WO2012071971A1 - 一种铈基复合氧化物催化剂、其制备方法及用途 - Google Patents
一种铈基复合氧化物催化剂、其制备方法及用途 Download PDFInfo
- Publication number
- WO2012071971A1 WO2012071971A1 PCT/CN2011/081962 CN2011081962W WO2012071971A1 WO 2012071971 A1 WO2012071971 A1 WO 2012071971A1 CN 2011081962 W CN2011081962 W CN 2011081962W WO 2012071971 A1 WO2012071971 A1 WO 2012071971A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- salt
- iron
- mixture
- molybdenum
- ammonium
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 33
- 150000003624 transition metals Chemical class 0.000 claims abstract description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 54
- 239000007789 gas Substances 0.000 claims description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 24
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 22
- 229910052707 ruthenium Inorganic materials 0.000 claims description 22
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 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 18
- 150000002505 iron Chemical class 0.000 claims description 16
- 150000002751 molybdenum Chemical class 0.000 claims description 16
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 150000003657 tungsten Chemical class 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 12
- 239000003546 flue gas Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- FUECGUJHEQQIFK-UHFFFAOYSA-N [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] FUECGUJHEQQIFK-UHFFFAOYSA-N 0.000 claims description 8
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 8
- 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 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 8
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 8
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 claims description 8
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical group [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 8
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims 16
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims 4
- 150000004714 phosphonium salts Chemical class 0.000 claims 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims 1
- 229910052712 strontium Inorganic materials 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 230000000694 effects Effects 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- ISWNJSHGUJYCFP-UHFFFAOYSA-N [Ce].[Sr] Chemical compound [Ce].[Sr] ISWNJSHGUJYCFP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NNLJGFCRHBKPPJ-UHFFFAOYSA-N iron lanthanum Chemical compound [Fe].[La] NNLJGFCRHBKPPJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- OUFGXIPMNQFUES-UHFFFAOYSA-N molybdenum ruthenium Chemical compound [Mo].[Ru] OUFGXIPMNQFUES-UHFFFAOYSA-N 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 231100000828 respiratory toxicity Toxicity 0.000 description 1
- AJTVWPGZWVJMEA-UHFFFAOYSA-N ruthenium tungsten Chemical compound [Ru].[Ru].[W].[W].[W] AJTVWPGZWVJMEA-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
-
- 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
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/202—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20769—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20776—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the invention relates to a catalyst, in particular to a ruthenium-based composite oxide catalyst for catalytically purifying nitrogen oxides, in particular to a mobile source represented by diesel exhaust gas and represented by a coal-fired power plant flue gas.
- a fixed source nitrogen oxide catalytically purified ruthenium-based composite oxide catalyst in particular to a ruthenium-based composite oxide catalyst for catalytically purifying nitrogen oxides, in particular to a mobile source represented by diesel exhaust gas and represented by a coal-fired power plant flue gas.
- a fixed source nitrogen oxide catalytically purified ruthenium-based composite oxide catalyst.
- the main energy sources currently used in the world are mostly fossil fuels such as coal and petroleum fuels.
- NO x can cause major environmental problems photochemical smog, acid rain, the greenhouse effect and ozone layer depletion, while having biological respiratory toxicity, causing great harm to the environment and human health. Therefore, how to effectively remove NO x become a hot issue in today's field of environmental protection.
- NSR NOJ storage - reduction technique
- HC-SCR hydrocarbon selective catalytic reduction of NO x
- N3 ⁇ 4-SCR ammonia-selective catalytic reduction of NO x
- NO direct catalytic decomposition technology began in the last century, and was once regarded as the best net lean NO x Method. Theoretically, NO has thermodynamic instability, but the activation energy of its decomposition reaction is as high as 364 kJ/mol. In order to facilitate the progress of the reaction, a suitable catalyst must be selected to reduce the activation energy barrier of the reaction. Previous studies have shown that many catalysts such as noble metals, metal oxides, zeolites, etc. can promote the decomposition of NO, but the presence of oxygen can inhibit the decomposition of NO, and the desorption of oxygen is the final step of the whole reaction. Therefore, the direct catalytic decomposition technology of NO is difficult to be practically applied to the treatment of lean exhaust gas such as diesel engines.
- NSR technology based on the three-way catalyst having excellent HC and NO x removal capability at the same time, in order to fit the NO x absorbent in the lean state of the engine adsorbed NO x to down; cyclical adjustment of the engine becomes rich burn state, the HC in the exhaust gas reduction of NO x, while the purpose of removal.
- the engine must be precisely controlled conditions, and periodically create a lean, fuel-rich atmosphere in order to maximize the efficiency of the NO x purification catalyst, thus increasing the difficulty of controlling the engine
- the creation of a rich combustion atmosphere increases fuel consumption and reduces the fuel economy of the diesel engine; in addition, the sensitivity of the NSR catalyst to sulfur limits its application.
- HC-SCR preclude the reduction of NO x by selective catalytic hydrocarbon, - generally preclude the use of alkanes and alkenes with high selectivity in the reduction of NO x catalyst, with which it can be divided into three groups Bian, (1) Metal Ion-exchanged molecular sieve catalysts, including ZSM series, ferrierite, mordenite, silicoaluminophosphate
- SAPO Y-type zeolite and L-type zeolite, etc.
- non-precious metal oxide type catalyst including A1 2 0 3 ,
- Si0 2 , Ti0 2 , Zr0 2 and the like are supported metal oxides of the carrier, and A1 2 0 3 , Si0 2 , Ti0 2 , Zr0 2 ,
- a double metal oxide composed of Cr 2 0 3 , Fe 2 0 3 , Co 3 0 4 , CuO, V 2 0 5 , Bi 2 0 3 , MgO, or the like,
- a rare earth perovskite type composite metal oxide such as LaA10 3 ; (3) a noble metal catalyst such as Pt, Pd, Rh, and Au in an atomic state, or exchanged on the zeolite, or supported on A1 2 0 3 , Si0 2 , Ti0 2 , Zr0 2 on.
- the catalyst for the HC-SCR method needs to disperse the catalytically active component by means of a carrier and increase its specific surface area, which results in a catalyst area of the carrier by the same amount of the active component. Large, therefore, when the method is used in a place where the use condition of a diesel vehicle or the like is limited, the catalyst takes up a large volume.
- NH 3 -SCR is considered to be the most promising technology for exhaust gas purification in diesel vehicles, and the technology has entered the practical stage. It is currently the most widely used flue gas denitration technology in the world.
- the N3 ⁇ 4-SCR catalyst for industrial applications is typically a V 2 0 5 -W0 3 (Mo0 3 )/Ti0 2 catalyst containing the toxicant vanadium (V).
- the catalyst not only uses a carrier, but also its active component may fall off during its use and enter the environment. Because V 5+ has great biological toxicity, it will pollute the environment and endanger human health. Therefore, its use in Europe and America is limited.
- the catalyst system has the disadvantages of narrow operating temperature window and easy to catalyze the conversion of S0 2 into S0 3 in the flue gas.
- the present invention provides a novel ruthenium composite for the first time.
- NO x catalyst of the present invention is preferably used for purification of diesel exhaust.
- the catalyst is a composite oxide catalyst which does not require a carrier to achieve a corresponding dispersion and catalytic effect.
- the composite oxide catalyst includes cerium (Ce) and at least one metal selected from the group consisting of: cerium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese ( Mn ), iron (Fe ), Cobalt (Co), nickel (Ni), copper (Cu), hexadium (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), niobium (Tc), niobium (Ru), Rh (R), palladium (Pd), silver (Ag), cadmium (Cd), yttrium (Hf), yttrium (Ta), tungsten (W), yttrium (Re), yttrium (Os), yttrium (Ir), Platinum (Pt), gold (Au).
- Ce cerium
- Sc cerium
- Ti titanium
- V vanadium
- Cr chromium
- Mn
- the transition metal is selected from the group consisting of tungsten (W), molybdenum (Mo), and iron (Fe), or a mixture of two or more thereof.
- the mixing is, for example, W/Mo, W/Fe, Mo/Fe or W/Mo/Fe.
- the molar ratio of the cerium (Ce) element to the transition metal element may be 0.2 to 5.0, preferably 0.5 to 4.5, 1.0 to 4.0, 1.5 to 3.5, 2.0 to 3.0 or the like.
- a cerium (Ce) element and a transition metal element are present in an oxide state in the composite oxide catalyst.
- the present inventors have found that the cerium (Ce) element and the oxide of the transition metal element form a solid solution in the composite oxide catalyst.
- the oxide of Ce is CeO x , which is an oxide mixture of different valence states Ce, such as a mixture of Ce 3+ and Ce 4+ .
- the oxide of the transition metal is a mixture of oxides of different valence states.
- An oxide of the transition metal such as WO x , which is an oxide mixture of different valence states W, such as a mixture of W 5+ and W 6+ ;
- MoO x which is an oxide mixture of different valence Mo,
- FeO x which is an oxide mixture of Fe in different valence states, such as a mixture of Fe 2+ and Fe 3+ .
- the ruthenium-based composite oxide catalyst is preferably CeO x -WO x , CeO x -MoO x , CeO x -FeO ⁇ .
- metal composite oxide catalyst or CeO x -WO x -MoO x , CeO x -WO x - FeO x, CeO x -MoO x -FeO x composite oxide catalyst, or CeO x -WO x -MoO x -FeO x complex oxide catalyst.
- the ruthenium-based composite oxide catalyst of the present invention may be prepared by a uniform precipitation method, a sol-gel method, a citric acid complex method, a hydrothermal synthesis method, or the like.
