CN106955714A - A kind of bigger serface is without vanadium denitration catalyst and its preparation method and application - Google Patents
A kind of bigger serface is without vanadium denitration catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN106955714A CN106955714A CN201710185607.5A CN201710185607A CN106955714A CN 106955714 A CN106955714 A CN 106955714A CN 201710185607 A CN201710185607 A CN 201710185607A CN 106955714 A CN106955714 A CN 106955714A
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- China
- Prior art keywords
- oxide
- salt
- catalyst
- cobalt
- concentration
- Prior art date
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- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- -1 silica modified titanium dioxide Chemical class 0.000 claims abstract description 17
- 239000003546 flue gas Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract 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 abstract description 3
- 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 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002751 molybdenum Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 150000002821 niobium Chemical class 0.000 claims description 4
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- 150000003657 tungsten Chemical class 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 2
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical group N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 4
- 241000790917 Dioxys <bee> Species 0.000 claims 2
- 229910003978 SiClx Inorganic materials 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 claims 2
- 150000007513 acids Chemical class 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 27
- 239000007789 gas Substances 0.000 abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 9
- 239000000779 smoke Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 230000001846 repelling effect Effects 0.000 description 4
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- 150000003681 vanadium Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical class O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 231100000636 lethal dose Toxicity 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- WLZALYOBOWIRBE-UHFFFAOYSA-N vanadium zinc Chemical compound [V].[Zn].[Zn].[Zn] WLZALYOBOWIRBE-UHFFFAOYSA-N 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8474—Niobium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention belongs to smoke catalytic purification techniques field, specially a kind of bigger serface is without vanadium denitration catalyst and its production and use.The denitrating catalyst of the present invention, using silica modified titanium dioxide as carrier, with the one or more in nickel oxide, cobalt/cobalt oxide, ferriferous oxide and cerium oxide for active component, with the one or more in tungsten oxide, molybdenum oxide and niobium oxide for auxiliary agent, it is advantageous that on the one hand effectively increasing the specific surface area of catalyst, denitration efficiency is significantly improved, the bio-toxicity of traditional vanadium system denitrating catalyst is on the other hand solved the problems, such as.Denitrating catalyst of the present invention has 100 ~ 150m2/ g specific surface area, can tolerate and contain 0~3000mg/m simultaneously3SO2With the nitrogen oxide containing gas of 0~20% vapor, in 280~450 DEG C and 3,000~100,000h‑1Under conditions of air speed, denitration efficiency is stable more than 90%, N2Selectivity is higher than 92%, with strong water resistant sulfur resistive ability, is particularly suitable for use in the discharged nitrous oxides control of thermal power station's flue gas.
Description
Technical field
The invention belongs to smoke catalytic purification techniques field, and in particular to a kind of bigger serface is without vanadium denitration catalyst
Preparation method and application.
Background technology
Nitrogen oxides（NO x ）Main component be nitric oxide（NO）And nitrogen dioxide（NO2）, to human eye and breathing
Road has strong impulse.Human body sucks nitrogen oxides and may result in lung's structural change for a long time, and serious harm human body is good for
Health.In addition nitrogen oxides can also trigger the environmental pollutions such as acid rain, ozone hole and destruction problem, to socio-economic development, life
State is balanced and the life production of people causes to have a strong impact on.In recent years, because country puts into effect regulation and the political affairs of nitrogen oxides emission reduction
Plan, the strict measure for carrying out discharged nitrous oxides control, national discharged nitrous oxides total amount drops year by year, but total amount still ten
Divide huge.According to《Environmental statistics annual report in 2015》, industrial nitrogen oxide emission accounts for national discharged nitrous oxides total amount
63.8%, wherein electric power, the nitrogen oxides of heating power production and supply industry discharge accounts for more than the 50% of industrial nitrogen oxide emission.Cause
This, by economical and efficient and environmental protection denitration technology be applied to industrial smoke discharged nitrous oxides control it is imperative.
