WO2005023421A1 - 窒素酸化物の接触分解のための触媒と方法 - Google Patents
窒素酸化物の接触分解のための触媒と方法 Download PDFInfo
- Publication number
- WO2005023421A1 WO2005023421A1 PCT/JP2004/013276 JP2004013276W WO2005023421A1 WO 2005023421 A1 WO2005023421 A1 WO 2005023421A1 JP 2004013276 W JP2004013276 W JP 2004013276W WO 2005023421 A1 WO2005023421 A1 WO 2005023421A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- rhodium
- zeolite
- oxides
- exhaust gas
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 249
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims description 40
- 238000000354 decomposition reaction Methods 0.000 title abstract description 13
- 239000010457 zeolite Substances 0.000 claims abstract description 73
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 69
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000007789 gas Substances 0.000 claims abstract description 54
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000010948 rhodium Substances 0.000 claims abstract description 49
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 49
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000446 fuel Substances 0.000 claims abstract description 38
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 36
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 27
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 23
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 230000000737 periodic effect Effects 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 8
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 7
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 7
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 7
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000004615 ingredient Substances 0.000 abstract 3
- 239000000843 powder Substances 0.000 description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 229910000510 noble metal Inorganic materials 0.000 description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 229910001868 water Inorganic materials 0.000 description 18
- 239000002002 slurry Substances 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 12
- 239000003638 chemical reducing agent Substances 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 230000001603 reducing effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- -1 alkali metal cation Chemical class 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 150000000703 Cerium Chemical class 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 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 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 4
- 229910052815 sulfur oxide Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000006255 coating slurry Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 150000001206 Neodymium Chemical class 0.000 description 1
- 150000001213 Praseodymium Chemical class 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group 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
- 239000011218 binary composite Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002796 luminescence method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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Definitions
- the present invention nitrogen oxides (mainly consisting of NO and N 0 2 Prefecture. Hereinafter referred N Ox.) Relates to a catalyst and process for the direct decomposition by the catalyst.
- the present invention provides a method for supplying fuel to a combustion chamber of a diesel engine or a gasoline engine in a periodic rich / lean fuel supply process (excursion process), burning the fuel, and contacting the generated exhaust gas.
- the present invention relates to a catalyst for directly decomposing N ⁇ x in exhaust gas and a method for directly decomposing N Ox in exhaust gas using such a catalyst.
- Such a catalyst and the method using it are suitable, for example, for reducing and removing harmful nitrogen oxides contained in exhaust gas from automobile engines.
- the present invention supplies fuel in a periodic rich / lean fuel supply process in the presence of sulfur oxides (mainly composed of so 2 and so 3 , hereinafter referred to as S Ox). And a highly durable catalyst for directly decomposing NOx in the exhaust gas generated by the combustion.
- sulfur oxides mainly composed of so 2 and so 3 , hereinafter referred to as S Ox.
- the term “excursion” means that the air-Z fuel ratio moves from its average value to both along the time axis or such an operation.
- the term “rich” means that the air / fuel ratio of the fuel in question is less than the stoichiometric air-Z fuel ratio, and the term “lean” means that the air of the fuel in question is This means that the fuel ratio is greater than the stoichiometric air / fuel ratio.
- the stoichiometric air / fuel ratio is about 14.5.
- “catalyst” means a catalyst or a structure including the same that operates to remove NOx during rich Z-lean combustion of fuel.
- “supplying fuel in a periodic rich Z-lean fuel supply process” means that combustion of fuel is mainly performed in a combustion chamber of a diesel engine / gasoline engine. Under the conditions (the oxygen concentration in the exhaust gas after combustion is usually about 5% to 10%), the atmosphere is periodically vibrated alternately between the above-mentioned rich condition and lean condition. Supplying, injecting or injecting fuel while adjusting the air / fuel ratio. Therefore, the rich / lean process is equivalent to the rich no-leaning condition.
- Vehicles with lean-burn engines can be driven with very low fuel-to-air ratios, resulting in lower fuel consumption than vehicles with conventional engines.
- the NOx storage-reduction system of such a lean burn engine reduces NOx by two periodic steps, 1-2 minutes apart.
- the NO on the platinum or rhodium catalyst is oxidized to N_ ⁇ 2, or the N 0 2 alkali compounds such as potassium carbonate or barium carbonate Ranaru Absorbed by absorbent.
- N_ ⁇ 2 the N 0 2 alkali compounds
- the rich condition is maintained for several seconds.
- This rich conditions the absorbed (stored) been N0 2 is released from the absorbent, hydrocarbons on a platinum or rhodium catalyst, is reduced to efficiently nitrogen by carbon monoxide or hydrogen.
- the N Ox storage one reducing system, if the absence of S_ ⁇ x, well operated over a long period of time. However, if there is S Ox, even under conditions of lean and Ritchii deviation, by irreversible absorption of S Ox in N_ ⁇ 2 absorption sites on the alkali compound, the catalyst system deteriorates sharply.
- the fuel is supplied to the combustion chamber in a short period of time and in an amount exceeding the stoichiometric amount.
- N ⁇ x is decomposed into nitrogen and oxygen without a reducing agent on rhodium and / or palladium reducing metal supported on zeolite A, and is rich.