- the precipitation method is preferably a homo-column precipitation method, which comprises the following steps:
- the onium salt is preferably at least one of cerium chloride, cerium nitrate, cerium ammonium nitrate, and strontium sulphate, and a mixture of two or more thereof.
- the salt of the transition metal includes a tungsten salt or a tungstate, a molybdenum salt or a molybdate, an iron salt or a mixture of two or more thereof.
- the tungsten salt or tungstate is preferably at least one of ammonium tungstate, ammonium paratungstate, tungsten nitrate, tungsten chloride, and tungsten acid, including a mixture of two or more thereof;
- the molybdenum salt or the molybdate is preferably At least one of ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, molybdenum nitrate, molybdenum chloride, molybdenum acid, including a mixture of two or more thereof;
- the iron salt is preferably iron nitrate or iron tungstate And at least one of iron molybdate, ferric chloride, and ferric sulfate, including a mixture of two or more thereof.
- the stirring time is preferably from 1 to 24 hours, further preferably from 4 to 15 hours, for example, 5h, 6h, 8h or 12h.
- the temperature is preferably from 60 to 100 ° C, more preferably from 70 to 98 ° C, still more preferably from 80 to 95 ° C.
- the washing is preferably carried out with deionized water, and the number of washings is preferably 1 to 5 times, for example, 2 to 4 times, including 3 times.
- the drying is preferably performed at 80 to 120 ° C; further preferably, it is dried in an oven at 80 to 120 ° C; the drying time is preferably from l to 36 h, more preferably from 2 to 2. 24h, further preferably 4 ⁇ 12h.
- the calcination is preferably calcined in a muffle furnace at 400 to 800 ° C in air; the calcination time is preferably from 1 to 24 h, preferably from 2 to 12 h, further preferably from 4 to 6 h.
- the reaction pressure is not particularly limited, but it is usually carried out by a normal pressure reaction.
- the sol-gel method comprises the following steps:
- the salt of Ce and the transition metal is mixed into a mixed solution, wherein the ratio of the lanthanum to the transition metal is 0.2 to 5.0 in terms of a molar ratio of the metal elements;
- the onium salt is preferably at least one of cerium chloride, cerium nitrate, cerium ammonium nitrate, and cerium strontium, and a mixture of two or more thereof.
- the salt of the transition metal includes a tungsten salt or a tungstate, a molybdenum salt or a molybdate, an iron salt or a mixture of two or more thereof.
- the tungsten salt or tungstate is preferably at least one of ammonium tungstate, ammonium paratungstate, tungsten nitrate, tungsten chloride, and tungsten acid, including a mixture of two or more thereof;
- the molybdenum salt or the molybdate is preferably At least one of ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, molybdenum nitrate, molybdenum chloride, molybdenum acid, including a mixture of two or more thereof;
- the iron salt is preferably iron nitrate or iron tungstate And at least one of iron molybdate, ferric chloride, and ferric sulfate, including a mixture of two or more thereof.
- the stirring time is preferably from 1 to 60 hours, further preferably from 4 to 48 hours, for example, 6h, 10h, 12h or 24h.
- the rest time is preferably from 1 to 10 d, further preferably from 2 to 7 d, such as 3d, 4d, 5d or 6d.
- the drying is preferably performed at 80 to 120 ° C; further preferably, it is dried in an oven at 80 to 120 ° C; the drying time is preferably from l to 36 h, more preferably from 2 to 2. 24h, further preferably 4 ⁇ 12h.
- the calcination is preferably calcined in a muffle furnace at 400 to 800 ° C in air; the calcination time is preferably 1 to 24 hours, preferably 2 to 12 hours, further preferably 4 to 6 hours.
- the citric acid complexing method comprises the following steps:
- a salt of Ce and a transition metal is mixed into a mixed solution, wherein the ratio of the lanthanum to the transition metal is 0.2 to 5.0 in terms of a molar ratio of the metal elements;
- the obtained product is dried and calcined in air at 400 to 800 ° C to obtain the ruthenium-based composite oxide catalyst.
- the onium salt is preferably at least one of cerium chloride, cerium nitrate, cerium ammonium nitrate, and strontium sulphate, and a mixture of two or more thereof.
- the salt of the transition metal includes a tungsten salt or a tungstate, a molybdenum salt or a molybdate, an iron salt or a mixture of two or more thereof.
- the tungsten salt or tungstate is preferably at least one of ammonium tungstate, ammonium paratungstate, tungsten nitrate, tungsten chloride, and tungsten acid, including a mixture of two or more thereof;
- the molybdenum salt or the molybdate is preferably At least one of ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, molybdenum nitrate, molybdenum chloride, molybdenum acid, including a mixture of two or more thereof;
- the iron salt is preferably iron nitrate or iron tungstate And at least one of iron molybdate, ferric chloride, and ferric sulfate, including a mixture of two or more thereof.
- the stirring time is preferably from 1 to 40 h, further preferably from 2 to 24 h, for example, 3 h, 5 h, 10h or 20h, etc.
- the rest time is preferably 1 to 4 days, for example, 2d or 3d.
- the drying is preferably performed at 80 to 120 ° C; further preferably, it is dried in an oven at 80 to 120 ° C; the drying time is preferably from l to 36 h, more preferably from 2 to 2. 24h, further preferably 4 ⁇ 12h.
- the calcination is preferably calcined in a muffle furnace at 400 to 800 ° C in air; the calcination time is preferably from 1 to 24 h, preferably from 2 to 12 h, further preferably from 4 to 6 h.
- the hydrothermal synthesis method comprises the following steps:
- a salt of Ce and a transition metal is mixed into a mixed solution, wherein the ratio of the lanthanum to the transition metal is 0.2 to 5.0 in terms of a molar ratio of the metal elements;
- the obtained product is centrifugally washed, dried, and calcined in air at 400 to 800 ° C to obtain the ruthenium-based composite oxide catalyst.
- the onium salt is preferably at least one of cerium chloride, cerium nitrate, cerium ammonium nitrate, and strontium sulphate, and a mixture of two or more thereof.
- the salt of the transition metal includes a tungsten salt or a tungstate, a molybdenum salt or a molybdate, an iron salt or a mixture of two or more thereof.
- the tungsten salt or tungstate is preferably at least one of ammonium tungstate, ammonium paratungstate, tungsten nitrate, tungsten chloride, and tungsten acid, including a mixture of two or more thereof;
- the molybdenum salt or the molybdate is preferably At least one of ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, molybdenum nitrate, molybdenum chloride, molybdenum acid, including a mixture of two or more thereof;
- the iron salt is preferably iron nitrate or iron tungstate And at least one of iron molybdate, ferric chloride, and ferric sulfate, including a mixture of two or more thereof.
- the standing time is preferably from 1 to 12 days, further preferably from 2 to 8 days, such as 3d, 4d, 5d or 6d.
- the drying is preferably performed at 80 to 120 ° C; further preferably, it is dried in an oven at 80 to 120 ° C; the drying time is preferably from l to 36 h, more preferably from 2 to 2. 24h, further preferably 4 ⁇ 12h.
- the calcination is preferably calcined in a muffle furnace at 400 to 800 ° C in air; the calcination time is preferably from 1 to 24 h, preferably from 2 to 12 h, further preferably from 4 to 6 h.
- the catalyst can be pulped according to actual needs, and then loaded onto various honeycomb ceramic supports to prepare a shaped catalyst for use, or can be used after extrusion molding.
- the catalyst is placed on the way of the exhaust gas pipeline, and a reducing agent and a tail gas are mixed in the upstream of the catalyst, and ammonia or urea is used as the reducing agent (ammonia gas is obtained after hydrolysis), and the amount of the reducing agent is 0.8 in the exhaust gas.
- the gas is preferably a mobile source nitrogen oxide gas, such as a diesel exhaust, or a stationary source nitrogen oxide gas, such as a coal fired power plant.
- the gas is preferably a diesel exhaust gas, that is, the method for catalytically purifying nitrogen oxides in the gas of the present invention, and is particularly suitable for catalytic purification of nitrogen oxides in diesel exhaust gas.
- the ruthenium-based composite oxide catalyst has a wide operating temperature window (especially in the low temperature region), and is suitable for an application environment in which the temperature of the exhaust gas of the vehicle is large; in the fixed source flue gas denitration, it is expected to be a low temperature Type SCR catalyst, used after flue gas desulfurization, to improve the service life of SCR catalyst;
- the prepared catalyst is tableted, ground, sieved, and taken from 40 to 60 mesh for use as catalyst A.
- Example 2
- Example 3 The other conditions were the same as in Example 1, and the Ce/W molar ratio was changed to 1.0 to obtain a catalyst B.
- Example 3
- Example 4 The other conditions were the same as in Example 1, and the Ce/W molar ratio was changed to 2.0 to obtain a catalyst C.
- Example 4
- Catalyst B was obtained by calcining Catalyst B in air at 800 ° C for 1 h.
- Example 2 The other conditions were the same as in Example 2, and the ammonium tungstate was changed to ammonium molybdate to prepare a catalyst E.
- Example 6 Other conditions were the same as in Example 2.
- the ammonium tungstate was changed to ferric nitrate, and the oxalic acid solution was changed to deionized water to prepare a catalyst F.
- the space velocity is 250,000 h and the reaction temperature is 150 ⁇ 450 °C.
- Both NO and N3 ⁇ 4 and by-products 0 2 0 , N0 2 were measured using an infrared gas cell. The reaction results are shown in Table 1.
