CN114682247B - Low-temperature denitration catalyst and preparation method and application thereof - Google Patents
Low-temperature denitration catalyst and preparation method and application thereof Download PDFInfo
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- CN114682247B CN114682247B CN202011609561.3A CN202011609561A CN114682247B CN 114682247 B CN114682247 B CN 114682247B CN 202011609561 A CN202011609561 A CN 202011609561A CN 114682247 B CN114682247 B CN 114682247B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 145
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 58
- 239000011593 sulfur Substances 0.000 claims abstract description 45
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 44
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000428 dust Substances 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 62
- 239000000843 powder Substances 0.000 claims description 57
- 238000001035 drying Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 23
- 239000003546 flue gas Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- -1 poly (perfluoroalkyl ethyl acrylate Chemical compound 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229920000058 polyacrylate Polymers 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 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 8
- 239000002253 acid Substances 0.000 claims description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012744 reinforcing agent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 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
- 230000032683 aging Effects 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 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 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000002751 molybdenum Chemical class 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000012688 phosphorus precursor Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 150000003681 vanadium Chemical class 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- 150000003754 zirconium Chemical class 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical group [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010099 solid forming Methods 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 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 compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 238000007580 dry-mixing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
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- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
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- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 2
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
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- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 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 2
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims 1
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
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- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
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- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 5
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 5
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 5
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- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 4
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- 238000010168 coupling process Methods 0.000 description 4
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- PGTMTTGPWLZNQO-UHFFFAOYSA-N 2-dodecyl-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane Chemical compound C(CCCCCCCCCCC)[SiH]1O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O1 PGTMTTGPWLZNQO-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical group C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
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- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 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 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
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- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000196 poly(lauryl methacrylate) Polymers 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
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- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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Abstract
The invention provides a low-temperature denitration catalyst, and a preparation method and application thereof. The catalyst consists of a carrier, an active component, an acidic modulation auxiliary agent, an alkaline modulation auxiliary agent, a redox modulation auxiliary agent and a water-resistant, sulfur-resistant and dust-resistant coating film; based on the mass of the carrier, the active component accounts for 1-30% of the mass of the carrier, the acidic modulation auxiliary agent accounts for 0.01-10% of the mass of the carrier, the alkaline modulation auxiliary agent accounts for 0.01-10% of the mass of the carrier, the redox modulation auxiliary agent accounts for 0.01-20% of the mass of the carrier, and the water-resistant, sulfur-resistant and dust-resistant coating film accounts for 0.01-10% of the mass of the carrier. The invention also provides a preparation method of the catalyst. The denitration catalyst provided by the invention has high water resistance, sulfur resistance and smoke resistance in low-temperature (below 300 ℃) smoke, and is suitable for selective catalytic reduction of nitrogen oxides in low-temperature smoke.
Description
Technical Field
The invention relates to a catalyst and a preparation method thereof, in particular to a low-temperature denitration catalyst and a preparation method thereof, and belongs to the technical field of catalysts.
Background
The low-temperature denitration is a novel technology for treating nitrogen oxides in the flue gas, has the advantage of relatively pure flue gas, and more importantly, greatly reduces the process modification cost, accords with the national conditions of China, and is hopeful to replace the current high-temperature denitration technology. However, the temperature of the low-temperature section is generally reduced to below 300 ℃, and the conventional high-temperature catalyst cannot meet the denitration efficiency at the temperature, so that the catalyst cannot normally operate and a novel low-temperature denitration catalyst is required.
At present, the low-temperature denitration catalyst is still concentrated in the metal oxide catalyst, and the temperature window of the catalyst is widened by adding Mn, fe, ce, V, mo and other elements, so that the low-temperature activity of the catalyst is improved.
For example, elements such as V, mo, nb, sb are added in the method of dipping, rotary evaporation auxiliary dipping and the like of CN106807356A, so that the low-temperature activity of the catalyst is enhanced, but the water resistance and sulfur resistance requirements of the catalyst cannot be obviously met by single or small amount of element modification. For some industrial boilers which are put into coal-fired power plant boilers, glass kiln furnaces and the like, the smoke is impure, and still contains sulfur dioxide, dust and a large amount of water to a certain extent after passing through a desulfurization and dust removal system, SO that most low-temperature catalysts are poisoned, lose activity, and the catalysts are prepared from 5% of water and 500ppm of SO 2 The activity continuously decreases under the conditions. Therefore, a method for finding the water-resistant and sulfur-resistant properties of the low-temperature denitration catalyst is necessary to modify the catalyst according to different working conditions.
CN104056658A is obtained by impregnating 3A molecular sieve with Mn with ethyl orthosilicate or the like 0.1-0.8 Mg 0.2-0.9 O x ，Mn 0.1- 0.8 Mg 0.2-0.9 O x The active component is added with the silicon dioxide component, so that the low-temperature denitration performance of the carbon-based denitration catalyst is improved, the silicon dioxide is only supported on the active component, the supporting method is only suitable for a small amount of powder catalyst by ultrasonic impregnation, the silicon dioxide is not supported on the whole surface of the catalyst, and in addition, the catalyst carrier is a carbon carrier.
