CN110947377B - 用于催化净化氮氧化物的铈锡基复合氧化物催化剂、制备方法及其应用 - Google Patents
用于催化净化氮氧化物的铈锡基复合氧化物催化剂、制备方法及其应用 Download PDFInfo
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- CN110947377B CN110947377B CN201911417967.9A CN201911417967A CN110947377B CN 110947377 B CN110947377 B CN 110947377B CN 201911417967 A CN201911417967 A CN 201911417967A CN 110947377 B CN110947377 B CN 110947377B
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- cerium
- tin
- catalyst
- salt
- composite oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- NZYYYKTZOWEGLS-UHFFFAOYSA-N [Sn].[Ce] Chemical compound [Sn].[Ce] NZYYYKTZOWEGLS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 238000000746 purification Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 20
- 229910052684 Cerium Inorganic materials 0.000 claims description 17
- 229910052718 tin Inorganic materials 0.000 claims description 17
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 150000000703 Cerium Chemical class 0.000 claims description 13
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 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 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 238000010668 complexation reaction Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 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 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 2
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims 1
- 239000000539 dimer Substances 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 claims 1
- 239000013638 trimer Substances 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003546 flue gas Substances 0.000 abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 229910052702 rhenium Inorganic materials 0.000 abstract description 2
- 229910052715 tantalum Inorganic materials 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- NUCRIADZUYCKMN-UHFFFAOYSA-N cerium(3+);oxygen(2-);tin(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Sn+4].[Sn+4].[Ce+3].[Ce+3] NUCRIADZUYCKMN-UHFFFAOYSA-N 0.000 abstract 1
- 239000010955 niobium Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 6
