CN103889554A - 用于制备二氧化铈-氧化锆-氧化铝复合氧化物的方法及其应用 - Google Patents
用于制备二氧化铈-氧化锆-氧化铝复合氧化物的方法及其应用 Download PDFInfo
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- CN103889554A CN103889554A CN201280052460.8A CN201280052460A CN103889554A CN 103889554 A CN103889554 A CN 103889554A CN 201280052460 A CN201280052460 A CN 201280052460A CN 103889554 A CN103889554 A CN 103889554A
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- CN
- China
- Prior art keywords
- zirconium
- cerium
- earth metal
- aluminum oxide
- compound
- Prior art date
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- -1 cerium (IV) compound Chemical class 0.000 claims abstract description 31
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 6
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 6
- 238000002485 combustion reaction Methods 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 18
- 150000002910 rare earth metals Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002912 waste gas Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 230000006641 stabilisation Effects 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 4
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 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
- 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
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims 2
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims 1
- OKJMLYFJRFYBPS-UHFFFAOYSA-J tetraazanium;cerium(4+);tetrasulfate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OKJMLYFJRFYBPS-UHFFFAOYSA-J 0.000 claims 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 5
- GTEJAEKKYCZWHX-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[Al+3].[Zr+4].[Ce+3] Chemical compound [O--].[O--].[O--].[O--].[O--].[Al+3].[Zr+4].[Ce+3] GTEJAEKKYCZWHX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000012066 reaction slurry Substances 0.000 abstract 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 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000758 substrate Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- GTLIZBSOPDMZRP-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[OH4+2].[Zr+4] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[OH4+2].[Zr+4] GTLIZBSOPDMZRP-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910004625 Ce—Zr Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 229910052878 cordierite Inorganic materials 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000006069 physical mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 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
