CN109701524A - Remove the catalyst and preparation method thereof of nitrogen oxides - Google Patents
Remove the catalyst and preparation method thereof of nitrogen oxides Download PDFInfo
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- CN109701524A CN109701524A CN201711016771.XA CN201711016771A CN109701524A CN 109701524 A CN109701524 A CN 109701524A CN 201711016771 A CN201711016771 A CN 201711016771A CN 109701524 A CN109701524 A CN 109701524A
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- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 133
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000000243 solution Substances 0.000 claims abstract description 62
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004033 plastic Substances 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 238000003980 solgel method Methods 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000004332 silver Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 9
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 235000015110 jellies Nutrition 0.000 claims description 5
- 239000008274 jelly Substances 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 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 description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000010944 silver (metal) Substances 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 238000002441 X-ray diffraction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 51
- 238000001035 drying Methods 0.000 abstract description 21
- 239000007789 gas Substances 0.000 abstract description 10
- 230000009467 reduction Effects 0.000 abstract description 10
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 150000001844 chromium Chemical class 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 44
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 36
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 238000005470 impregnation Methods 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000013019 agitation Methods 0.000 description 22
- 239000003921 oil Substances 0.000 description 22
- 238000010992 reflux Methods 0.000 description 22
- 238000010792 warming Methods 0.000 description 22
- 229910052593 corundum Inorganic materials 0.000 description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 238000012986 modification Methods 0.000 description 18
- 229910001961 silver nitrate Inorganic materials 0.000 description 18
- 229910001923 silver oxide Inorganic materials 0.000 description 18
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- 206010013786 Dry skin Diseases 0.000 description 17
- 239000011572 manganese Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 14
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 14
- 239000003638 chemical reducing agent Substances 0.000 description 12
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 5
- 239000008246 gaseous mixture Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Inorganic materials O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- LSDSZZKMMNCFMR-UHFFFAOYSA-N nitric acid titanium Chemical compound [Ti].O[N+]([O-])=O LSDSZZKMMNCFMR-UHFFFAOYSA-N 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- -1 alkali metal cation Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 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 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910015427 Mo2O3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium 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
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 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
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TYOIKSXJQXGLFR-UHFFFAOYSA-N niobium nitric acid Chemical compound [Nb].[N+](=O)(O)[O-] TYOIKSXJQXGLFR-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
The present invention relates to a kind of catalyst for removing nitrogen oxides, mainly solve the problem of to exist in the prior art that catalyst is active low under cryogenic or poor selectivity cannot be removed effectively nitrogen oxides under the high temperature conditions.The present invention is by using sol-gel method (SOL-GEL method), by the aqueous solution or alcoholic solution of a certain amount of aluminium isopropoxide, it is added drop-wise in inorganic silver, copper, iron or/and aqueous solution of chromium salt, by plastic, aging, drying and roasting and etc. be made alumina load catalyst, the technical solution modified again with IVB, VB family metal oxide, preferably solves the problems, such as this.The catalyst is used to remove in the reaction of nitrous oxides exhaust gas, can effective nitrogen oxides reduction, not only there is high catalytic activity and longer service life, and prepare easy, price is lower, is suitble to industrial application.
Description
Technical field
The present invention relates to catalyst of a kind of nitrogen oxides reduction and preparation method thereof, more particularly to a kind of carbon monoxide
Catalyst of catalyzing and reducing nitrogen oxides and preparation method thereof.
Background technique
With the fast development of countries in the world modern industry, atmosphere pollution have become one get worse global ask
Topic, NOx is generally acknowledged one of Air Pollutant Discharge.China is the developing country based on fire coal, when longer from now on
In, energy resource structure of the China based on coal will not change, and the nitrogen oxides that fire coal generates is to generate acid rain, photochemical fog
And the principal element that relevant environment is destroyed.Acid rain can cause soil productivity, crops, forest, inland lake, building etc.
Injury.In addition, NOx can induce many human body diseases, especially there are high risks to upgrowth and development of children to human health.Choosing
Selecting property catalytic reduction method is to be translated into N with additional reducing agent removing NOx2And O2Method, referred to as SCR (Selective
Catalytic Reduction) method, wherein with NH3NH as reducing agent3- SCR method is to apply most, technology most in the world
A kind of mature denitration technology is invented by Eegelhard company, the U.S., and has applied for patent in nineteen fifty-nine, and Japan takes the lead in
The 1970s is to the method achieve industrialization.It is to be in temperature using catalyst iron, vanadium, chromium, cobalt, nickel and alkali metal
NOx is reduced to N at 200~450 DEG C2.Its main chemical reaction is as follows:
4NH3+ 6NO=5N2+6H2O (1)
8NH3+6NO2=7N2+12H2O (2)
In the case where no catalyst, these reaction can only within the scope of very narrow temperature (980 DEG C or so) progress, lead to
It crosses and selects suitable catalyst, reaction temperature can be reduced, and can extend to the 290~430 of suitable power plant's actual condition
DEG C range.Therefore, the selection of catalyst is crucial in SCR method.Requirement to catalyst is active high, service life length, good economy performance
Do not generate secondary pollution.