- NO x conversion catalyst B was significantly better than Catalyst E and F.
- Catalyst B is 250,000 h "1 under space velocity conditions, the temperature range of 200 ⁇ 450 ° C can achieve NO x conversion rate of more than 80%, and the selectivity in N 2 is greater than 97%.
- Catalyst D 800 ° C after high temperature firing can still be obtained at a space velocity of 250,000 h-1 conditions, the conversion of NO x to achieve more than 80% in the temperature range of 300 ⁇ 450 ° C, and N 2 selectivity greater than 98 % , indicating that the catalyst has excellent resistance to high temperature sintering.
- reaction space velocity was investigated on a fixed bed reactor using Catalyst B.
- the catalysts were used in amounts of 0.3 ml, 0.12 ml, and 0.06 ml, respectively.
- Catalyst B can achieve a NO ⁇ ization rate of 98% or more in the temperature range of 200 ⁇ 450 °C under the condition of a space velocity of 100,000 h" 1 , and the N 2 formation selectivity is greater than 98%, showing Very wide operating temperature window.
- Catalyst B can achieve a NO ratio of more than 90% in the temperature range of 250 ⁇ 450 °C, and the N 2 selectivity is greater than 98%, indicating that The catalyst has very excellent resistance to high space velocity reaction.
- the present invention is not limited to the above detailed process equipment and process flow, that is, it does not mean that the present invention must be implemented by relying on the detailed process equipment and process flow described above. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, and addition of auxiliary components, selection of specific means, etc., are all within the scope of the present invention.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
一种錚基复合氧化物催化剂、 其制备方法及用途
技术领域
本发明涉及一种催化剂,具体涉及一种用于催化净化氮氧化物的铈基复合氧 化物催化剂, 特别涉及一种用于以柴油车尾气为代表的移动源和以燃煤电厂烟 气为代表的固定源氮氧化物催化净化的铈基复合氧化物催化剂。
背景技术
目前世界上使用的主要能源, 多是化石燃料, 比如煤和石油燃料。 煤在燃 烧后产生的烟气中, 除含有硫氧化物 (SOx ) 夕卜, 还含有氮氧化物(NOx, 主要 指 NO和 N02 )。石油燃料, 比如车用汽油和车用柴油,在燃烧后排放的尾气中, NOx也占了很大比重。
NOx的存在会引起光化学烟雾、 酸雨、 温室效应和臭氧层破坏等重大环境 问题, 同时具有生物呼吸毒性, 对生态环境和人类健康造成巨大的危害。 因此, 如何有效去除 NOx成为当今环境保护领域的热点问题。
随着石油资源日趋短缺, C02减排压力增大, 燃油经济性好和动力性强的 柴油车越来越受到重视。 与装有三效催化剂的汽油车相比, 以 NO;^o PM为特 征的尾气污染成为制约柴油车推广应用的瓶颈。 柴油车已成为我国机动车 NOx 和 PM排放的主要分担者, 成为机动车尾气治理中的重点和难点。 柴油车尾气 排放具有温度低、 氧含量高、 含有大量颗粒物和少量硫等特点, 因此其 NO 々 净化消除难度较大。
目前,针对柴油机尾气 NOx净化的技术方案主要有 NO直接催化分解技术,
NOJ 存-还原技术 (NSR), 碳氢化合物选择性催化还原 NOx (HC-SCR)、 氨选择 性催化还原 NOx(N¾-SCR)。
NO直接催化分解技术始于上个世纪, 且一度被视为最理想的稀燃 NOx净
化方法。 从理论上看, NO 具有热力学不稳定性, 但其分解反应的活化能高达 364kJ/mol。 为了促进该反应的进行, 必须选择合适的催化剂, 以降低反应活化 能垒。 已有的研究表明, 许多催化剂如贵金属、 金属氧化物、 沸石等均能促进 NO的分解,但氧的存在可以抑制 NO分解反应的进行,且氧的脱附为整个反应 的决速步骤。 因此, NO直接催化分解技术很难实际应用于柴油机等稀燃尾气处 理。
NSR技术立足于三效催化剂优异的 HC和 NOx同时去除能力, 配合以 NOx 吸附剂, 在发动机稀燃状态下将 NOx吸附下来; 周期性调整发动机成为浓燃状 态, 利用尾气中的 HC还原 NOx, 达到同时去除的目的。 但是, 要使该技术付 诸实施, 必须精确控制发动机的工况, 周期性地营造稀燃、 浓燃的氛围以最大 限度地发挥该催化剂的 NOx净化效率, 这样就增加了发动机控制的难度; 同时, 浓燃气氛的营造增大了燃油的消耗, 降低了柴油机的燃油经济性; 另外, NSR 催化剂对硫的敏感性也限制了其应用。
HC-SCR釆用碳氢化合物选择性催化还原 NOx, —般釆用烷烃和烯烃在催 化剂上高选择性地还原 NOx, 其所釆用的催化剂可以分为 3大类, ( 1 )金属离 子交换的分子筛催化剂, 包括 ZSM系列、 镁碱沸石、 丝光沸石、 磷酸硅铝沸石
( SAPO )、 Y型沸石和 L型沸石等;( 2 )非贵金属氧化物型催化剂,包括以 A1203、
Si02、 Ti02、 Zr02等为载体的负载型金属氧化物,以及 A1203、 Si02、 Ti02、 Zr02、
Cr203、 Fe203、 Co304、 CuO、 V205、 Bi203、 MgO等相互构成的双金属氧化物,
LaA103等稀土钙钛矿型复合金属氧化物; (3 )贵金属催化剂, 如 Pt、 Pd、 Rh 和 Au等以原子状态形式, 或交换在沸石上, 或负载在 A1203、 Si02、 Ti02、 Zr02 上。 所述 HC-SCR法釆用的催化剂均需要借助载体来分散催化活性组分, 并增 大其比表面积, 这就导致在活性组分相同的情况下, 借助载体的催化剂面积较
大, 因此所述方法在用于柴油车等使用条件受限的场所时, 催化剂占用体积大。
NH3-SCR被认为是最有希望全面应用于柴油车尾气净化的技术, 且该技术 目前已经进入了实用化阶段, 其是目前国际上应用最为广泛的烟气脱硝技术。 工业化应用 的 N¾-SCR 催化剂通常是含有毒物质钒 ( V ) 的 V205-W03(Mo03)/Ti02催化剂。 所述催化剂不仅使用载体, 而且其活性组分在 使用过程中, V会发生脱落进而进入到环境中。 由于 V5+具有很大的生物毒性, 由此会污染环境, 进而危害人体健康, 因此其使用在欧美是受限的。 同时该催 化剂体系具有操作温度窗口较窄、 易催化烟气中的 S02转化为 S03等缺点。
因此,开发新型具有高 NH3-SCR活性、宽操作温度窗口、适应高空速环境、 无毒无害的非钒催化剂体系用于以柴油车尾气为代表的移动源和以燃煤电厂烟 气为代表的固定源 NOx的催化消除, 具有非常重要的环境意义。
发明内容
针对现有技术的不足, 为了解决现有金属氧化物催化剂体系操作温度窗口 窄、 低温活性差、 N2选择性低、 对反应空速敏感等缺点, 本发明首次提供了一 种新型铈基复合氧化物催化剂及其制备方法, 可用作以柴油车尾气为代表的移 动源和以燃煤电厂烟气为代表的固定源 NOx催化净化。 本发明优选用于柴油车 尾气的 NOx催化净化。
因此, 本发明的目的之一在于提供一种用于催化净化氮氧化物的铈基复合 氧化物催化剂。
所述催化剂为复合氧化物催化剂, 其不需要载体即可达到相应的分散和催 化效果。
所述复合氧化物催化剂包括铈(Ce )和至少一种选自过渡金属的金属, 所 述过渡金属包括: 钪(Sc )、 钛(Ti )、 钒(V )、 铬(Cr )、 锰(Mn )、 铁(Fe )、
钴(Co)、镍(Ni)、 铜(Cu)、辞(Zn)、 钇( Y)、锆(Zr)、 铌(Nb)、 钼(Mo)、 锝 ( Tc )、 钌 ( Ru )、 铑 ( Rh )、 钯 ( Pd )、 银 ( Ag )、 镉( Cd )、铪( Hf )、钽 ( Ta )、 钨(W)、 铼(Re)、 锇(Os)、 铱(Ir)、 铂(Pt)、 金(Au)。
