the hydrogen consumption peak obtained by in peak area of CuAl 2 O 4, the peak area ratio of CuO x and CuAl 2 O 4 of CuAl 2 O 4 to the peak area ((CuAl 2 O 4 / ( CuO x + CuAl 2 O 4)) × 100) is 50 % Or less is preferable.
本発明者の研究結果から、Ｃｕ被覆量を高めても、ＣｕＡｌ２Ｏ４の含有量が多くなると、触媒活性種であるＣｕ元素の触媒活性が阻害されることが分かってきた。
かかる観点から、上記ピーク面積率（（ＣｕＡｌ２Ｏ４／（ＣｕＯｘ+ＣｕＡｌ２Ｏ４））×１００）は５０％以下であるのが好ましく、中でも４５％以下、その中でも４０％以下であるのがさらに好ましい。
後述するように、窒素雰囲気下で焼成することにより、Ｃｕ被覆量を高めつつ、ＣｕＡｌ２Ｏ４の生成を抑制することができることが確認されている。但し、かかる方法に限定するものではなく、前述したような水素や一酸化炭素などの還元雰囲気でも、窒素雰囲気での焼成と同様の効果を得ることができると考えられる。From the research results of the present inventors, it has been found that even if the Cu coating amount is increased, the catalytic activity of Cu element which is a catalytically active species is inhibited when the content of CuAl 2 O 4 increases.
From such a viewpoint, the peak area ratio ((CuAl 2 O 4 / (CuO x + CuAl 2 O 4 )) × 100) is preferably 50% or less, particularly 45% or less, and more preferably 40% or less. Is more preferable.
As will be described later, it has been confirmed that by firing in a nitrogen atmosphere, the formation of CuAl 2 O 4 can be suppressed while increasing the Cu coating amount. However, the present invention is not limited to such a method, and it is considered that the same effect as firing in a nitrogen atmosphere can be obtained even in a reducing atmosphere such as hydrogen and carbon monoxide as described above.
また、ピーク面積(水素消費量)から、ＣｕＡｌ２Ｏ４量を定量すると、ＣｕＡｌ２Ｏ４の含有量は本排気ガス浄化触媒中１５質量％以下であるのが好ましい。
本排気ガス浄化触媒において、ＣｕＡｌ２Ｏ４の含有量を１５質量％以下とすることで、触媒活性が良好に維持されることになる。
かかる観点から、ＣｕＡｌ２Ｏ４の含有量が１０質量％以下であるのがより一層好ましく、特に９質量％以下であるのがさらに好ましい。Further, when the amount of CuAl 2 O 4 is quantitatively determined from the peak area (hydrogen consumption), the content of CuAl 2 O 4 is preferably 15% by mass or less in the present exhaust gas purification catalyst.
In this exhaust gas purification catalyst, when the content of CuAl 2 O 4 is 15% by mass or less, the catalytic activity is favorably maintained.
From this viewpoint, the content of CuAl 2 O 4 is more preferably 10% by mass or less, and particularly preferably 9% by mass or less.
＜本排気ガス浄化触媒の製造方法＞
本排気ガス浄化触媒は、例えば硝酸銅を水に溶解して水溶液を作製し、これにアルミナを入れて含浸させてスラリーとし、このスラリーを乾燥させた後、６００〜１０００℃、好ましくは６００〜９００℃で、窒素雰囲気下で焼成（「Ｎ２焼成」とも称する）することにより得ることができる。
また、上記スラリーを基材に塗布し、６００〜１０００℃、好ましくは６００〜９００℃でＮ２焼成することにより得ることができる。
但し、かかる製法に限定するものではない。<Method for producing the present exhaust gas purification catalyst>
The exhaust gas purifying catalyst is prepared by dissolving copper nitrate in water to prepare an aqueous solution, impregnated with alumina to make a slurry, and drying the slurry, then 600 to 1000 ° C., preferably 600 to It can be obtained by firing at 900 ° C. in a nitrogen atmosphere (also referred to as “N 2 firing”).
