CN101291730A - 脱NOx催化剂的制备方法 - Google Patents
脱NOx催化剂的制备方法 Download PDFInfo
- Publication number
- CN101291730A CN101291730A CNA2006800384768A CN200680038476A CN101291730A CN 101291730 A CN101291730 A CN 101291730A CN A2006800384768 A CNA2006800384768 A CN A2006800384768A CN 200680038476 A CN200680038476 A CN 200680038476A CN 101291730 A CN101291730 A CN 101291730A
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- Prior art keywords
- precursor
- oxide
- vanadium
- titanium dioxide
- tungsten
- Prior art date
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000002243 precursor Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 38
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 28
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 20
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 25
- -1 titanium alkoxide Chemical class 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 230000026030 halogenation Effects 0.000 claims description 3
- 238000005658 halogenation reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 150000003608 titanium Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 12
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- 239000002912 waste gas Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003570 air Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012702 metal oxide precursor Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- LQZQHERYTMMCGH-UHFFFAOYSA-N ethanol;tungsten Chemical compound [W].CCO LQZQHERYTMMCGH-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 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
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- UXWCUTZFIBANES-UHFFFAOYSA-N [W+2]=O.[O-2].[O-2].[Ti+4] Chemical compound [W+2]=O.[O-2].[O-2].[Ti+4] UXWCUTZFIBANES-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal 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
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
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- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J37/08—Heat treatment