- 239000001099 ammonium carbonate Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000013618 particulate matter Substances 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SKHGCOGHICVSIW-UHFFFAOYSA-N [W].[Sn].[Ce] Chemical compound [W].[Sn].[Ce] SKHGCOGHICVSIW-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- -1 aluminum-silicon-titanium Chemical compound 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WPNJAUFVNXKLIM-UHFFFAOYSA-N Moxonidine Chemical compound COC1=NC(C)=NC(Cl)=C1NC1=NCCN1 WPNJAUFVNXKLIM-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UFDQEJWXJCPYSX-UHFFFAOYSA-I S(=O)(=O)([O-])[O-].[NH4+].[Nb+5].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[NH4+].[Nb+5].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] UFDQEJWXJCPYSX-UHFFFAOYSA-I 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910020874 Sn-M Inorganic materials 0.000 description 1
- 229910008890 Sn—M Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- GJAROXYKDRBDBI-UHFFFAOYSA-J [W+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [W+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJAROXYKDRBDBI-UHFFFAOYSA-J 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 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 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000000428 dust Substances 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 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 description 1
- 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 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
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Abstract
本发明涉及一种用于催化净化氮氧化物的铈锡基复合氧化物催化剂、制备方法及其应用。所述催化剂具有如下化学组成:铈锡氧化物和M的氧化物,所述M选自P、Ti、Zr、V、Mn、Fe、Cu、Al、Si、Ni、Hf、Nb、Ta、Cr、Mo、W或Re中的任意1种或至少2种的组合。本发明采用无毒无害的原料,通过简单易行的方法制备出具有催化活性高、水热稳定性高、N2生成选择性优异、操作温度窗口宽、能适应高空速反应条件等特点的铈锡基复合氧化物催化剂,适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装置。
Description
技术领域
本发明涉及催化剂领域,涉及一种稀土基复合氧化物催化剂、制备方法及其应用,具体涉及一种用于催化净化氮氧化物的铈锡基复合氧化物催化剂、制备方法及其应用。
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、石油和天然气。煤在燃烧后产生的烟气中,除含有硫氧化物(SOx)外,还含有氮氧化物(NOx,主要指NO和NO2)。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。
大气中NOx的存在会引起灰霾、光化学烟雾、酸雨等重大环境问题;同时NOx具有生物呼吸毒性,对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,CO2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NOx和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NOx的净化消除难度较大。