Further, the slurry was applied to the substrate, 600 to 1000 ° C., preferably can be obtained by N 2 calcined at 600 to 900 ° C..
However, it is not limited to this manufacturing method.
Ｎ２焼成することにより、Ｃｕ被覆量を高めつつ、ＣｕＡｌ２Ｏ４の生成を抑制することができる。しかも、Ｎ２焼成することにより、Ｃｕ０〜１価の比率を高めることができる。大気焼成では、Ｃｕ０〜１価よりもＣｕ２価の比率が高まるのに対し、Ｎ２焼成では、逆にＣｕ２価よりもＣｕ０〜１価の比率が高まり易いことが確認されている。By firing N 2, it is possible to suppress the formation of CuAl 2 O 4 while increasing the Cu coating amount. Moreover, the ratio of Cu 0 to 1 valence can be increased by firing N 2 . The air annealing, while increasing the ratio of Cu2 valence than Cu0~1 valence, the N 2 firing, it is easy increased Cu0~1 monovalent ratio is confirmed than Cu2 valence reversed.
＜本排気ガス浄化触媒の特徴と用途＞
本排気ガス浄化触媒は、触媒活性種としての貴金属を担持することなく、排気ガス浄化触媒性能を発揮することができる。すなわち、炭化水素（ＨＣ）及び一酸化炭素（ＣＯ）は酸化し、且つ、窒素酸化物（ＮＯx）を還元して浄化する触媒活性を備えており、中でもＮＯxの還元性能及びＣＯの酸化性能が特に優れている。よって、ＣＯ、ＨＣ及びＮＯｘを酸化還元することができる三元触媒として有効利用することができる。もっとも、貴金属を担持することを妨げるものではない。<Characteristics and applications of this exhaust gas purification catalyst>
The present exhaust gas purification catalyst can exhibit exhaust gas purification catalyst performance without supporting a noble metal as a catalytically active species. That is, hydrocarbon (HC) and carbon monoxide (CO) oxidize, and have catalytic activity to reduce and purify nitrogen oxide (NO x ), and in particular, NO x reduction performance and CO oxidation. The performance is particularly excellent. Therefore, it can be effectively used as a three-way catalyst that can oxidize and reduce CO, HC, and NO x . However, it does not preclude carrying noble metals.
本排気ガス浄化触媒は、ペレット状などの適宜形状に成形され、単独で触媒として用いることもできるし、また、セラミックス又は金属材料からなる基材に担持された形態として用いることもできる。 The present exhaust gas purification catalyst is formed into an appropriate shape such as a pellet and can be used alone as a catalyst, or can be used as a form supported on a substrate made of ceramics or a metal material.
本排気ガス浄化触媒は、ハニカム形状を呈する基材表面に、例えばバインダーや水酸化ＢａなどのＮＯＸ吸蔵剤と共に触媒層を形成することで三元触媒を作製することができる。この触媒層は、単層構造であっても、二層以上の多層構造であってもよい。The present exhaust gas purifying catalyst can be on the surface of the substrate exhibiting a honeycomb shape to produce a three-way catalyst by forming a catalyst layer with the NO X storage such as for example a binder or a hydroxide Ba. This catalyst layer may have a single layer structure or a multilayer structure of two or more layers.
より具体的には、本排気ガス浄化触媒と、必要に応じて無機多孔質体、ＯＳＣ材、ＮＯＸ吸蔵剤、バインダーなどとを、水を混合・撹拌してスラリーとし、得られたスラリーを、例えばセラミックハニカム体などの基材に塗工し、これを焼成して、基材表面に触媒層を形成するようにして製造することができる。More specifically, the present exhaust gas purifying catalyst, the inorganic porous material as required, OSC materials, NO X absorbent, and the like as a binder, mixing water and stirring to form a slurry and the resulting slurry For example, it can be produced by coating a base material such as a ceramic honeycomb body and firing it to form a catalyst layer on the surface of the base material.