Non-selective reductant method refers under the action of catalyst, with CO, H in original atmosphere2、CH4Deng for reducing agent, make
NO catalysis reduction generates N2, while the O in reducing agent and gas source2Reaction generates CO2And H2O.In this denitrification process, reaction
Need to be by means of catalyst action, and reducing agent and NOxAnd O2All react, non-selectivity, so referred to as non-selective catalytic is also
Original reaction.Custom catalysts have platinum and palladium, due to releasing a large amount of heat in reaction process, waste heat boiler should be arranged in process and give
Recycling, the method fuel consumption is big, and noble metal is needed to make catalyst, need to add heat recovery apparatus, and investment is big, thus it is external gradually
It is eliminated.Patent in relation to the removing of ammine selectivity catalytic reduction at low temperature NOx has very much.
United States Patent (USP) US6685897 discloses a kind of catalyst that molecular sieve is exchanged with alkali metal cation, the catalysis
Agent has high specific surface and big pore structure, and catalyst operating temperature range is 150~450 DEG C.
United States Patent (USP) US4925825 proposes a kind of using ammonia as reducing agent, the method for catalytic reduction of NOx, the catalysis used
Agent is with TiO2-V2O5-Mo2O3For active component, it is greater than 350 DEG C using temperature, this is that one kind is suitable for using under mesophilic condition
Catalyst for reduction of oxides of nitrogen.
Chinese patent CN01131952.6 discloses a kind of catalyst of ammonia selective reducing nitrogen oxide, which is
Copper, the Mn complex oxide catalyst of alumina load, under conditions of 150~350 DEG C of reaction temperature, catalyst has high
Activity and stability.
Chinese patent CN87100737A discloses a kind of catalysis by nitrogen oxide selective reduction for nitrogen in the presence of ammonia
Agent, the catalyst also contain a small amount of oxide selected from vanadium and copper as helping and urge using cobalt oxide and zeolite as main active component
Agent.The catalyst belongs to mixed oxide type catalyst, at 350 DEG C, the NOx of 1600ppm can be made to reduce 90%.
Chinese patent CN201410527707.8 disclose a kind of reduction of nitrogen oxides ammonia selective catalysis catalyst and its
Include active component Fe using, catalyst composition, rare earth element auxiliary agent (La, Ce or Sm) and molecular sieve carrier (Beta or
The mixture of Beta and ZSM-5).It, can be under excess oxygen by nitrogen oxides using above-mentioned catalyst using ammonia as reducing agent
It is converted into harmless nitrogen.
Chinese patent CN201410781282.3 discloses a kind of for the compound of ammine selectivity catalytic reduction nitrous oxides
Oxide catalyst and preparation method thereof is mainly used in the purification of the nitrogen oxides in factory's flue gas and motor-vehicle tail-gas.
The catalyst is mainly made of the rare earth oxide of manganese oxide and different content, it is characterised in that catalyst is to ammonia selective catalyst
Nitrogen oxides reduction reaction has extraordinary low temperature active and very strong water resistant and sulfur poisoning resistance, in 50-300 DEG C of temperature
The conversion ratio of range nitrogen oxides can reach 80% or more.
We are water-soluble by a certain amount of aluminium isopropoxide by using sol-gel method for the reaction for removing nitrogen oxides
Liquid or alcoholic solution are added drop-wise in inorganic silver salt solution, by plastic, aging, drying and roasting and etc. that aluminium oxide is made is negative
The catalyst of load, then modified with IVB, VB family metal oxide, obtained catalyst is used to remove the reaction of nitrogen oxides
In, can effective nitrogen oxides reduction, catalyst have high activity and highly selective and longer service life.
Summary of the invention
The first technical problem to be solved by the present invention be existing ammonia selective reducing nitrogen oxide catalyst activity it is not high,
The problem of stability difference, provides a kind of catalyst for removing nitrogen oxides, which has reactivity height, stability high
Feature.
The second technical problem to be solved by the present invention is to provide the corresponding reduction of one of one kind and solution technical problem
The preparation method of nitrogen oxide catalyst.The characteristics of this method has cost of material low, and preparation is simple.
The third technical problem to be solved by the present invention be the catalyst activity of existing ammonia selective reducing nitrogen oxide not
High, stability difference problem provides a kind of method of new Carbon monoxide reduction nitrogen oxides, and this method is for removing nitrogen oxidation
When the reaction of object, have the characteristics that catalyst activity is high, stability is high.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of removing nitrogen oxides is urged
Agent, catalyst include following components by weight percentage:
A) 80~95% aluminium oxide；
B) 0~3% at least one of periodic table of elements Section IV B or VB race metal oxide are selected from.
C) 5~15% selected from least one of Cu, Ag, Fe, Cr element or its oxide；
D) 0~5% selected from least one of Ce, Mn metal oxide.
