CN116135304A - Denitration catalyst and preparation method and application thereof - Google Patents
Denitration catalyst and preparation method and application thereof Download PDFInfo
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- CN116135304A CN116135304A CN202111353561.6A CN202111353561A CN116135304A CN 116135304 A CN116135304 A CN 116135304A CN 202111353561 A CN202111353561 A CN 202111353561A CN 116135304 A CN116135304 A CN 116135304A
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- mixed solution
- denitration catalyst
- denitration
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- 239000003054 catalyst Substances 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 68
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 32
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 239000010937 tungsten Substances 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 39
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 22
- 239000003546 flue gas Substances 0.000 claims description 22
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 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 6
- 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 claims description 6
- 239000004254 Ammonium phosphate Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 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 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 5
- 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 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- 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 4
- 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 description 4
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000779 smoke Substances 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 4
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005696 Diammonium phosphate Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- LUYWGGWGYMURNR-UHFFFAOYSA-M [O-2].[O-2].[OH-].O.P.[V+5] Chemical compound [O-2].[O-2].[OH-].O.P.[V+5] LUYWGGWGYMURNR-UHFFFAOYSA-M 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- 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 3
- 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 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 16
- 239000011593 sulfur Substances 0.000 abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 abstract description 16
- 230000009467 reduction Effects 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000006378 damage Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000004088 simulation Methods 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
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 210000002345 respiratory system Anatomy 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 petrochemical Chemical compound 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/8472—Vanadium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a denitration catalyst and a preparation method and application thereof, wherein in the preparation method of the denitration catalyst, a vanadium source and oxalic acid are dissolved in deionized water, heated and stirred, and uniformly mixed to obtain a first mixed solution; adding the auxiliary agent precursor into the first mixed solution, and stirring and uniformly mixing to obtain a second mixed solution; the auxiliary agent precursor comprises one or more of a tungsten source, a molybdenum source, a nickel source and a zirconium source; adding a phosphorus source into the second mixed solution, and stirring and uniformly mixing to obtain a third mixed solution; adding the titanium dioxide carrier into the third mixed solution, stirring and evaporating the titanium dioxide carrier at 60-100 ℃ to obtain an evaporated matter, and roasting the evaporated matter to obtain the denitration catalyst in a monodisperse state. The denitration catalyst has the advantages of low temperature water resistance, sulfur resistance and the like, on one hand, the reduction of the specific surface area of the catalyst in the roasting process can be effectively reduced, the denitration effect is obviously improved, and on the other hand, the problem that the activity of the traditional vanadium-based catalyst is sharply reduced due to low-temperature poisoning caused by water and sulfur is solved.
Description
Technical Field
The invention belongs to the field of flue gas denitration in atmospheric pollution control, and particularly relates to a denitration catalyst and a preparation method and application thereof.
Background
With the rapid development of the economic society, energy consumption is continuously increasing. The present situation that the energy consumption structure is dominated by coal is difficult to change in a quite long period in the future in China, which is the second potential energy production country and the consumption country in the world at present; and coal consumption causes soot-type atmospheric pollution, resulting in emission of a large amount of harmful gases such as nitrogen oxides and the like.
NO x Has serious harm to human health, ecological environment and regional climate. For example, the binding capacity of NO and hemoglobin is strong, oxygen deficiency is easy to cause after human inhalation, and the respiratory tract mucosa is damaged; NO (NO) 2 Has strong stimulation to the respiratory system of animals; in addition, with NO and NO 2 NO of the main part x Is shaped likeThe main reasons for acid rain and photochemical smog are as follows: NO in atmosphere x Nitric acid or nitrous acid formed by combining with water in the air is an important component for composing acid rain, and deterioration of an aquatic ecosystem can be caused after sedimentation; NO in motor vehicle exhaust x The chemical reaction with hydrocarbon under the irradiation of ultraviolet ray to generate photochemical smog, which can cause serious influence and damage to human health and ecological system; thus, NO is required x And effective emission reduction is carried out.