目前,氨选择性催化还原NOx(NH3-SCR)是国际上应用最为广泛的烟气脱硝技术。工业化应用的NH3-SCR催化剂通常是含有毒物质钒(V)的V2O5-WO3(MoO3)/TiO2催化剂,该类催化剂在使用过程中,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,因此欧美日已限制其在柴油车尾气NOx净化中的应用。更为重要的是,随着欧VI、国六等排放法规的实施,需要将柴油车颗粒物捕集装置(DPF)与NOx净化装置联合使用,以大幅度降低柴油机颗粒物(PM)和NOx的排放,DPF再生会产生700℃以上的高温,这对后置NOx净化催化剂的水热稳定性提出了更为苛刻的要求。在这样的高温、含水的条件下,传统的钒基催化剂会发生载体晶型的转化,导致活性的大幅度降低,满足不了欧VI、国六等排放法规的要求。
CN 103433028A公开了一种船机用三效脱除NOx、CO和HC的催化剂,所述催化剂以铈锡钨复合氧化物为催化活性组分,以钴、铁、铜、镧、钼、锰、锆、银、钇氧化物中一种或几种为助催化剂,以铝硅钛复合氧化物为载体,以载体质量为基准,催化活性组分的质量百分含量为5%~30%,助催化剂的质量百分含量为0.1%~20%,其中所述的催化剂活性组分中Ce、Sn与W元素摩尔比为1:(0.1~3):(0.01~3),所述的载体中Al、Si与Ti元素摩尔比为1:(0.05~2):(0.05~100)。该催化剂脱除NOx效率高,活性温度窗口宽泛,低温协同催化脱除CO和HC效率高,催化剂组分无毒、环境友好、机械强度高、抗震性能优良,热稳定性能良好,制备工艺简单,成本低。该催化剂的不足之处为:该专利通过将铈锡钨饱和溶液、助催化剂前驱体饱和溶液、载体前驱体等直接物理混合的方法制备催化剂,活性组份Ce-W-Sn间的相互作用微弱,且未排除所用可溶性盐中阴离子的干扰。所述催化剂在低温条件下(400℃)即发生了相分离,在700℃即有CeW复合结晶相的析出,其热稳定性有待提升;使用空速低(7200/h),难以适用于柴油车尾气净化对催化剂耐高空速的要求。
因此,开发新型具有高NH3-SCR活性、高水热稳定性、宽操作温度窗口、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、水热稳定性差等缺点,本发明首次提供了一种新型铈锡基复合氧化物催化剂、制备方法及其应用,可用于氮氧化物(例如燃烧废气中的氮氧化物)的催化净化。本发明的催化剂适用范围广,既可以用于以柴油车尾气为代表的移动源NOx催化净化,还可以用于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。
为达上述目的,本发明采用以下技术方案:
第一方面,本发明提供一种用于催化净化氮氧化物的铈锡基复合氧化物催化剂,所述催化剂具有如下化学组成:铈氧化物、锡氧化物和无定型MOx,M元素选自磷(P)、钛(Ti)、锆(Zr)、V(钒)、Mn(锰)、Fe(铁)、Cu(铜)、Al(铝)、Si(硅)、Ni(镍)、铪(Hf)、铌(Nb)、钽(Ta)、铬(Cr)、钼(Mo)、钨(W)或铼(Re)中的任意1种或至少2种的组合;
MOx以单聚体、低聚体或无定型团簇的形式分散于铈氧化物和锡化物表面,其中,x为满足元素化合价平衡所需的O的量;
铈元素、锡元素和M元素的摩尔比为1:(0.05~5.0):(0.05~3.5),且M元素和Sn元素的摩尔比为(0.01~3):1。
所述单聚体指单个MOx,所述低聚体指2个或者3个MOx通过氧桥连接,所述无定型团簇指多个MOx通过氧桥连接。举例来说,当M为正六价金属元素,如W+6或Mo+6时,所述单聚体指-O-M(=O)2-;所述低聚体指-O-M(=O)2-O-M(=O)2-或-O-M(=O)2-O-M(=O)2-O-M(=O)2-;所述无定型团簇指(-O-M(=O)2)n(n为大于3的整数,例如4、5、6或7等)。
所述铈(Ce)元素、锡(Sn)元素和M元素的摩尔比为1:(0.05~5.0):(0.05~3.5),例如1:1.5:3.5、、1:0.05:2、1:0.05:1、1:0.05:0.1、1:0.1:3.5、1:0.1:3、1:0.1:1.5、1:0.1:0.5、1:0.1:0.05、1:0.5:3.5、1:0.5:2.5、1:0.5:2、1:0.5:1、1:0.5:0.05、1:1.5:3.5、1:1.5:2.5、1:1.5:1、1:1.5:0.5、1:2:3.5、1:2:2、1:2:1.5、1:2:0.5、1:2:0.05、1:3.5:3.5、1:3.5:2、1:3.5:1.5、1:3.5:0.5、1:3.5:0.05、1:4.5:3.5、1:4.5:3、1:4.5:2.5、1:4.5:1.5、1:4.5:1、1:4.5:0.1或1:4.5:0.05等,M元素和Sn元素的摩尔比为(0.01~3):1,例如0.01:1、0.05:1、0.1:1、0.2:1、0.3:1、0.4:1、0.5:1、0.8:1、1:1、1.5:1、2:1、2.3:1、2.5:1或3:1等。