上記の基材としては、セラミックス等の耐火性材料や金属材料を挙げることができる。
セラミック製基材の材質としては、耐火性セラミック材料、例えばコージライト、コージライト−アルファアルミナ、窒化ケイ素、ジルコンムライト、スポジュメン、アルミナ−シリカマグネシア、ケイ酸ジルコニウム、シリマナイト（sillimanite）、ケイ酸マグネシウム、ペタライト（petalite）、アルファアルミナおよびアルミノシリケート類などを挙げることができる。
金属製基材の材質としては、耐火性金属、例えばステンレス鋼または鉄を基とする他の適切な耐食性合金などを挙げることができる。Examples of the base material include refractory materials such as ceramics and metal materials.
The material of the ceramic substrate includes refractory ceramic materials such as cordierite, cordierite-alpha alumina, silicon nitride, zircon mullite, spojumen, alumina-silica magnesia, zirconium silicate, sillimanite, magnesium silicate, Examples include petalite, alpha alumina, and aluminosilicates.
The material of the metal substrate can include refractory metals such as other suitable corrosion resistant alloys based on stainless steel or iron.
上記基材の形状は、ハニカム状、フィルター状、ペレット状、球状を挙げることができる。
ハニカム材料としては、例えばセラミックス等のコージェライト質のものを用いることができる。また、フェライト系ステンレス等の金属材料からなるハニカムを用いることもできる。
ハニカム形状の基材を用いる場合、例えば基材内部を流体が流通するように、基材内部に平行で微細な気体流通路、すなわちチャンネルを多数有するモノリス型基材を使用することができる。この際、モノリス型基材の各チャンネル内壁表面に、触媒組成物をウォッシュコートなどによってコートして触媒層を形成することができる。Examples of the shape of the substrate include a honeycomb shape, a filter shape, a pellet shape, and a spherical shape.
As the honeycomb material, for example, cordierite material such as ceramics can be used. A honeycomb made of a metal material such as ferritic stainless steel can also be used.
When a honeycomb-shaped substrate is used, for example, a monolith type substrate having a large number of parallel and fine gas flow passages, that is, channels, can be used so that fluid flows through the substrate. At this time, the catalyst layer can be formed by coating the inner wall surface of each channel of the monolith substrate with the catalyst composition by wash coating or the like.
上記無機多孔質体としては、例えばシリカ、アルミナおよびチタニア化合物から成る群から選択される化合物の多孔質体、例えばアルミナ、シリカ、シリカ−アルミナ、アルミノ−シリケート類、アルミナ−ジルコニア、アルミナ−クロミアおよびアルミナ−セリアから選択される化合物からなる多孔質体を挙げることができる。 Examples of the inorganic porous material include a porous material of a compound selected from the group consisting of silica, alumina and titania compounds, such as alumina, silica, silica-alumina, alumino-silicates, alumina-zirconia, alumina-chromia, and the like. The porous body which consists of a compound selected from an alumina-ceria can be mentioned.
上記ＯＳＣ材、すなわち酸素ストレージ能（ＯＳＣ：Oxygen Storage Capacity）を有する助触媒としては、例えばセリウム化合物、ジルコニウム化合物、セリア・ジルコニア複合酸化物、セリア・ジルコニア・アルミナ複合酸化物などを挙げることができる。 Examples of the above-mentioned OSC material, that is, a co-catalyst having oxygen storage capacity (OSC) include a cerium compound, a zirconium compound, a ceria / zirconia composite oxide, a ceria / zirconia / alumina composite oxide, and the like. .