The control of the nitrogen oxides mainly adopts the low combustion technology and the flue gas denitration, according to the requirements of national economy sustainable development, the national restrictions on the emission requirements are more and more strict, the emission is reduced only by the low combustion technology, the emission standard can not be achieved far, and the flue gas denitration is a method for reducing the emission of the nitrogen oxides generally. The SCR is the flue gas denitration technology which is the absolute mainstream at present and is the most successful in commercialization, and is the most effective denitration technology which is accepted worldwide when the removal rate of nitrogen oxides is required to be more than 50%, the occupied area is small, the improvement in the original flow is facilitated, and meanwhile, the operation is simple and the technology is mature; the main factor in the SCR denitration technology is a catalyst, and the cost of the catalyst can be about half of the initial investment of an SCR system; the quality of the catalyst is related to the denitration effect, and the service life of the catalyst is influenced, so that the subsequent running cost of SCR is further influenced.
Currently commercial vanadium-titanium denitration catalyst (V 2 O 5 /TiO 2 ) The catalytic performance is excellent in the middle temperature section (350-450 ℃); however, a large number of industrial boilers, such as coke oven flue gas, steel, cement, glass, petrochemical, nitric acid production industries, etc., cannot directly use the medium-high Wen Tuoxiao catalyst due to the low temperature. Therefore, development of a novel low-temperature denitration catalyst, maintenance of high activity and high stability of the low-temperature denitration catalyst and sulfur resistance and water resistance are difficulties which are urgently needed to be solved in the denitration technology.
In recent years, research has found that manganese-based catalysts have higher activity in low temperature SCR reactions, but SO is present in small amounts in the mixed gas 2 Can seriously affect the activity of the destruction catalyst; at low temperature
Oxidized to SO 3 Can react with the catalytically active material to form stable sulfate compounds to deactivate the catalyst or in the presence of H 2 O and NH 3 The reaction produces refractory ammonium bisulfate or ammonium sulfate to clog the active sites of the catalyst, etc., making it difficult for the catalyst to exert an ideal purification effect. Meanwhile, the too narrow catalyst activity temperature window limits the stable exertion of the catalyst activity; therefore, the development of the catalyst with high-efficiency sulfur-resistant water-resistant and denitration performance under the low-temperature condition has important significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a denitration catalyst and a preparation method and application thereof, wherein the denitration catalyst has the advantages of low temperature water resistance, sulfur resistance and the like, on one hand, the reduction of the specific surface area of the catalyst in the roasting process can be effectively reduced, the denitration effect is obviously improved, and on the other hand, the problem that the activity of the traditional vanadium-based catalyst is rapidly reduced due to low-temperature poisoning caused by the existence of water and sulfur is solved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a denitration catalyst, which comprises a titanium dioxide carrier, and an active component and an auxiliary agent which are loaded on the titanium dioxide carrier;
the active components are distributed on the titanium dioxide carrier in a monodisperse state;
the active component is selected from one or more of vanadium oxide, phosphorus vanadium oxide and cerium oxide;
the auxiliary agent comprises one or more of tungsten oxide, molybdenum oxide, nickel oxide and zirconium oxide;
the specific surface area of the denitration catalyst is 120-150 m 2 /g。
Preferably, the active component accounts for 1-20wt% of the weight of the titanium dioxide carrier; the auxiliary agent accounts for 1-20wt% of the weight of the titanium dioxide carrier.
According to a second aspect of the invention, there is provided a method for preparing a denitration catalyst according to the first aspect of the invention, comprising the steps of:
s1, dissolving a vanadium source and oxalic acid in deionized water, heating and stirring, and uniformly mixing to obtain a first mixed solution;
s2, adding the auxiliary agent precursor into the first mixed solution, and stirring and uniformly mixing to obtain a second mixed solution; the auxiliary agent precursor comprises one or more of a tungsten source, a molybdenum source, a nickel source and a zirconium source;
s3, adding a phosphorus source into the second mixed solution, and stirring and uniformly mixing to obtain a third mixed solution;
and S4, adding the titanium dioxide carrier into the third mixed solution, stirring and evaporating the titanium dioxide carrier at 60-100 ℃ to obtain an evaporated matter, and roasting the evaporated matter to obtain the denitration catalyst.
Preferably, in the step S1:
the vanadium source is selected from one or more of ammonium metavanadate, vanadyl oxalate and vanadyl sulfate; and/or
A cerium source is also added into the first mixed solution, and the cerium source is selected from one or more of cerium nitrate, cerium chloride and cerium sulfate; and/or
In the heating and stirring process, the heating temperature is 70-80 ℃; and/or
In the first mixed solution, the concentration of oxalic acid is 2-4 times of the concentration of vanadium sources.