- a method for removing generated oxygen with a reducing agent under the conditions has been proposed in Japanese Patent Application Laid-Open No. 2001-149758. This method inherently has high S Ox durability because it is not necessary to absorb NOx into alkaline compounds under lean conditions.
- this method has a problem that the N Ox purification rate is inferior to that of the N ⁇ ⁇ x storage and reduction system. There is.
- the present invention burns fuel supplied by a periodic rich / lean fuel supply system over a wide temperature range even in the presence of oxygen, sulfur oxides or water, and reduces NOx in exhaust gas generated by this combustion.
- An object of the present invention is to provide a catalyst and a method for directly decomposing, or directly and reductively decomposing with high durability. Disclosure of the invention
- a catalyst for supplying and burning fuel under periodic rich-no-lean conditions contacting generated exhaust gas, and catalytically directly decomposing nitrogen oxides in the exhaust gas.
- (C) a mixture of an oxide of at least two elements selected from cerium, zirconium, praseodymium, neodymium, terbium, samarium, gadolinium and lanthanum, and Z or a composite oxide
- a second catalyst component consisting of at least one selected from
- a catalyst for contacting directly and reductively decomposing nitrogen oxides in exhaust gas characterized by comprising:
- fuel is supplied and burned under periodic rich / lean conditions, and the generated exhaust gas is brought into contact with a catalyst to directly decompose nitrogen oxides in the exhaust gas.
- a second catalyst component consisting of at least one selected from
- a method for catalytically directly and reductively decomposing nitrogen oxides in exhaust gas characterized by comprising: Brief Description of Drawings
- FIG. 1 is a schematic diagram showing a mechanism in which nitrogen oxides are directly decomposed into nitrogen and oxygen in a catalytic reaction of nitrogen oxides in exhaust gas using a catalyst according to the present invention.
- FIG. 2 is a graph showing a change with time of a concentration of a main component in a gas when a nitrogen oxide in an exhaust gas is catalytically reacted using an example of the catalyst according to the present invention.
- FIG. 3 is a graph showing the amount of nitrogen generated in the gas when the nitrogen oxides in the exhaust gas are catalytically reacted using the catalysts of Examples 1, 10, 11 and Comparative Example 1 of the present invention. It is a graph which shows a change with time.
- to directly decompose nitrogen oxides means to decompose NOx directly to nitrogen and oxygen by the action of a catalyst.
- the catalyst for catalytically directly decomposing nitrogen oxides according to the present invention comprises:
- a second catalyst component consisting of at least one selected from
- the catalyst according to the present invention can contain various additives, for example, to provide coating properties as a slurry on an inert substrate, and, for example, to improve its strength. Can also include various additives.
- the total amount of the first catalyst component, the second catalyst component and the third catalyst component accounts for at least 80% by weight, preferably at least 95% by weight. Occupy.
- the ratio of the first catalyst component is in the range of 25 to 75% by weight, and the ratio of the second and third catalyst components is 12.5 to 37.5% by weight, respectively. % Range.
- the ratio of the first, second and third catalyst components is out of the above range, the direct resolution of NOx of the first catalyst component, the concentration effect of NOx of the second catalyst component and the third The NOx purification rate decreases as the complement effect of N ⁇ x purification of the catalyst component decreases.
- the first catalyst component preferably contains at least one noble metal selected from rhodium and palladium or an oxide thereof in the range of 0.05 to 2% by weight in terms of metal.
- the first catalyst component when the ratio of the above-mentioned noble metal or its oxide exceeds 2% by weight in terms of metal, the noble metal formed by reduction of the oxide under the rich condition is oxidized under the lean condition. As a result, under lean conditions, the selectivity of direct decomposition by catalytic reaction of NO with the first catalyst component becomes insufficient.
- the proportion of the noble metal or its oxide in the first catalyst component is less than 0.05% by weight in terms of metal, the obtained catalyst has poor catalytic reaction activity.
- the first catalyst component preferably contains the above-mentioned noble metal or its oxide in the range of 0.1 to 1% by weight in terms of metal.
- NOx can be directly decomposed most efficiently under lean conditions.
- the noble metal or its oxide is highly dispersed and supported on zeolite, and the average particle size of the noble metal or its oxide is preferably Less than 10 nm, particularly preferably less than 6 nm, most preferably less than 3 nm.
- the average particle size of such a noble metal or its oxide can be measured, for example, by observation with a transmission electron microscope (TEM).
- TEM transmission electron microscope
- TEM transmission electron microscope
- the zeolite supporting the noble metal or its oxide not only has a role as a carrier for the noble metal or its acid, but also has Under rich conditions, it also has a role as a cocatalyst by increasing the reducing power of the oxide of the noble metal to the noble metal and suppressing the oxidation of the noble metal to the oxide.
- the zeolite used as one of the first catalyst components preferably has a specific surface area before supporting the noble metal in the range of 200 to 900 m 2 / g.
- the zeolite used in the present invention is generally
- M indicates a cation
- n indicates the valence of the cation M
- w indicates the number of water molecules per unit cell
- X and y indicate the total number of tetrahedrons per unit cell
- X indicates It is an integer between 10 and about 100
- yZx indicates a value between about 10 and about 300.