本发明的铈锡基复合氧化物催化剂中,铈(Ce)元素、锡(Sn)元素和M元素在复合氧化物催化剂中均以氧化物态存在,且M的氧化物为无定型MOx。本发明的铈锡基复合氧化物催化剂和可以表示为CeOy-SnOz-MOx,其中的x、y和z相互独立,由各原子所带正负价电子平衡确定。
本发明所述的催化净化氮氧化物也即氨选择性催化还原氮氧化物。
本发明提供了一种铈锡基复合氧化物催化剂,通过引入无定型MOx,一方面显著降低了SnO2的表面能,使催化剂制备过程中800℃高温烧结(例如800℃)后仍能保持纳米颗粒;另一方面,Ce-Sn-M三元体系中,M与CeO2的复合结晶被抑制,使得催化剂制备过程中高温烧结(例如800℃)后M仍然能高度分散于SnO2和CeO2的表面,充当反应活性位点。同时,在经过更高温度(例如900℃,1000℃)的水热老化处理后,该催化剂仍然能维持分散状态不变。相比于传统的铈锡催化剂及其改性催化剂,本发明的铈锡基复合氧化物催化剂具有操作温度窗口宽,NOx转化率高、N2生成选择性好以及抗高温水热老化能力好的优点。
以下作为本发明优选的技术方案,但不作为对本发明提供的技术方案的限制,通过以下优选的技术方案,可以更好的达到和实现本发明的技术目的和有益效果。
优选地,所述低聚体包括二聚体-O-M(=O)2-O-M(=O)2-和/或三聚体-O-M(=O)2-O-M(=O)2-O-M(=O)2-。
优选地,所述铈锡基复合氧化物催化剂中,CeO2的粒径为5-35nm(例如5nm、8nm、10nm、15nm、20nm、25nm、30nm或35nm等),SnO2的粒径为1-10nm(例如1nm、3nm、5nm、7nm、8nm或10nm等),所述SnO2的粒径小于CeO2的粒径。本发明的铈锡基复合氧化物催化剂中,M的氧化物未见结晶相,且其高度分散于较大晶粒尺寸的CeO2和较小晶粒尺寸的SnO2表面,可以获得更高的稳定性。
优选地,M元素和Sn元素的摩尔比为(0.2~0.4):1,在此范围内,可以更好地降低SnO2的表面能、抑制M与CeO2的复合结晶。
优选地,所述M元素选自钨(W)、钼(Mo)或铌(Nb)中的任意1种或至少2种的组合。优选为Nb或W中的任意一种,或者W和Nb按摩尔比(0.1~10):1的组合,所述摩尔比例如0.1:1、0.5:1、1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1或10:1等。针对本发明的催化剂,单独引入无定型氧化铌或者单独引入无定型氧化钨可以更好实现高温稳定性。引入无定型氧化钨和无定型氧化铌按上述摩尔比的组合,W和Nb协同作用进一步抑制了铈锡复合氧化物在高温制备过程中的结晶过程和高温水热老化处理过程中的再结晶过程,同时维持了W、Nb元素自身的高度分散,从而有利于活性位点的维持,可以兼顾优异的低温活性和高温稳定性。
优选地,所述M元素为W元素,且铈(Ce)元素、锡(Sn)元素和M元素的摩尔比为1:(0.1~4.5):(0.08~3.0),M元素和锡元素的摩尔比为(0.05~3.5):1。通过该摩尔比的限定,可以实现催化剂的酸性位点与氧化还原位点的调控和相组成的优化,进而获得更加优异的催化剂综合性能。
第二方面,本发明提供如第一方面所述的催化剂的制备方法,所述制备方法包括共沉淀法、溶胶-凝胶法、柠檬酸络合法、水热合成法或浸渍法等。
所述共沉淀法包括如下步骤:
(1)将铈盐、锡盐和M盐配成混合溶液;
(2)以过量沉淀剂,在20℃~95℃(例如20℃、25℃、30℃、35℃、40℃、50℃、65℃、80℃或90℃等)温度条件下搅拌0.5h~48h(例如0.5h、2h、5h、8h、12h、15h、18h、20h、24h、28h、32h、36h、40h或44h等)进行反应;
(3)进行抽滤和洗涤,得到滤饼;
(4)将滤饼烘干,于500℃~1000℃(例如500℃、600℃、700℃、800℃、900℃或1000℃等)在空气中焙烧,得到所述铈锡基复合氧化物催化剂;
所述混合溶液中,以金属元素的摩尔比计,铈元素、锡元素和M元素的摩尔比为1:(0.05~5.0):(0.05~3.5),且M元素和Sn元素的摩尔比为(0.01~3):1。
本发明所述过量沉淀剂是指,当沉淀剂与铈盐、锡盐和M盐反应形成铈锡基复合氧化物催化剂的化学反应结束之后,依然有沉淀剂剩余。
优选地,所述沉淀剂包括尿素、氨水、碳酸氨、碳酸氢铵、碳酸钠、碳酸氢氨、碳酸钾或碳酸氢钾中的任意一种或至少两种的组合,在保持金属前驱体溶液一致的条件下,以氨水为沉淀剂制备的催化剂获得了最优的NH3-SCR反应性能,且氨水能在室温条件下实现对金属元素的沉淀过程,故优选沉淀剂为氨水。
所述溶胶-凝胶法包括如下步骤:
(1)将铈盐、锡盐和M盐配成混合溶液;
(2)在室温条件下搅拌0.5h~72h(例如0.5h、1h、3h、6h、8h、10h、12h、15h、18h、20h、24h、28h、32h、36h、40h、42h、50h、55h、60h、62h、66h或70h等),得到溶胶;
(3)将所得溶胶在常温常压下静置0.5h~12d(例如0.5h、3h、10h、15h、24h、1.5d、3d、6d、8d、10d或12d等),得到凝胶;
(4)将凝胶烘干,于500℃~1000℃(例如500℃、600℃、700℃、800℃、900℃或1000℃等)在空气中焙烧,得到所述铈锡基复合氧化物催化剂;