SCR（Selective Catalytic Reduction, SCR）It is at present in the world using the most
One of extensive gas denitrifying technology, its reaction mechanism is using additional urea or ammonia as reducing agent, in denitrating catalyst
Catalytic action under by the NO in flue gas x Nontoxic nitrogen and water is reduced into, the performance of its core denitrating catalyst is determined
The application conditions and scope of SCR technology, and the ratio table of the denitration efficiency of denitrating catalyst again with catalyst under normal circumstances
Area is proportionate.Current industrialized denitrating catalyst is mainly vanadium series catalyst（Such as V2O5/WO3-TiO2And V2O5/MoO3-
TiO2）, its specific surface area is 50 ~ 60m2/ g, the temperature window of application is 300 ~ 400 DEG C, is widely used in thermal power station's nitrogen oxides
Emission control.But, the active component V of vanadium series catalyst2O5With strong bio-toxicity, can to the respiratory system of human body and
Skin causes serious injury, and half lethal dose is 10mg/kg.The vanadium series catalyst of inactivation is because regeneration cost is higher and can select
Direct landfill disposal, causes secondary pollution.In addition, V2O5With by SO2It is oxidized to SO3Catalytic action.Flue gas is urged by vanadium system
The SO generated after agent3With the NH of escape3With vapor reaction generation ammonium sulfate and ammonium hydrogen sulfate, corrosion downstream pipe and equipment.
Therefore, need badly exploitation it is a kind of with NO_x Reduction by Effective efficiency without vanadium denitration catalyst, the traditional vanadium system denitrating catalyst of substitution, innovation
Thermal power station's gas denitrifying technology.
Publication No. CN103894184A Chinese invention patent discloses a kind of high-specific surface area vanadium zinc system and is modified denitration
Catalyst, utilizes metatitanic acid and H2O2Between the chemical process of interionic complexing redisperse improve the specific surface area of catalyst,
The denitration efficiency of catalyst is effectively increased, but its specific surface area is still no more than 100m2/ g, and still by extremely toxic substance V2O5
It is used as active component.Publication No. CN103406127A patent document discloses a kind of catalysis of nontoxic low-temperature denitration catalysis
Agent, the catalyst has more than 80% denitration efficiency at 120 ~ 250 DEG C using manganese oxide as major catalyst, but the patent is not examined
Examine catalyst interval in sulfur-bearing, aqueous and thermal power station's flue-gas temperature（300~400℃）Under the conditions of denitration performance, limit this
The practical ranges of catalyst.Therefore, a kind of specific surface area is developed big, denitration efficiency is high, while having strong sulfur resistive water resistant
There is performance actual application value to have wide market prospects without vanadium denitration catalyst.
The content of the invention
It is an object of the invention to provide a kind of specific surface area is big, denitration efficiency it is high without vanadium denitration catalyst and its preparation
Method, and application of the above-mentioned catalyst in the discharged nitrous oxides control aspect of thermal power station's flue gas is provided.
The bigger serface that the present invention is provided is without vanadium denitration catalyst, using silica modified titanium dioxide as carrier,
With the one or more in nickel oxide, cobalt/cobalt oxide, ferriferous oxide and cerium oxide for active component, with tungsten oxide, molybdenum
One or more in oxide and niobium oxide are auxiliary agent, i.e., be made up of carrier, active component and the part of auxiliary agent three；Wherein,
On the basis of silica modified TiO 2 carrying weight, silica accounts for the 1 ~ 40% of carrier quality, and active component accounts for load
The 1 ~ 40% of weight, auxiliary agent accounts for the 0.1 ~ 15% of carrier quality.
Preparation method of the bigger serface that the present invention is provided without vanadium denitration catalyst（That is active component and auxiliary agent dipping is negative
Carry）, comprise the following steps that：
By one kind in the one or more in a certain amount of nickel salt, cobalt salt, molysite and cerium salt, with tungsten salt, molybdenum salt and niobium salt or
It is a variety of, it is dissolved in a certain amount of deionized water, is sufficiently stirred for disperseing to form mixed liquor；By a certain amount of silica modified two
Titanium dioxide carrier adds above-mentioned mixed liquor, and 80 ~ 100 DEG C of stirrings are evaporated；Collection is evaporated product and small in 250 ~ 650 DEG C of roastings 3 ~ 8
When, obtain finished catalyst.