In above-mentioned technical proposal, it is preferred that the content of component d) is 0.1~3%；More preferably 0.2~2%.
In above-mentioned technical proposal, it is preferred that component c) is selected from Ag, and component d) is selected from Mn.
In above-mentioned technical proposal, it is preferred that component c) is selected from Cr, and component d) is selected from Ce.
In above-mentioned technical proposal, it is preferred that the content of the component c) in terms of catalyst weight percent is 2~10%.
In above-mentioned technical proposal, it is preferred that the metal oxide in periodic table of elements Section IV B or VB race
Preferably one of titanium oxide, zirconium oxide, vanadium oxide or niobium oxide or at least one.
In above-mentioned technical proposal, it is preferred that do not contain element silicon or its oxide in catalyst.
In above-mentioned technical proposal, it is preferred that in terms of catalyst weight percent, the content of bismuth oxide is 0.1~1.8%；
It is furthermore preferred that the content of bismuth oxide is 0.5~1.5%.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: the catalyst of removing nitrogen oxides
Preparation method, comprising the following steps:
A) aqueous solution or alcoholic solution I is made in aluminium isopropoxide；
B) silver soluble, copper, iron or/and chromic salts are dissolved in water, obtain solution II；
C) above-mentioned solution II is added dropwise in solution I, heating plastic obtains jelly III；
D) it removes to roast after solvent in jelly III and obtains catalyst precarsor IV；
E) catalyst needed for being obtained after catalyst precarsor IV roasting.
In above-mentioned technical proposal, it is preferred that the catalyst precarsor IV that step d) is obtained first passes through the metal containing IVB and/or VB race
Salting liquid is modified, then after roasting after needed for catalyst.
In above-mentioned technical proposal, it is preferred that the temperature of plastic is 90~150 DEG C, after removing the solvent in jelly, roasting
Temperature is 500~1200 DEG C, and calcining time 4~8 hours, the solid after roasting ground granulation as needed, and preferred granularity is 10
~60 mesh, using IVB, VB race metal salt solution impregnation catalyst agent precursor, the preferably time is 12~48 hours, at 80~120 DEG C
It roasts after drying in 450~600 DEG C up to required catalyst.Wherein inorganic silver, copper, iron, chromic salts are selected from nitrate or oxalates
At least one of.Further, gelling temperature preferred scope be 60~100 DEG C, after plastic maturing temperature preferred scope be 600~
1000℃。
In order to solve the above-mentioned technical problem three, The technical solution adopted by the invention is as follows: a kind of nitrogen oxides reduction
Method, using reducing agent and nitrogen oxides as raw material, operating pressure is 0~0.5MPa, and gas volume air speed is 600~5000h-1,
The operation temperature of reaction unit is 150~450 DEG C.
In above-mentioned technical proposal, it is preferred that operating pressure is 0~0.3MPa
In above-mentioned technical proposal, it is preferred that gas volume air speed is 800~3000h-1。
In above-mentioned technical proposal, it is preferred that the operation temperature of reaction unit is 200~350 DEG C.
In above-mentioned technical proposal, it is preferred that reducing agent NH3, carbon monoxide, one of hydrogen or methane or at least one
Kind.
In above-mentioned technical proposal, it is preferred that reducing agent is carbon monoxide.Technical solution of the present invention, by using oxidation
Aluminium is carrier, catalyst removal nitrogen oxides better performances；It is living especially when catalyst is prepared using sol-gal process
Property central distribution it is more uniform, catalyst have better performance.
The present invention is single carrier by selective oxidation aluminium, and the de- of function admirable has been prepared by sol-gel method
Denitrification catalyst；When preferred catalyst components b) and component c) is combined, there is more preferably catalytic performance；It can be effective gram
The disadvantage that poor catalyst stability, transformation efficiency of the oxides of nitrogen be not high in the prior art is taken, by optimizing reaction condition, nitrogen oxidation
Object conversion ratio achieves preferable technical effect up to 100%.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
After aluminium isopropoxide containing 95 grams of aluminium oxide is dissolved in water, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise containing 5 grams
The silver nitrate solution of silver oxide, while violent electromagnetic agitation maintain 70 DEG C of oil bath temperature, load onto reflux condensing tube, and stirring three is small
When after colloidal sol solidify, stop stirring, be warming up to 100 DEG C, evaporate solvent 12 hours.It is transferred to a crucible, it is small to dry 24 with infrared lamp
When, it is then transferred to 700 DEG C of muffle furnace and roasts 6 hours, be crushed to 40~60 mesh to get required containing Ag2The Ag/Al of O 5%2O3
Catalyst.
The reactivity worth of carbon monoxide under low temperature catalyzing and reducing nitrogen oxides is carried out on normal miniature fixed-bed reactor
It investigates.Catalyst loading is 1.05 grams, and gaseous mixture group becomes NO 1.1%, CO 5%, and remaining is nitrogen, gas space velocity 2400h-1, 250 DEG C of reaction temperature, NO conversion ratio such as table 1 shows.