Preferably, in the step S1:
the concentration of vanadium element in the first mixed solution is 0.001-0.1 mol/L; and/or
When the cerium source is added into the first mixed solution, the concentration of cerium element is 0.001-1.0 mol/L.
Preferably, in the step S2:
the tungsten source is selected from one or more of ammonium metatungstate, ammonium paratungstate, sodium tungstate and potassium tungstate; and/or
The molybdenum source is selected from one or more of ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate and ammonium octamolybdate; and/or
The nickel source is selected from one or more of nickel nitrate, nickel acetate or nickel chloride; and/or
The zirconium source is selected from one or more of zirconium nitrate, zirconium oxychloride, zirconium acetate or zirconium sulfate.
Preferably, in the step S2:
when the auxiliary agent precursor contains a tungsten source, the concentration of tungsten element in the second mixed solution is 0.001-1.0 mol/L; and/or
When the auxiliary agent precursor contains a molybdenum source, the concentration of molybdenum element in the second mixed solution is 0.001-1.0 mol/L; and/or
When the auxiliary agent precursor contains a nickel source, the concentration of nickel element in the second mixed solution is 0.001-1.0 mol/L; and/or
When the auxiliary agent precursor contains a zirconium source, the concentration of zirconium element in the second mixed solution is 0.001-1.0 mol/L.
Preferably, in the step S3:
the phosphorus source is selected from one or more of phosphoric acid, ammonium phosphate, monoammonium phosphate and diammonium phosphate; and/or
The concentration of the phosphorus element in the third mixed solution is 0.001-0.1 mol/L; and/or
In the step S4: in the roasting process, the roasting temperature is 250-650 ℃ and the roasting time is 2-6 h.
In a third aspect, the invention provides an application of the denitration catalyst in flue gas denitration at 150-300 ℃ and 5000-150000 h -1 Under the condition of airspeed, the denitration efficiency of the denitration catalyst in nitrogen oxide flue gas is over 95 percent, and N is 2 The selectivity is higher than 95%; and/or
The nitrogen oxide smoke contains 0-3000 mg/m 3 SO of (2) 2 And 5% -20% H 2 Under the condition of O, the denitration efficiency of the denitration catalyst is more than 85 percent, and N is 2 The selectivity is higher than 90%.
The denitration catalyst provided by the invention has the beneficial effects of a preparation method and application:
1. according to the denitration catalyst and the preparation method and application thereof, titanium dioxide is used as a carrier, one or more of vanadium oxide, phosphorus vanadium oxide and cerium oxide are used as active components, and one or more of tungsten oxide, molybdenum oxide, nickel oxide and zirconium oxide are used as auxiliary agents, so that the denitration catalyst has the advantages of low temperature water resistance, sulfur resistance and the like, on one hand, the reduction of the specific surface area of the catalyst in the roasting process can be effectively reduced, the denitration effect is obviously improved, and on the other hand, the problem that the activity of the traditional vanadium-based catalyst is rapidly reduced due to low-temperature poisoning caused by water and sulfur is solved;
2. the denitration catalyst of the invention is used at 150-300 ℃ and 5000-150000 h -1 Under the condition of airspeed, the denitration efficiency is stabilized to be more than 95 percent, N 2 The selectivity is higher than 95 percent, and the content of the catalyst is 0 to 3000mg/m 3 SO of (2) 2 And 5% -20% H 2 The nitrogen oxide smoke of O still keeps more than 85 percent, N 2 The selectivity is higher than 90%, and the catalyst has strong sulfur and water resistance, and is particularly suitable for controlling the emission of nitrogen oxides of fixed source flue gas of glass, steel, coking coke ovens and the like.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
in fig. 1, (a) shows the distribution of active components and titania carrier in the denitration catalyst of the present invention, and (b) shows the distribution of active components and titania carrier in the conventional catalyst;
FIG. 2 is a graph showing the comparison of the activity of the denitration catalyst prepared in example 1 of the present invention and a conventional V-W-Ti commercial catalyst at 100 to 250 ℃;
FIG. 3 is a graph showing the comparison of the activity of the denitration catalyst prepared in example 2 of the present invention with that of a conventional V-W-Ti commercial catalyst at 150 to 180 ℃.