Wherein, the nickel salt is the one or more in nickel nitrate, nickel chloride and nickel sulfate, and nickel element is dense in its solution
Spend for 0.001 ~ 1.0mol/L；The cobalt salt is cobalt member in the one or more in cobalt nitrate, cobalt chloride and cobaltous sulfate, its solution
The concentration of element is 0.001 ~ 1.0mol/L；The molysite be frerrous chloride, ferrous sulfate, iron chloride and ferric nitrate in one kind or
A variety of, the concentration of ferro element is 0.001 ~ 1.0mol/L in its solution；The cerium salt is in cerous sulfate, cerous nitrate and cerium chloride
The concentration of Ce elements is 0.001 ~ 1.0mol/L in one or more, its solution；The tungsten salt be ammonium metatungstate, ammonium paratungstate,
The concentration of wolfram element is 0.001 ~ 1.0mol/L in one or more in sodium tungstate and potassium tungstate, its solution；The molybdenum salt is
One or more in ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate and ammonium octamolybdate, the concentration of its Molybdenum in Solution element is
0.001~1.0mol/L；The niobium salt is the concentration of niobium element in the one or more in niobium oxalate and columbium pentachloride, its solution
For 0.001 ~ 1.0mol/L.
Wherein, the preparation method of silica modified titania support is as follows：
A certain amount of titanium salt and Ludox are dissolved in a certain amount of deionized water, stirred scattered, mixed liquor is formed；Continue
Ammoniacal liquor is added into the mixed liquor under stirring, pH of mixed=8 ~ 10 are adjusted；After aging 0.5 ~ 12 hour, the above-mentioned mixed liquor of suction filtration,
Washing and filtering product is to filtrate pH=7；Filtration product is dried 2 ~ 24 hours at 80 ~ 120 DEG C, is calcined 3 ~ 8 at 400 ~ 650 DEG C afterwards
Hour, obtain silica modified titania support；
Wherein, the titanium salt is the one or more in titanium tetrachloride, titanium sulfate, titanyl sulfate and butyl titanate, its solution
The concentration of middle titanium elements is 0.1 ~ 1.0mol/L；The Ludox is acidic silicasol, the fraction of quality containing silica 20 ~ 30%；
The ammoniacal liquor contains NH3Mass fraction 18 ~ 25%.
The advantage for the denitrating catalyst that the present invention is provided is：Specific surface area is big（100~150m2/g）, it is tolerable to contain simultaneously
0~3000mg/m3SO2With the nitrogen oxide containing gas of 0~20% vapor, in 280~450 DEG C and 3,000~100,000h-1
Under conditions of air speed, denitration efficiency is stable more than 90%, N2Selectivity is higher than 92%, with strong water resistant sulfur resistive ability, especially fits
Discharged nitrous oxides for thermal power station's flue gas are controlled, i.e., the middle temperature smoke denitrating for sulfur-rich stationary source is handled.
Embodiment
The present invention is described in further detail below by specific embodiment.It should be understood that these embodiments are only used for
The bright present invention rather than limitation the scope of the present invention.The experimental method of unreceipted actual conditions, is generally pressed in the following example
More solito condition, or according to the condition proposed by manufacturer.
Embodiment 1：
1. the preparation of silica modified titania support：By 0.075mol titanyl sulfates and 16g acidic silicasols
（25%）It is dissolved in 100ml deionized waters, stirs scattered, forms mixed liquor；By ammoniacal liquor under lasting stirring（25%）In addition
Mixed liquor is stated, pH of mixed=9 are adjusted；After aging 10 hours, the above-mentioned mixed liquor of suction filtration, washing and filtering product to filtrate pH=7；Cross
Filter product to dry at 80 DEG C 12 hours, be calcined 3 hours at 550 DEG C afterwards, obtain silica modified titania support.