[embodiment 2]
After aluminium isopropoxide containing 90 grams of aluminium oxide is dissolved in ethanol solution, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise
The mixed solution of the manganese nitrate composition of silver nitrate and 3 grams of manganese oxide containing 5 grams of silver oxides, while violent electromagnetic agitation, maintain oil
70 DEG C of bath temperature, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 100 DEG C, evaporates solvent
12 hours.It is transferred to a crucible, is dried 24 hours with infrared lamp, 700 DEG C of muffle furnace is then transferred to and roasts 6 hours, be crushed to 40
~60 mesh, then using nitric acid titanium solution incipient impregnation 12 hours containing 2 grams of titanium oxide, in 450 DEG C of Muffle furnaces after 120 DEG C of dryings
It roasts up to required 2%TiO2Modification contains Ag2O 5%, contain MnO23% Ag-Mn/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 3]
After aluminium isopropoxide containing 92 grams of aluminium oxide is dissolved in ethanol solution, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise
The mixed solution of the manganese nitrate composition of silver nitrate and 3 grams of manganese oxide containing 5 grams of silver oxides, while violent electromagnetic agitation, maintain oil
70 DEG C of bath temperature, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 100 DEG C, evaporates solvent
12 hours.It is transferred to a crucible, is dried 24 hours with infrared lamp, 700 DEG C of muffle furnace is then transferred to and roasts 6 hours, be crushed to 40
~60 mesh contain Ag to get required2O 5%, contain MnO23% Ag-Mn/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 4]
After aluminium isopropoxide containing 90 grams of aluminium oxide is dissolved in ethanol solution, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise
The mixed solution of the manganese nitrate composition of silver nitrate and 3 grams of manganese oxide containing 5 grams of silver oxides, while violent electromagnetic agitation, maintain oil
70 DEG C of bath temperature, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 100 DEG C, evaporates solvent
12 hours.It is transferred to a crucible, is dried 24 hours with infrared lamp, 700 DEG C of muffle furnace is then transferred to and roasts 6 hours, be crushed to 40
~60 mesh, then using nitric acid niobium solution incipient impregnation 12 hours containing 2 grams of niobium oxide, in 450 DEG C of Muffle furnaces after 120 DEG C of dryings
It roasts up to required 2%NbO2Modification contains Ag2O 5%, contain MnO23% Ag-Mn/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 5]
After aluminium isopropoxide containing 90 grams of aluminium oxide is dissolved in ethanol solution, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise
The mixed solution of the manganese nitrate composition of silver nitrate and 3 grams of manganese oxide containing 5 grams of silver oxides, while violent electromagnetic agitation, maintain oil
70 DEG C of bath temperature, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 100 DEG C, evaporates solvent
12 hours.It is transferred to a crucible, is dried 24 hours with infrared lamp, 700 DEG C of muffle furnace is then transferred to and roasts 6 hours, be crushed to 40
~60 mesh, then using zirconium nitrate solution incipient impregnation 12 hours containing 2 grams of zirconium oxides, in 450 DEG C of Muffle furnaces after 120 DEG C of dryings
It roasts up to required 2%ZrO2Modification contains Ag2O 5%, contain MnO23% Ag-Mn/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 6]
After aluminium isopropoxide containing 90 grams of aluminium oxide is dissolved in ethanol solution, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise
The mixed solution of the manganese nitrate composition of silver nitrate and 3 grams of manganese oxide containing 5 grams of silver oxides, while violent electromagnetic agitation, maintain oil
70 DEG C of bath temperature, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 100 DEG C, evaporates solvent
12 hours.It is transferred to a crucible, is dried 24 hours with infrared lamp, 700 DEG C of muffle furnace is then transferred to and roasts 6 hours, be crushed to 40
~60 mesh first using nitric acid titanium solution incipient impregnation 12 hours containing 0.5 gram of titanium oxide, then use and contain 1.5 grams of zirconium oxides
It zirconium nitrate solution incipient impregnation 12 hours, roasts after 120 DEG C of dryings in 450 DEG C of Muffle furnaces up to required 0.5%TiO2With
1.5%ZrO2Modification contains Ag2O 5%, contain MnO23% Ag-Mn/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 7]
After aluminium isopropoxide containing 90 grams of aluminium oxide is dissolved in ethanol solution, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise
The mixed solution of the manganese nitrate composition of silver nitrate and 3 grams of manganese oxide containing 5 grams of silver oxides, while violent electromagnetic agitation, maintain oil
70 DEG C of bath temperature, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 100 DEG C, evaporates solvent
12 hours.It is transferred to a crucible, is dried 24 hours with infrared lamp, 700 DEG C of muffle furnace is then transferred to and roasts 6 hours, be crushed to 40
~60 mesh first using nitric acid titanium solution incipient impregnation 12 hours containing 1.5 grams of titanium oxide, then use and contain 0.5 gram of zirconium oxide
It zirconium nitrate solution incipient impregnation 12 hours, roasts after 120 DEG C of dryings in 450 DEG C of Muffle furnaces up to required 1.5%TiO2With
0.5%ZrO2Modification contains Ag2O 5%, contain MnO23% Ag-Mn/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 8]
After aluminium isopropoxide containing 90 grams of aluminium oxide is dissolved in ethanol solution, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise
The mixed solution of the manganese nitrate composition of silver nitrate and 3 grams of manganese oxide containing 5 grams of silver oxides, while violent electromagnetic agitation, maintain oil
70 DEG C of bath temperature, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 100 DEG C, evaporates solvent
12 hours.It is transferred to a crucible, is dried 24 hours with infrared lamp, 700 DEG C of muffle furnace is then transferred to and roasts 6 hours, be crushed to 40
~60 mesh, first using Ammonium Vanadate Solution incipient impregnation 12 hours containing 0.2 gram of vanadic anhydride, then using containing 1.8 grams of oxidations
The zirconium nitrate solution incipient impregnation of zirconium 12 hours roasts after 120 DEG C of dryings in 450 DEG C of Muffle furnaces up to required 0.2%V2O5With
1.8%ZrO2Modification contains Ag2O 5%, contain MnO23% Ag-Mn/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 9]
After aluminium isopropoxide containing 90 grams of aluminium oxide is dissolved in ethanol solution, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise
The mixed solution of the manganese nitrate composition of silver nitrate and 3 grams of manganese oxide containing 5 grams of silver oxides, while violent electromagnetic agitation, maintain oil
70 DEG C of bath temperature, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 100 DEG C, evaporates solvent
12 hours.It is transferred to a crucible, is dried 24 hours with infrared lamp, 700 DEG C of muffle furnace is then transferred to and roasts 6 hours, be crushed to 40
~60 mesh, first using Ammonium Vanadate Solution incipient impregnation 12 hours containing 1.8 grams of vanadic anhydrides, then using containing 0.2 gram of oxidation
The zirconium nitrate solution incipient impregnation of zirconium 12 hours roasts after 120 DEG C of dryings in 450 DEG C of Muffle furnaces up to required 1.8%V2O5With
0.2%ZrO2Modification contains Ag2O 5%, contain MnO23% Ag-Mn/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 10]
After aluminium isopropoxide containing 80 grams of aluminium oxide is dissolved in water, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise containing 15 grams
The mixed solution of the manganese nitrate of the silver nitrate of silver oxide and 2 grams of manganese oxide composition, while violent electromagnetic agitation, maintain oil bath temperature
70 DEG C, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 150 DEG C, evaporates solvent 12 hours.
It is transferred to a crucible, is dried 24 hours with infrared lamp, 500 DEG C of muffle furnace is then transferred to and roasts 8 hours, be crushed to 40~60 mesh,
Again using zirconium nitrate solution incipient impregnation 12 hours containing 3 grams of zirconium oxides, roasted after 80 DEG C of dryings in 600 DEG C of Muffle furnaces to obtain the final product
Required 3%ZrO2Modification contains Ag2O 15%, contain MnO22% Ag-Mn/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 11]
After aluminium isopropoxide containing 80 grams of aluminium oxide is dissolved in water, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise containing 12 grams
The mixed solution of the cerous nitrate of the chromium+oxalic acid of chromium oxide and 5 grams of cerium oxide composition, while violent electromagnetic agitation, maintain oil bath temperature
70 DEG C, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 90 DEG C, evaporates solvent 20 hours.
It is transferred to a crucible, is dried 24 hours with infrared lamp, 1200 DEG C of muffle furnace is then transferred to and roasts 4 hours, be crushed to 40~60 mesh,
Again using Ammonium Vanadate Solution incipient impregnation 48 hours containing 3 grams of vanadic anhydrides, roasted after 100 DEG C of dryings in 550 DEG C of Muffle furnaces
It burns up to required 3%V2O5Modification contains Cr2O312%, contain CeO25% Cr-Ce/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 12]
After aluminium isopropoxide containing 85 grams of aluminium oxide is dissolved in water, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise containing 13 grams
The iron nitrate solution of iron oxide, while violent electromagnetic agitation maintain 70 DEG C of oil bath temperature, load onto reflux condensing tube, and stirring three is small
When after colloidal sol solidify, stop stirring, be warming up to 150 DEG C, evaporate solvent 12 hours.It is transferred to a crucible, it is small to dry 24 with infrared lamp
When, it is then transferred to 500 DEG C of muffle furnace and roasts 8 hours, be crushed to 40~60 mesh, then using the niobium oxalate for containing 2 grams of columbium dioxides
It solution incipient impregnation 12 hours, roasts after 120 DEG C of dryings in 600 DEG C of Muffle furnaces up to required 2%NbO2Modification contains Fe2O3
13% Fe/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 13]
After aluminium isopropoxide containing 90 grams of aluminium oxide is dissolved in ethanol solution, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise
Copper nitrate solution containing 8 grams of copper oxide, while violent electromagnetic agitation maintain 70 DEG C of oil bath temperature, load onto reflux condensing tube, stir
Colloidal sol solidifies after three hours, stops stirring, is warming up to 150 DEG C, evaporates solvent 8 hours.It is transferred to a crucible, dries 24 with infrared lamp
Hour, it is then transferred to 800 DEG C of muffle furnace and roasts 6 hours, be crushed to 40~60 mesh, then using the titanium chloride for containing 2 grams of titanium oxide
It solution incipient impregnation 48 hours, roasts after 120 DEG C of dryings in 500 DEG C of Muffle furnaces up to required 2%TiO2Modification contains CuO
8% Cu/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 14]
After aluminium isopropoxide containing 90 grams of aluminium oxide is dissolved in ethanol solution, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise
The mixed solution of the manganese nitrate composition of silver nitrate and 1 gram of manganese oxide containing 8 grams of silver oxides, while violent electromagnetic agitation, maintain oil
70 DEG C of bath temperature, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 150 DEG C, evaporates solvent
12 hours.It is transferred to a crucible, is dried 24 hours with infrared lamp, 500 DEG C of muffle furnace is then transferred to and roasts 8 hours, be crushed to 40
~60 mesh, then using zirconium nitrate solution incipient impregnation 12 hours containing 1 gram of zirconium oxide, in 600 DEG C of Muffle furnaces after 120 DEG C of dryings
It roasts up to required 1%ZrO2Modification contains Ag2O 8%, contain MnO21% Ag-Mn/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 15]
After aluminium isopropoxide containing 85 grams of aluminium oxide is dissolved in water, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise containing 10 grams
The mixed solution of the cerous nitrate of the chromium+oxalic acid of chromium oxide and 2 grams of cerium oxide composition, while violent electromagnetic agitation, maintain oil bath temperature
70 DEG C, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 150 DEG C, evaporates solvent 8 hours.
It is transferred to a crucible, is dried 24 hours with infrared lamp, 800 DEG C of muffle furnace is then transferred to and roasts 6 hours, be crushed to 40~60 mesh,
Again using fluorine niobic acid ammonium salt solution incipient impregnation 48 hours containing 3 grams of columbium dioxides, roasted after 120 DEG C of dryings in 500 DEG C of Muffle furnaces
It burns up to required 3%NbO2Modification contains Cr2O310%, contain CeO22% Cr-Ce/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 16]
After aluminium isopropoxide containing 92 grams of aluminium oxide is dissolved in water, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise containing 6 grams
The iron nitrate solution of iron oxide, while violent electromagnetic agitation maintain 70 DEG C of oil bath temperature, load onto reflux condensing tube, and stirring three is small
When after colloidal sol solidify, stop stirring, be warming up to 150 DEG C, evaporate solvent 12 hours.It is transferred to a crucible, it is small to dry 24 with infrared lamp
When, it is then transferred to 500 DEG C of muffle furnace and roasts 8 hours, be crushed to 40~60 mesh, then is molten using the zirconium nitrate containing 2 grams of zirconium oxides
It liquid incipient impregnation 12 hours, roasts after 120 DEG C of dryings in 600 DEG C of Muffle furnaces up to required 2%ZrO2Modification contains Fe2O36%
Fe/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 17]
After aluminium isopropoxide containing 92 grams of aluminium oxide is dissolved in ethanol solution, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise
Copper nitrate solution containing 5 grams of copper oxide, while violent electromagnetic agitation maintain 70 DEG C of oil bath temperature, load onto reflux condensing tube, stir
Colloidal sol solidifies after three hours, stops stirring, is warming up to 150 DEG C, evaporates solvent 8 hours.It is transferred to a crucible, dries 24 with infrared lamp
Hour, it is then transferred to 800 DEG C of muffle furnace and roasts 6 hours, be crushed to 40~60 mesh, then using the zirconium nitrate for containing 3 grams of zirconium oxides
It solution incipient impregnation 48 hours, roasts after 120 DEG C of dryings in 500 DEG C of Muffle furnaces up to required 3%ZrO2Modification contains CuO
5% Cu/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 18]
90 grams of aluminum oxide micro-spheres are taken, the mixing with the manganese nitrate of the silver nitrate for containing 5 grams of silver oxides and 3 grams of manganese oxide composition is molten
Liquid steeped overnight evaporates solvent, and 700 DEG C of muffle furnace are transferred to after ground and mixed and is roasted 6 hours, then uses the nitre of 2 grams of titanium oxide
Sour titanium solution incipient impregnation 12 hours roasts 2% up to conventional method preparation in 600 DEG C of Muffle furnaces after 120 DEG C of dryings
TiO2Modification contains Ag2O 5%, contain MnO23% Ag-Mn/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 19]
85 grams of aluminum oxide micro-spheres are taken, with the mixing of the cerous nitrate of the chromium+oxalic acid for containing 10 grams of chromium oxide and 2 grams of cerium oxide composition
Solution steeped overnight evaporates solvent, and 700 DEG C of muffle furnace are transferred to after ground and mixed and is roasted 6 hours, then using containing 3 grams of niobium oxide
Nitric acid niobium solution incipient impregnation 48 hours, after 100 DEG C of dryings in 550 DEG C of Muffle furnaces roast up to conventional method preparation
3%NbO2Modification contains Cr2O310%, contain CeO22% Cr-Ce/Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 20]
85 grams of aluminum oxide micro-spheres are taken, with the iron nitrate solution steeped overnight for containing 13 grams of iron oxide, evaporate solvent, ground and mixed
After be transferred to 700 DEG C of muffle furnace and roast 6 hours, then using containing niobium oxalate solution incipient impregnation 12 hours of 2 grams of columbium dioxides,
The 2%NbO up to conventional method preparation is roasted in 600 DEG C of Muffle furnaces after 120 DEG C of dryings2Modification contains Fe2O313% Fe/
Al2O3Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 21]
After aluminium isopropoxide containing 94.6 grams of aluminium oxide is dissolved in water, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise and contains
The bismuth nitrate solution of 0.4 gram of bismuth oxide, the silver nitrate solution containing 5 grams of silver oxides, while violent electromagnetic agitation maintain oil bath temperature