所述混合溶液中,以金属元素的摩尔比计,铈元素、锡元素和M元素的摩尔比为1:(0.05~5.0):(0.05~3.5),且M元素和Sn元素的摩尔比为(0.01~3):1。
所述柠檬酸络合法包括如下步骤:
(1)将铈盐、锡盐和M盐配成混合溶液;
(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℃(例如20℃、25℃、30℃、35℃、40℃、50℃、65℃、80℃或90℃等)温度条件下搅拌0.5h~48h(例如0.5h、2h、5h、8h、12h、15h、18h、20h、24h、28h、32h、36h、40h或44h等);
(4)在常温常压下静置0.5h~5d(例如0.5h、3h、10h、15h、24h、1.5d、3d或5d等);
(5)将所得产物烘干,于500℃~1000℃(例如500℃、600℃、700℃、800℃、900℃或1000℃等)在空气中焙烧,得到所述铈锡基复合氧化物催化剂;
所述混合溶液中,以金属元素的摩尔比计,铈元素、锡元素和M元素的摩尔比为1:(0.05~5.0):(0.05~3.5),且M元素和Sn元素的摩尔比为(0.01~3):1。
所述水热合成法包括如下步骤:
(1)将铈盐、锡盐和M盐配成混合溶液;
(2)在室温条件下搅拌0.5h~2h(例如0.5h、1h、1.3h、1.5h或2h等)后,将溶液移至内衬聚四氟乙烯的不锈钢反应釜内;
(3)将反应釜在80℃~200℃(例如80℃、90℃、100℃、120℃、125℃、135℃、150℃、170℃、180℃或200℃等)条件下放置1d~12d(例如1d、3d、5d、8d、10d或12d等);
(4)将所得产物离心洗涤、烘干,于500℃~1000℃(例如500℃、600℃、700℃、800℃、900℃或1000℃等)在空气中焙烧,得到所述铈锡基复合氧化物催化剂;
所述混合溶液中,以金属元素的摩尔比计,铈元素、锡元素和M元素的摩尔比为1:(0.05~5.0):(0.05~3.5),且M元素和Sn元素的摩尔比为(0.01~3):1。
所述浸渍法包括如下步骤:
(1)将铈盐和锡盐配成混合溶液;
(2)以过量沉淀剂,在20℃~95℃(例如20℃、25℃、30℃、35℃、40℃、50℃、65℃、80℃、90℃或95℃等)温度条件下搅拌0.5h~48h(例如0.5h、2h、5h、8h、12h、15h、18h、20h、24h、28h、32h、36h、40h或44h等);
(3)进行抽滤和洗涤,得到滤饼;
(4)将滤饼烘干,于500℃~1000℃(例如500℃、600℃、700℃、800℃、900℃或1000℃等)在空气中焙烧,得到所述铈锡复合氧化物催化剂;
(5)配制M盐溶液,将适量的铈锡复合氧化物催化剂加入到M盐溶液中;
(6)在40℃~95℃(例如40℃、50℃、60℃、70℃、75℃、80℃、82℃、85℃、88℃、90℃或95℃等)温度条件下搅拌0.5h~48h(例如0.5h、2h、5h、8h、12h、15h、18h、20h、24h、28h、32h、36h、40h或45h等)至溶液完全蒸干,或在40℃~70℃温度条件下真空旋转蒸发2h~6h(例如2h、3h、4h、5h或6h)至溶液完全蒸干;
(7)于500℃~1000℃(例如500℃、600℃、700℃、800℃、900℃或1000℃等)在空气中焙烧,得到所述铈锡基复合氧化物催化剂。
以金属元素的摩尔比计,步骤(1)所述混合溶液中,锡和铈的摩尔比为0.05~5.0,步骤(5)所述M盐溶液和铈锡复合氧化物催化剂的使用量满足:M和铈的摩尔比为0.05~3.5,M和Sn的摩尔比为(0.01~3):1。
本发明所述过量沉淀剂是指,当沉淀剂与铈盐、锡盐和M盐反应形成铈锡基复合氧化物催化剂的化学反应结束之后,依然有沉淀剂剩余。
优选地,所述沉淀剂包括尿素、氨水、碳酸氨、碳酸氢铵、碳酸钠、碳酸氢氨、碳酸钾或碳酸氢钾中的任意一种或至少两种的组合,在保持金属前驱体溶液一致的条件下,以氨水为沉淀剂制备的催化剂获得了最优的NH3-SCR反应性能,且氨水能在室温条件下实现对金属元素的沉淀过程,故优选沉淀剂为氨水。
针对上述几种制备方法中涉及到的铈盐、锡盐和M盐作如下优选,所述优选在各制备方法中相互独立:
优选地,所述铈盐包括氯化亚铈、硝酸铈、硝酸铈铵或硫酸铈中的任意1种或至少2种的组合。
优选地,所述锡盐包括氯化锡、草酸亚锡、硝酸锡或硫酸锡中的任意1种或至少2种的组合。
优选地,所述M盐包括M的盐类和/或酸盐类。以元素W为例,其盐可以是钨盐或钨酸盐,比如钨酸铵、仲钨酸铵、偏钨酸铵、硝酸钨、氯化钨或硫酸钨等;以元素Mo为例,其盐可以是钼盐或钼酸盐,比如钼酸铵、二钼酸铵、四钼酸铵、硝酸钼、氯化钼或硫酸钼等;以元素Nb为例,其盐可以是氯化铌、硝酸铌、草酸铌或硫酸铌铵盐等。
优选地,所述M盐中的M元素选自W、Mo或Nb中的任意1种或至少2种的组合,优选为Nb或W中的任意一种,或者W和Nb按摩尔比(0.1~10):1的组合;
优选地,所述煅烧温度为750℃~850℃,例如750℃、775℃、800℃、820℃或850℃等。
按照此优选的M元素种类和煅烧温度,结合前述的摩尔比限定,可以更好地提升催化剂的性能。