上記ＮＯＸ吸蔵剤としては、例えばアルカリ土類金属やアルカリ金属を挙げることができる。中でも、マグネシウム、バリウム、ホウ素、トリウム、ハフニウム、ケイ素、カルシウムおよびストロンチウムから成る群から選択される金属のうちの一種又は二種以上を選択可能である。その中でも、低温でのより良好なＮＯ吸着性の観点から、バリウムが好ましい。Examples of the NO X storage agent include alkaline earth metals and alkali metals. Of these, one or more metals selected from the group consisting of magnesium, barium, boron, thorium, hafnium, silicon, calcium, and strontium can be selected. Among these, barium is preferable from the viewpoint of better NO adsorption at low temperatures.
上記バインダー成分としては、有機系バインダーや無機系バインダー、例えばジルコニアゾルやアルミナゾル等の水溶液を使用することができる。 As the binder component, an organic binder or an inorganic binder, for example, an aqueous solution such as zirconia sol or alumina sol can be used.
＜語句の説明＞
本明細書において「Ｘ〜Ｙ」（Ｘ，Ｙは任意の数字）と表現する場合、特にことわらない限り「Ｘ以上Ｙ以下」の意と共に、「好ましくはＸより大きい」或いは「好ましくはＹより小さい」の意も包含する。
また、「Ｘ以上」（Ｘは任意の数字）或いは「Ｙ以下」（Ｙは任意の数字）と表現した場合、「Ｘより大きいことが好ましい」或いは「Ｙ未満であることが好ましい」旨の意図も包含する。<Explanation of words>
In the present specification, when expressed as “X to Y” (X and Y are arbitrary numbers), unless otherwise specified, “X is preferably greater than X” or “preferably Y”. It also includes the meaning of “smaller”.
In addition, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.
以下、本発明を下記実施例及び比較例に基づいてさらに詳述する。 Hereinafter, the present invention will be further described in detail based on the following examples and comparative examples.
＜実施例１＞
硝酸銅水溶液にＬａ１質量％含有θ−Ａｌ2Ｏ3粉末を加えて撹拌した後、ジルコニアゾルを添加することで、Ｃｕ担持アルミナスラリーを得た。
Φ４０ｍｍ×Ｌ６０ｍｍ（３００セル）：担体容積０．０７５４Ｌの合志技研製ステンレスハニカム基材に、上記で得たスラリーを１６５ｇ／Ｌ塗布し、過剰なスラリーを吹き払った後、１００℃の熱風がスラリー塗布面に直接あたるようにして乾燥させた。
次に、４５０℃で１時間焼成して硝酸根を除去した後、窒素中６００℃で４時間焼成して、実施例１の触媒（サンプル）を得た。
なお、スラリー中の各成分は、酸化銅１１．３質量部、Ｌａ１質量％含有アルミナ８０．２質量部、ジルコニアゾル８．５質量部であった。<Example 1>
A Cu-containing alumina slurry was obtained by adding a 1 mass% La-containing θ-Al 2 O 3 powder to a copper nitrate aqueous solution and stirring, and then adding a zirconia sol.
Φ40 mm × L60 mm (300 cells): 165 g / L of the slurry obtained above was applied to a stainless honeycomb substrate made of Goshi Giken with a carrier volume of 0.0754 L, and after excess slurry was blown off, hot air at 100 ° C. was slurried. It was made to dry so that it might touch the application surface directly.
Next, after calcination at 450 ° C. for 1 hour to remove nitrate radicals, the catalyst (sample) of Example 1 was obtained by calcination at 600 ° C. for 4 hours in nitrogen.
The components in the slurry were 11.3 parts by mass of copper oxide, 80.2 parts by mass of alumina containing 1% by mass of La, and 8.5 parts by mass of zirconia sol.