- the above-mentioned zeolite is a heat-resistant zeolite having the above-mentioned unit cell formula (I) (wherein, M represents an alkali metal cation or an alkali metal cation, and aluminum is part or all, particularly preferably, All may be substituted with other metal elements), by treating it with an aqueous solution of ammonium salt or peatonic acid, and substituting part or all of M with ammonium ions or hydrogen ions. Can be.
- typical starting materials are Na—] 3-zeolite, Na—mordenite, Na—ZSM-5, Na—USY (ultrastable Y-type zeolite) or Metallosilicates (where the aluminum is part or all of the other metal element, especially Fe, Ga, Zn, La, Cu, Mo, Cr, Ge, Ti or Zeolite substituted by B).
- a typical ammonium salt is ammonium sulfate, and a typical acid is sulfuric acid.
- 3-zeolite is most preferable because it has not only durability at high temperatures but also an excellent effect of supporting the noble metal or its acid.
- Zeolite is a crystalline aluminum silicate having a polycrystalline structure, and] 3-zeolite has a special crystal structure and can be identified by an X-ray diffraction peak.
- 3- zeolite Contact Keru S i 0 2 / AI 2O3 molar ratio will vary depending manufacturing conditions Zeoraito, usually between about 2 0 to about 3 0 0.
- the first catalyst component in which the noble metal or its oxide is supported on zeolite can be prepared by various methods.
- the following method can be exemplified. That is, a water-soluble salt of the noble metal element, for example, a nitrate is applied to the zeolite by a usual method such as an impregnation method or an ion exchange method, and then the obtained product is treated in an acidic or reducing atmosphere. By firing at a temperature of 300 to 900 ° C. to generate a noble metal or an oxide thereof, the first catalyst component can be obtained.
- an aqueous slurry of zeolite is prepared, and a water-soluble salt of the noble metal element, for example, nitrate is added to the slurry so that hydroxide of the noble metal is not formed. While preserving H at about 4.0, fix the precious metal ion at the ion exchange site of zeolite.
- the noble metal ion-exchanged zeolite is washed with water, and excess zeolite is removed from the zeolite to obtain a zeolite supporting the noble metal ion.
- the product thus obtained is placed in an oxidizing atmosphere such as air or a reducing atmosphere such as hydrogen, at a temperature in the range of 300 to 900, preferably 400 to 600 ° C.
- the above-mentioned noble metal or its oxide is formed on zeolite, and thus, a catalyst comprising the ion-exchanged zeolite carrying the above-mentioned noble metal or its oxide can be obtained as a powder.
- the second catalyst component is
- (c) A mixture of oxides of at least two elements selected from cerium, zirconium, praseodymium, neodymium, terbium, samarium, gadolinium and lanthanum, and Z or composite oxides And at least one member selected from the group consisting of: That is, the second catalyst component is composed of the component (a), the component (b), the component (c), or a mixture of two or more thereof.
- Such a catalyst component can be obtained as a powder, for example, by the following method. That is, first, a water-soluble salt of an element constituting the catalyst component, for example, an aqueous solution of a nitrate is neutralized or heated and hydrolyzed to form a hydroxide, and then the obtained product is oxidized. Alternatively, firing may be performed at a temperature of 300 to 900 ° C. in a reducing atmosphere.
- the second catalyst component can also be obtained by calcining a commercially available hydroxide or oxide of the above element as described above.
- a composite oxide of at least two elements is preferably used, and a binary or ternary composite oxide is particularly preferred. Used.
- the catalyst according to the present invention further comprises, in addition to the first catalyst component and the second catalyst component described above,
- Such a third catalyst component is conventionally known by using a water-soluble salt of a noble metal such as platinum, rhodium and / or palladium, for example, a nitrate or a complex salt, by a usual impregnation method or an ion exchange method. It can be obtained as a powder by supporting it on a carrier such as alumina, silica-alumina, zeolite, titania and the like. Among these carriers, alumina having particularly excellent supportability and heat resistance is preferably used. In such a third catalyst component, the loading amount of the noble metal or its oxide is usually in the range of 0.5 to 3% by weight.
- the catalyst according to the invention can be obtained in powder form, as described above.
- such a powder catalyst can be formed into various shapes such as, for example, a honeycomb, a ring, a sphere, and the like.
- appropriate additives such as a molding aid, a reinforcing material, an inorganic fiber, an organic binder, and the like can be used.
- the catalyst according to the present invention has a catalyst structure having a catalyst layer on the surface thereof (for example, by coating it) on the surface of an inert substrate for support having an arbitrary shape, for example, by a wet coating method.
- an inert substrate for support having an arbitrary shape, for example, by a wet coating method.
- the inert substrate is, for example, a clay ore such as cordierite.
- a metal such as stainless steel, preferably a heat-resistant metal such as Fe—Cr—A1
- its shape is honeycomb, annular, or spherical. And so on.
- the catalyst structure has a high purification activity for nitrogen oxides during the rich-no-lean process.
- the catalyst layer is preferably formed to have a thickness of 20 m or more from the surface.
- it is not necessary to increase the thickness of the catalyst layer, which is usually up to 200; Even if the thickness of the catalyst layer exceeds 200 m, the catalyst structure does not improve its performance in terms of catalytic activity in proportion to such a thickness. It is not preferable in terms of cost.
- a catalyst layer is formed on the honeycomb base material wall by impregnating the catalyst into the wall of the porous honeycomb base material as a slurry
- a catalyst having a thickness of 20 m or more from both sides of the wall body is required.