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910001017 Alperm Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 239000010410 layer 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide 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
- 238000005245 sintering Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
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Abstract
公开了用于制备二氧化铈-氧化锆-氧化铝复合氧化物的方法。该方法包括将铈(IV)化合物和锆(IV)化合物与铝氧化物的浆料在高于40℃的温度合并以制备反应浆料,然后将反应浆料与沉淀剂接触以将不可溶的铈和锆化合物沉淀到铝氧化物上并形成铈-锆-铝氧化物颗粒,和煅烧铈-锆-铝氧化物颗粒以生成二氧化铈-氧化锆-氧化铝复合氧化物。该制备二氧化铈-氧化锆-氧化铝复合氧化物的方法提供了具有高氧储存/释放容量的材料,适于强化清洁内燃机废气的催化剂。
Description
发明领域
本发明涉及用于制备二氧化铈-氧化锆-氧化铝复合氧化物的方法,和通过本发明的方法制备的复合氧化物的应用。
发明背景
内燃机产生含有多种污染物(包括烃、一氧化碳和氮氧化物)的废气。许多不同的技术已经应用到排气***以在废气进入大气之前对其进行清洁。对于汽车应用来说,最常用的催化剂是“三效催化剂”(TWC)。TWC起到三个主要作用:(1)氧化CO;(2)氧化未燃烧的烃;和(3)将NOx还原为N2。
TWC需要谨慎的发动机管理技术以确保发动机在或接近化学计量条件(空气/燃料比,λ=1)运行。但是,在运行周期中的各个阶段,需要发动机在非化学计量条件运行。当发动机富燃运转时(λ<1),例如在加速时,由于废气组分的还原属性,更难以在催化剂表面上进行氧化反应。结果是,TWC经发展引入一种组分,其在运行周期的较贫燃期间(λ>1)储存氧,在较富燃期间释放氧以扩展有效的操作范围(operating envelope)。
铈-锆复合氧化物广泛用作三效催化剂中的氧储存组分(OSC),并且是许多环境催化剂中的关键组分,这是由于它们独特的氧储存/释放性能和良好的水热稳定性。但是,当暴露于升高的温度,铈-锆混合氧化物仍会发生剧烈烧结,这通常还导致它们氧储存容量的显著降低。为了进一步改进热稳定性,对具有另外的元素的铈-锆复合氧化物进行了研究。
已经报道了将氧化铝引入铈-锆氧化物,作为改进该材料的耐热性和增强氧储存/释放性能的手段。在日本公开7-300315中,将铈-锆盐前体浸渍到氧化铝氧化物上。在美国专利5,883,037中,将铈-锆氢氧化物沉淀,然后与混合氧化铝以形成混合物。在美国专利6,306,794和6,150,288,以及PCT国际申请WO2006/070201中,描述了通过铈/锆/铝盐前体的共沉淀来制备均匀的铝-铈-锆复合氧化物。在美国申请公布2007/0191220A1中,描述了在铈-锆氧化物上具有氧化铝表面涂层的材料。在美国申请公布2011/0171092A1中,将铈-锆复合氧化物与γ-氧化铝粉、氧化锆粉和含有铂和铑化合物的水一起球磨,以生成浆液,然后将该浆液涂覆到流通式整料上以生成废气净化催化剂。
在二氧化铈-氧化锆-氧化铝复合氧化物的制备以及它们在废气处理***中的应用仍需要进一步的改进。本发明人已经发现了制备二氧化铈-氧化锆-氧化铝复合氧化物的新方法,该方法提供了具有用于清洁内燃机废气的增强的氧储存/释放容量的材料。
发明内容
本发明包括用于制备二氧化铈-氧化锆-氧化铝复合氧化物的方法和该材料的应用。该方法包括在高于40℃的温度将铈(IV)化合物和锆(IV)化合物与铝氧化物的浆料合并以生成反应浆料,然后将该反应浆料与沉淀剂接触以将不可溶的铈和锆化合物沉淀到氧化铝上以形成铈-锆-铝氧化物颗粒,并煅烧该铈-锆-铝氧化物颗粒以生成二氧化铈-氧化锆-氧化铝复合氧化物。二氧化铈-氧化锆-氧化铝复合氧化物用作TWC上的组分,并表现出改进的CO、NOx和烃转化率。
发明详细说明
本发明是用于制备二氧化铈-氧化锆-氧化铝复合氧化物的方法。该方法包括首先在高于40℃的温度将铈(IV)化合物和锆(IV)化合物与铝氧化物的浆料合并以生成反应浆料。
尽管本发明的方法不受到对具体铈(IV)化合物的选择的限制,但是可用于本发明中适合的铈(IV)化合物包括但不限于铈(IV)的硝酸盐、硝酸铵盐、硫酸盐、硫酸铵盐、醇盐(例如异丙醇盐)及其混合物。优选的铈(IV)化合物包括硝酸铈(IV)和硝酸铵铈(IV)。
适合的锆(IV)化合物包括但不限于锆(IV)的羧酸盐(例如醋酸盐、柠檬酸盐)、卤化物(例如氯化物、溴化物)、卤氧化物(例如氯氧化物)、碳酸盐、硝酸盐、含氧硝酸盐、硫酸盐及其混合物。优选的锆(IV)化合物包括含氧硝酸锆(IV)和氯氧化锆(IV)。
可用于本发明的实践的适合的铝氧化物是含有主要比例的氧化铝(Al2O3)的固体氧化物,优选为多孔的,其中具有遍布其结构的很多孔、空隙和间隙。总的来说,适合的铝氧化物进一步的特征在于具有相对于其质量的大比表面积。在此使用并且本领域中一般用来表示表面积与质量关系的术语是“比表面积”。出于本发明的目的,铝氧化物优选具有至少10m2/g的比表面积,更优选为50m2/g至500m2/g,最优选为80m2/g至300m2/g。
优选的铝氧化物包括各种形式的氧化铝,包括公知的氧化铝如α-氧化铝、θ-氧化铝、ζ-氧化铝、γ-氧化铝和活性氧化铝。活性氧化铝是部分羟基化的铝氧化物,其化学组成可以由式Al2O(3-x)(OH)2x来代表,其中x范围为约0-0.8。
铝氧化物优选具有大于0.05μm(微米)的平均粒度,更优选为约0.11μm-约400μm,最优选为大于1μm,尤其是1μm-约40μm.