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- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/07—Producing by vapour phase processes, e.g. halide oxidation
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B01D—SEPARATION
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- B01D2255/20723—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/207—Transition metals
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Abstract
本发明是可用于纯化来自燃烧工艺的尾气和废气的金属氧化物催化剂的制备方法。该方法包括使二氧化钛前体、氧化钒前体和氧化钨前体在氧气存在下在至少1000℃的温度下反应。
Description
发明领域
本发明涉及制备金属氧化物催化剂的方法。该催化剂可用于纯化来自燃烧工艺的尾气和废气。
发明背景
在氧气存在下化石燃料或煤的高温燃烧导致产生不想要的氮氧化物(NOx)。大量研究和商业努力寻求防止产生这些公知的污染物,或者在它们释放到空气中之前除去这些物质。另外,联邦法律发布了愈加苛刻的要求以降低释放到大气中的氮氧化物量。
从燃烧的排放气体中除去NOx的方法是本领域众所周知的。选择性催化还原方法尤其有效。在这一方法中,在催化剂存在下,氮氧化物被氨气(或另一还原剂,例如存在于废气流出物内的未燃烧的烃)还原并形成氮气。有效地选择性催化还原脱NOx的催化剂包括各种混合的金属氧化物催化剂,其中包括承载在锐钛矿形式的二氧化钛上的氧化钒(参见例如美国专利No.4048112)和氧化钛以及钼、钨、铁、钒、镍、钴、铜、铬或铀的至少一种氧化物(参见例如美国专利No.4085193)。
用于选择性催化还原NOx的尤其有效的催化剂是含二氧化钛、五氧化二钒和三氧化钨和/或三氧化钼的金属氧化物催化剂(美国专利No.3279884)。制备这些催化剂的目前方法是多步法,其中将来自硫酸盐工艺的二氧化钛前体(水解物)首先在含水溶胶-凝胶工艺中沉淀,然后将钨的前体(通常为对钨酸铵)沉积在沉淀物料上,使该混合物脱水,干燥,和最后煅烧到所需的结晶度,获得在表面上具有氧化钨的二氧化钛物料(参见例如美国专利Nos.3279884和4085193)。通常,在随后的步骤中,氧化钒前体也分散在二氧化钛-氧化钨物料上,以赋予该催化剂高的活性,和这要求另一沉积和煅烧工序。
悬而未决的美国申请序列号No.10/968706教导了生产由二氧化钛、氧化钒和承载的金属氧化物组成的催化剂。在沉积氧化钒之前,将该承载的金属氧化物(W、Mo、Cr、Sc、Y、La、Zr、Hf、Nb、Ta、Fe、Ru和Mn中的一种或多种)首先沉积在二氧化钛上。在沉积氧化钒之前,氧化钛承载的金属氧化物的等电点小于或等于3.75的pH。
总之,为了开发改进的选择性催化还原方法,以在氮氧化物释放到大气内之前除去它们,要求新催化剂和新催化剂的制备方法。有效地生产催化剂且投资花费、时间和能量下降的一步法是尤其理想的。
发明概述
本发明是生产用作脱NOx催化剂的金属氧化物的方法。该方法包括使二氧化钛前体、氧化钒前体和氧化钨前体在氧气存在下在至少1000℃的温度下反应。与通过常规方法生产的催化剂相比,通过本发明方法生产的催化剂对于通过氨气破坏氮氧化物令人惊奇地更加有效。
发明详述
本发明的方法包括使二氧化钛前体、氧化钒前体和氧化钨前体在氧气存在下在至少1000℃的温度下反应。二氧化钛前体是含钛的化合物,所述化合物当在氧气存在下经历高温时形成二氧化钛。尽管本发明的方法不限于选择特定的二氧化钛前体,但可用于本发明的合适的钛化合物包括但不限于烷醇钛和卤化钛。优选的烷醇钛是四异丙醇钛、四乙醇钛和四丁醇钛。特别优选四乙醇钛。优选的卤化钛包括三氯化钛和四氯化钛。
氧化钒前体是含钒的化合物,所述化合物当在氧气存在下经历高温时形成氧化钒。尽管本发明的方法不限于选择特定的氧化钒前体,但可用于本发明的合适的钒化合物包括但不限于卤化钒、卤氧化钒、烷醇钒和乙酰丙酮化钒。
氧化钨前体是含钨的化合物,所述化合物当在氧气存在下经历高温时形成氧化钨。尽管本发明的方法不限于选择特定的氧化钨前体,但可用于本发明的合适的钨化合物包括但不限于烷醇钨、卤化钨、卤氧化钨、钨酸和钨酸铵。
金属氧化物催化剂优选包括0.1-20wt%的氧化钨,0.2-10wt%的氧化钒,和余量的二氧化钛;更优选4-15wt%的氧化钨和1-3wt%的氧化钒。
为了增加金属氧化物催化剂的热稳定性,可有利地添加额外的氧化物前体。合适的添加剂包括二氧化硅源、氧化铝源、氧化铈源、氧化镧源、氧化锆源、及其混合物。添加剂是当在氧气存在下经历高温时形成二氧化硅、氧化铝、氧化铈、氧化镧或氧化锆的化合物。