Detailed Description
In order to better understand the above technical solution of the present invention, the technical solution of the present invention is further described below with reference to examples.
The denitration catalyst provided by the inventionAn agent comprising a titanium dioxide carrier, an active component and an auxiliary agent carried on the titanium dioxide carrier; the active component is selected from one or more of vanadium oxide, vanadium phosphorus oxide and cerium oxide; the auxiliary agent comprises one or more of tungsten oxide, molybdenum oxide, nickel oxide and zirconium oxide. Wherein the active component accounts for 1 to 20 percent of the weight of the titanium dioxide carrier; the auxiliary agent accounts for 1-20% of the weight of the titanium dioxide carrier. The specific surface area of the denitration catalyst is 120-150 m 2 /g。
In combination with the steps shown in (a) and (b) in fig. 1, unlike the conventional catalyst in which the active components are formed into particles and aggregated on the carrier (see (b) in fig. 1), the active components 2 are uniformly distributed and distributed on the titanium dioxide carrier 12 in a monodispersed state (see (a) in fig. 1), and the activity and the denitration efficiency of the denitration catalyst are effectively improved by the dispersing mode.
The preparation method of the denitration catalyst provided by the invention comprises the following steps:
s1, dissolving a vanadium source and oxalic acid in deionized water, heating and stirring, and uniformly mixing to obtain a first mixed solution;
the specific process is as follows: dissolving a vanadium source and oxalic acid in deionized water, or dissolving a vanadium source, a cerium source and oxalic acid in deionized water together, heating to 70-80 ℃, fully stirring to disperse the materials, and uniformly mixing to obtain a first mixed solution; wherein the vanadium source adopts vanadium salt, and is specifically selected from one or more of ammonium metavanadate, vanadyl oxalate and vanadyl sulfate, and the concentration of vanadium element in the first mixed solution is 0.001-0.1 mol/L; in the first mixed solution, the concentration of oxalic acid is 2-4 times of the concentration of vanadium sources; the cerium source adopts cerium salt, and is specifically selected from one or more of cerium nitrate, cerium chloride and cerium sulfate, and when the cerium source is added into the first mixed solution, the concentration of cerium element is 0.001-1.0 mol/L.
S2, adding the auxiliary agent precursor into the first mixed solution, and stirring and uniformly mixing to obtain a second mixed solution; the auxiliary agent precursor comprises one or more of a tungsten source, a molybdenum source, a nickel source and a zirconium source;
the specific process is as follows: and (2) adding an auxiliary agent precursor into the first mixed solution obtained in the step (S1), stirring and dissolving, and uniformly mixing to obtain a second mixed solution, wherein the auxiliary agent precursor comprises one or more of a tungsten source, a molybdenum source, a nickel source and a zirconium source. Wherein the tungsten source adopts tungsten salt, and is specifically selected from one or more of ammonium metatungstate, ammonium paratungstate, sodium tungstate and potassium tungstate; the molybdenum source adopts molybdenum salt, and is specifically selected from one or more of ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate and ammonium octamolybdate; the nickel source adopts nickel salt, and is specifically selected from one or more of nickel nitrate, nickel acetate or nickel chloride; the zirconium source adopts zirconium salt, and is specifically selected from one or more of zirconium nitrate, zirconium oxychloride, zirconium acetate or zirconium sulfate. When the auxiliary agent precursor contains a tungsten source, the concentration of tungsten element in the second mixed solution is 0.001-1.0 mol/L; when the auxiliary agent precursor contains a molybdenum source, the concentration of molybdenum element in the second mixed solution is 0.001-1.0 mol/L; when the auxiliary agent precursor contains a nickel source, the concentration of nickel element in the second mixed solution is 0.001-1.0 mol/L; when the auxiliary agent precursor contains a zirconium source, the concentration of zirconium element in the second mixed solution is 0.001-1.0 mol/L.