- the wall of the honeycomb substrate preferably has a thickness of 40 m or more so as to have a layer.
- a method for supplying and burning fuel under periodic rich Z-lean conditions contacting the generated exhaust gas with a catalyst, and catalytically directly decomposing nitrogen oxides in the exhaust gas.
- the above-mentioned catalyst is used as the above-mentioned catalyst.
- FIG. 1 is a schematic diagram showing the mechanism of direct decomposition of NOx into nitrogen and oxygen using the catalyst of the present invention. That is, as shown in FIG. 1, under lean conditions (i.e., under oxidizing conditions) adsorption at a portion of N_ ⁇ _X in the exhaust gas, as NO or N_ ⁇ 2 on the second catalyst component in the catalyst , concentrated and, N0 2, which is enriched in this way is decomposed into NO and oxygen.
- lean conditions i.e., under oxidizing conditions
- the oxygen accumulated on the first catalyst component is reduced and removed from the first catalyst component,
- the first catalyst component is regenerated under rich conditions. Therefore, according to the present invention, sets the lean period suitable hereby, by appropriately setting the period of the rich Z lean, it is possible to obtain a high N_ ⁇ X purification rate.
- a third catalyst component comprising a carrier supported on the noble metal is to Sani ⁇ NO in N_ ⁇ _X, on the second catalyst component N_ ⁇ x Promotes adsorption and enrichment to NO, and as a result, increases the efficiency of decomposition of NO on the first catalyst component into nitrogen and oxygen.
- the entire amount of NOx adsorbed and concentrated on the second catalyst component is not directly decomposed on the first catalyst component but adsorbed and collected, and the residue of the concentrated NOx is rich.
- the second catalyst component is desorbed from the second catalyst component, and the NOx purification rate is reduced.
- the third catalyst component reduces the NOx, thereby preventing the NOx purification rate from decreasing.
- the third catalyst component improves the responsiveness of the catalytic reaction when the atmosphere of the exhaust gas is switched from lean to rich conditions, and as a result, the removal of the accumulated oxygen and the return of the first catalyst component. It is also important that the swift action be taken.
- All of the catalysts according to the present invention are not only excellent in resistance to heat but also excellent in resistance to sulfur oxides, and reduce NOx in exhaust gas from automobiles of diesel engines and lean gasoline engines. It is suitable for use as a catalyst for denitration.
- the catalyst is used in a catalytic reaction under the condition that the combustion atmosphere of the fuel oscillates between the rich condition and the lean condition as described above.
- the period of the catalytic reaction (that is, the time from the rich atmosphere (or lean atmosphere) to the next rich atmosphere (or lean atmosphere)) is preferably from 5 to 120 seconds, particularly preferably from 10 to 120 seconds. ⁇ 100 seconds.
- the time under the rich condition and the time under the lean condition are each usually in the range of 0.5 to 100 seconds, preferably in the range of 4.5 to 90 seconds.
- the rich condition is usually formed by periodically injecting the fuel into the combustion chamber of the engine at an air-Z fuel ratio of 10 to 14 by weight.
- Typical exhaust gases under rich conditions are hundreds of ppm of NOx, 5-10% by volume of water, 2-3% by volume of water, 2-3% by volume of hydrogen, thousands of ppm by volume. Hydrocarbons and 0.5-0.5% by volume of oxygen.
- Lean conditions usually use the engine when using gasoline as fuel. It is formed by periodically injecting fuel at an air / fuel ratio of 20-40 by weight into the combustion chamber of the fuel.
- Typical exhaust gases under lean conditions are several hundred ppm by volume of NOx, 5 to 10% by volume of water, thousands of ppm by volume to 2% by volume, and thousands of volume by volume ppm to 2% by volume of hydrogen. It contains several thousand parts per million by volume of hydrocarbons and 5 to 10% by volume of oxygen.
- the preferred temperature for the catalytic direct (and reductive decomposition) of NOx using the catalyst according to the present invention depends on the individual gas composition, but in a rich process, an effective catalytic reaction for NOx over a long period of time. In order to have activity, it is usually in the range of 100 to 40 Ot, preferably in the range of 150 to 350 ° C. In such a reaction temperature range, the exhaust gas is preferably treated at a space velocity in the range 5000 to 100000 h-i. Industrial applicability
- the slurry was aged for 1 hour to obtain ⁇ -zeolite loaded with oral dimeion.
- the obtained zeolite carrying rhodium ions thus obtained was filtered off and ion-exchanged water , And 0.5% of rhodium ion was supported as rhodium] to obtain a 3-zeolite powder.
- 3-zeolite powder was heated and calcined at 500 ° C. for 3 hours in air to obtain 0.5% rhodium metal in terms of rhodium (based on ⁇ -zeolite powder catalyst). To obtain a powdery i3-zeolite catalyst.
- Example 2 In the same manner as in Example 1, except that 50.4 Og of an aqueous rhodium nitrate solution was used, 0.75% of rhodium metal (based on a 3-zeolite powder catalyst) was supported in the same manner as in Example 1. e-zeolite powder catalyst was obtained.