CN104525275a adopts a lifting-dipping method to cover polysiloxane on the surface of the SCR denitration catalyst, and the aim is to increase the contact area between the flue gas and the reaction surface of the SCR denitration catalyst, so as to ensure the reduction efficiency of the denitration reaction.
The development difficulty of the low-temperature denitration catalyst is that three points are: firstly, how to have good denitration efficiency at low temperature; second, the flue gas has a certain content of SO 2 And water vapor, SO 2 And O in flue gas 2 H and H 2 The O-bonding produces ammonia bisulfate, which has a dew point temperature of 270 ℃ and a high viscosity, and can adhere soot in the flue gas to the surface of the catalyst to deactivate the catalyst.Third, even if the pre-dedusting treatment is carried out under the condition of low-temperature flue gas, the flue gas still has a certain content of smoke dust (usually still contains 10-30 mg/Nm) 3 Smoke) which may contain some basic metals, alkaline earth metals and heavy metals, which are usually toxic to the denitration catalyst, low temperature denitration catalysts having a certain resistance to smoke poisoning remain an important point.
How to resist SO for denitration catalyst under low temperature flue gas 2 The prior patents and documents mainly focus on modulating active components and carriers of the catalyst, and technical researches and reports on blocking and inhibiting the generation of ammonium bisulfate are not available, on the other hand, the technical reports on how to improve the smoke resistance of the low-temperature denitration catalyst are very rare. The catalyst is comprehensively modulated from the acidity and alkalinity and the oxidation and reduction property, and is combined with the surface property modulation of the catalyst, so that the catalyst can be blocked and inhibited from generating ammonium bisulfate, and the water resistance, sulfur resistance and dust resistance of the low-temperature denitration catalyst can be greatly improved.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a low-temperature denitration (flue gas with the temperature lower than 300 ℃) nitro-catalyst with high water resistance and sulfur resistance and a preparation method thereof.
In order to achieve the technical aim, the invention firstly provides a low-temperature denitration catalyst which consists of a carrier, an active component, an acid modulation auxiliary agent, an alkaline modulation auxiliary agent, a redox modulation auxiliary agent and a water-resistant, sulfur-resistant and dust-resistant coating film; wherein,
based on the mass of the carrier, the active component accounts for 1-30% of the mass of the carrier, the acidic modulation auxiliary agent accounts for 0.01-10% of the mass of the carrier, the alkaline modulation auxiliary agent accounts for 0.01-10% of the mass of the carrier, the redox modulation auxiliary agent accounts for 0.01-20% of the mass of the carrier, and the water-resistant, sulfur-resistant and dust-resistant coating film accounts for 0.01-10% of the mass of the carrier.
The low-temperature denitration catalyst of the invention can exist in the following form: the active components, the acidic modulation auxiliary agent, the alkaline modulation auxiliary agent and the redox modulation auxiliary agent are loaded on a carrier, and the water-resistant, sulfur-resistant and dust-resistant coating film is coated on the outer surface of the catalyst.
The low-temperature denitration catalyst disclosed by the invention has the advantages that the acid-base and oxidation reactivity are modulated by the redox modulation auxiliary agent, the acid modulation auxiliary agent and the alkaline modulation auxiliary agent in a synergistic manner, so that the denitration catalytic activity is improved; the catalyst is modulated by the synergic cooperation of a plurality of auxiliary agents (acid modulation auxiliary agent, alkaline modulation auxiliary agent and redox modulation auxiliary agent), and the water-resistant, sulfur-resistant and dust-resistant coating film is introduced to inhibit the formation of the ammonium sulfate salt, so that the water-resistant, sulfur-resistant and dust-resistant performances of the catalyst are improved. Has wide application prospect in low-temperature flue gas denitration reaction. In addition, the invention discloses that the water-resistant, sulfur-resistant and smoke-resistant film is introduced by the surface modification technology for the first time, so that the smoke-resistant performance of the low-temperature denitration catalyst can be remarkably improved.
In one embodiment of the invention, the carrier employed is titanium dioxide; preferably, the carrier is anatase titanium dioxide, and the specific surface area of the anatase titanium dioxide is 60m 2 /g-200m 2 And/g. The anatase titanium dioxide of this specific surface area contributes to the dispersion of the active ingredient and the dispersion of the inert silica.
In one embodiment of the invention, the active components are molybdenum oxide and vanadium oxide; wherein the mol ratio of molybdenum oxide to vanadium oxide in the active component is 1: (0.1-5).
In one specific embodiment of the invention, the water-resistant, sulfur-resistant and dust-resistant coating film is obtained by coating a solution of a water-resistant, sulfur-resistant and dust-resistant auxiliary agent on the surface of a catalyst; the solute of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent solution is one or a combination of a plurality of fluorine-containing polyacrylate, dimethyl cyclosiloxane and silicone oil.