合适的二氧化硅源包括但不限于烷醇硅、卤化硅和硅烷。优选的烷醇硅是原硅酸四乙酯、原硅酸四甲酯和类似物。特别优选原硅酸四乙酯。优选的硅烷包括氢化硅烷、烷基硅烷、烷基烷氧基硅烷和烷基卤代硅烷。合适的氧化铝源包括但不限于卤化铝、三烷醇铝例如三异丙醇铝、和乙酰丙酮化铝。合适的氧化铈源包括但不限于卤化铈、烷醇铈、乙酸铈和乙酰丙酮化铈。合适的氧化镧源包括但不限于卤化镧、烷醇镧、乙酸镧和乙酰丙酮化镧。合适的氧化锆源包括但不限于烷醇锆、卤化锆、卤氧化锆、乙酸锆和乙酰丙酮化锆。
若使用额外的氧化物前体,则所述金属氧化物催化剂优选含有1-20wt%该额外的氧化物,更优选2-10wt%。
本发明的方法包括使以上的氧化物前体在氧气存在下在至少1000℃的温度下反应。优选地,在1200-3000℃的温度下发生反应。反应压力范围优选为5-100psig。
在所述方法中要求氧气。尽管任何氧源是合适的,但优选分子氧。对于完全燃烧二氧化钛、氧化钨、氧化钒和额外的金属氧化物的前体所要求的用量来说,氧的用量优选比化学计量量大约10%,以避免未反应的前体。
在氧气存在下金属氧化物前体的高温反应产生金属氧化物是本领域的技术人员众所周知的。任何这些已知的方法适合于本发明。例如,存在许多商业和公开的方法用于通过使二氧化钛前体和氧气在高温反应区内反应来生产二氧化钛颗粒。例如,美国专利No.3512219公开了制备二氧化钛的高温方法和装置。美国专利No.6627173教导了用氧化锌、氧化镁和氧化铝掺杂的二氧化钛的制备方法,其中在四氯化钛进入火焰氧化或火焰水解反应器之前被气化。作为另一实例,美国专利No.5075090公开了一种方法,其中将有机金属钛前体溶解在有机溶剂内并喷洒到高温燃烧区中。二氧化钛前体和氧气在高温下的反应极快且得到二氧化钛。
本发明的方法可在适合于高温氧化反应的任何已知的反应器内发生。为了实践本发明,可使用任何常规类型的抗腐蚀的反应容器。该容器必须具有这种设计、结构和尺寸,以便优选提供反应物和产物在反应区内和经过反应区的连续流动,并允许控制速率、混合速度、温度和因此停留时间分布。例如,可使用具有多个二氧化钛前体原料物流的不同反应器结构,以产生二氧化钛,如在美国专利No.6387347中所述。
在氧气存在下各种金属氧化物前体反应的优选停留时间为0.1-100毫秒,最优选0.2至2毫秒。平均停留时间(t)是反应器体积(V)和反应物的体积流量(Q)的函数,且可简述为:
t=(Q/V)
典型地,(在给定的温度和压力下)平均停留时间越长,则颗粒越大。在实践中,在反应容器内停留时间的分布是混合强度、气体密度和温度曲线的复杂函数。可根据流体力学和颗粒生长的众所周知的理论,计算所要求的理想停留时间。为了实践本发明的方法,相对(以上)方程式所述的预期的工艺条件调节反应器中反应区的物理参数,以实现所需的粒度和比表面积。
可例如通过调节金属氧化物前体通过其中进入反应区内的狭缝或孔隙的宽度,从而控制流量。本领域的技术人员将理解,如果存在充足的能量来驱动反应物通过,则狭缝宽度的增加通常会增加反应物的液滴尺寸并导致具有较低比表面积的较大颗粒。
二氧化钛前体、氧化钒前体、氧化钨前体和任选地额外的氧化物前体可以蒸气形式加入到反应区中,或者它们可溶解在有机溶剂内。优选地,在氧化物前体引入到反应区之前,将其溶解在有机溶剂内。尤其优选将氧化物前体溶解在有机溶剂内并特别地以气溶胶形式喷洒在火焰氧化反应区中。可使用生成液滴的任何常规的装置来制备气溶胶,其中包括离心雾化器、双流体雾化器、电喷雾化器、喷雾器、Collison喷雾器、超声喷雾器、振动孔隙气溶胶发生器和类似装置。
催化剂颗粒的粒度取决于雾化设备的效率和前体在溶液内的浓度。液滴的平均直径可根据反应器装置的细节、所使用的分散气体的用量和溶液的性能(密度、表面张力和粘度)而变化。常见的液滴直径为0.2-200微米,优选为2-20微米。优选维持浓度在2-25wt%范围内。
用于溶解前体的有机溶剂可以是甲醇、乙醇、异丙醇、正丙醇、二甲苯、甲苯和类似物。若使用溶剂,则尤其优选二甲苯和甲苯。对于火焰氧化反应来说,溶剂的热焓量对于维持火焰温度在1500-2200K的所需水平下来说是重要的。这要求10-30kJ/gm的净燃烧热。
除了金属氧化物前体以外,优选使用载体气体。合适的载体气体的实例包括空气、氮气、氧气、蒸汽、氩气、氦气、二氧化碳和类似物。在这些当中,优选空气和氮气。
二氧化钛前体、氧化钒前体、氧化钨前体和任选地额外的氧化物前体的添加顺序对于本发明的方法来说不是关键的。在本发明的一个实施方案中,将二氧化钛前体、氧化钒前体、氧化钨前体和任选地额外的氧化物前体同时喂入到高温反应区内。在本发明的另一实施方案中,将各种前体单独地加入到高温反应区内。
对于火焰氧化工艺来说,借助天然气的导燃火焰,点燃引入到反应器内的反应物,或者可通过任何其他方式例如激光、放电和加热金属线来点燃它们。