2. active component and auxiliary agent dip loading：By 0.025mol ferrous sulfate heptahydrates, the water cerous nitrates of 0.003mol six and
0.0017mol niobium oxalates are dissolved in 100ml deionized waters, are sufficiently stirred for disperseing to form mixed liquor；10g is silica modified
Titania support adds above-mentioned mixed liquor, and 80 DEG C of stirrings are evaporated；Collection is evaporated product and is calcined 3 hours at 550 DEG C, obtains into
Product catalyst.
3. the performance test of catalyst：Specific surface area of catalyst is 133m2/ g, is automatically compared by Tristar II 3020
Surface area and the test of pore analysis instrument are obtained；0.5g catalyst is taken to be put into fixed bed quartz tube reactor, quartzy bore=8mm,
Simulated flue gas is by NO, NH3、O2And N2Composition, wherein NO 500ppm, NH3 500ppm、O23%, air speed 40,000h-1, reaction temperature
280 ~ 450 DEG C of degree, reaction end gas Antaris IGS gas analyzer on-line checkings.In this test condition, catalyst is de-
Nitre stabilised efficiency is more than 97%, N2Selectivity is more than 98%.
4. sulfur resistive water repelling property is tested：It is extra in simulated flue gas to add SO2And vapor so that SO2Concentration is 2700mg/
m3, vapor volume ratio is 20%, and other test conditions are constant.In this test condition, the denitration efficiency of catalyst is still stablized
More than 94%, N2Selectivity is more than 97%.
Embodiment 2：
1. the preparation of silica modified titania support：By 0.01mol titanium tetrachlorides and 8g acidic silicasols（25%）
It is dissolved in 100ml deionized waters, stirs scattered, forms mixed liquor；By ammoniacal liquor under lasting stirring（20%）Add above-mentioned mixing
Liquid, adjusts pH of mixed=8；After aging 3 hours, the above-mentioned mixed liquor of suction filtration, washing and filtering product to filtrate pH=7；Filtration product
Dried at 100 DEG C 8 hours, be calcined 3 hours at 500 DEG C afterwards, obtain silica modified titania support.
2. active component and auxiliary agent dip loading：By the water nickel nitrates of 0.01mol six, 0.01mol CoCL2 6H2Os and
0.0006mol ammonium metatungstates are dissolved in 100ml deionized waters, are sufficiently stirred for disperseing to form mixed liquor；10g is silica modified
Titania support add above-mentioned mixed liquor, 90 DEG C of stirrings are evaporated；Collection is evaporated product and is calcined 3 hours at 550 DEG C, obtains
Finished catalyst.
3. the performance test of catalyst：Specific surface area of catalyst is 103m2/ g, is automatically compared by Tristar II 3020
Surface area and the test of pore analysis instrument are obtained；0.5g catalyst is taken to be put into fixed bed quartz tube reactor, quartzy bore=8mm,
Simulated flue gas is by NO, NH3、O2And N2Composition, wherein NO 1000ppm, NH31000ppm、O23%, air speed 80,000h-1, reaction
280 ~ 450 DEG C of temperature, reaction end gas Antaris IGS gas analyzer on-line checkings.In this test condition, catalyst
Denitration efficiency is stable more than 95%, N2Selectivity is more than 94%.
4. sulfur resistive water repelling property is tested：It is extra in simulated flue gas to add SO2And vapor so that SO2Concentration is 1300mg/
m3, vapor volume ratio is 20%, and other test conditions are constant.In this test condition, the denitration efficiency of catalyst is still stablized
More than 92%, N2Selectivity is more than 92%.
Embodiment 3：
1. the preparation of silica modified titania support：By 0.087mol butyl titanates and 12g acidic silicasols
（25%）It is dissolved in 100ml deionized waters, stirs scattered, forms mixed liquor；By ammoniacal liquor under lasting stirring（18%）In addition
Mixed liquor is stated, pH of mixed=10 are adjusted；After aging 2 hours, the above-mentioned mixed liquor of suction filtration, washing and filtering product to filtrate pH=7；Cross
Filter product to dry at 110 DEG C 6 hours, be calcined 3 hours at 600 DEG C afterwards, obtain silica modified titania support.