＜実施例２〜７、比較例１〜３＞
表１に示すように、酸化銅の質量％、アルミナ種、焼成温度、焼成雰囲気を変更した以外、実施例１と同様の手順にて、実施例２〜７及び比較例１〜３の触媒（サンプル）を得た。
なお、比較例３については、実施例１と同様にＣｕ担持アルミナスラリーを調製及びステンレスハニカム基材への塗布・乾燥を行い、４５０℃で１時間焼成して硝酸根を除去して作製した。しかし、窒素中６００℃で４時間の焼成は行わなかった。<Examples 2-7, Comparative Examples 1-3>
As shown in Table 1, the catalysts of Examples 2 to 7 and Comparative Examples 1 to 3 were prepared in the same procedure as Example 1 except that the copper oxide mass%, the alumina species, the firing temperature, and the firing atmosphere were changed. Sample).
In Comparative Example 3, a Cu-supported alumina slurry was prepared, applied to a stainless honeycomb substrate and dried in the same manner as in Example 1, and fired at 450 ° C. for 1 hour to remove nitrate radicals. However, the baking was not performed at 600 ° C. for 4 hours in nitrogen.
＜ＸＰＳによる表面分析＞
Ｘ線光電子分光分析（XPS：X-ray Photoelectron Spectroscopy）により、実施例・比較例で得た触媒（サンプル）表面の分析を行った。
XPSの分析装置としてアルバック・ファイ株式会社製のＱｕａｎｔｕｍ２０００（ビーム条件：５０Ｗ、２００μｍ径）を用い、解析ソフトウェアとして「ＭｕｌｔｉＰａｃｋ ｖｅｒ．６．１」を用いて状態・半定量用ナロー測定を行った。Ｘ線源として、Ａｌ−Ｋα線（１４８６．８ｅＶ）を用いて、１７ｋＶ×０．０２３Ａで操作した。
帯電補正：Ｃ１ｓを２８４．０ｅＶとして帯電補正を行った。<Surface analysis by XPS>
The surface of the catalyst (sample) obtained in Examples and Comparative Examples was analyzed by X-ray photoelectron spectroscopy (XPS).
Quantum 2000 (beam condition: 50 W, 200 μm diameter) manufactured by ULVAC-PHI Co., Ltd. was used as an XPS analyzer, and “MultiPack ver. 6.1” was used as analysis software to perform state / semi-quantitative narrow measurement. Using an Al-Kα ray (1486.8 eV) as an X-ray source, operation was performed at 17 kV × 0.023 A.
Charging correction: Charging correction was performed with C1s set to 284.0 eV.
より具体的には、実施例・比較例で得た触媒（サンプル）について、Ｘ線光電子分光装置（ＸＰＳ）を用いて、上記条件で触媒表面を分析し、得られたＸ線光電子分光スペクトルにおいて、Ｃｕ２ｐの結合エネルギーに対応するＣｕ０〜２価の光電子を検出して得られるピーク面積及びＡｌ２ｐの結合エネルギーに対応するＡｌ酸化物の光電子を検出して得られるピーク面積の合計面積を１００％としたときのＣｕ２ｐのピーク面積の割合（表１の「Ｃｕ被覆率」）を求めた。
また、Ｘ線光電子分光装置（ＸＰＳ）を用いて上記条件でＣｕ表面を分析し、９２５ｅＶ〜９４０ｅＶのピーク及び９２５ｅＶ〜９３５ｅＶのピークを波形分離し、９２５ｅＶ〜９４０ｅＶのピーク面積（Ｃｕ０〜２価に相当）に対する、９２５ｅＶ〜９３５ｅＶのピーク面積（Ｃｕ０〜１価に相当）の比率（表１の「Ｃｕ０〜１価の面積率（％）」）を算出した。
なお、Ｘ線光電子分光装置（ＸＰＳ）は、粒子表面から約十ｎｍまでの深さの元素成分について半定量分析を行うことができる。More specifically, for the catalysts (samples) obtained in the examples and comparative examples, the surface of the catalyst was analyzed using the X-ray photoelectron spectrometer (XPS) under the above conditions. The total area of the peak area obtained by detecting Cu0 to divalent photoelectrons corresponding to the binding energy of Cu2p and the peak area obtained by detecting the photoelectrons of Al oxide corresponding to the binding energy of Al2p is 100%. The ratio of the peak area of Cu2p ("Cu coverage" in Table 1) was determined.