S3, adding the phosphorus source into the second mixed solution, and stirring and uniformly mixing to obtain a third mixed solution;
the specific process is as follows: adding a phosphorus source into the second mixed solution obtained in the step S2, stirring and dissolving, and uniformly mixing to obtain a third mixed solution, wherein the phosphorus source adopts phosphoric acid and salts thereof, and is specifically selected from one or more of phosphoric acid, ammonium phosphate, monoammonium phosphate and diammonium phosphate; the concentration of the phosphorus element in the third mixed solution is 0.001-0.1 mol/L.
And S4, adding the titanium dioxide carrier into the third mixed solution, stirring and evaporating the titanium dioxide carrier at 60-100 ℃ to obtain an evaporated matter, and roasting the evaporated matter to obtain the denitration catalyst.
The specific process is as follows: and (3) adding the titanium dioxide carrier into the third mixed solution obtained in the step (S3), stirring and evaporating the titanium dioxide carrier at 60-100 ℃ to obtain an evaporated matter, and roasting the evaporated matter at 250-650 ℃ for 2-6 hours to obtain the denitration catalyst.
The specific surface area of the denitration catalyst prepared by the method is 120-150 m 2 Per gram, when the denitration catalyst is applied in the flue gas denitration process, the denitration catalyst is used at 150-300 ℃ and 5000-150000 h -1 Conditions of airspeedThe denitration efficiency of the denitration catalyst in the nitrogen oxide flue gas is more than 95%, and N is 2 The selectivity is higher than 95%; and the nitrogen oxide smoke contains 0-3000 mg/m 3 SO of (2) 2 And 5% -20% H 2 Under the condition of O, the denitration efficiency of the denitration catalyst is more than 85 percent, N 2 The selectivity is higher than 90%. The denitration catalyst has strong low-temperature water-resistant and sulfur-resistant capability, effectively solves the problem that the activity of the traditional vanadium-based catalyst is suddenly reduced due to the existence of water and sulfur at low temperature, and is particularly suitable for controlling the emission of nitrogen oxides of fixed source flue gas such as glass, steel, coking coke ovens and the like.
The denitration catalyst of the present invention, and the preparation method and application thereof are further described below with reference to specific examples.
Example 1
Preparation of denitration catalyst in this example: adding 0.01mol of ammonium metavanadate, 0.03mol of oxalic acid and 0.03mol of cerous nitrate hexahydrate into 200mL of deionized water in sequence, heating to 80 ℃, and fully stirring and dispersing to form a first mixed solution; adding 0.005mol of ammonium heptamolybdate and 0.01mol of ammonium phosphate, and stirring and dissolving uniformly to obtain a third mixed solution; then 10g of titanium dioxide carrier is added into the third mixed solution, stirred and evaporated to dryness at 80 ℃, and the evaporated matter is collected and roasted for 3 hours at 500 ℃ to obtain the denitration catalyst.
The components of the denitration catalyst are as follows: the carrier is TiO 2 The active component is CeO 2 And V 2 O 5 。
Performance test of denitration catalyst: the specific surface area of the denitration catalyst is 120m 2 And/g, by a Tristar II 3020 full-automatic specific surface area and pore analyzer. 0.5g of the prepared denitration catalyst is put into a fixed bed quartz tube reactor, the inner diameter of a quartz tube is=0.8 cm, and the simulation flue gas is formed by NO and NH 3 、O 2 And N 2 Composition of NO 1000ppm, NH 3 1000 ppm、O 2 3%, airspeed 40,000h -1 The reaction temperature is 150-300 ℃, and the reaction tail gas is detected on line by using an Antaris IGS gas analyzer. Under the test condition, the denitration efficiency of the denitration catalyst is stabilized to be more than 95 percent, N 2 The selectivity is above 96%。
Test of sulfur and water resistance of the catalyst: additional SO addition to simulated flue gas 2 SO that SO 2 The concentration is 500mg/m 3 At the same time add H 2 O, so that H 2 The volume fraction of O was 20% and the other test conditions were unchanged. Under the test condition, the denitration efficiency of the catalyst is still stabilized to be more than 92 percent, N 2 The selectivity is over 94 percent.