作为优选, 所述过渡金属选自钨(W)、 钼 (Mo)、 铁(Fe) 中的任意一种 或其 2者或以上的混合。 所述混合例如 W/Mo、 W/Fe、 Mo/Fe或 W/Mo/Fe。
在所述铈 (Ce) 元素和过渡金属元素的摩尔比为可以为 0.2 ~ 5.0, 优选 0.5-4.5, 1.0-4.0, 1.5-3.5, 2.0~3.0等。
所述铈基复合氧化物催化剂中, 铈(Ce)元素和过渡金属元素在复合氧化 物催化剂中均以氧化物态存在。 本发明发现, 所述铈(Ce)元素和过渡金属元 素的氧化物在复合氧化物催化剂中形成固溶体。
所述 Ce的氧化物为 CeOx, 其为不同价态 Ce的氧化物混合体, 比如 Ce3+ 和 Ce4+的混合物。
所述过渡金属的氧化物为不同价态的氧化物的混合体。 所述过渡金属的氧 化物,例如 WOx,其为不同价态 W的氧化物混合体, 比如 W5+和 W6+的混合物; MoOx, 其为不同价态 Mo的氧化物混合体 , 比如 Mo5+和 Mo6+的混合物; FeOx, 其为不同价态 Fe的氧化物混合体, 比如 Fe2+和 Fe3+的混合物。
所述铈基复合氧化物催化剂, 优选 CeOx-WOx、 CeOx-MoOx、 CeOx-FeO^ . 金属复合氧化物催化剂,或 CeOx-WOx-MoOx、 CeOx-WOx-FeOx、 CeOx-MoOx-FeOx 复合氧化物催化剂, 或 CeOx-WOx-MoOx-FeOx复合氧化物催化剂。
本发明的目的之一还在于提供一种铈基复合氧化物催化剂的制备方法。 本 发明所述铈基复合氧化物催化剂,其制备方法可以为均匀沉淀法、溶胶-凝胶法、 柠檬酸络合法和水热合成法等。
I. 均匀沉淀法
所述沉淀法优选为均勾沉淀法, 其包括如下步骤:
(1 ) 将 Ce和过渡金属的盐配成混合溶液, 所述混合溶液中, 以金属元素 的摩尔比计, 铈和过渡金属的比例为 0.2 ~ 5.0;
( 2 ) 以过量尿素作为沉淀剂, 在 60 ~ 100 °C温度条件下搅拌 0.5 ~ 48h;
(3) 进行抽滤和洗涤, 得到滤饼;
(4) 将滤饼烘干, 于 400~800°C在空气中焙烧,得到所述铈基复合氧化物 催化剂。
步骤(1 ) 中, 所述铈盐优选氯化亚铈、 硝酸铈、 硝酸铈铵、 石克酸铈中的至 少一种, 包括其二者或二者以上的混合物。
步骤(1 ) 中, 所述过渡金属的盐包括钨盐或钨酸盐、 钼盐或钼酸盐、 铁盐 或其二者或二者以上的混合物。 所述钨盐或钨酸盐优选为钨酸铵、 仲钨酸铵、 硝酸钨、 氯化钨、 酸钨中的至少一种, 包括其二者或二者以上的混合物; 钼 盐或钼酸盐优选为钼酸铵、 二钼酸铵、 四钼酸铵、 硝酸钼、 氯化钼、 酸钼中 的至少一种, 包括其二者或二者以上的混合物; 铁盐优选为硝酸铁、 钨酸铁、 钼酸铁、 氯化铁、 硫酸铁中的至少一种, 包括其二者或二者以上的混合物。
步骤( 2 )中, 所述搅拌时间优选 l~24h, 进一步优选 4 ~ 15h, 例如 5h、 6h、 8h或 12h等。
步骤(2) 中, 所述温度优选为 60 ~ 100 °C, 更优选 70~98°C, 进一步优选 80~95°C。
步骤(3) 中, 所述洗涤优选釆用去离子水洗涤, 洗涤次数优选 1~5次, 例 如 2~4次, 包括 3次。
步骤(4)中, 所述烘干优选于 80~120°C下烘干; 进一步优选放入烘箱中于 80~120°C烘干; 更烘干时间优选为 l~36h, 更优选 2~24h, 进一步优选 4~12h。
步骤(4)中, 所述焙烧优选经马弗炉于 400 ~800°C空气中焙烧; 所述焙烧 时间优选 l~24h, 优选 2~12h, 进一步优选 4 ~ 6h。
所述均勾沉淀法, 其反应压力没有特别限定, 但通常釆用常压反应。
II. 溶胶-凝胶法
所述溶胶-凝胶法, 包括如下步骤:
(1) 将 Ce和过渡金属的盐配成混合溶液, 所述混合溶液中, 以金属元素 的摩尔比计, 铈和过渡金属的比例为 0.2 ~ 5.0;
(2) 在室温条件下搅拌 0.5~72h, 得到溶胶;
(3) 将所得溶胶在常温常压下静置 0.5 ~12d, 得到凝胶;
(4) 将凝胶烘干, 于 400~800°C在空气中焙烧,得到所述铈基复合氧化物 催化剂。
步骤(1) 中, 所述铈盐优选氯化亚铈、 硝酸铈、 硝酸铈铵、 石克酸铈中的至 少一种, 包括其二者或二者以上的混合物。
步骤(1) 中, 所述过渡金属的盐包括钨盐或钨酸盐、 钼盐或钼酸盐、 铁盐 或其二者或二者以上的混合物。 所述钨盐或钨酸盐优选为钨酸铵、 仲钨酸铵、 硝酸钨、 氯化钨、 酸钨中的至少一种, 包括其二者或二者以上的混合物; 钼 盐或钼酸盐优选为钼酸铵、 二钼酸铵、 四钼酸铵、 硝酸钼、 氯化钼、 酸钼中 的至少一种, 包括其二者或二者以上的混合物; 铁盐优选为硝酸铁、 钨酸铁、 钼酸铁、 氯化铁、 硫酸铁中的至少一种, 包括其二者或二者以上的混合物。
步骤( 2 )中,所述搅拌时间优选 l~60h,进一步优选 4 ~ 48h,例如 6h、 10h、 12h或 24h等。
步骤(3)中, 所述静置时间优选 l~10d, 进一步优选 2~7d, 例如 3d、 4d、 5d或 6d等。
步骤(4)中, 所述烘干优选于 80~120°C下烘干; 进一步优选放入烘箱中于 80~120°C烘干; 更烘干时间优选为 l~36h, 更优选 2~24h, 进一步优选 4~12h。
步骤(4)中, 所述焙烧优选经马弗炉于 400 ~800°C空气中焙烧; 所述焙烧 时间优选 l~24h, 优选 2~12h, 进一步优选 4 ~ 6h。
III. 柠檬酸络合法
所述柠檬酸络合法, 包括如下步骤:
( 1 ) 将 Ce和过渡金属的盐配成混合溶液, 所述混合溶液中, 以金属元素 的摩尔比计, 铈和过渡金属的比例为 0.2 ~ 5.0;
(2) 向混合溶液中加入一定量柠檬酸, 金属离子总量与柠檬酸的摩尔比 为 0.5-5.0;
(3) 在 20 ~ 95°C温度条件下搅拌 0.5 ~ 48h;
(4) 在常温常压下静置 0.5 ~5d;
(5) 将所得产物烘干, 于 400~800°C在空气中焙烧, 得到所述铈基复合氧 化物催化剂。
步骤(1 ) 中, 所述铈盐优选氯化亚铈、 硝酸铈、 硝酸铈铵、 石克酸铈中的至 少一种, 包括其二者或二者以上的混合物。
步骤(1 ) 中, 所述过渡金属的盐包括钨盐或钨酸盐、 钼盐或钼酸盐、 铁盐 或其二者或二者以上的混合物。 所述钨盐或钨酸盐优选为钨酸铵、 仲钨酸铵、 硝酸钨、 氯化钨、 酸钨中的至少一种, 包括其二者或二者以上的混合物; 钼 盐或钼酸盐优选为钼酸铵、 二钼酸铵、 四钼酸铵、 硝酸钼、 氯化钼、 酸钼中 的至少一种, 包括其二者或二者以上的混合物; 铁盐优选为硝酸铁、 钨酸铁、 钼酸铁、 氯化铁、 硫酸铁中的至少一种, 包括其二者或二者以上的混合物。
步骤( 3 )中, 所述搅拌时间优选 l~40h, 进一步优选 2 ~ 24h, 例如 3h、 5h、
10h或 20h等。
步骤(4 ) 中, 所述静置时间优选 l~4d, 例如 2d或 3d等。
步骤(5 )中, 所述烘干优选于 80~120°C下烘干; 进一步优选放入烘箱中于 80~120°C烘干; 更烘干时间优选为 l~36h, 更优选 2~24h, 进一步优选 4~12h。
步骤(5 )中, 所述焙烧优选经马弗炉于 400 ~ 800°C空气中焙烧; 所述焙烧 时间优选 l~24h, 优选 2~12h, 进一步优选 4 ~ 6h。
IV. 水热合成法
所述水热合成法, 包括如下步骤:
( 1 ) 将 Ce和过渡金属的盐配成混合溶液, 所述混合溶液中, 以金属元素 的摩尔比计, 铈和过渡金属的比例为 0.2 ~ 5.0;
( 2 ) 在室温条件下搅拌 0.5~2h后, 将溶液移至内衬聚四氟乙烯的不锈钢 反应蒼内;
( 3 ) 将反应釜在 80 200 °C条件下放置 1 ~ 12d;
( 4 ) 将所得产物离心洗涤、 烘干, 于 400~800°C在空气中焙烧, 得到所述 铈基复合氧化物催化剂。
步骤(1 ) 中, 所述铈盐优选氯化亚铈、 硝酸铈、 硝酸铈铵、 石克酸铈中的至 少一种, 包括其二者或二者以上的混合物。
步骤(1 ) 中, 所述过渡金属的盐包括钨盐或钨酸盐、 钼盐或钼酸盐、 铁盐 或其二者或二者以上的混合物。 所述钨盐或钨酸盐优选为钨酸铵、 仲钨酸铵、 硝酸钨、 氯化钨、 酸钨中的至少一种, 包括其二者或二者以上的混合物; 钼 盐或钼酸盐优选为钼酸铵、 二钼酸铵、 四钼酸铵、 硝酸钼、 氯化钼、 酸钼中 的至少一种, 包括其二者或二者以上的混合物; 铁盐优选为硝酸铁、 钨酸铁、 钼酸铁、 氯化铁、 硫酸铁中的至少一种, 包括其二者或二者以上的混合物。
步骤(3 )中, 所述放置时间优选 l~12d, 进一步优选 2 ~ 8d, 例如 3d、 4d、 5d或 6d等。 步骤(4 )中, 所述烘干优选于 80~120°C下烘干; 进一步优选放入烘箱中于 80~120°C烘干; 更烘干时间优选为 l~36h, 更优选 2~24h, 进一步优选 4~12h。 步骤(4 )中, 所述焙烧优选经马弗炉于 400 ~ 800°C空气中焙烧; 所述焙烧 时间优选 l~24h, 优选 2~12h, 进一步优选 4 ~ 6h。 本发明的目的之一还在于提供一种催化净化气体中氮氧化物的方法, 所述 方法使用本发明所述的铈基复合氧化物催化剂。 该催化剂可以根据实际需要进 行制浆, 然后负载到各种蜂窝陶瓷载体上, 制备成成型的催化剂进行使用, 也 可以通过挤压成型后进行使用。 使用时将催化剂置于尾气管道途中, 在催化剂 的上游喷入还原剂和尾气混合, 还原剂釆用氨气或尿素 (水解后可得到氨气), 还原剂用量为尾气中氮氧化物的 0.8~1.2倍,富氧条件下在 4艮宽的温度窗口内可 以将 NOx还原为 N2和 ¾0, 同时具备很高的 N2选择性和抗硫抗水性能。 所述气体优选为移动源含氮氧化物气体, 例如柴油车尾气, 或固定源含氮 氧化物气体, 例如燃煤电厂烟气。 所述气体优选为柴油车尾气, 即本发明的所述催化净化气体中氮氧化物的 方法, 特别适用于柴油车尾气中氮氧化物的催化净化。 本发明具有如下优点:
( 1 ) 所述铈基复合氧化物催化剂的操作温度窗口宽 (尤其在低温区的活性 好), 适用于机动车尾气温度变化幅度大的应用环境; 在固定源烟气脱硝方面, 有望作为低温型 SCR催化剂, 应用于烟气脱硫之后, 以提高 SCR催化剂的使 用寿命;
( 2 ) 对反应空速不敏感, 适用于机动车尾气净化高空速的特性, 将其应用
于固定源烟气脱硝时可以大幅度降低催化剂的使用量, 降低成本、 节约空间;
( 3 ) 具有非常优异的 N2生成选择性;
( 4 ) 具有非常好的抗高温烧结能力和抗水抗硫性能;
( 5 )釆用无毒组分, 有效减少了对人体健康和生态环境的危害。
具体实施方式
为便于理解本发明, 本发明列举实施例如下。 本领域技术人员应该明了, 所述实施例仅仅用于帮助理解本发明, 不应视为对本发明的具体限制。
实施例 1
将钨酸铵溶于草酸溶液(钨酸铵与草酸的质量比为 1 : 1 ), 并向该溶液中加 入硝酸铈溶液, 配制 Ce/W摩尔比为 0.5的溶液并混合均匀, 向该溶液中加入过 量尿素, 并在 90 °C温度条件下连续搅拌 12 h, 然后进行抽滤和洗涤, 将滤饼放 入烘箱中于 100°C烘干过夜,最后经马弗炉于 500 °C空气中焙烧 5h制得粉末状 催化剂。
将制得的催化剂压片、 研碎、 过筛, 取 40 ~ 60目备用, 称为催化剂 A。 实施例 2
其它条件如实施例 1不变, 改变 Ce/W摩尔比为 1.0, 制得催化剂 B。 实施例 3
其它条件如实施例 1不变, 改变 Ce/W摩尔比为 2.0, 制得催化剂 C。 实施例 4
将催化剂 B在 800 °C空气中焙烧 1 h制得催化剂 D。
实施例 5
其它条件如实施例 2不变, 改变钨酸铵为钼酸铵, 制得催化剂 E。
实施例 6
其它条件如实施例 2不变, 改变钨酸铵为硝酸铁, 改变草酸溶液为去离子 水, 制得催化剂 F。
实施例 7
用实施例 1-6制得的铈钨复合氧化物催化剂 A、 B、 C和 D, 以及铈钼复合 氧化物催化剂 E和铈铁复合氧化物催化剂 F在固定床反应器上进行 N¾选择性 催化还原 NOx反应活性的考察。
催化剂的使用量为 0.12 ml,反应混合气的组成为: [NO] = [NH3] = 500 ppm, [02] = 5%, N2作平衡气, 气体总流量为 500 ml/min, 空速为 250,000 h , 反应 温度 150 ~ 450 °C。 NO和 N¾及副产物 Ν20 , N02均利用红外气体池测定。 反 应结果如表 1所示。
表 1 不同 Ce/W摩尔比及经高温焙烧后的催化剂与 Ce-Mo和 Ce-Fe复合氧 化物催化剂的活性评价结果
由表 1可知, 催化剂 B的 NOx转化率明显好于催化剂 E和 F。 催化剂 B在
250,000 h"1空速条件下, 200 ~ 450°C的温度范围内均可实现 80%以上的 NOx转 化率, 且在 N2选择性均大于 97%。
经过 800 °C高温焙烧得到的催化剂 D仍可以在 250,000 h-1 空速条件下, 300 ~ 450°C的温度范围内实现 80%以上的 NOx转化率,且 N2生成选择性均大于 98% , 说明该催化剂具有非常优异的抗高温烧结能力。
实施例 8
使用催化剂 B, 在固定床反应器上考察反应空速对催化剂活性的影响。 催化剂的使用量分别为 0.3 ml、 0.12 ml、 0.06 ml,反应混合气的组成为: [NO] = [NH3] = 500 pm, [02] = 5%, N2作平衡气, 气体总流量为 500 ml/min, 相应 空速分别为 100,000 h 、 250,000 h 、 500,000 h"1 , 反应温度 150 ~ 450°C。 NO 和 N¾及副产物 N20, N02均利用红外气体池测定。 反应结果如表 2所示。
表 2 反应空速对催化剂 B活性的影响
催化剂 B在空速为 100,000 h"1的条件下, 在 200 ~ 450 °C的温度范围内均可 实现 98%以上的 NO ^化率, 且 N2生成选择性均大于 98%, 表现出了非常宽 的操作温度窗口。
即使在 500,000 h"1的高空速条件下, 催化剂 B仍然可以在 250 ~ 450 °C的温 度范围内均可实现 90%以上的 NO 化率, 且 N2选择性均大于 98%, 说明该
催化剂具有非常优异的抗高空速反应性能。
实施例 9
使用催化剂 B, 在自制的微型固定床反应器上考察 S02对催化剂活性的影 响。 催化剂的使用量为 0.12ml, 反应混合气的组成为: [NO]=[N¾]=500 ppm, [02]=5%, [SO2]=100ppm, N2作平衡气, 空速为 250,00οί!—1 , 反应温度为 250°C。 NO和 N¾及副产物 N20, N02均利用红外气体池测定。 活性测试结果表明, 该催化剂有很好的抗 S02中毒能力,在考察的 24h内, NOx转化率保持在 100%。 流程, 但本发明并不局限于上述详细工艺设备和工艺流程, 即不意味着本发明 必须依赖上述详细工艺设备和工艺流程才能实施。 所属技术领域的技术人员应 该明了, 对本发明的任何改进, 对本发明产品各原料的等效替换及辅助成分的 添加、 具体方式的选择等, 均落在本发明的保护范围和公开范围之内。
Claims
1、 一种用于催化净化氮氧化物的铈基复合氧化物催化剂, 其特征在于, 所 述催化剂包括铈氧化物和至少一种选自过渡金属的金属氧化物。
2、如权利要求 1所述的催化剂,其特征在于,所述过渡金属包括:钪(Sc)、 钛(Ti)、 钒( V)、 铬(Cr)、 锰(Mn)、 铁(Fe)、 钴 (Co), 镍(Ni)、 铜(Cu)、 辞(Zn)、 钇(Y)、锆(Zr)、铌(Nb)、 钼(Mo)、锝(Tc)、 钌(Ru)、铑(Rh)、 钯( Pd )、银 ( Ag )、镉( Cd )、 铪( Hf )、 钽( Ta )、钨( W )、铼 ( Re ),锇 ( Os )、 铱(Ir)、 铂 (Pt)、 金(Au)或其 2者或 2者以上的混合物;
优选地, 所述过渡金属选自钨(W)、 钼 (Mo)、 铁(Fe) 中的任意一种或 其 2者或以上的混合;
所述混合例如 W/Mo、 W/Fe、 Mo/Fe或 W/Mo/Fe;
优选地, 所述铈基复合氧化物催化剂, 优选为 CeOx-WOx、 CeOx-MoOx、 CeOx-FeOx双金属复合氧化物催化剂, 或 CeOx-WOx-MoOx、 CeOx-WOx-FeOx、 CeOx-MoOx-FeOx复合氧化物催化剂, 或 CeOx-WOx-MoOx-FeOx复合氧化物催化 剂;
优选地, 所述铈(Ce)元素和过渡金属元素的氧化物在复合氧化物催化剂 中形成固溶体。
3、 如权利要求 1或 2所述的催化剂, 其特征在于, 所述铈 ( Ce )元素和过 渡金属元素的摩尔比为 0.2-5.0,优选 0.5~4.5, 例如 1.0~4.0、 1.5-3.5, 2.0~3.0。
4、 一种如权利要求 1-3之一所述的铈基复合氧化物催化剂的制备方法, 所 述制备方法为均匀沉淀法、 溶胶-凝胶法、 柠檬酸络合法或水热合成法。
5、 如权利要求 4所述的制备方法, 其特征在于, 所述均匀沉淀法包括如下 步骤:
(1 ) 将 Ce和过渡金属的盐配成混合溶液, 所述混合溶液中, 以金属元素 的摩尔比计, 铈和过渡金属的比例为 0.2 ~ 5.0;
(2) 以过量尿素作为沉淀剂, 在 80 ~ 95 °C温度条件下搅拌 0.5~48h;
(3) 进行抽滤和洗涤, 得到滤饼;
(4) 将滤饼烘干, 于 400~800°C在空气中焙烧, 得到所述铈基复合氧化 物催化剂;
优选地, 所述步骤(1 ) 中, 所述铈盐优选氯化亚铈、 硝酸铈、 硝酸铈铵、 硫酸铈中的至少一种, 包括其二者或二者以上的混合物;
优选地, 所述步骤(1 ) 中, 所述过渡金属的盐包括鵠盐或钨酸盐、 钼盐或 钼酸盐、铁盐或其二者或二者以上的混合物。 所述钨盐或钨酸盐优选为钨酸铵、 仲钨酸铵、 硝酸钨、 氯化钨、 硫酸鵠中的至少一种, 包括其二者或二者以上的 混合物; 钼盐或钼酸盐优选为钼酸铵、 二钼酸铵、 四钼酸铵、 硝酸钼、 氯化钼、 硫酸钼中的至少一种, 包括其二者或二者以上的混合物; 铁盐优选为硝酸铁、 钨酸铁、 钼酸铁、 氯化铁、 硫酸铁中的至少一种, 包括其二者或二者以上的混 合物;
优选地, 所述步骤( 2 )中, 所述搅拌时间优选 l~24h, 进一步优选 4 ~ 15h, 例如 5h、 6h、 8h或 12h;
优选地, 所述步骤(2) 中, 所述温度优选为 60~100°C, 更优选 70~98 °C, 进一步优选 80 ~ 95 °C;
优选地, 所述步骤(3) 中, 所述洗涤优选釆用去离子水洗涤, 洗涤次数优 选 1-5次, 例如 2~4次, 包括 3次;
优选地, 所述步骤(4) 中, 所述烘干优选于 80~120°C下烘干; 进一步优 选放入烘箱中于 80〜: 120 °C烘干; 更烘干时间优选为 l~36h, 更优选 2~24h, 进 一步优选 4~12h;
2 优选地, 所述步骤(4) 中, 所述焙烧优选经马弗炉于 400 ~800°C空气中 焙烧; 所述焙烧时间优选 l~24h, 优选 2~12h, 进一步优选 4 ~ 6h。
6、 如权利要求 4所述的制备方法, 其特征在于, 所述溶胶-凝胶法包括如 下步骤:
(1) 将 Ce和过渡金属的盐配成混合溶液, 所述混合溶液中, 以金属元素 的摩尔比计, 铈和过渡金属的比例为 0.2 ~ 5.0;
(2) 在室温条件下搅拌 0.5~72h, 得到溶胶;
(3) 将所得溶胶在常温常压下静置 0.5 ~12d, 得到凝胶;
(4) 将凝胶烘干, 于 400~800°C在空气中焙烧, 得到所述铈基复合氧化 物催化剂;
优选地, 所述步骤(1) 中, 所述铈盐优选氯化亚铈、 硝酸铈、 硝酸铈铵、 硫酸铈中的至少一种, 包括其二者或二者以上的混合物;