优选地,铝氧化物是经稀土金属或碱土金属稳定化的铝氧化物,更优选该经稀土金属或碱土金属稳定化的铝氧化物含有选自镧、钕、镨、钇、钡和锶的稀土金属或碱土金属。优选地,该经稀土金属或碱土金属稳定化的铝氧化物包含0.1-20wt%的稀土金属或碱土金属。
将铈和锆化合物与铝氧化物浆料合并以生成反应浆料可以通过任何常规方法来实现。优选地,首先通过将铝氧化物加入溶剂来形成铝氧化物浆料。溶剂优选为水。铝氧化物浆料优选含有0.1-50wt%的铝氧化物,更优选为1-20wt%。然后将浆料加热至高于40℃的温度,优选高于50℃,最优选为60℃-100℃的温度,然后加入铈(IV)化合物锆(IV)化合物。加入铈和锆的顺序并不特别关键,因此可见先加入铈,可以先加入锆,或者可以同时加入铈和锆化合物。
任选地,还可以将稀土金属或过渡金属化合物与铈化合物、锆化合物和铝氧化物浆料合并以形成反应浆料。将稀土金属或过渡金属化合物加入铝浆料可以在加热至高于40℃的温度之前,在加入铈(IV)化合物和/或锆(IV)化合物之前或之后,或者与加入铈(IV)化合物和/或锆(IV)化合物同时。稀土金属优选选自镧、钕、镨和钇化合物。过渡金属优选选自铁、锰、钴和铜化合物。优选地,加入稀土金属或过渡金属化合物以使得反应浆料中稀土金属或过渡金属:铈和锆的摩尔比((稀土金属或过渡金属的摩尔数)/(铈的摩尔数+锆的摩尔数))为0.001-10。
通常,用来制备二氧化铈-氧化锆-氧化铝复合氧化物的方法包括形成反应混合物,其中浆料添加剂的重量比(定义为二氧化铈的重量百分比,氧化锆的重量比,和Al2O3的重量比)优选包括以下重量比:CeO2:ZrO2:Al2O3=0.1-70:0.1-70:95-10,更优选为5-60:5-60:90-20。Ce:Zr的重量比优选为0.05-19,更优选为0.25-1.5。
形成反应浆料之后,将该反应浆料与沉淀剂接触以使不可溶的铈和锆物类沉淀到铝氧化物上并形成铈-锆-铝氧化物颗粒。
沉淀剂是能够使可溶的铈(IV)化合物和可溶的锆(IV)化合物从水溶液中沉淀出来的任何化合物。沉淀剂通常为碱性化合物,可以选自任何适合的碱性材料,优选例如碱金属和碱土金属碳酸盐、铵和烷基铵碳酸盐、铵和烷基铵氢氧化物、碱金属和碱土金属氢氧化物、水溶性有机碱化合物及其混合物。沉淀剂优选为氢氧化铵或氢氧化钠。
通过沉淀步骤形成后,铈-锆-铝氧化物颗粒优选通过使用本领域公知的技术进行分离。这些包括过滤、倾析、蒸发、洗涤或喷雾干燥。优选地,铈-锆-铝氧化物颗粒经过滤,然后用水或另一种溶剂洗涤以分离颗粒,之后煅烧。在另一实施方案中,铈-锆-铝氧化物颗粒经过喷雾干燥(或快速干燥)以形成颗粒尺寸的微球。通过使浆料混合物进行快速干燥,清除水同时活化铈-锆-铝氧化物,从而形成微球。得到的微球通常粒度为5-100微米。
最后煅烧铈-锆-铝氧化物颗粒以生成二氧化铈-氧化锆-氧化铝复合氧化物产物。煅烧通常通过加热铈-锆-铝氧化物颗粒来进行,优选在氧化气氛例如空气或氮/氧混合物下,在升高的温度进行。煅烧的优选温度范围为400-1000℃。通常,约0.5-24小时的煅烧时间将足以生成二氧化铈-氧化锆-氧化铝复合氧化物产物。
本发明还包括通过本发明的方法制备的二氧化铈-氧化锆-氧化铝复合氧化物,和包含一种或多种铂族金属和二氧化铈-氧化锆-氧化铝复合氧化物的三效催化剂。铂族金属(PGM)优选为铂、钯、铑或其混合物;特别优选铂、铑及其混合物。PGM适合的负载量为0.04-7.1g/L(1-200g/ft3)催化剂体积。