Example 2
Preparation of denitration catalyst in this example: adding 0.01mol of ammonium metavanadate and 0.04mol of oxalic acid into 200mL of deionized water in sequence, heating to 80 ℃, and fully stirring and dispersing to form a first mixed solution; then 0.002mol of ammonium metatungstate, 0.01mol of nickel nitrate and 0.01mol of phosphoric acid are respectively added, and uniformly stirred and dissolved to obtain a third mixed solution; then 10g of titanium dioxide carrier is added into the mixed solution, stirred and evaporated to dryness at 80 ℃, and the evaporated matter is collected and roasted for 3 hours at 350 ℃ to obtain the denitration catalyst.
The components of the denitration catalyst are as follows: the carrier is TiO 2 The active component is V 2 O 5 And NiO.
Performance test of denitration catalyst: specific surface area of denitration catalyst is 145m 2 And/g, by a Tristar II 3020 full-automatic specific surface area and pore analyzer. 0.5g of the prepared denitration catalyst is put into a fixed bed quartz tube reactor, the inner diameter of a quartz tube is=0.8 cm, and the simulation flue gas is formed by NO and NH 3 、O 2 And N 2 Composition of 500ppm NO, NH 3 500 ppm、O 2 3, airspeed 30000h -1 The reaction temperature is 150-300 ℃, and the reaction tail gas is detected on line by an AntarisIGS gas analyzer. Under the test condition, the denitration efficiency of the denitration catalyst is stabilized to be more than 97 percent, N 2 The selectivity is over 96 percent.
Sulfur and water resistance test of denitration catalyst: additional SO addition to simulated flue gas 2 SO that SO 2 The concentration is 1,500mg/m 3 At the same time add H 2 O, so that H 2 The volume fraction of O was 10% and the other test conditions were unchanged. Under the test conditions, the denitration efficiency of the denitration catalyst still remainsStabilized at 90% or more, N 2 The selectivity is more than 92 percent.
Example 3
Preparation of denitration catalyst in this example: adding 0.01mol of ammonium metavanadate, 0.03mol of oxalic acid and 0.005mol of cerous nitrate hexahydrate into 200mL of deionized water in sequence, heating to 80 ℃, and fully stirring and dispersing to form a first mixed solution; then 0.002mol of sodium tungstate, 0.01mol of zirconium sulfate and 0.01mol of ammonium dihydrogen phosphate are respectively added, and uniformly stirred and dissolved to obtain a third mixed solution; then 10g of titanium dioxide carrier is added into the third mixed solution, stirred and evaporated to dryness at 80 ℃, and the evaporated matter is collected and roasted for 3 hours at 550 ℃ to obtain the denitration catalyst.
The components of the denitration catalyst are as follows: the carrier is TiO 2 The active component is V 2 O 5 And CeO 2 。
Performance test of denitration catalyst: the specific surface area of the denitration catalyst is 105m 2 And/g, by a Tristar II 3020 full-automatic specific surface area and pore analyzer. 0.5g of the prepared denitration catalyst is put into a fixed bed quartz tube reactor, the inner diameter of a quartz tube is=0.8 cm, and the simulation flue gas is formed by NO and NH 3 、O 2 And N 2 Composition of NO 1500ppm, NH 2 1500 ppm、O 2 3%, space velocity 50000h -1 The reaction temperature is 150-300 ℃, and the reaction tail gas is detected on line by using an Antaris IGS gas analyzer. Under the test condition, the denitration efficiency of the denitration catalyst is stabilized to be more than 96 percent, N 2 The selectivity is over 94 percent.
Sulfur and water resistance test of denitration catalyst: additional SO addition to simulated flue gas 2 SO that SO 2 The concentration is 500mg/m 3, and H is added additionally 2 O, so that H 2 The volume fraction of O was 10% and the other test conditions were unchanged. Under the test condition, the denitration efficiency of the denitration catalyst is still stabilized to be more than 92%, and the N2 selectivity is more than 90%.
Example 4
The preparation of the denitration catalyst in the invention comprises the following steps: adding 0.01mol of vanadyl oxalate and 0.02mol of oxalic acid into 200mL of deionized water in sequence, heating to 80 ℃, and fully stirring and dispersing to form a first mixed solution; then 0.02mol of ammonium heptamolybdate, 0.0005mol of ammonium metatungstate and 0.01mol of ammonium phosphate are respectively added, and uniformly stirred and dissolved to obtain a third mixed solution; then 10g of titanium dioxide carrier is added into the third mixed solution, stirred and evaporated to dryness at 80 ℃, and the evaporated matter is collected and roasted for 3 hours at 350 ℃ to obtain the denitration catalyst.