优选地, 所述步骤(1) 中, 所述过渡金属的盐包括鵠盐或钨酸盐、 钼盐或 钼酸盐、铁盐或其二者或二者以上的混合物。 所述钨盐或钨酸盐优选为钨酸铵、 仲钨酸铵、 硝酸钨、 氯化钨、 硫酸鵠中的至少一种, 包括其二者或二者以上的 混合物; 钼盐或钼酸盐优选为钼酸铵、 二钼酸铵、 四钼酸铵、 硝酸钼、 氯化钼、 硫酸钼中的至少一种, 包括其二者或二者以上的混合物; 铁盐优选为硝酸铁、 钨酸铁、 钼酸铁、 氯化铁、 硫酸铁中的至少一种, 包括其二者或二者以上的混 合物;
优选地, 所述步骤( 2 )中, 所述搅拌时间优选 l~60h, 进一步优选 4 ~ 48h, 例如 6h、 10h、 12h或 24h;
优选地, 所述步骤(3)中, 所述静置时间优选 l~10d, 进一步优选 2~7d, 例如 3d、 4d、 5d或 6d;
3 优选地, 所述步骤(4) 中, 所述烘干优选于 80~120°C下烘干; 进一步优 选放入烘箱中于 80〜: 120 °C烘干; 更烘干时间优选为 l~36h, 更优选 2~24h, 进 一步优选 4~12h;
优选地, 所述步骤(4) 中, 所述焙烧优选经马弗炉于 400 ~800°C空气中 焙烧; 所述焙烧时间优选 l~24h, 优选 2~12h, 进一步优选 4 ~ 6h。
7、 如权利要求 4所述的制备方法, 其特征在于, 所述柠檬酸络合法包括如 下步骤:
(1 ) 将 Ce和过渡金属的盐配成混合溶液, 所述混合溶液中, 以金属元素 的摩尔比计, 铈和过渡金属的比例为 0.2 ~ 5.0;
(2) 向混合溶液中加入一定量柠檬酸, 金属离子总量与柠檬酸的摩尔比 为 0.5-5.0;
(3) 在 20 ~ 95°C温度条件下搅拌 0.5 ~ 48h;
(4) 在常温常压下静置 0.5 ~5d;
(5) 将所得产物烘干, 于 400~800°C在空气中焙烧, 得到所述铈基复合 氧化物催化剂;
优选地, 所述步骤(1 ) 中, 所述铈盐优选氯化亚铈、 硝酸铈、 硝酸铈铵、 硫酸铈中的至少一种, 包括其二者或二者以上的混合物;
优选地, 所述步骤(1 ) 中, 所述过渡金属的盐包括鵠盐或钨酸盐、 钼盐或 钼酸盐、铁盐或其二者或二者以上的混合物。 所述钨盐或钨酸盐优选为钨酸铵、 仲钨酸铵、 硝酸钨、 氯化钨、 硫酸鵠中的至少一种, 包括其二者或二者以上的 混合物; 钼盐或钼酸盐优选为钼酸铵、 二钼酸铵、 四钼酸铵、 硝酸钼、 氯化钼、 硫酸钼中的至少一种, 包括其二者或二者以上的混合物; 铁盐优选为硝酸铁、 钨酸铁、 钼酸铁、 氯化铁、 硫酸铁中的至少一种, 包括其二者或二者以上的混
4 合物;
优选地, 所述步骤( 3 )中, 所述搅拌时间优选 l~40h, 进一步优选 2 ~ 24h, 例如 3h、 5h、 10h或 20h;
优选地, 所述步骤(4 ) 中, 所述静置时间优选 l~4d, 例如 2d或 3d;
优选地, 所述步骤(5 ) 中, 所述烘干优选于 80~120°C下烘干; 进一步优 选放入烘箱中于 80〜: 120 °C烘干; 更烘干时间优选为 l~36h, 更优选 2~24h, 进 一步优选 4~12h;
优选地, 所述步骤(5 ) 中, 所述焙烧优选经马弗炉于 400 ~ 800°C空气中 焙烧; 所述焙烧时间优选 l~24h, 优选 2~12h, 进一步优选 4 ~ 6h。
8、 如权利要求 4所述的制备方法, 其特征在于, 所述水热合成法, 包括如 下步骤:
( 1 ) 将 Ce和过渡金属的盐配成混合溶液, 所述混合溶液中, 以金属元素 的摩尔比计, 铈和过渡金属的比例为 0.2 ~ 5.0;
( 2 ) 在室温条件下搅拌 0.5~2h后, 将溶液移至内衬聚四氟乙烯的不锈钢 反应蒼内;
( 3 ) 将反应釜在 80 200 °C条件下放置 1 ~ 12d;
( 4 ) 将所得产物离心洗涤、 烘干, 于 400~800°C在空气中焙烧, 得到所 述铈基复合氧化物催化剂;
优选地, 所述步骤(1 ) 中, 所述铈盐优选氯化亚铈、 硝酸铈、 硝酸铈铵、 硫酸铈中的至少一种, 包括其二者或二者以上的混合物;
优选地, 所述步骤(1 ) 中, 所述过渡金属的盐包括鵠盐或钨酸盐、 钼盐或 钼酸盐、铁盐或其二者或二者以上的混合物。 所述钨盐或钨酸盐优选为钨酸铵、 仲钨酸铵、 硝酸钨、 氯化钨、 硫酸鵠中的至少一种, 包括其二者或二者以上的 混合物; 钼盐或钼酸盐优选为钼酸铵、 二钼酸铵、 四钼酸铵、 硝酸钼、 氯化钼、 硫酸钼中的至少一种, 包括其二者或二者以上的混合物; 铁盐优选为硝酸铁、 钨酸铁、 钼酸铁、 氯化铁、 硫酸铁中的至少一种, 包括其二者或二者以上的混 合物;
优选地, 所述步骤(3 )中, 所述放置时间优选 l~12d, 进一步优选 2 ~ 8d, 例如 3d、 4d、 5d或 6d;
优选地, 所述步骤(4 ) 中, 所述烘干优选于 80~120°C下烘干; 进一步优 选放入烘箱中于 80〜: 120 °C烘干; 更烘干时间优选为 l~36h, 更优选 2~24h, 进 一步优选 4~12h;
优选地, 所述步骤(4 ) 中, 所述焙烧优选经马弗炉于 400 ~ 800°C空气中 焙烧; 所述焙烧时间优选 l~24h, 优选 2~12h, 进一步优选 4 ~ 6h。
9、 一种催化净化气体中氮氧化物的方法, 所述方法使用如权利要求 1所述 的铈基复合氧化物催化剂。
10、 如权利要求 9所述的方法, 其特征在于, 所述催化剂制浆后负载到各 种蜂窝陶瓷载体上, 制备成成型的催化剂进行使用, 或通过挤压成型后进行使 用;
优选地, 将催化剂置于尾气管道途中, 在催化剂的上游喷入还原剂和尾气 混合, 还原剂釆用氨气或尿素, 还原剂用量为尾气中氮氧化物的 0.8 1.2倍; 优选地, 所述气体为移动源含氮氧化物气体, 例如柴油车尾气, 或固定源 含氮氧化物气体, 例如燃煤电厂烟气; 所述气体优选为柴油车尾气。
6
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/823,950 US9498770B2 (en) | 2010-12-01 | 2011-11-09 | Ce-based composite oxide catalyst, preparation method and application thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201010568133.0A CN102000560B (zh) | 2010-12-01 | 2010-12-01 | 一种用于催化净化氮氧化物的铈基复合氧化物催化剂 |
CN201010568133.0 | 2010-12-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012071971A1 true WO2012071971A1 (zh) | 2012-06-07 |
Family
ID=43808414
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2011/081962 WO2012071971A1 (zh) | 2010-12-01 | 2011-11-09 | 一种铈基复合氧化物催化剂、其制备方法及用途 |
Country Status (3)
Country | Link |
---|---|
US (1) | US9498770B2 (zh) |
CN (1) | CN102000560B (zh) |
WO (1) | WO2012071971A1 (zh) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108465471A (zh) * | 2018-04-20 | 2018-08-31 | 安徽工业大学 | 一种协同脱除二噁英和氮氧化物的铈基催化剂的生产系统及方法 |
CN110743569A (zh) * | 2019-11-08 | 2020-02-04 | 中国石油化工股份有限公司 | 一种工艺炉烟气co深度净化方法、催化剂组合物及制备方法和应用 |
CN112403483A (zh) * | 2020-12-03 | 2021-02-26 | 浙江盛旺环境工程有限公司 | 中低温非金属矿基scr脱硝脱汞催化剂材料及制备方法 |
CN112547120A (zh) * | 2020-06-15 | 2021-03-26 | 清华大学 | 分子筛催化剂及其制备方法和用途 |
CN114345321A (zh) * | 2021-12-31 | 2022-04-15 | 广州工业智能研究院 | 一种抗硫性Ce-Mn-Zr催化剂及其制备方法与应用 |
CN115845867A (zh) * | 2021-09-23 | 2023-03-28 | 重庆理工大学 | 一种用于NH3-SCR降解的Mn基脱硝催化剂的制备方法及应用 |
CN115869960A (zh) * | 2022-12-16 | 2023-03-31 | 南京红宝丽醇胺化学有限公司 | 一种Ni-Co-Ce-Cr催化剂及其制备方法与应用 |
Families Citing this family (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102000560B (zh) | 2010-12-01 | 2014-03-26 | 中国科学院生态环境研究中心 | 一种用于催化净化氮氧化物的铈基复合氧化物催化剂 |
CN102303911B (zh) * | 2011-08-12 | 2013-09-25 | 湖州师范学院 | 铁酸铈纳米粉体的微波制备方法 |
CN102351248B (zh) * | 2011-09-13 | 2013-06-12 | 武汉理工大学 | 钼酸铈材料的合成方法 |
CN103170326A (zh) * | 2013-04-03 | 2013-06-26 | 中国科学院生态环境研究中心 | 一种钒铈氧化物催化剂、制备方法及其用途 |