三效催化剂优选涂覆在基底上。该基底优选为陶瓷基底或金属基底。陶瓷基底可以由任何适合的耐火材料制成,例如氧化铝、二氧化硅、二氧化钛、二氧化铈、氧化锆、氧化镁、沸石、氮化硅、碳化硅、硅酸锆、硅酸镁、硅铝酸盐和金属硅铝酸盐(例如堇青石和锂辉石),或者其任意两种或多种的混合物或混合氧化物。特别优选堇青石(一种镁硅铝酸盐)和碳化硅。
金属基底可以由任何适合的金属制成,特别是耐热金属和金属合金,例如钛和不锈钢以及含有铁、镍、铬和/或铝还有其他痕量金属的铁素体合金。
基底可以是过滤器基底或流通式基底,最优选为流通式基底,尤其是蜂窝状整料。基底通常经设计以提供机动车废气从中穿过的许多通道。通道的表面负载有催化剂。
三效催化剂可以通过任何已知手段加入到基底。例如,可以将复合氧化物或含PGM的复合氧化物催化剂作为活化涂层(一种结合到基底表面的多孔的高表面积层)施涂并结合到基底。活化涂层通常从水基浆料施涂到基底,然后干燥和在高温煅烧。只要将复合氧化物活化涂覆到基底上,则PGM金属可以负载到干燥的活化涂层载体层上(通过浸渍、离子交换等),然后干燥和煅烧。
本发明还包括处理来自内燃机的废气,特别是用于处理来自汽油机的废气。该方法包括将废气与本发明的三效催化剂接触。
以下实施例只用于阐释本发明。本领域技术人员将会认识到处于本发明的精神和权利要求书的范围之内的许多改变。
实施例1:制备Ce-Zr-Al复合氧化物
催化剂1A:将蒸馏水(495kg)中的La掺杂的γ-氧化铝(22.5kg,含有4%La2O3,d50=20μm)的浆料加热到70℃,然后加入硝酸铈(IV)水溶液(37.2kg,16.3wt%的Ce)、含氧硝酸锆水溶液(27.0kg,14.6wt%的Zr)和氢氧化铵水溶液(31kg,29wt%的NH4OH)。将反应混合物在70℃加热1小时,同时保持pH值在8以上,然后过滤和用蒸馏水洗涤。在静态烘箱中将湿饼滤液在110℃在空气中加热12小时,然后在空气中在500℃煅烧4小时以获得催化剂1A。催化剂1A含有21wt%的CeO2和15wt%的ZrO2。
催化剂1B:按照催化剂1A的程序制备催化剂1B,只是使用含有4%La2O3的胶态勃姆石(3.23kg,d50=70nm)代替La掺杂的γ-氧化铝,并在70kg蒸馏水成浆,使用5.30kg硝酸铈(IV)溶液、3.86kg含氧硝酸锆溶液和4.5kg氢氧化铵溶液来制备催化剂1B。催化剂1B含有21wt%的CeO2和15wt%的ZrO2。
对比实施例2:制备氧化铝和Ce-Zr氧化物的物理混合物
对比催化剂2:通过以下来制备Ce-Zr氧化物和Al2O3的物理混合物:将含有4%La2O3的γ-氧化铝与铈-锆复合氧化物共混,该铈-锆复合氧化物通过将硝酸铈(IV)水溶液(18.2kg,7.7wt%的Ce)、含氧硝酸锆水溶液(6.3kg,14.8wt%的Zr)和氢氧化铵水溶液(7kg,29wt%的NH4OH)在70℃合并来生成,然后在70℃加热1小时同时保持pH值在8以上,然后过滤和用蒸馏水洗涤。在静态烘箱中将湿饼滤液在110℃在空气中加热12小时,然后在空气中在500℃煅烧4小时以获得对比催化剂2。对比催化剂2含有21wt%的CeO2和15wt%的ZrO2。
实施例3:实验室测试程序和结果
通过在1000℃在空气中烧制4小时来对催化剂1A和1B和对比催化剂的粉末样品进行热耐久性测试。烧制后,使用BET表面积、XRD晶体结构和氧释放容量对样品进行表征。
BET表面积结果列于表1。催化剂1A具有最高的表面积,然后是对比催化剂2,再然后是催化剂1B。催化剂1B表面积较低归因于与γ-氧化铝相比勃姆石的热耐久性较低。催化剂1A和对比催化剂2均采用γ-氧化铝。催化剂1A具有更高的表面积,表明本发明方法对于增大表面积的益处。