本发明采用无毒无害的原料,通过简单易行的方法制备出具有催化活性高、高水热稳定性、N2生成选择性优异、操作温度窗口宽、能适应高空速反应条件等特点的铈锡基复合氧化物催化剂,适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装置。
第三方面,本发明的目的还在于提供一种催化净化气体中的氮氧化物的方法,所述方法使用第一方面所述的铈锡基复合氧化物催化剂。
本发明所述的催化剂可以根据实际需要进行制浆,负载到载体(例如各种蜂窝陶瓷载体)上,制备成成型的催化剂用于催化净化氮氧化物,也可以通过挤压成型后用于催化净化氮氧化物。
使用时将催化剂置于待处理气体(例如尾气)管道途中,在催化剂的上游喷入还原剂和尾气混合,还原剂采用氨气或尿素(水解后可得到氨气),还原剂摩尔量为尾气中氮氧化物的0.8倍~1.2倍,富氧条件下在很宽的温度窗口内可以将NOx还原为N2和H2O,同时具备优异的水热稳定性、N2选择性。
优选地,所述待处理气体包括移动源含氮氧化物气体或者固定源含氮氧化物气体,优选为柴油车尾气。
本发明的催化剂特别适用于柴油车尾气中氮氧化物的催化净化。
与已有技术相比,本发明具有如下优点:
(1)本发明所述铈锡基复合氧化物催化剂的水热稳定性好、操作温度窗口宽,适用于废气温度变化幅度大的应用环境,尤其适用于机动车尾气氮氧化物的催化净化;
(2)具有非常优异的N2生成选择性,可达到大于99%;
(3)具有非常好的抗高温烧结能力,经过800℃~900℃,16h水热老化试验所得的催化剂仍可在120,000h-1空速条件下,保持与老化前催化剂几乎相当的宽窗口,高NOx转化率以及N2生成选择性;
(4)本发明的铈锡基复合氧化物催化剂优化铈元素、锡元素和M元素的摩尔比和M元素种类,使其在1:(0.05~5.0):(0.05~3.5),且M元素和Sn元素的摩尔比为(0.01~3):1,可以获得优异的综合性能,经检测,催化剂在120,000h-1空速条件下,250~500℃的温度范围内均可实现90%以上的NOx转化率,且在N2选择性均大于98%,经过800~900℃、16h水热老化得到的催化剂仍可在120,000h-1空速条件下,300~500℃的温度范围内实现90%以上的NOx转化率,且N2生成选择性均大于99%,该催化剂具有非常优异的抗高温水热老化能力。
(5)采用无毒组分,有效减少了对人体健康和生态环境的危害。
附图说明
图1为实施例1-5以及对比例1所述催化剂的氮转化率随温度变化的关系图;
图2为实施例3、6和7所述催化剂的氮转化率随温度变化的关系图;
图3a-图3d依次为实施例3催化剂的场发射扫描电子显微镜图、Sn、W和Ce元素分布结果;
图4为实施例3、6和7所述催化剂的XRD对比图。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。
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
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
将偏钨酸铵、硝酸铈、氯化锡依次溶于去离子水,配制Ce:Sn:W摩尔比为1:0.8:0.6(W和Sn的摩尔比为0.75:1)的溶液并混合均匀,向该溶液中加入30mL氨水,并在25℃条件下连续搅拌12h,然后进行抽滤和洗涤,将滤饼放入烘箱中于100℃烘干过夜,最后经马弗炉于800℃空气中焙烧3h制得目标催化剂。
将制得的催化剂研碎、过筛,得到的催化剂颗粒大小在40-60目之间,该催化剂称为催化剂A。
实施例2
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
其它条件如实施例1不变,将沉淀剂氨水换为40g尿素,沉淀温度设置为90℃,制得催化剂B。
实施例3
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
其它条件如实施例1不变,改变Ce:Sn:W摩尔比为1:2:0.5(W和Sn的摩尔比为0.25:1),制得催化剂C1。
实施例4
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
其他条件如实施例1不变,改变Ce:Sn:W摩尔比为1:1.5:0.5(W和Sn的摩尔比为0.33:1),制得催化剂C2。
实施例5
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
其他条件如实施例1不变,改变Ce:Sn:W摩尔比为1:1:0.1(W和Sn的摩尔比为0.01:1),制得催化剂C3。
实施例6
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
将催化剂C1在800℃、含水10%的空气中老化16h,制得催化剂D。
实施例7
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
将催化剂C1在900℃、含水10%的空气中老化16h,制得催化剂E。
实施例8
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