- ion-exchanged water 1 7 0 0 mL cerium nitrate (C e (N_ ⁇ 3) 3 ⁇ 6 H 2 ⁇ ) 103. 77 g and Okishi zirconium (Z R_ ⁇ (N0 3) 2) 84. 45 g and lanthanum nitrate - by dissolving the (L a (N0 3) 3 6H 2 0) 7. 97 g, to prepare an aqueous solution. 0.1N ammonia water is added to this aqueous solution, and the above cerium salt, oxyzirconium salt and lanthanum salt are added. Was neutralized and hydrolyzed, and then aged at 80 for 1 hour.
- the product was separated from the resulting slurry by filtration, dried at 120 ° C for 24 hours, and calcined in air at 500 ° C for 3 hours to obtain a ceria / zirconia / lanthanum oxide composite oxide.
- a powder (weight ratio of 22 / 73Z5 based on oxide, specific surface area 80 g) was obtained.
- Example 3 0.75% of the above rhodium metal supported] 30 g of zeolite powder catalyst, 15 g of the above ceria / zirconia / lanthanum oxide composite acid powder and platinum on alumina prepared in Example 1 Using 15 g of the catalyst powder supporting 2%, a honeycomb catalyst structure having a catalyst layer having a thickness of 20 tm and comprising the above catalyst was obtained in the same manner as in Example 1 below.
- Example 3 Example 3
- Example 2 In the same manner as in Example 1, except that 66.67 g of an aqueous solution of rhodium nitrate was used, 1% of rhodium metal in terms of mouth dia. (Based on a / 3-zeolite powder catalyst) was supported. A zeolite powder catalyst was obtained.
- cerium nitrate in deionized water 1 7 0 OmL (C e (N_rei_3) 3 ⁇ 6H 2 0) 7 7.
- 0.1 N ammonia water was added to the aqueous solution to neutralize and hydrolyze the cerium salt, oxyzirconium salt and praseodymium salt, and then aged at 80 ° C for 1 hour.
- the product was separated from the resulting slurry by filtration, dried at 120 ° C for 24 hours, and calcined in air at 500 ° C for 3 hours to obtain ceria-zirconia Z praseodymium oxide composite oxide powder.
- a powder (oxide-based weight ratio 47/3 3/22, specific surface area 205 m ⁇ g) was obtained.
- Example 4 3% zeolite powder catalyst supporting 1% of the above rhodium metal] 15 g of ceria Z zirconia / praseodymium oxide composite oxide powder and 2% of platinum supported on alumina prepared in Example 1 Using 15 g of the thus-prepared catalyst powder, a honeycomb catalyst structure having a catalyst layer having a thickness of 20 m and comprising the above catalyst was obtained as a catalyst in the same manner as in Example 1 below.
- Example 4
- Hydrogen type ZSM-5—Zeolite (Zeolyst International) CVB 324, calcined at 500 ° C in air as zeolite, S i ⁇ ⁇ 2 / A 1 ⁇ 2 ⁇ 3 molar ratio 30), and 0.75% of rhodium metal in terms of rhodium was reduced in the same manner as in Example 1 except that 56.40 g of an aqueous rhodium nitrate solution was used. A supported ZSM-5-zeolite powder catalyst was obtained.
- cerium nitrate in 1 7 0 0 mL deionized water (C e (N0 3) 3 ⁇ 6 H 2 ⁇ ) 109. 43 g and Okishi zirconium (Z r 0 (N_ ⁇ 3) 2) 31. 27 g and neodymium nitrate (Nd (N0 3) 3 ⁇ 6H 2 ⁇ ) 15. dissolved and 63 g, to prepare an aqueous solution. 0.1N ammonia water was added to the aqueous solution to neutralize and hydrolyze the cerium salt, oxyzirconium salt and neodymium salt, and then aged at 80 ° C for 1 hour.
- Example 2 a honeycomb catalyst structure having a catalyst layer having a thickness of 20 xm and made of the above catalyst was obtained as a catalyst.
- Example 5 30 g of ZSM-5-zeolite powder catalyst supporting 0.75% of the above rhodium metal, 15 g of the above-mentioned ceria / zirconia / neodymium oxide composite oxide powder, and 2% of platinum and 0.5% of rhodium on the above alumina Using 15 g of the catalyst powder supporting the catalyst, a honeycomb catalyst structure having a catalyst layer having a thickness of 20 m and comprising the above catalyst was obtained in the same manner as in Example 1 below.
- Example 5 30 g of ZSM-5-zeolite powder catalyst supporting 0.75% of the above rhodium metal, 15 g of the above-mentioned ceria / zirconia / neodymium oxide composite oxide powder, and 2% of platinum and 0.5% of rhodium on the above alumina
- Example 6 15 g of the US Y-zeolite powder catalyst supporting 0.5% of the above rhodium metal, 15 g of the ceria powder prepared in Example 1, and 15 g of the catalyst powder supporting 2% of platinum and 1% of palladium on the above alumina Using g, a honeycomb catalyst structure having a catalyst layer having a thickness of 20 nm and comprising the above catalyst was obtained as a catalyst in the same manner as in Example 1 below.
- Example 6 Example 6
- Example 7 a honeycomb catalyst structure having a 20 / im-thick catalyst layer was obtained as a catalyst in the same manner as in Example 1 below.
- Example 7
- This slurry was dried at 80 ° C using a rotary evaporator (RE 111, manufactured by Buch). After obtaining palladium-supported) 3-zeolite in this way, it was further calcined in air at 500 for 1 hour to give palladium metal 1% () 3-zeolite powder catalyst in terms of palladium. -Based zeolite powder catalyst was obtained.