催化剂的XRD测试证明催化剂1A和催化剂1B表现出单一的Ce0.5Zr0.5O2晶相。相反,对比催化剂2表现出混合的铈-锆相。这些结果清楚地证明本发明的方法可以得到更好的相均一性。
通过H2-TPR(程序升温还原)实验来确定氧释放峰值温度。在可以分配给将Ce(IV)还原为Ce(III)和从Ce(IV)释放氧的多种温度,催化剂的H2-TPR结果均给出一个主要峰,不过对比催化剂2的峰非常宽。结果示于表1。从催化剂1A和1B的氧释放出现在比对比催化剂2更低的温度。
在100-500℃、500-600℃和600-900℃三个温度范围确定Ce(IV)还原为Ce(III)的百分比。结果示于表2。结果显示,在100-500℃的低温范围,催化剂1A与对比催化剂2相比具有约两倍的Ce(IV)还原量,还证明通过本发明的方法制备的材料在较低温度可以更有效地释放氧。
在较低温度更有效地释放氧的能力,对于环境排放补救中的催化剂应用来说,是需要的特性。
实施例4:发动机测试程序和结果
对比催化剂4A是商业三效(Pd-Rh)催化剂,采用通过将商业铈-锆混合氧化物(Ce:Zr=1摩尔比)与商业La-稳定化的氧化铝(4%La2O3)以0.57:1重量比共混而生成的Ce-Zr-Al混合氧化物。
催化剂4B与对比催化剂4A相同,只是将对比催化剂4A中所用的Ce-Zr-Al混合氧化物用催化剂1A的二氧化铈-氧化锆氧化铝复合氧化物代替。
根据废气排放联邦测试程序(FTP)按照EPA认证程序和容差对对比催化剂4A和催化剂4B进行测试。
2.3L发动机机动车FTP测试:将三效催化剂在汽油机中在924℃的最高温度老化100小时。在2.3L汽油机动车上测试经老化的催化剂(4A和4B)在FTP周期期间的排气管NOx、烃(HC)和CO排放。结果示于表3,其显示了当使用催化剂4B时,与对比催化剂4A相比,排放中百分比降低。
3.5L发动机机动车FTP测试:将三效催化剂在汽油机中在877℃的最高温度老化100小时。在3.5L汽油机动车上测试经老化的催化剂(4A和4B)在FTP周期期间的排气管NOx、HC和CO排放。结果示于表3,其显示了当使用催化剂4B时,与对比催化剂4A相比,排放中百分比降低。
发动机测试结果显示,对于采用本发明的二氧化铈-氧化锆-氧化铝复合氧化物的三效催化剂体系来说,NOx、CO和烃排放显著降低。
表1:测试结果
催化剂 | BET S.A.(m2/g) | H2-TPR中的峰值温度(℃)1 |
1A | 95 | 455 |
1B | 73 | 508 |
2* | 83 | 540 |
*对比实施例
1在空气中1000℃/4h
表2:在三个温度范围的铈还原(IV至III)
温度范围(℃) | 催化剂1A | 催化剂1B | 对比催化剂2* |
100-500 | 48.4% | 27.7% | 23.7% |
500-600 | 19.9% | 40.3% | 36.1% |
600-900 | 31.8% | 29.2% | 40.3% |
*对比实施例
表3:与对比催化剂4A相比,使用催化剂4B的排放减少
发动机 | NOx减少(%) | CO减少(%) | NMHC1减少(%) |
2.3L | 2 | 15 | 12 |
3.5L | 5 | 24 | 29 |
1NMHC=非甲烷烃
Claims (16)
1.用于制备二氧化铈-氧化锆-氧化铝复合氧化物的方法,所述方法包括:
(a)将铈(IV)化合物和锆(IV)化合物与铝氧化物的浆料在高于40℃的温度合并以生成反应浆料;
(b)将反应浆料与沉淀剂接触以将不可溶的铈和锆化合物沉淀到铝氧化物上并形成铈-锆-铝氧化物颗粒;和