2. active component and auxiliary agent dip loading：By the water ferric nitrates of 0.02mol nine, 0.012mol cobalt nitrate hexahydrates and
0.001mol ammonium heptamolybdates are dissolved in 100ml deionized waters, are sufficiently stirred for disperseing to form mixed liquor；10g is silica modified
Titania support add mixed liquor in, 100 DEG C of stirrings are evaporated；Collection is evaporated product and is calcined 3 hours at 500 DEG C, obtains
Finished catalyst.
3. the performance test of catalyst：Specific surface area of catalyst is 108m2/ g, is automatically compared by Tristar II 3020
Surface area and the test of pore analysis instrument are obtained；0.5g catalyst is taken to be put into fixed bed quartz tube reactor, quartzy bore=8mm,
Simulated flue gas is by NO, NH3、O2And N2Composition, wherein NO 1000ppm, NH31000ppm、O23%, air speed 40,000h-1, reaction
280 ~ 450 DEG C of temperature, reaction end gas Antaris IGS gas analyzer on-line checkings.In this test condition, catalyst
Denitration efficiency is stable more than 98%, N2Selectivity is more than 97%.
4. sulfur resistive water repelling property is tested：It is extra in simulated flue gas to add SO2And vapor so that SO2Concentration is 2700mg/
m3, vapor volume ratio is 10%, and other test conditions are constant.In this test condition, the denitration efficiency of catalyst is still stablized
More than 96%, N2Selectivity is more than 95%.
Embodiment 4：
1. the preparation of silica modified titania support：By 0.075mol titanyl sulfates and 16g acidic silicasols
（25%）It is dissolved in 100ml deionized waters, stirs scattered, forms mixed liquor；By ammoniacal liquor under lasting stirring（25%）In addition
Mixed liquor is stated, pH of mixed=9 are adjusted；After aging 10 hours, the above-mentioned mixed liquor of suction filtration, washing and filtering product to filtrate pH=7；Cross
Filter product to dry at 80 DEG C 12 hours, be calcined 3 hours at 550 DEG C afterwards, obtain silica modified titania support.
2. active component and auxiliary agent dip loading：By 0.02mol Iron trichloride hexahydrates, the water cerium chlorides of 0.005mol six and
The water nickel chlorides of 0.015mol six, 0.0003mol ammonium metatungstates and 0.0007mol niobium oxalates are dissolved in 100ml deionized waters, fully
Dispersed with stirring formation mixed liquor；Titania support silica modified 10g is added into above-mentioned mixed liquor, 80 DEG C of stirrings are steamed
It is dry；Collection is evaporated product and is calcined 3 hours at 450 DEG C, obtains finished catalyst.
3. the performance test of catalyst：Specific surface area of catalyst is 145m2/ g, is automatically compared by Tristar II 3020
Surface area and the test of pore analysis instrument are obtained；0.5g catalyst is taken to be put into fixed bed quartz tube reactor, quartzy bore=8mm,
Simulated flue gas is by NO, NH3、O2And N2Composition, wherein NO 500ppm, NH3 500ppm、O23%, air speed 100,000h-1, reaction
280 ~ 450 DEG C of temperature, reaction end gas Antaris IGS gas analyzer on-line checkings.In this test condition, catalyst
Denitration efficiency is stable more than 99%, N2Selectivity is more than 99%.
4. sulfur resistive water repelling property is tested：It is extra in simulated flue gas to add SO2And vapor so that SO2Concentration is 1300mg/
m3, vapor volume ratio is 10%, and other test conditions are constant.In this test condition, the denitration efficiency of catalyst is still stablized
More than 95%, N2Selectivity is more than 97%.