- Example 8 30 g of j3-zeolite powder catalyst supporting 1% of the above palladium metal, prepared in Example 1 Using 15 g of the ceria powder thus prepared and 15 g of the catalyst powder having 2% platinum supported on alumina prepared in Example 1, a catalyst layer having a thickness of 20 m was formed in the same manner as in Example 1 below. A honeycomb catalyst structure was obtained as a catalyst.
- Example 8
- 3-zeolite powder catalyst supporting 1% of palladium metal were used.
- Example 9 0.2 g of the above-mentioned rhodium metal and 1% of palladium metal were supported] 30 g of a 3-zeolite powder catalyst, 15 g of the seria powder prepared in Example 1 and 2% of platinum on the alumina prepared in Example 1 Using 15 g of the supported catalyst powder, a honeycomb catalyst structure having a 20 m-thick catalyst layer was obtained as a catalyst in the same manner as in Example 1 below.
- Example 9 0.2 g of the above-mentioned rhodium metal and 1% of palladium metal were supported] 30 g of a 3-zeolite powder catalyst, 15 g of the seria powder prepared in Example 1 and 2% of platinum on the alumina prepared in Example 1 Using 15 g of the supported catalyst powder, a honeycomb catalyst structure having a 20 m-thick catalyst layer was obtained as a catalyst in the same manner as in Example 1 below.
- Example 9 Example 9
- Example 10 45 g of ⁇ -zeolite powder catalyst supporting 0.5% of the rhodium metal prepared in Example 1 and 7.5 g of ceria powder, and catalyst powder supporting 2% of platinum on alumina 7. Using 5 g, an eight-way catalyst structure having a catalyst layer having a thickness of 20 m was obtained as a catalyst in the same manner as in Example 1 below.
- Example 10 45 g of ⁇ -zeolite powder catalyst supporting 0.5% of the rhodium metal prepared in Example 1 and 7.5 g of ceria powder, and catalyst powder supporting 2% of platinum on alumina 7. Using 5 g, an eight-way catalyst structure having a catalyst layer having a thickness of 20 m was obtained as a catalyst in the same manner as in Example 1 below.
- Example 10 45 g of ⁇ -zeolite powder catalyst supporting 0.5% of the rhodium metal prepared in Example 1 and 7.5 g of ceria powder, and catalyst powder supporting 2% of platinum on alumina 7. Using 5 g, an eight-
- Example 11 30 g of ⁇ -zeolite powder catalyst supporting 0.5% of rhodium metal prepared in Example 1, 7.5 g of ceria powder, and catalyst powder supporting 2% of platinum on alumina 22. Using 5 g, a honeycomb catalyst structure having a catalyst layer having a thickness of 20 m was obtained as a catalyst in the same manner as in Example 1 below.
- Example 11
- Example 12 30 g of ⁇ -zeolite powder catalyst supporting 0.5% of the rhodium metal prepared in Example 1, 22.5 g of ceria powder, and a catalyst supporting 2% of platinum on alumina Using 7.5 g of the powder, an 82 cam catalyst structure having a catalyst layer having a thickness of 20 jm was obtained as a catalyst in the same manner as in Example 1 below.
- Example 12 30 g of ⁇ -zeolite powder catalyst supporting 0.5% of the rhodium metal prepared in Example 1, 22.5 g of ceria powder, and a catalyst supporting 2% of platinum on alumina Using 7.5 g of the powder, an 82 cam catalyst structure having a catalyst layer having a thickness of 20 jm was obtained as a catalyst in the same manner as in Example 1 below.
- Example 12 30 g of ⁇ -zeolite powder catalyst supporting 0.5% of the rhodium metal prepared in Example 1, 22.5 g of ceria powder, and a catalyst supporting 2% of platinum on alumina Using
- Example 1 Each of which supported 0.5% of the rhodium metal prepared in Example 1; 15 g of 3-zeolite powder catalyst, 22.5 g of ceria powder, and catalyst powder having 2% of platinum supported on alumina A honeycomb catalyst structure having a catalyst layer having a thickness of 20 m was obtained as a catalyst in the same manner as in Example 1 using 22.5 g of the catalyst. Comparative Example 1
- Example 2 In the same manner as in Example 1 except that 16.80 g of an aqueous rhodium nitrate solution (0.90% as rhodium) was used, 0.25% of rhodium metal (based on i8-zeolite powder catalyst) was supported. / 3—Zeolite powder catalyst was prepared. 60 g of this 3-zeolite powder catalyst was mixed with 12 g of silica sol (Snowtex N (20% by weight as silica) manufactured by Nissan Chemical Industries, Ltd.) and an appropriate amount of water. This mixture was pulverized with a planetary mill for 5 minutes to obtain a slurry for coating, which was used on a honeycomb substrate made of cordierite having 400 cells per square inch. The slurry was applied to obtain a honeycomb catalyst structure having a catalyst layer having a thickness of 20 am made of the above catalyst as a catalyst.
- silica sol Snowtex N (20% by weight as silica
- composition of the mixed gas used for the NOx decomposition experiment under the rich conditions is as follows.