70 DEG C, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 100 DEG C, evaporates solvent 12 hours.
It is transferred to a crucible, is dried 24 hours with infrared lamp, 700 DEG C of muffle furnace is then transferred to and roasts 6 hours, be crushed to 40~60 mesh,
Contain Ag up to required2The Ag/Al of O 5%2O3Catalyst.
The reactivity worth of carbon monoxide under low temperature catalyzing and reducing nitrogen oxides is carried out on normal miniature fixed-bed reactor
It investigates.Catalyst loading is 1.05 grams, and gaseous mixture group becomes NO 1.1%, CO 5%, and remaining is nitrogen, gas space velocity 2400h-1, 250 DEG C of reaction temperature, NO conversion ratio such as table 1 shows.
[embodiment 22]
After aluminium isopropoxide containing 94 grams of aluminium oxide is dissolved in water, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise containing 1 gram
The bismuth nitrate solution of bismuth oxide, the silver nitrate solution containing 5 grams of silver oxides, while violent electromagnetic agitation maintain 70 DEG C of oil bath temperature,
Reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 100 DEG C, evaporates solvent 12 hours.Transfer
To a crucible, dried 24 hours with infrared lamp, be then transferred to 700 DEG C of muffle furnace and roast 6 hours, be crushed to 40~60 mesh to get
It is required to contain Ag2The Ag/Al of O 5%2O3Catalyst.
The reactivity worth of carbon monoxide under low temperature catalyzing and reducing nitrogen oxides is carried out on normal miniature fixed-bed reactor
It investigates.Catalyst loading is 1.05 grams, and gaseous mixture group becomes NO 1.1%, CO 5%, and remaining is nitrogen, gas space velocity 2400h-1, 250 DEG C of reaction temperature, NO conversion ratio such as table 1 shows.
[embodiment 23]
After aluminium isopropoxide containing 93.6 grams of aluminium oxide is dissolved in water, is sufficiently stirred, it is placed in three-necked bottle, is added dropwise and contains
The bismuth nitrate solution of 1.4 grams of bismuth oxides, the silver nitrate solution containing 5 grams of silver oxides, while violent electromagnetic agitation maintain oil bath temperature
70 DEG C, reflux condensing tube is loaded onto, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 100 DEG C, evaporates solvent 12 hours.
It is transferred to a crucible, is dried 24 hours with infrared lamp, 700 DEG C of muffle furnace is then transferred to and roasts 6 hours, be crushed to 40~60 mesh,
Contain Ag up to required2The Ag/Al of O 5%2O3Catalyst.
The reactivity worth of carbon monoxide under low temperature catalyzing and reducing nitrogen oxides is carried out on normal miniature fixed-bed reactor
It investigates.Catalyst loading is 1.05 grams, and gaseous mixture group becomes NO 1.1%, CO 5%, and remaining is nitrogen, gas space velocity 2400h-1, 250 DEG C of reaction temperature, NO conversion ratio such as table 1 shows.