其它条件如实施例3不变,改变钨酸铵为钼酸铵,制得催化剂F。
实施例9
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
将草酸铌、硝酸铈、氯化锡依次溶于去离子水中,配制Ce:Sn:Nb摩尔比为1:2:1(Nb和Sn的摩尔比为0.5:1)的溶液并混合均匀,向该溶液中加入40mL氨水,并在25℃温度条件下连续搅拌12h,然后进行抽滤和洗涤,将滤饼放入烘箱中于90℃烘干过夜,最后经马弗炉于800℃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G。
实施例10
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
将偏钨酸铵、草酸铌、硝酸铈、氯化锡依次溶于去离子水中,配置Ce:Sn:W:Nb摩尔比为1:2:0.24:0.76(W+Nb和Sn的摩尔比为0.5:1)的溶液并混合均匀,向混合溶液中加入柠檬酸,金属离子总量与柠檬酸的摩尔比为1;在30℃温度条件下搅拌24h;在常温常压下静置3d;将所得产物烘干,经马弗炉于500℃空气中焙烧3h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,制得催化剂H。
实施例11
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
将硝酸铈和氯化锡依次溶于去离子水中,配置Ce:Sn摩尔比为1:2的溶液并混合均匀,以30mL氨水为沉淀剂,在30℃搅拌12h,进行抽滤和洗涤,得到滤饼;将滤饼烘干,于600℃在空气中焙烧,得到铈锡复合氧化物载体;将0.6g(NH4)3PO4溶解于去离子水中配成溶液,将2g铈锡复合氧化物载体加入到上述溶液中,在80℃温度条件下搅拌至水溶液完全蒸干;于600℃在空气中焙烧,得到15%wt.POx/Ce1Sn2Ox催化剂(x为满足元素化合价平衡所需的O的量),制得催化剂I。
实施例12
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
其它条件如实施例3不变,将焙烧温度替换为500℃,制得催化剂K。
实施例13
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
其它条件如实施例3不变,将焙烧温度替换为900℃,制得催化剂L。
实施例14
本实施例提供一种铈锡基复合氧化物催化剂,其制备方法如下:
其它条件如实施例3不变,将偏钨酸铵替换为偏钨酸铵和草酸铌按照摩尔比4:1的混合物,制得催化剂M。
对比例1
本对比例与实施例5的区别在于不添加钨酸铵,制备得到的催化剂J。
应用例
用实施例1-14和对比例1制得的铈锡基复合氧化物催化剂在固定床反应器上进行NH3选择性催化还原NOx反应活性的考察。
催化剂的使用量为0.5g,反应混合气的组成为:[NO]=[NH3]=500ppm,[O2]=5vol.%,5vol.%H2O,N2作平衡气,气体总流量为500ml/min,空速为120,000h-1,反应温度150~500℃。NO和NH3及副产物N2O,NO2均利用红外气体池测定。反应结果如表1所示。
图1为实施例1-5以及对比例1所述催化剂的氮转化率随温度变化的关系图。
图2为实施例3、6和7所述催化剂的氮转化率随温度变化的关系图。
图3a-图3d为实施例3所述催化剂的场发射扫描电子显微镜图和相应的元素分布结果,由图可知,Sn元素和Ce元素各自团聚,而W元素在催化剂表面均匀分布。
图4为实施例3、6和7所述催化剂的XRD对比图,由图可知,三种催化剂均只检测到立方相CeO2和四方相SnO2的衍射谱图,未见任何含钨晶相,结合图3元素分析结果,证明了M以无定型状态存在。
表1铈锡基复合氧化物催化剂的活性评价结果
由表1可知,催化剂C1和C2的NH3-SCR性能明显好于催化剂A、B和C3,说明Ce、Sn和W的摩尔比存在优选范围,当铈元素、锡元素和M元素的摩尔比为1:(0.05~5.0):(0.05~3.5),且M元素和Sn元素的摩尔比为(0.2~0.4):1时效果更佳;催化剂C1和C2在120,000h-1空速条件下,250~500℃的温度范围内均可实现90%以上的NOx转化率,且N2选择性均大于98%。
经过800℃、16h水热老化得到的催化剂D仍可以在120,000h-1空速条件下,250~500℃的温度范围内实现90%以上的NOx转化率,且N2生成选择性均大于99%;经过900℃、16h水热老化得到的催化剂E仍可以在120,000h-1空速条件下,300~500℃的温度范围内实现90%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水热老化能力。
通过实施例1与实施例2的对比,采用沉淀剂氨水制得的催化剂的性能优于采用沉淀剂尿素制得的催化剂。
通过实施例3和实施例12的对比,较低温度焙烧处理(500℃)显著改善了低温NH3-SCR活性,这主要因为低温焙烧获得的催化剂具有更大的比表面积,从而有利于更多的酸性位点和氧化还原位点的耦合与分散。