The components of the denitration catalyst are as follows: the carrier is TiO 2 The active component is V 2 O 5 And MoO 3 。
Performance test of denitration catalyst: the specific surface area of the denitration catalyst is 140m 2 And/g, by a Tristar II 3020 full-automatic specific surface area and pore analyzer. 0.5g of the prepared denitration catalyst is put into a fixed bed quartz tube reactor, the inner diameter of a quartz tube is=0.8 cm, and the simulation flue gas is formed by NO and NH 3 、O 2 And N 2 Composition of NO 1000ppm, NH 3 1000ppm、O 2 3, airspeed 30000h -1 The reaction temperature is 150-300 ℃, and the reaction tail gas is detected on line by using an Antaris IGS gas analyzer. Under the test condition, the denitration efficiency of the denitration catalyst is stabilized to be more than 95 percent, N 2 The selectivity is above 93%.
Sulfur and water resistance test of denitration catalyst: additional SO addition to simulated flue gas 2 SO that SO 2 The concentration is 1000 mg/m 3 At the same time add H 2 O, so that H 2 The volume fraction of O was 15% and the other test conditions were unchanged. Under the test condition, the denitration efficiency of the denitration catalyst is still stabilized to be more than 92 percent, N 2 The selectivity is more than 95%.
Performance testing
(1) Activity test at 100-250 ℃): the low-temperature denitration catalyst prepared in example 1 and the conventional V-W-Ti commercial catalyst are subjected to activity test in a laboratory, 0.5g of the catalyst is taken out of the two catalysts, the two catalysts are respectively put into a fixed bed quartz tube reactor, the inner diameter of the quartz tube is=0.8 cm, and the simulated flue gas is formed by NO and NH 3 、O 2 And N 2 Composition of NO 1000ppm, NH 3 1000ppm、SO 2 500ppm，O 2 3, airspeed 30000h -1 The reaction temperature is 150-250 ℃ and the final reaction is carried outThe tail gas is detected on line by using an Antaris IGS gas analyzer to obtain an activity comparison graph of the two catalysts at different temperatures shown in figure 2, the activity of the catalyst of the embodiment 1 is far higher than that of the traditional catalyst within the range of 150-250 ℃, the catalyst of the embodiment 1 has better low-temperature activity and sulfur resistance, and the denitration efficiency of the catalyst of the embodiment 1 can reach more than 90% at about 200 ℃. It can be seen that the activity of the denitration catalyst prepared in example 1 is significantly higher than that of the conventional V-W-Ti commercial catalyst at the same temperature.
(2) Activity test at 150-180 ℃): the denitration catalyst prepared in example 2 and the conventional V-W-Ti commercial catalyst are both made into honeycomb shapes, then a unit with the length of 500mm (the cross section size is 150mm multiplied by 150 mm) and without obvious physical damage is taken as a sample to be tested, two ends of the catalyst sample are wound with high-temperature-resistant ceramic fiber cotton, the catalyst sample is put into a reactor, gaps at two ends of the catalyst are tightly sealed by the ceramic fiber cotton, and reaction gas of 500ppm NO is introduced x 、500ppm NH 3 Air and 500ppm SO x And 5% water vapor, and performing denitration performance test, wherein the reaction test temperature interval is 150-180 ℃, and finally, a denitration efficiency comparison chart of the two catalysts at different temperatures shown in fig. 3 is obtained, so that the denitration efficiency of the denitration catalyst in the embodiment 2 is over 90% at different temperatures, and is obviously higher than that of the conventional V-W-Ti commercial catalyst.
It will be appreciated by persons skilled in the art that the above embodiments are provided for illustration only and not for limitation of the invention, and that variations and modifications of the above described embodiments are intended to fall within the scope of the claims of the invention as long as they fall within the true spirit of the invention.