在反应和催化剂颗粒形成之后,优选将金属氧化物催化剂与载体气体和反应副产物相分离,然后通过一种或多种设备,例如过滤器、旋风分离器、静电分离器、袋滤器、滤片、洗涤器和类似装置,收集所述金属氧化物催化剂。完成反应时的气体由载体气体、氧化物前体化合物的分解产物和溶剂蒸气组成。
令人惊奇且预料不到地发现,与通过常规方法生产的催化剂相比,通过本发明方法生产的金属氧化物催化剂更加有效地通过氨气选择性催化还原氮氧化物。此外,即使在高温下生产它们,所需的锐钛矿相也占主导(>90wt%的锐钛矿)。
下述实施例仅仅用于阐述本发明。本领域的技术人员要意识到在本发明的精神和本发明的范围内的各种变化。
对比例1:常规的催化剂制备
对比催化剂1A:在25ml烧瓶内,在60℃下混合单乙醇胺(0.185g)、去离子水(20ml)和五氧化钒(0.184g),直到五氧化钒溶解。然后在该溶液内搅拌承载在锐钛矿二氧化钛上的10wt%氧化钨(10g,DT 52,获自Millennium Inorganic Chemical,Inc.)。真空蒸发溶剂,并在110℃下干燥粉末过夜。将干燥的样品在空气中在600℃下煅烧6小时,产生对比催化剂1A。最终的五氧化钒负载为1.8wt%。
对比催化剂1B:根据1A的工序制备1B,所不同的是用承载在锐钛矿二氧化钛上的10wt%氧化钨和9wt%二氧化硅(10g,DT 58,获自Millennium Inorganic Chemical,Inc.)替代氧化钛载体。
实施例2:火焰喷洒合成催化剂
催化剂2A:通过在甲苯(300ml)内溶解异丙醇钛(40.6g)、乙醇钨(2.3g)、异丙醇钒(0.76g),制备导致10wt%氧化钨、1.8wt%氧化钒和余量TiO2的粉末的前体溶液。保持溶液内总的金属浓度为0.5M,并通过注射器泵经毛细管喂入(流量5ml/min),且通过5l/min氧气分散,从而形成微细的喷雾。通过调节在喷嘴处的孔隙间隙,保持毛细管尖端的压降恒定为1.5bar。火焰温度为约2000K。引入稀释空气,以冷却反应产物,并在过滤器上收集二氧化钛。
催化剂2A的比表面积为102m2/gm,和锐钛矿含量(相对于总的二氧化钛)为93wt%。
催化剂2B:根据2A的工序制备催化剂2B,所不同的是通过在甲苯(300ml)内溶解异丙醇钛(40.6g)、乙醇钨(2.3g)、异丙醇钒(0.38g)和原硅酸四乙酯(0.83g),制备导致10wt%氧化钨、0.9wt%氧化钒、2wt%二氧化硅和余量TiO2的粉末的前体溶液。
催化剂2B的比表面积为101m2/gm,和锐钛矿含量(相对于总的二氧化钛)为95wt%。
催化剂2C:根据2A的工序制备催化剂2C,所不同的是通过在甲苯(300ml)内溶解异丙醇钛(40.6g)、乙醇钨(2.3g)、异丙醇钒(0.38g)和原硅酸四乙酯(2.08g),制备导致10wt%氧化钨、0.9wt%氧化钒、5wt%二氧化硅和余量TiO2的粉末的前体溶液。
催化剂2C的比表面积为101m2/gm,和锐钛矿含量(相对于总的二氧化钛)为96wt%。
实施例3:选择性催化还原试验
在固定床反应器内,使用催化剂粉末(1A-2C),测定NO的转化率。反应器原料的组成为300ppm NO,360ppm NH3,3vol%O2,10vol%H2O和余量N2。气体时空速度(GHSV)为83,000h-1,和反应器原料向上流动,以防止压降增加。在220℃、270℃和320℃下测量催化剂性能。通过首先建立稳态,同时使流出物物流通过反应器,以测定催化剂的性能,然后在不存在反应的情况下绕过反应器以进行浓度测量,从而进行测量。通过相对差测定转化率。
表1的结果表明,与通过常规方法制备的催化剂相比,通过本发明方法生产的催化剂对于通过氨气破坏氮氧化物的活性显著更大。
表1:选择性催化还原结果
*对比例
11A的结果是两个单独的试验的平均值。
Claims (12)
1.一种生产金属氧化物催化剂的方法,该方法包括使二氧化钛前体、氧化钒前体和氧化钨前体在氧气存在下在至少1000℃的温度下反应。
2.权利要求1的方法,其中二氧化钛前体选自烷醇钛和卤化钛。
3.权利要求1的方法,其中氧化钒前体选自卤化钒、卤氧化钒、烷醇钒和乙酰丙酮化钒。
4.权利要求1的方法,其中氧化钨前体选自烷醇钨、卤化钨、卤氧化钨、钨酸和钨酸铵。
5.权利要求1的方法,其中金属氧化物催化剂包括0.1-20wt%的氧化钨、0.2-10wt%的氧化钒、和余量的二氧化钛。
6.权利要求1的方法,其中在选自二氧化硅源、氧化铝源、氧化铈源、氧化镧源、氧化锆源、及其混合物的额外的氧化物前体存在下发生反应,形成含二氧化钛、氧化钒、氧化钨和额外的氧化物的金属氧化物催化剂。
7.权利要求6的方法,其中金属氧化物催化剂包括0.1-20wt%的氧化钨、0.2-7wt%的氧化钒、1-20wt%的额外氧化物和余量的二氧化钛。
8.权利要求1的方法,其中将二氧化钛前体、氧化钒前体和氧化钨前体的溶液形成为液滴,然后火焰氧化。
9.权利要求1的方法,其中将二氧化钛前体、氧化钒前体和氧化钨前体同时加入到反应中。