In addition, the Cu surface was analyzed under the above conditions using an X-ray photoelectron spectrometer (XPS), and the peaks of 925 eV to 940 eV and the peaks of 925 eV to 935 eV were separated into waveforms, and the peak area of 925 eV to 940 eV (Cu 0 to divalent). The ratio (corresponding to Cu0 to monovalent area ratio (%) in Table 1) of the peak area (corresponding to Cu0 to monovalent) of 925 eV to 935 eV was calculated.
The X-ray photoelectron spectrometer (XPS) can perform semi-quantitative analysis on elemental components at a depth of about 10 nm from the particle surface.
＜平均粒子径の測定＞
アルミナの平均粒子径（Ｄ５０）はレーザー回折・散乱式粒度径分布を用いて測定し、表１に示した。
レーザー回折粒子径分布測定装置用自動試料供給機（日機装株式会社製「Ｍｉｃｒｏｔｏｒａｃ ＳＤＣ」）を用い、サンプル（粉体）を水溶性溶媒に投入し、５０％の流速中、３０Ｗの超音波を３６０秒間照射した後、日機装株式会社製レーザー回折粒度分布測定機「ＭＴ３０００ＩＩ」を用いて粒度分布を測定し、得られた体積基準粒度分布のチャートからＤ５０を測定した。この際、測定条件は、粒子屈折率１．５、粒子形状真球形、溶媒屈折率１．３、セットゼロ３０秒、測定時間３０秒、２回測定の平均値として求めた。<Measurement of average particle diameter>
The average particle size (D50) of alumina was measured using a laser diffraction / scattering particle size distribution and shown in Table 1.
Using an automatic sample feeder for a laser diffraction particle size distribution measuring device (“Microtorac SDC” manufactured by Nikkiso Co., Ltd.), a sample (powder) is charged into a water-soluble solvent, and 30 W ultrasonic waves are transmitted at a flow rate of 50%. After irradiation for 2 seconds, the particle size distribution was measured using a laser diffraction particle size distribution analyzer “MT3000II” manufactured by Nikkiso Co., Ltd., and D50 was measured from the obtained volume-based particle size distribution chart. At this time, the measurement conditions were determined as an average value of particle refractive index 1.5, particle shape true sphere, solvent refractive index 1.3, set zero 30 seconds, measurement time 30 seconds, and twice measurement.
＜Ｈ2−ＴＰＲ＞
Ｈ２による昇温反応法（Ｈ２−ＴＰＲ）により、実施例・比較例で得た触媒粉体（サンプル）の水素消費ピークを測定した。
具体的には、熱伝導型検出器を備えた流通式管型反応器を用いて、２％水素（アルゴンバランス）を流通して常温〜８００℃の条件の下、Ｈ２−ＴＰＲの測定を行った。なお、Ｈ２−ＴＰＲ測定でみられる１００〜３５０℃の水素消費ピークをＣｕＯｘ、３５０℃以上に現れる水素消費ピークをＣｕＡｌ２Ｏ４として前記ＣｕＯｘ及びＣｕＡｌ２Ｏ４のピーク面積において、ＣｕＯｘ及びＣｕＡｌ２Ｏ４のピーク面積に対するＣｕＡｌ２Ｏ４のピーク面積率（（ＣｕＡｌ２Ｏ４／（ＣｕＯｘ+ＣｕＡｌ２Ｏ４））×１００、表１の「ＣｕＡｌ２Ｏ４ピーク面積率（％）」を求めた。また、得られたピーク面積(水素消費量)からＣｕＡｌ２Ｏ４の定量を行い、表１の「触媒中のＣｕＡｌ２Ｏ４量（質量％）」を求めた。<H 2 -TPR>
Heating the reaction method using H 2 by (H 2-TPR), hydrogen was measured consumption peaks of the catalyst powder obtained in Examples and Comparative Examples (samples).