- the gas under the lean condition was prepared by injecting oxygen into the mixed gas used under the rich condition, and its composition is as follows.
- H 2 1. 8% by volume rich gas atmosphere periodically 10-120 seconds, allowed to oscillate between Li Ichin conditions, 1Z10 of Rich Z lean time width is rich time. Also, the space velocity under lean conditions
- the gas composition under lean conditions was NO 1000 ppm, oxygen 9 volume%, and balance was helium.
- 15 volume% hydrogen was injected into the rich gas.
- the reaction gas on the outlet side was continuously observed for nitrogen, N ⁇ x, oxygen and hydrogen using a quadrupole mass spectrometer (Omnis Yuichi manufactured by Balza).
- the reaction was carried out at a temperature of 200 and a catalyst weight Z gas flow rate ratio (W / F) of 0.06 g ⁇ sec Zcc.
- FIG. 2 shows a profile of a reaction for directly decomposing nitrogen oxides in exhaust gas using the catalyst of Example 1 described above.
- the time when hydrogen was injected into the rich gas was defined as time 0 (second). did Then, after a few seconds, the hydrogen concentration scales over, and the oxygen concentration sharply decreases, and the gas conditions become rich.At this time, the N ⁇ x concentration decreases and N ⁇ x is a decomposition product. It was found that the nitrogen concentration increased, and thereafter, the hydrogen concentration in the gas decreased, and the generation of nitrogen continued even under lean conditions with little reducing agent.
- nitrogen is generated under a gas condition in which no reducing agent (hydrogen) is present, and therefore, unlike the selective reduction reaction of NO by the reducing agent, It shows that NOx is directly decomposed on the catalyst.
- FIG. 3 shows the change over time of the nitrogen concentration generated by the catalytic reaction of the exhaust gas, particularly in the reactions using the catalysts of Examples 1, 10, 11 and Comparative Example 1.
- the catalyst according to Example 1 when the catalyst according to Example 1 was used, the amount of nitrogen generated during the lean period was the largest. That is, of the three types of catalysts examined, the catalyst according to Example 1 was the most excellent in the activity of directly decomposing nitrogen oxides.
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Abstract
Description
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EP04772958A EP1671699A4 (en) | 2003-09-08 | 2004-09-06 | CATALYST AND DEVICE FOR CONTACT DECOMPOSITION OF STAIN OXIDE |
US10/570,629 US7422731B2 (en) | 2003-09-08 | 2004-09-06 | Catalyst and method for contact decomposition of nitrogen oxides |
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JP2003315093A JP4236543B2 (ja) | 2003-09-08 | 2003-09-08 | 窒素酸化物の接触分解のための触媒と方法 |
JP2003-315093 | 2003-09-08 |
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US (1) | US7422731B2 (ja) |
EP (1) | EP1671699A4 (ja) |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114585438A (zh) * | 2019-10-21 | 2022-06-03 | 巴斯夫公司 | 再生效率增强的低温NOx吸附剂 |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3912294B2 (ja) * | 2003-02-19 | 2007-05-09 | トヨタ自動車株式会社 | 内燃機関の排気浄化方法および排気浄化装置 |
CA2606513C (en) * | 2005-04-29 | 2015-12-22 | W.R. Grace & Co.-Conn. | Nox reduction compositions for use in partial burn fcc processes |
JP2007130580A (ja) * | 2005-11-10 | 2007-05-31 | Toyota Motor Corp | 排ガス浄化装置及び排ガス浄化方法 |
BRPI0715693B1 (pt) * | 2006-08-19 | 2018-10-23 | Umicore Ag & Co Kg | filtro de partículas diesel revestido cataliticamente, processo para sua produção e uso do mesmo |
EP1916029B1 (en) * | 2006-10-23 | 2014-06-04 | Haldor Topsoe A/S | Method and apparatus for the purifiction of exhaust gas from a compression ignition engine |
TWI449572B (zh) * | 2006-11-29 | 2014-08-21 | Umicore Shokubai Japan Co Ltd | Oxidation catalyst and the oxidation catalyst using an exhaust gas purification system |
ATE460973T1 (de) * | 2008-04-11 | 2010-04-15 | Umicore Ag & Co Kg | Abgasreinigungssystem zur behandlung von motorenabgasen mittels scr-katalysator |
US7976805B2 (en) * | 2008-05-16 | 2011-07-12 | Siemens Energy, Inc. | Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst |
JP5447377B2 (ja) * | 2008-07-31 | 2014-03-19 | 日産自動車株式会社 | 排気ガス浄化触媒 |