10.权利要求1的方法,其中将二氧化钛前体、氧化钒前体和氧化钨前体单独地加入到反应中。
11.权利要求1的方法,其中在1200至3000℃的温度下发生反应。
12.权利要求1的方法,其中在5至100psig的压力下发生反应。
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US11/303,625 US20070142224A1 (en) | 2005-12-16 | 2005-12-16 | DeNOx catalyst preparation method |
US11/303,625 | 2005-12-16 |
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US20110159109A1 (en) * | 2008-09-02 | 2011-06-30 | Drexel University | Titania dispersion and method for making |
WO2010028017A2 (en) * | 2008-09-02 | 2010-03-11 | Drexel University | Metal or metal oxide deposited fibrous materials |
US8148295B2 (en) | 2009-02-16 | 2012-04-03 | Millennium Inorganic Chemicals, Inc. | Catalyst promoters in vanadium-free mobile catalyst |
US7879759B2 (en) * | 2009-02-16 | 2011-02-01 | Augustine Steve M | Mobile DeNOx catalyst |
US9839901B2 (en) * | 2014-11-14 | 2017-12-12 | Rgf Enviornmental Group, Inc. | Device, system, and method for producing advanced oxidation products |
BR112021017597A2 (pt) * | 2019-03-08 | 2021-11-09 | Johnson Matthey Plc | Catalisador de redução catalítica seletiva, revestimento washcoat, e, método de preparação de um catalisador de redução catalítica seletiva |
CN111203208B (zh) * | 2020-01-09 | 2022-11-01 | 华侨大学 | 一种促abs分解的低温钒钛基scr脱硝催化剂及其制备方法 |
KR102438438B1 (ko) * | 2020-11-25 | 2022-09-01 | 한서대학교 산학협력단 | 고정배출원의 배기가스 처리 저온 탈질촉매 및 그 제조방법 |
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US3512219A (en) * | 1965-10-19 | 1970-05-19 | American Potash & Chem Corp | Injection reactor for titanium dioxide production |
US4048112A (en) * | 1973-09-10 | 1977-09-13 | Mitsubishi Chemical Industries Ltd. | Catalyst for selective reduction of nitrogen oxides |
US4085193A (en) * | 1973-12-12 | 1978-04-18 | Mitsubishi Petrochemical Co. Ltd. | Catalytic process for reducing nitrogen oxides to nitrogen |
US5075090A (en) * | 1988-01-12 | 1991-12-24 | Vista Chemical Company | Process for preparing small particle size mixed metal oxides |
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BRPI0616070A2 (pt) | 2011-06-07 |
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