Specifically, using a flow-type tubular reactor equipped with a heat conduction type detector, H 2 -TPR was measured under conditions of normal temperature to 800 ° C. by flowing 2% hydrogen (argon balance). went. In addition, in the peak area of CuO x and CuAl 2 O 4 , the hydrogen consumption peak at 100 to 350 ° C. seen in H 2 -TPR measurement is CuO x , and the hydrogen consumption peak that appears at 350 ° C. or more is CuAl 2 O 4. x and CuAl 2 O CuAl 2 O 4 of the peak area ratio to the peak area of 4 ((CuAl 2 O 4 / (CuO x + CuAl 2 O 4)) × 100, "CuAl 2 O 4 peak area ratio of Table 1 ( In addition, CuAl 2 O 4 was quantified from the obtained peak area (hydrogen consumption amount), and “CuAl 2 O 4 amount (mass%) in the catalyst” in Table 1 was determined.
なお、表１中のＣｕＡｌ２Ｏ４ピーク面積率（％）＝０の場合は、ＣｕがすべてＣｕＯｘとしてアルミナに担持された状態を指し、０より大きい場合は、Ｃｕの一部はＣｕＯｘとしてアルミナに担持され、一部はＣｕＡｌ２Ｏ４のようにアルミナに固溶された状態で存在していることを指す。
また、実施例６及び比較例２では触媒中の酸化銅の含有量が他の材料よりも多かったため、Ｈ２−ＴＰＲによる水素消費ピークが他と異なる挙動を示し、ＣｕＡｌ２Ｏ４の正確なピークを抽出することができなかった。そのため、「ＣｕＡｌ２Ｏ４のピーク面積率」及び「触媒中のＣｕＡｌ２Ｏ４量」は定量不可とした。しかし、ＸＲＤから実施例６ではＣｕの大部分がＣｕＯｘ、比較例２ではＣｕの大部分がＣｕＡｌ２Ｏ４として存在することが確認された。When the CuAl 2 O 4 peak area ratio (%) in Table 1 is 0, it means that Cu is supported on alumina as CuO x , and when it is larger than 0, a part of Cu is CuO x. It is supported on alumina and a part thereof is present in a solid solution state in alumina such as CuAl 2 O 4 .
Further, in Example 6 and Comparative Example 2, the content of copper oxide in the catalyst was higher than that of other materials. Therefore, the hydrogen consumption peak due to H 2 -TPR showed a behavior different from the others, and the accurate of CuAl 2 O 4 A peak could not be extracted. Therefore, "CuAl 2 peak area ratio of O 4" and "CuAl 2 O 4 content in the catalyst" was quantified impossible. However, XRD confirmed that the majority of Cu was present as CuO x in Example 6 and the majority of Cu as CuAl 2 O 4 in Comparative Example 2.
＜排気ガス浄化性能評価試験＞
各実施例・比較例で得られた触媒（浄化性能評価サンプル）を、下記組成のモデルガス中のＣＯ、ＨＣおよびＮＯｘそれぞれの５０％浄化率に到達する温度（℃）を測定して、各々の触媒の三元浄化性能を評価した。評価条件は下記の通りである。<Exhaust gas purification performance evaluation test>
The catalyst (purification performance evaluation sample) obtained in each of the examples and comparative examples was measured for temperatures (° C.) at which 50% purification rates of CO, HC and NO x in the model gas having the following composition were reached, The three-way purification performance of each catalyst was evaluated. The evaluation conditions are as follows.