CN103240079B (zh) * | 2013-05-30 | 2015-05-20 | 中国科学院生态环境研究中心 | 一种铈锆钨复合氧化物催化剂、制备方法及其用途 |
CN103990451A (zh) * | 2014-05-28 | 2014-08-20 | 南京理工大学 | 一种高效铈钨氧化物催化剂的简易制备方法 |
CN104209146B (zh) * | 2014-06-09 | 2017-01-25 | 深圳市天得一环境科技有限公司 | 用于降解氮氧化物的纳米球状多孔弱光光触媒、制备方法及其应用 |
CN104209145B (zh) * | 2014-06-09 | 2017-01-25 | 深圳市天得一环境科技有限公司 | 用于降解甲醛的纳米球状多孔弱光光触媒、制备方法及其应用 |
CN104399444B (zh) * | 2014-10-30 | 2017-09-26 | 浙江建业化工股份有限公司 | 用于制备胺的催化剂、合成工艺以及胺 |
CN104857950B (zh) * | 2015-03-27 | 2018-01-26 | 西安交通大学 | 一种具有中空多壳微球结构的锰铈复合氧化物低温脱硝催化剂 |
CN105126819B (zh) * | 2015-09-01 | 2018-10-30 | 中国石油大学(北京) | 一种同时消除nh3、no和碳烟颗粒的复合氧化物催化剂及其制备方法和用途 |
CN105233814A (zh) * | 2015-10-21 | 2016-01-13 | 南京理工大学 | 一种核壳结构的铈基氧化物催化剂、制备方法及其用途 |
CN105561974B (zh) * | 2015-12-25 | 2018-11-13 | 南京工业大学 | 一种柴油机尾气scr脱硝用催化剂及其制备方法 |
CN105664917A (zh) * | 2016-01-08 | 2016-06-15 | 南京理工大学 | 一种分层结构的铈基氧化物催化剂、制备方法及其用途 |
CN106513005A (zh) * | 2016-10-27 | 2017-03-22 | 上海理工大学 | 一种铁基复合氧化物催化剂的制备方法 |
CN106946282B (zh) * | 2017-02-27 | 2018-12-28 | 广东省稀有金属研究所 | 一种多孔铈基复合氧化物的制备方法 |
CN109529859A (zh) * | 2018-12-19 | 2019-03-29 | 济南大学 | 一种用于汽车尾气催化净化的多功能介孔铈基固溶体催化剂 |
CN109876796B (zh) * | 2019-04-04 | 2021-08-24 | 上海理工大学 | 一种铈钨复合氧化物scr脱硝催化剂及其制备方法 |
CN111167475B (zh) * | 2019-12-31 | 2022-08-09 | 南京环福新材料科技有限公司 | 一种同时脱硝脱汞脱二噁英催化剂及其制备方法 |
CN111167433A (zh) * | 2020-01-09 | 2020-05-19 | 上海理工大学 | 铈锡复合氧化物scr脱硝催化剂的制备方法及催化剂 |
CN111545217B (zh) * | 2020-04-22 | 2024-03-29 | 佛山市顺德区美的洗涤电器制造有限公司 | 一种复合催化材料及其制备方法与应用 |
CN111992223A (zh) * | 2020-08-03 | 2020-11-27 | 山东清硕环境科技有限公司 | 一种用于燃气锅炉烟气净化的催化剂及其制备方法 |
CN114345331A (zh) * | 2020-10-13 | 2022-04-15 | 北京锋测生物科技有限公司 | 一种利用激光制备负载型铂族催化剂的方法 |
CN112495386A (zh) * | 2020-12-07 | 2021-03-16 | 山东公用同太环保科技有限公司 | 一种铈铜铁三元复合氧化物催化剂及制备方法和应用 |
US12053762B2 (en) * | 2020-12-15 | 2024-08-06 | Alliance For Sustainable Energy, Llc | Atomically dispersed catalysts to promote low temperature biogas upgrading |
CN113101966A (zh) * | 2021-03-01 | 2021-07-13 | 华南理工大学 | 一种scr烟气脱硝催化剂及其制备方法 |
CN113398939B (zh) * | 2021-03-29 | 2024-07-23 | 上海中船临港船舶装备有限公司 | 用于VOCs治理的铁铈复合氧化物催化剂及制备方法 |
WO2022257153A1 (en) * | 2021-06-11 | 2022-12-15 | Dic Corporation | Ceria particles and method for producing the same |
CN113663668B (zh) * | 2021-09-01 | 2023-04-07 | 南大恩洁优环境技术(江苏)股份公司 | 一种VOCs净化用炭纤维负载室温催化剂及其制备方法 |
CN114433074B (zh) * | 2022-01-20 | 2023-07-14 | 大连海事大学 | 一种花瓣状锰铈复合氧化物脱硝催化剂及其制备方法 |
CN114602544A (zh) * | 2022-03-29 | 2022-06-10 | 潍柴动力股份有限公司 | 一种改性Cu-CHA分子筛复合催化剂及其制备方法和应用 |
CN114950457B (zh) * | 2022-05-13 | 2024-05-28 | 浙江树人学院 | 一种铁掺杂钒酸铈基固溶体烟气脱硝催化剂的制备方法 |
CN115445627A (zh) * | 2022-09-29 | 2022-12-09 | 武汉工程大学 | 一种铈镍铜复合氧化物脱硝催化剂及其制备方法与应用 |
CN115869936B (zh) * | 2022-11-17 | 2024-08-13 | 安徽元琛环保科技股份有限公司 | 一种宽温铈基脱硝催化剂的制备方法及用其制备的催化剂 |
CN116371399A (zh) * | 2023-03-28 | 2023-07-04 | 南京大学 | 一种铌改性铈硅混合氧化物催化剂的制备方法及其应用 |
CN116422352B (zh) * | 2023-04-21 | 2024-07-05 | 江西中科鸿虔新材料有限公司 | 一种磷钨酸改性的铁基mof衍生物材料的制备方法及其应用 |
CN117205918B (zh) * | 2023-05-23 | 2024-07-23 | 南京工业大学 | 一种纳米花状同时脱硝脱VOCs稀土基催化剂及其制备方法 |
CN117427644A (zh) * | 2023-09-25 | 2024-01-23 | 内蒙古大学 | 一种用于低温CO催化氧化的Co3O4-CeO2催化剂及其制备方法 |
CN118543346A (zh) * | 2024-07-30 | 2024-08-27 | 中国科学院过程工程研究所 | 一种铈基复合催化剂及其制备方法和应用 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1593752A (zh) * | 2004-07-01 | 2005-03-16 | 国电热工研究院 | 一种用于电站烟气scr脱硝中的催化剂及其制作方法 |
CN101204650A (zh) * | 2006-12-20 | 2008-06-25 | 中国科学院生态环境研究中心 | 一种烟气脱硝的铈钛复合氧化物催化剂 |
CN101314127A (zh) * | 2007-05-31 | 2008-12-03 | 中国科学院大连化学物理研究所 | 用于选择性还原氮氧化物的氧化物催化剂及其制造方法和用途 |
CN101507920A (zh) * | 2009-03-24 | 2009-08-19 | 中国科学院过程工程研究所 | 一种低温选择性催化还原氮氧化物的催化剂的制备方法 |
CN101785994A (zh) * | 2010-03-09 | 2010-07-28 | 中国科学院生态环境研究中心 | 一种用于氨选择性催化还原氮氧化物的纳米晶铈钛复合氧化物催化剂 |
CN102000560A (zh) * | 2010-12-01 | 2011-04-06 | 中国科学院生态环境研究中心 | 一种用于催化净化氮氧化物的铈基复合氧化物催化剂 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1984000702A1 (en) * | 1982-08-19 | 1984-03-01 | Univ Southern Australia | Catalysts |
EP0130835B1 (en) * | 1983-07-01 | 1990-05-02 | Hitachi, Ltd. | High temperature stable catalyst, process for preparing same and process for conducting chemical reaction using same |
US5866498A (en) * | 1992-09-28 | 1999-02-02 | Ford Global Technologies, Inc. | Composite catalysts for hydrocarbon oxidation |
JP4204692B2 (ja) * | 1998-03-30 | 2009-01-07 | 株式会社日本触媒 | 窒素酸化物除去用触媒、その製造方法、およびその触媒を用いた窒素酸化物除去方法 |