Table 1
[comparative example 1]
After the silica solution of the aluminium isopropoxide and 42 grams of silica that contain 50 grams of aluminium oxide is dissolved in ethanol solution, is sufficiently stirred,
It is placed in three-necked bottle, the mixed solution of the manganese nitrate composition of silver nitrate and 3 grams of manganese oxide containing 5 grams of silver oxides is added dropwise, together
When violent electromagnetic agitation, maintain 70 DEG C of oil bath temperature, load onto reflux condensing tube, colloidal sol solidifies after stirring three hours, stop stirring,
100 DEG C are warming up to, is evaporated solvent 12 hours.It is transferred to a crucible, is dried 24 hours with infrared lamp, is then transferred to muffle furnace 700
DEG C roasting 6 hours, 40~60 mesh were crushed to get required containing Ag2O 5%, contain MnO23% Ag-Mn/Al2O3-SiO2Catalysis
Agent.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[comparative example 2]
It will be hydrolyzed, be placed in three-necked bottle containing the ethyl orthosilicates of 92 grams of silica, is added dropwise containing 5 grams of silver oxides
The mixed solution of the manganese nitrate of silver nitrate and 3 grams of manganese oxide composition, while violent electromagnetic agitation, maintain 70 DEG C of oil bath temperature, dress
Upper reflux condensing tube, colloidal sol solidifies after stirring three hours, stops stirring, is warming up to 100 DEG C, evaporates solvent 12 hours.It is transferred to
One crucible is dried 24 hours with infrared lamp, is then transferred to 700 DEG C of muffle furnace and is roasted 6 hours, is crushed to 40~60 mesh to get institute
Ag need to be contained2O 5%, contain MnO23% Ag-Mn/SiO2Catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[comparative example 3]
92 grams of ZSM-5 molecular sieves are taken, with the manganese nitrate mixed solution leaching of silver nitrate and 3 grams of manganese oxide containing 5 grams of silver oxides
Stain is stayed overnight, and solvent is evaporated, and 700 DEG C of muffle furnace are transferred to after ground and mixed and is roasted 6 hours, is crushed to 40~60 mesh to get required
Containing Ag2O 5%, contain MnO23% Ag-Mn/ZSM-5 catalyst.
Catalyst is evaluated using the reaction condition of embodiment 1, is as a result listed in table 1.
[embodiment 24]
The catalyst made from Examples 1 to 20 carries out carbon monoxide under low temperature on normal miniature fixed-bed reactor
The reactivity worth of catalyzing and reducing nitrogen oxides is investigated.Catalyst loading is 1.05 grams, and gaseous mixture group becomes NO 1.1%, CO
5%, remaining is nitrogen, gas space velocity 2400h-1, 200~350 DEG C of reaction temperature, reaction result such as table 2 shows.
[embodiment 25]
It is investigated using the experiment condition of catalyst made from embodiment 15 and embodiment 21 using methane as reducing agent
Influence of the reaction temperature to NO conversion ratio, is as a result listed in table 2.
Table 2
Claims (10)
1. a kind of catalyst for removing nitrogen oxides, catalyst includes following components by weight percentage:
A) 80~95% aluminium oxide；
B) 0~3% at least one of periodic table of elements Section IV B or VB race metal oxide are selected from.
C) 5~15% selected from least one of Cu, Ag, Fe, Cr element or its oxide；
D) 0~5% selected from least one of Ce, Mn metal oxide.
2. it is according to claim 1 removing nitrogen oxides catalyst, it is characterised in that the content of component d) be 0.1~
3%；Preferably 0.2~2%.
3. removing the catalyst of nitrogen oxides according to claim 1, it is characterised in that component c) is selected from Ag, and component d) is selected from
Mn。
4. removing the catalyst of nitrogen oxides according to claim 1, it is characterised in that component c) is selected from Cr, and component d) is selected from
Ce。
5. removing the catalyst of nitrogen oxides according to claim 1, it is characterised in that the group in terms of catalyst weight percent
Dividing content c) is 2~10%.
6. removing the catalyst of nitrogen oxides according to claim 1, it is characterised in that be selected from periodic table of elements Section IV B or VB
Metal oxide in race is selected from one of titanium oxide, zirconium oxide, vanadium oxide or niobium oxide or at least one.
7. removing the catalyst of nitrogen oxides according to claim 1, it is characterised in that catalyst passes through sol-gel method
(SOL-GEL) it is prepared.
8. removing the catalyst of nitrogen oxides according to claim 1, it is characterised in that aluminium oxide is in catalyst with amorphous
State exists, and does not have the characteristic diffraction peak of aluminium oxide in the XRD spectra of catalyst.
9. removing the preparation method of the catalyst of nitrogen oxides described in claim 7, comprising the following steps:
A) aqueous solution or alcoholic solution I is made in aluminium isopropoxide；
B) silver soluble, copper, iron or/and chromic salts are dissolved in water, obtain solution II；
C) above-mentioned solution II is added dropwise in solution I, heating plastic obtains jelly III；
D) it removes to roast after solvent in jelly III and obtains catalyst precarsor IV；
E) catalyst needed for being obtained after catalyst precarsor IV roasting.
10. the preparation method of removing nitrogen oxide catalyst according to claim 9, it is characterised in that step d) is obtained
Catalyst precarsor IV first through modified containing IVB and/or VB race metal salt solution, then after roasting after needed for catalyst.
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| CN113244949A (en) * | 2021-06-28 | 2021-08-13 | 中汽研（天津）汽车工程研究院有限公司 | High-durability BEA molecular sieve catalyst with core-shell structure, preparation method and application thereof |
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| CN113797933A (en) * | 2021-10-22 | 2021-12-17 | 中国海洋石油集团有限公司 | Copper-chromium catalyst and preparation method and application thereof |
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