(c)煅烧铈-锆-铝氧化物颗粒以生成二氧化铈-氧化锆-氧化铝复合氧化物。
2.根据权利要求1所述的方法,其中温度处于60-100℃的范围。
3.根据权利要求1所述的方法,其中铈(IV)化合物选自铈硝酸盐、铈硝酸铵盐、铈硫酸盐、铈硫酸铵盐、铈醇盐及其混合物。
4.根据权利要求1所述的方法,其中锆(IV)化合物选自锆羧酸盐、锆卤化物、锆卤氧化物、锆碳酸盐、锆硝酸盐、锆含氧硝酸盐、锆硫酸盐及其混合物。
5.根据权利要求1所述的方法,其中铝氧化物具有大于1微米的平均粒度。
6.根据权利要求1所述的方法,其中铝氧化物是经稀土金属或碱土金属稳定化的铝氧化物。
7.根据权利要求6所述的方法,其中经稀土金属或碱土金属稳定化的铝氧化物包含0.1-20wt%的稀土金属或碱土金属。
8.根据权利要求6所述的方法,其中经稀土金属或碱土金属稳定化的铝氧化物含有选自镧、钕、镨、钇、钡和锶的稀土金属或碱土金属。
9.根据权利要求1所述的方法,其中将稀土金属或过渡金属化合物与铈(IV)化合物、锆(IV)化合物和铝氧化物的浆料合并以生成反应浆料。
10.根据权利要求9所述的方法,其中反应浆料的稀土金属或过渡金属:铈和锆的摩尔比为0.001-10。
11.根据权利要求1所述的方法,其中沉淀剂选自碱金属和碱土金属碳酸盐、铵和烷基铵碳酸盐、铵和烷基铵氢氧化物、碱金属和碱土金属氢氧化物、水溶性有机碱化合物及其混合物。
12.根据权利要求1所述的方法,其中在煅烧步骤(c)之前,使铈-锆-铝氧化物颗粒经过选自过滤、洗涤和喷雾干燥的一个或多个步骤。
13.根据权利要求1所述的方法,其中煅烧步骤(c)在400-1000℃的温度进行。
14.通过根据权利要求1所述的方法制备的二氧化铈-氧化锆-氧化铝复合氧化物。
15.三效催化剂,其包含一种或多种铂族金属和通过根据权利要求1所述的方法制备的二氧化铈-氧化锆-氧化铝复合氧化物。
16.用于处理来自内燃机的废气的方法,其包括将废气与根据权利要求15所述的三效催化剂接触。
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- 2012-10-18 EP EP12783753.2A patent/EP2771097A1/en not_active Withdrawn
- 2012-10-18 RU RU2014121200/05A patent/RU2014121200A/ru not_active Application Discontinuation
- 2012-10-18 BR BR112014009980A patent/BR112014009980A2/pt not_active IP Right Cessation
- 2012-10-18 WO PCT/US2012/060747 patent/WO2013062842A1/en active Application Filing
- 2012-10-18 KR KR1020147013758A patent/KR20140087017A/ko not_active Application Discontinuation
- 2012-10-18 JP JP2014538843A patent/JP2014534156A/ja active Pending
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CN106268740B (zh) * | 2016-08-23 | 2019-04-30 | 昆明新光能源环保科技有限公司 | 一种用于液氮洗尾气中低浓度可燃组分缺氧燃烧的负载型催化剂及其制备方法和应用 |