通过实施例3和实施例13的对比,较高温度焙烧处理(900℃)显著改善了高温NH3-SCR活性,这主要因为高温焙烧处理抑制了催化剂在高温段对氨气的非选择性氧化过程,从而有利于更多的NH3参与到NH3-SCR反应中。
通过实施例3和实施例14的对比,W和Nb按照特定摩尔比使用可以兼具优异的低温活性和高温稳定性,这主要是因为W和Nb的协同作用。
申请人声明,本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程,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。
申请人声明,本发明通过上述实施例来说明本发明的详细方法,但本发明并不局限于上述详细方法,即不意味着本发明必须依赖上述详细方法才能实施。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 (14)
1.一种用于催化净化氮氧化物的铈锡基复合氧化物催化剂,其特征在于,所述催化剂具有如下化学组成:铈氧化物、锡氧化物和无定型MO x ,M元素选自Nb或W中的任意一种,或者W和Nb按摩尔比 (0.1~10):1的组合;MO x 以单聚体、低聚体或无定型团簇的形式分散于铈氧化物和锡氧化物表面,其中,x为满足元素化合价平衡所需的O的量;铈元素、锡元素和M元素的摩尔比为1:(1.5~2.0):(0.5~1.0),且M元素和Sn元素的摩尔比为(0.2~0.8):1;
所述铈锡基复合氧化物催化剂通过共沉淀法或柠檬酸络合法制备得到,
所述共沉淀法包括如下步骤:(1)将铈盐、锡盐和M盐配成混合溶液;(2)以过量氨水,在20℃~95℃温度条件下搅拌0.5h~48h进行反应;(3)进行抽滤和洗涤,得到滤饼;(4)将滤饼烘干,于800℃~900℃在空气中焙烧,得到所述铈锡基复合氧化物催化剂;
所述柠檬酸络合法包括如下步骤:(1)将铈盐、锡盐和M盐配成混合溶液;(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℃温度条件下搅拌0.5h~48h;(4)在常温常压下静置0.5h~5d;(5)将所得产物烘干,于800℃~900℃在空气中焙烧,得到所述铈锡基复合氧化物催化剂。
2.根据权利要求1所述的催化剂,其特征在于,所述低聚体包括二聚体和/或三聚体。
3.根据权利要求1所述的催化剂,其特征在于,所述铈锡基复合氧化物催化剂中,CeO2的粒径为5-35 nm,SnO2的粒径为1-10 nm,所述SnO2的粒径小于CeO2的粒径。
4.根据权利要求1所述的催化剂,其特征在于,M元素和Sn元素的摩尔比为(0.2~0.4):1。
5.根据权利要求1所述的催化剂,其特征在于,所述M元素为W元素。
6.如权利要求1所述的催化剂的制备方法,其特征在于,通过共沉淀法或柠檬酸络合法制备铈锡基复合氧化物催化剂;
所述共沉淀法包括如下步骤:
(1)将铈盐、锡盐和M盐配成混合溶液;
(2)以过量氨水,在20℃~95℃温度条件下搅拌0.5h~48h进行反应;
(3)进行抽滤和洗涤,得到滤饼;
(4)将滤饼烘干,于800℃~900℃在空气中焙烧,得到所述铈锡基复合氧化物催化剂;
所述混合溶液中,以金属元素的摩尔比计,铈元素、锡元素和M元素的摩尔比为1:(1.5~2.0):(0.5~1.0),且M元素和Sn元素的摩尔比为(0.2~0.8):1;
所述柠檬酸络合法包括如下步骤:
(1)将铈盐、锡盐和M盐配成混合溶液;
(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℃温度条件下搅拌0.5h~48h;
(4)在常温常压下静置0.5h~5d;
(5)将所得产物烘干,于800℃~900℃在空气中焙烧,得到所述铈锡基复合氧化物催化剂;
所述混合溶液中,以金属元素的摩尔比计,铈元素、锡元素和M元素的摩尔比为1:(1.5~2.0):(0.5~1.0),且M元素和Sn元素的摩尔比为(0.2~0.8):1。
7.根据权利要求6所述的制备方法,其特征在于,所述铈盐包括氯化亚铈、硝酸铈、硝酸铈铵或硫酸铈中的任意1种或至少2种的组合。
8.根据权利要求6所述的制备方法,其特征在于,所述锡盐包括氯化锡、草酸亚锡、硝酸锡或硫酸锡中的任意1种或至少2种的组合。
9.根据权利要求6所述的制备方法,其特征在于,所述M盐包括M的盐类和/或酸盐类。
10.一种催化净化气体中的氮氧化物的方法,其特征在于,所述方法使用如权利要求1所述的铈锡基复合氧化物催化剂。
11.根据权利要求10所述的方法,其特征在于,将权利要求1所述的铈锡基复合氧化物催化剂负载到载体上,制备成型得到催化剂,以其用于催化净化气体中的氮氧化物。
12.根据权利要求11所述的方法,其特征在于,使用时,将催化剂置于待处理气体管道途中,在催化剂的上游喷入还原剂和待处理气体混合,还原剂采用氨气和/或尿素,还原剂摩尔量为待处理气体中氮氧化物的0.8倍~1.2倍。
13.根据权利要求12所述的方法,其特征在于,所述待处理气体包括移动源含氮氧化物气体或者固定源含氮氧化物气体。
14.根据权利要求13所述的方法,其特征在于,所述待处理气体为柴油车尾气。
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