BRPI1011478B1 (pt) * | 2009-03-04 | 2018-01-30 | Nissan Motor Co.,Ltd | catalisador purificador de gás de exaustão e método para a fabricação do mesmo |
JP5041103B2 (ja) | 2009-11-17 | 2012-10-03 | 日産自動車株式会社 | 排ガス浄化用触媒及びその製造方法 |
DE102009053951A1 (de) * | 2009-11-18 | 2011-05-19 | Süd-Chemie AG | Alterungsstabiler Rh-Zeolith Katalysator |
PL224172B1 (pl) | 2011-08-08 | 2016-11-30 | Univ Jagielloński | Katalizator do bezpośredniego rozkładu tlenku azotu i sposób wytwarzania katalizatora do bezpośredniego rozkładu tlenku azotu |
US8835346B2 (en) * | 2012-07-27 | 2014-09-16 | Basf Corporation | Catalyst materials |
KR101459436B1 (ko) * | 2012-12-17 | 2014-11-07 | 현대자동차 주식회사 | 내연 기관용 가스 정화 촉매 |
PL235905B1 (pl) | 2013-06-05 | 2020-11-16 | Univ Jagiellonski | Monolityczny katalizator do równoczesnego usuwania NOx i cząstek węglowych w szczególności z gazów odlotowych elektrowni węglowych oraz sposób wytwarzania monolitycznego katalizatora do równoczesnego usuwania NOx i cząstek węglowych w szczególności z gazów odlotowych elektrowni węglowych |
US9868111B2 (en) | 2016-02-27 | 2018-01-16 | Toyota Motor Engineering & Manufacturing North America, Inc. | Catalyst for direct NOx decomposition and a method of forming and using the catalyst |
CN112469490A (zh) * | 2018-08-02 | 2021-03-09 | 日本碍子株式会社 | 多孔质复合体 |
KR20210106509A (ko) * | 2018-12-27 | 2021-08-30 | 니키 유니바사루 가부시키가이샤 | 암모니아 분해용 촉매 및 배기 가스의 처리 방법 |
EP4052787A1 (en) * | 2021-03-02 | 2022-09-07 | Johnson Matthey Public Limited Company | Nox storage material |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07232064A (ja) * | 1994-02-23 | 1995-09-05 | Toyota Motor Corp | 排気ガス浄化用触媒 |
JPH08173815A (ja) * | 1994-12-22 | 1996-07-09 | Toyota Motor Corp | 排ガス浄化用触媒 |
JPH09215922A (ja) * | 1996-02-09 | 1997-08-19 | Toyota Motor Corp | 排ガス浄化用触媒 |
JPH11290686A (ja) * | 1998-04-10 | 1999-10-26 | Nissan Motor Co Ltd | 排気ガス浄化用触媒 |
JP2000157867A (ja) * | 1998-11-25 | 2000-06-13 | Toyota Motor Corp | 排ガス浄化用触媒 |
JP2002079096A (ja) * | 2000-09-08 | 2002-03-19 | Toyota Motor Corp | 吸収還元型NOx浄化用触媒 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0148358B1 (de) * | 1983-11-10 | 1991-04-03 | KAT-TEC Gesellschaft für Katalysatortechnik mbH | Katalysator zur Verbrennung und Umwandlung von Gasen und höheren Kohlenwasserstoffen, sowie Vorrichtung zur Reduktion von Stickoxiden und Abgasnachverbrenner mit einem solchen Katalysator |
DE69427932T2 (de) * | 1993-05-10 | 2002-04-04 | Cosmo Oil Co. Ltd., Tokio/Tokyo | Katalysator zur katalytischen Reduktion von Stickstoffoxiden |
JP3517973B2 (ja) * | 1993-09-30 | 2004-04-12 | マツダ株式会社 | 排気ガス浄化用触媒、該排気ガス浄化用触媒の製造方法及び、排気ガス浄化用ハニカム触媒の製造方法 |
JPH0910594A (ja) * | 1995-04-28 | 1997-01-14 | Mazda Motor Corp | 排気ガス浄化用触媒 |
US6040265A (en) * | 1996-02-21 | 2000-03-21 | Asec Manufacturing General Partnership | Methods of making highly dispersed substantially uniform cerium and zirconium mixed-metal-oxide composite supports for exhaust conversion catalysts |
JP2004508189A (ja) * | 2000-09-18 | 2004-03-18 | ヴァルティオン テクンニィルリネン ツッツキムスケスクス | 窒素酸化物の接触還元のための触媒と方法 |
JP3845274B2 (ja) * | 2001-06-26 | 2006-11-15 | ダイハツ工業株式会社 | 排ガス浄化用触媒 |
-
2003
- 2003-09-08 JP JP2003315093A patent/JP4236543B2/ja not_active Expired - Fee Related
-
2004
- 2004-09-06 WO PCT/JP2004/013276 patent/WO2005023421A1/ja active Application Filing
- 2004-09-06 US US10/570,629 patent/US7422731B2/en not_active Expired - Fee Related
- 2004-09-06 EP EP04772958A patent/EP1671699A4/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07232064A (ja) * | 1994-02-23 | 1995-09-05 | Toyota Motor Corp | 排気ガス浄化用触媒 |
JPH08173815A (ja) * | 1994-12-22 | 1996-07-09 | Toyota Motor Corp | 排ガス浄化用触媒 |
JPH09215922A (ja) * | 1996-02-09 | 1997-08-19 | Toyota Motor Corp | 排ガス浄化用触媒 |
JPH11290686A (ja) * | 1998-04-10 | 1999-10-26 | Nissan Motor Co Ltd | 排気ガス浄化用触媒 |
JP2000157867A (ja) * | 1998-11-25 | 2000-06-13 | Toyota Motor Corp | 排ガス浄化用触媒 |
JP2002079096A (ja) * | 2000-09-08 | 2002-03-19 | Toyota Motor Corp | 吸収還元型NOx浄化用触媒 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1671699A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114585438A (zh) * | 2019-10-21 | 2022-06-03 | 巴斯夫公司 | 再生效率增强的低温NOx吸附剂 |
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