CN106268740A (zh) * | 2016-08-23 | 2017-01-04 | 昆明新光能源环保科技有限公司 | 一种用于液氮洗尾气中低浓度可燃组分缺氧燃烧的负载型催化剂及其制备方法和应用 |
US11117097B2 (en) | 2016-10-04 | 2021-09-14 | Johnson Matthey Public Limited Company | NOx adsorber catalyst |
CN109922884A (zh) * | 2016-10-04 | 2019-06-21 | 庄信万丰股份有限公司 | NOx吸附剂催化剂 |
CN110545901A (zh) * | 2017-03-29 | 2019-12-06 | 庄信万丰股份有限公司 | NOx吸附剂催化剂 |
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CN111447997A (zh) * | 2018-01-08 | 2020-07-24 | 太平洋工业发展公司 | 制造用于废气处理的介孔储氧材料的方法、所述储氧材料及其用途 |
CN113260595A (zh) * | 2019-01-04 | 2021-08-13 | 太平洋工业发展公司 | 纳米晶体级的铈-锆氧化物材料及其制备方法 |
CN113260595B (zh) * | 2019-01-04 | 2024-04-16 | 太平洋工业发展公司 | 纳米晶体级的铈-锆氧化物材料及其制备方法 |
CN113365948A (zh) * | 2019-01-29 | 2021-09-07 | 太平洋工业发展公司 | 纳米晶体尺寸的铈-锆-铝氧化物材料及其制备方法 |
CN110560056B (zh) * | 2019-08-30 | 2022-11-01 | 无锡威孚环保催化剂有限公司 | 通用小型汽油机尾气催化剂及其制备方法 |
CN110560056A (zh) * | 2019-08-30 | 2019-12-13 | 无锡威孚环保催化剂有限公司 | 通用小型汽油机尾气催化剂及其制备方法 |
CN114845810A (zh) * | 2020-08-31 | 2022-08-02 | 株式会社Lg化学 | 氧化铈-氧化锆复合氧化物的制备方法、氧化铈-氧化锆复合氧化物、包含其的催化剂和丁二烯的制备方法 |
CN115916921A (zh) * | 2021-06-14 | 2023-04-04 | 第一稀元素化学工业株式会社 | 复合氧化物粉末、摩擦材料组合物及摩擦材料 |
Also Published As
Publication number | Publication date |
---|---|
KR20140087017A (ko) | 2014-07-08 |
JP2014534156A (ja) | 2014-12-18 |
WO2013062842A1 (en) | 2013-05-02 |
EP2771097A1 (en) | 2014-09-03 |
US20130108530A1 (en) | 2013-05-02 |
BR112014009980A2 (pt) | 2019-09-24 |
RU2014121200A (ru) | 2015-12-10 |
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