US20090099014A1 (en) * | 2005-07-12 | 2009-04-16 | Masahide Miura | Exhaust gas purifying catalyst and process for producing it |
EP1934140A4 (en) * | 2005-10-12 | 2008-11-05 | Valorbec Soc En Comandite | SILICA NANOBOITIERS AND METHODS OF ELEMENTS AND USES THEREOF |
CN101164694A (zh) * | 2006-10-20 | 2008-04-23 | 德古萨股份公司 | 用于催化气相氧化的混合氧化物催化剂 |
EP2332646B1 (en) * | 2008-09-17 | 2020-07-15 | Nippon Shokubai Co., Ltd. | Catalyst for ammonia decomposition, process for producing same, and method of treating ammonia |
US8017097B1 (en) * | 2010-03-26 | 2011-09-13 | Umicore Ag & Co. Kg | ZrOx, Ce-ZrOx, Ce-Zr-REOx as host matrices for redox active cations for low temperature, hydrothermally durable and poison resistant SCR catalysts |
-
2010
- 2010-12-01 CN CN201010568133.0A patent/CN102000560B/zh active Active
-
2011
- 2011-11-09 US US13/823,950 patent/US9498770B2/en active Active
- 2011-11-09 WO PCT/CN2011/081962 patent/WO2012071971A1/zh active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1593752A (zh) * | 2004-07-01 | 2005-03-16 | 国电热工研究院 | 一种用于电站烟气scr脱硝中的催化剂及其制作方法 |
CN101204650A (zh) * | 2006-12-20 | 2008-06-25 | 中国科学院生态环境研究中心 | 一种烟气脱硝的铈钛复合氧化物催化剂 |
CN101314127A (zh) * | 2007-05-31 | 2008-12-03 | 中国科学院大连化学物理研究所 | 用于选择性还原氮氧化物的氧化物催化剂及其制造方法和用途 |
CN101507920A (zh) * | 2009-03-24 | 2009-08-19 | 中国科学院过程工程研究所 | 一种低温选择性催化还原氮氧化物的催化剂的制备方法 |
CN101785994A (zh) * | 2010-03-09 | 2010-07-28 | 中国科学院生态环境研究中心 | 一种用于氨选择性催化还原氮氧化物的纳米晶铈钛复合氧化物催化剂 |
CN102000560A (zh) * | 2010-12-01 | 2011-04-06 | 中国科学院生态环境研究中心 | 一种用于催化净化氮氧化物的铈基复合氧化物催化剂 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108465471A (zh) * | 2018-04-20 | 2018-08-31 | 安徽工业大学 | 一种协同脱除二噁英和氮氧化物的铈基催化剂的生产系统及方法 |
CN110743569A (zh) * | 2019-11-08 | 2020-02-04 | 中国石油化工股份有限公司 | 一种工艺炉烟气co深度净化方法、催化剂组合物及制备方法和应用 |
CN112547120A (zh) * | 2020-06-15 | 2021-03-26 | 清华大学 | 分子筛催化剂及其制备方法和用途 |
CN112403483A (zh) * | 2020-12-03 | 2021-02-26 | 浙江盛旺环境工程有限公司 | 中低温非金属矿基scr脱硝脱汞催化剂材料及制备方法 |
CN112403483B (zh) * | 2020-12-03 | 2023-09-08 | 浙江盛旺环境工程有限公司 | 中低温非金属矿基scr脱硝脱汞催化剂材料及制备方法 |
CN115845867A (zh) * | 2021-09-23 | 2023-03-28 | 重庆理工大学 | 一种用于NH3-SCR降解的Mn基脱硝催化剂的制备方法及应用 |
CN114345321A (zh) * | 2021-12-31 | 2022-04-15 | 广州工业智能研究院 | 一种抗硫性Ce-Mn-Zr催化剂及其制备方法与应用 |
CN115869960A (zh) * | 2022-12-16 | 2023-03-31 | 南京红宝丽醇胺化学有限公司 | 一种Ni-Co-Ce-Cr催化剂及其制备方法与应用 |
Also Published As
Publication number | Publication date |
---|---|
CN102000560B (zh) | 2014-03-26 |
US20130202513A1 (en) | 2013-08-08 |
US9498770B2 (en) | 2016-11-22 |
CN102000560A (zh) | 2011-04-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2012071971A1 (zh) | 一种铈基复合氧化物催化剂、其制备方法及用途 | |
Xu et al. | A review of Mn-based catalysts for low-temperature NH 3-SCR: NO x removal and H 2 O/SO 2 resistance | |
JP5185942B2 (ja) | 選択接触還元のためのバナジウム不含の触媒およびその製造方法 | |
US10919025B2 (en) | N2O removal from automotive exhaust for lean/rich systems | |
CN103240079B (zh) | 一种铈锆钨复合氧化物催化剂、制备方法及其用途 | |
US20230042287A1 (en) | Cerium-tin-based composite oxide catalyst for catalyzing purification of nitrogen oxide, preparation method and application thereof | |
CA2991061A1 (en) | Nitrous oxide removal catalysts for exhaust systems | |
CN102302930B (zh) | 用于氨选择性催化还原氮氧化物的过渡金属掺杂的铈钛复合氧化物催化剂 | |
JP2017522170A (ja) | 排ガスを処理するための触媒物品 | |
CN107308944B (zh) | 一种二氧化钛基催化剂及其制备方法和应用 | |
CN101028594A (zh) | 低温选择性催化还原氮氧化物的复合氧化物催化剂 | |
WO2023284304A1 (zh) | 锰基复合氧化物催化剂及其制备方法和用途 | |
CN102764645A (zh) | 一种选择性催化还原氮氧化物的催化剂、其制备方法及用途 | |
WO2009094891A1 (fr) | Catalyseur au cu-ce-al permettant d'enlever des particules de suie et du nox simultanément, et procédé de préparation associé | |
US20110195007A1 (en) | CATALYST FOR REMOVING NOx FROM EXHAUST GAS OF LEAN-BURNING AUTOMOBILES OR INCINERATORS | |
CN107233895B (zh) | 一种机动车尾气净化用氧化催化剂及其制备方法 | |
CN109701524A (zh) | 脱除氮氧化物的催化剂及其制备方法 | |
WO2014083309A1 (en) | Bimetallic catalyst | |
JP3788141B2 (ja) | 排気ガス浄化システム | |
CN102909024B (zh) | 两段三效汽车尾气净化非贵金属催化剂 | |
JP2851444B2 (ja) | 排気ガス浄化方法 | |
CN102000589A (zh) | 一种低温氨选择性催化还原脱硝催化剂的制备方法 | |
JPH07308578A (ja) | 排ガス浄化用触媒 | |
CN101642715B (zh) | 用于选择催化还原氮氧化物的铈的焦磷酸盐催化剂及制法 | |
CN111151234A (zh) | 一种舰船用脱硝催化剂及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11844961 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13823950 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11844961 Country of ref document: EP Kind code of ref document: A1 |