All documents referred in the present invention are all incorporated as reference in this application, independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (6)
1. a kind of bigger serface is without vanadium denitration catalyst, it is characterised in that the catalyst is by carrier, active component and auxiliary agent
Composition, wherein, the carrier is silica modified titanium dioxide, and the active component is nickel oxide, cobalt/cobalt oxide, iron
One or more in oxide and cerium oxide, the auxiliary agent is one kind in tungsten oxide, molybdenum oxide and niobium oxide
Or it is a variety of；On the basis of silica modified TiO 2 carrying weight, silica accounts for the 1 ~ 40% of carrier quality, activity
Component accounts for the 1 ~ 40% of carrier quality, and auxiliary agent accounts for the 0.1 ~ 15% of carrier quality.
2. preparation method of the bigger serface as claimed in claim 1 without vanadium denitration catalyst, it is characterised in that specific steps
It is as follows：
By one kind in the one or more in a certain amount of nickel salt, cobalt salt, molysite and cerium salt, with tungsten salt, molybdenum salt and niobium salt or
It is a variety of, it is dissolved in a certain amount of deionized water, is sufficiently stirred for disperseing to form mixed liquor；By a certain amount of silica modified two
Titanium dioxide carrier adds above-mentioned mixed liquor, and 80 ~ 100 DEG C of stirrings are evaporated；Collection is evaporated product and small in 250 ~ 650 DEG C of roastings 3 ~ 8
When, obtain finished catalyst.
3. preparation method of the bigger serface as claimed in claim 2 without vanadium denitration catalyst, it is characterised in that the nickel salt
For the one or more in nickel nitrate, nickel chloride and nickel sulfate, the concentration of nickel element is 0.001 ~ 1.0mol/L in its solution；Institute
State cobalt salt be the concentration of cobalt element in the one or more in cobalt nitrate, cobalt chloride and cobaltous sulfate, its solution for 0.001 ~
1.0mol/L；The molysite is iron in the one or more in frerrous chloride, ferrous sulfate, iron chloride and ferric nitrate, its solution
The concentration of element is 0.001 ~ 1.0mol/L；The cerium salt is the one or more in cerous sulfate, cerous nitrate and cerium chloride, and its is molten
The concentration of Ce elements is 0.001 ~ 1.0mol/L in liquid；The tungsten salt is in ammonium metatungstate, ammonium paratungstate, sodium tungstate and potassium tungstate
One or more, the concentration of wolfram element is 0.001 ~ 1.0mol/L in its solution；The molybdenum salt is ammonium dimolybdate, four molybdic acids
One or more in ammonium, ammonium heptamolybdate and ammonium octamolybdate, the concentration of its Molybdenum in Solution element is 0.001 ~ 1.0mol/L；It is described
Niobium salt is that the concentration of niobium element in the one or more in niobium oxalate and columbium pentachloride, its solution is 0.001 ~ 1.0mol/L.
4. preparation method of the bigger serface as claimed in claim 2 without vanadium denitration catalyst, it is characterised in that the dioxy
The preparation method of titania support that SiClx is modified is：
A certain amount of titanium salt and Ludox are dissolved in a certain amount of deionized water, stirred scattered, mixed liquor is formed；Continue
Ammoniacal liquor is added into above-mentioned mixed liquor under stirring, pH of mixed=8 ~ 10 are adjusted；After aging 0.5 ~ 12 hour, the above-mentioned mixed liquor of suction filtration,
Washing and filtering product is to filtrate pH=7；Filtration product is dried 2 ~ 24 hours at 80 ~ 120 DEG C, is calcined 3 ~ 8 at 400 ~ 650 DEG C afterwards
Hour, obtain silica modified titania support.
5. preparation method of the bigger serface as claimed in claim 4 without vanadium denitration catalyst, it is characterised in that：In titanium dioxide
In the preparation of the titania support of Si modification, the titanium salt is in titanium tetrachloride, titanium sulfate, titanyl sulfate and butyl titanate
One or more, the concentration of titanium elements is 0.1 ~ 1.0mol/L in its solution；The Ludox is acidic silicasol, containing dioxy
SiClx mass fraction 20 ~ 30%；The ammoniacal liquor contains NH3Mass fraction 18 ~ 25%.
6. a kind of bigger serface as claimed in claim 1 without vanadium denitration catalyst thermal power station's flue gas discharged nitrous oxides
Application in control.
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Application publication date: 20170718 |