Claims (9)
1. The denitration catalyst is characterized by comprising a titanium dioxide carrier, and an active component and an auxiliary agent which are loaded on the titanium dioxide carrier;
the active components are distributed on the titanium dioxide carrier in a monodisperse state;
the active component is selected from one or more of vanadium oxide, phosphorus vanadium oxide and cerium oxide;
the auxiliary agent comprises one or more of tungsten oxide, molybdenum oxide, nickel oxide and zirconium oxide,
the specific surface area of the denitration catalyst is 120-150 m 2 /g。
2. The denitration catalyst according to claim 1, wherein the active component accounts for 1 to 20wt% of the weight of the titania carrier; the auxiliary agent accounts for 1-20wt% of the weight of the titanium dioxide carrier.
3. A method for preparing a denitration catalyst according to any one of claims 1 to 2, characterized by comprising the steps of:
s1, dissolving a vanadium source and oxalic acid in deionized water, heating and stirring, and uniformly mixing to obtain a first mixed solution;
s2, adding the auxiliary agent precursor into the first mixed solution, and stirring and uniformly mixing to obtain a second mixed solution; the auxiliary agent precursor comprises one or more of a tungsten source, a molybdenum source, a nickel source and a zirconium source;
s3, adding a phosphorus source into the second mixed solution, and stirring and uniformly mixing to obtain a third mixed solution;
and S4, adding the titanium dioxide carrier into the third mixed solution, stirring and evaporating the titanium dioxide carrier at 60-100 ℃ to obtain an evaporated matter, and roasting the evaporated matter to obtain the denitration catalyst.
4. A method for preparing a denitration catalyst according to claim 3, wherein in step S1:
the vanadium source is selected from one or more of ammonium metavanadate, vanadyl oxalate and vanadyl sulfate; and/or
A cerium source is also added into the first mixed solution, and the cerium source is selected from one or more of cerium nitrate, cerium chloride and cerium sulfate; and/or
In the heating and stirring process, the heating temperature is 70-80 ℃;
in the first mixed solution, the concentration of oxalic acid is 2-4 times of the concentration of vanadium sources.
5. The method for preparing a denitration catalyst according to claim 4, wherein in the step S1:
the concentration of vanadium element in the first mixed solution is 0.001-0.1 mol/L;
when the cerium source is added into the first mixed solution, the concentration of cerium element is 0.001-1.0 mol/L.
6. A method for preparing a denitration catalyst according to claim 3, wherein in step S2:
the tungsten source is selected from one or more of ammonium metatungstate, ammonium paratungstate, sodium tungstate and potassium tungstate; and/or
The molybdenum source is selected from one or more of ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate and ammonium octamolybdate; and/or
The nickel source is selected from one or more of nickel nitrate, nickel acetate or nickel chloride;
the zirconium source is selected from one or more of zirconium nitrate, zirconium oxychloride, zirconium acetate or zirconium sulfate.
7. The method for preparing a denitration catalyst according to claim 6, wherein in the step S2:
when the auxiliary agent precursor contains a tungsten source, the concentration of tungsten element in the second mixed solution is 0.001-1.0 mol/L; and/or
When the auxiliary agent precursor contains a molybdenum source, the concentration of molybdenum element in the second mixed solution is 0.001-1.0 mol/L; and/or
When the auxiliary agent precursor contains a nickel source, the concentration of nickel element in the second mixed solution is 0.001-1.0 mol/L; and/or
When the auxiliary agent precursor contains a zirconium source, the concentration of zirconium element in the second mixed solution is 0.001-1.0 mol/L.
8. A process for preparing a denitration catalyst as claimed in claim 3, wherein,
in the step S3:
the phosphorus source is selected from one or more of phosphoric acid, ammonium phosphate, monoammonium phosphate and diammonium phosphate; and/or
The concentration of the phosphorus element in the third mixed solution is 0.001-0.1 mol/L; and/or
In the step S4: in the roasting process, the roasting temperature is 250-650 ℃ and the roasting time is 2-6 h.
9. The use of a denitration catalyst according to claim 1 or 2 for denitration of flue gas, characterized in that,
at 150-300 ℃ and 5000-150000 h -1 Under the condition of airspeed, the denitration efficiency of the denitration catalyst in nitrogen oxide flue gas is over 95 percent, and N is 2 The selectivity is higher than 95%; and/or
The nitrogen oxide smoke contains 0-3000 mg/m 3 SO of (2) 2 And 5% -20% H 2 Under the condition of O, the denitration efficiency of the denitration catalyst is more than 85 percent, and N is 2 The selectivity is higher than 90%.
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