（モデルガス組成）
ＣＯ：１．２５％
Ｃ３Ｈ６：１７４０ｐｐｍ
ＮＯ：２４５０ｐｐｍ
Ｏ２：０．６％
ＣＯ２：１４％
Ｈ２Ｏ：１０％
Ｎ２：残部
Ａ／Ｆ：１４．５
ガス流速：２５Ｌ／ｍｉｎ
昇温速度：２０℃／ｍｉｎ(Model gas composition)
CO: 1.25%
C 3 H 6 : 1740 ppm
NO: 2450ppm
O 2 : 0.6%
CO 2 : 14%
H 2 O: 10%
N 2 : remainder A / F: 14.5
Gas flow rate: 25L / min
Temperature increase rate: 20 ° C / min
上記実施例・比較例並びにこれまで本発明者が行ってきた試験結果から、アルミナ粒子の表面にＣｕ元素が存在してなる構成を備えた排気ガス浄化触媒に関しては、Ｘ線光電子分光法（ＸＰＳ）で測定される、Ｃｕ２ｐ及びＡｌ２ｐの各ピーク面積の合計面積を１００％としたとき、Ｃｕ２ｐのピーク面積の割合（「Ｃｕ被覆率」）が７〜２８％であれば、触媒活性成分として貴金属を担持しなくても、優れた触媒活性を発揮することが分かった。 From the above-mentioned Examples / Comparative Examples and the results of tests conducted by the present inventor, the X-ray photoelectron spectroscopy (XPS) is applied to the exhaust gas purification catalyst having a structure in which Cu elements are present on the surface of alumina particles. ), The total area of each peak area of Cu2p and Al2p is 100%, and if the ratio of the peak area of Cu2p (“Cu coverage”) is 7 to 28%, noble metal as a catalyst active component It was found that excellent catalytic activity can be exhibited even without supporting.
さらに、上記実施例・比較例並びにこれまで本発明者が行ってきた試験結果から、前記Ｃｕの２ｐ軌道の結合エネルギーをＸ線光電子分光法で測定して得られる、９２５ｅＶ〜９４０ｅＶのピーク面積（Ｃｕ０〜２価に相当）に対する、９２５ｅＶ〜９３５ｅＶのピーク面積（Ｃｕ０〜１価に相当）の比率（「Ｃｕ０〜１価の面積率」）が５０％以上であれば、触媒活性をさらに高めることができることが分かった。 Furthermore, from the above-mentioned Examples / Comparative Examples and the results of tests conducted by the present inventor, the peak area (925 eV to 940 eV) obtained by measuring the binding energy of the Cu 2p orbital by X-ray photoelectron spectroscopy ( If the ratio of the peak area of 925 eV to 935 eV (corresponding to Cu0 to 1 valence) relative to Cu0 to 2 valence (“Cu0 to 1 valence”) is 50% or more, the catalytic activity is further enhanced. I found out that
また、上記実施例・比較例並びにこれまで本発明者が行ってきた試験結果から、ＣｕＯｘ（０≦ｘ≦１）及びＣｕＡｌ２Ｏ４を含み、Ｈ２による昇温反応法（Ｈ２−ＴＰＲ）により得られる水素消費ピークにおける前記ＣｕＯｘ及びＣｕＡｌ２Ｏ４のピーク面積において、ＣｕＯｘ及びＣｕＡｌ２Ｏ４のピーク面積に対するＣｕＡｌ２Ｏ４のピーク面積率（（ＣｕＡｌ２Ｏ４／（ＣｕＯｘ+ＣｕＡｌ２Ｏ４））×１００）が５０％以下であれば、触媒活性をさらに高めることができることが分かった。Further, from the above Examples and Comparative Examples and the test results to date present inventors have carried out, CuO x (0 ≦ x ≦ 1) and CuAl 2 O 4 wherein the warm reaction method by H 2 (H 2 - in the peak area of the CuO x and CuAl 2 O 4 in the hydrogen consumption peak obtained by TPR), the peak area ratio of CuO x and CuAl 2 O 4 of CuAl 2 O 4 to the peak area ((CuAl 2 O 4 / ( CuO It has been found that if x + CuAl 2 O 4 )) × 100) is 50% or less, the catalytic activity can be further increased.
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