In one embodiment of the invention, the acidic modulation aid is one or a combination of a plurality of oxides of F, B, br, P; preferably, the molar ratio of F, B, br, P in the acidic modulation aid is (0-10): (0-10): (0-10): (0-5).
In one embodiment of the invention, the alkaline modulation auxiliary agent is one or a combination of a plurality of oxides of Mg, K, ca, al; preferably, the molar ratio of Mg, K, ca, al in the alkaline modulation aid is (0-10): (0-10): (0-10): (0-5);
in one embodiment of the invention, the redox modulation aid is one or a combination of several oxides of Ce, mn and Zr; preferably, the molar ratio of Ce, mn, zr in the redox flow control additive is (0-10): (0-10): (0-10).
In order to achieve the technical aim, the invention also provides a preparation method of the low-temperature denitration catalyst, which comprises the following steps:
dissolving a precursor of an active component, a precursor of an acidic modulation auxiliary agent, a precursor of an alkaline modulation auxiliary agent and a precursor of a redox modulation auxiliary agent in water, adding oxalic acid or citric acid (better dispersing and dissolving the precursors), and stirring and dispersing in a water bath at 25-70 ℃ to form a mixed solution; wherein the mass ratio of oxalic acid or citric acid to the active components is 0.1-3:1, a step of;
adding the carrier into the mixed solution, drying at 60-120 ℃ for 6-24 h, and roasting at 200-700 ℃ for 1-12 h to obtain powder;
the powder is directly or after being molded, the powder or the molded powder is coated in a solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent in a complete soaking mode, the soaking time is 0.01h-24h, and the volume ratio of the powder or the molded powder to the solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent is 1: drying at 110 deg.c for 3 hr and roasting at 200-500 deg.c for 0-12 hr to obtain low temperature denitration catalyst.
The preparation method of the low-temperature denitration catalyst comprises the step of preparing a mixed solution.
In one embodiment of the invention, the precursors of the active components used are molybdenum salt precursors and vanadium salt precursors.
Wherein the molybdenum salt precursor is one or a combination of at least two of ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate and ammonium octamolybdate.
Wherein the vanadium salt precursor is one or a combination of at least two of ammonium metavanadate, vanadyl oxalate and vanadyl sulfate.
In one embodiment of the present invention, the precursor of the acid modulation auxiliary agent is one or a combination of more of fluorine precursor, bromine precursor, boron precursor and phosphorus precursor.
Wherein the fluorine precursor is ammonium fluoride.
Wherein the boron precursor is boric acid or ammonium borate.
Wherein the bromine precursor is ammonium bromide.
Wherein the phosphorus precursor is one or a combination of more of phosphoric acid, monoammonium phosphate and diammonium phosphate.
In one embodiment of the present invention, the precursor of the alkaline modulation auxiliary is one or a combination of a plurality of magnesium salt precursor, potassium salt precursor, calcium salt precursor and aluminum salt precursor.
Wherein the magnesium salt precursor is one or a combination of at least two of magnesium nitrate, magnesium chloride, magnesium sulfate and magnesium acetate.
Wherein the potassium salt precursor is one or a combination of at least two of potassium nitrate, potassium chloride and cobalt sulfate.
Wherein the calcium salt is one or a combination of at least two of calcium nitrate, calcium sulfate and calcium chloride.
Wherein the aluminum salt is one or a combination of at least two of aluminum nitrate, aluminum chloride and aluminum sulfate.
In one embodiment of the present invention, the redox additive precursor is one or more of cerium salt precursor, manganese salt precursor and zirconium salt precursor.
Wherein the cerium salt precursor is one or a combination of at least two of cerium nitrate, cerium sulfate and cerium chloride.
Wherein the manganese salt precursor is one or a combination of at least two of manganese nitrate, manganous sulfate, manganous chloride, manganous acetate and manganous chloride.
Wherein the zirconium salt precursor is one or a combination of at least two of zirconium nitrate, zirconium sulfate, zirconium chloride and zirconium oxychloride.
The preparation method of the low-temperature denitration catalyst comprises the step of loading active components and auxiliary agents on a carrier. Mixing the mixed solution containing the active component and the auxiliary agent with the carrier by adopting an isovolumetric impregnation or an oversubstance impregnation method; wherein, the equal volume impregnation uniformly impregnates the carrier in the mixed solution; the excessive volume impregnation is carried out by immersing the carrier in the mixed solution, then carrying out ultrasonic dispersion for 30min-3h, standing overnight, and then carrying out subsequent treatment.
The precursor of the carrier is immersed into the impregnating solution, the mixed solution is dripped onto the surface of the carrier at a slow speed, the mixture is properly stirred after each dripping until the surface of the carrier is uniform in color, then dripping is continued, and finally the mixed solution and the carrier are uniformly mixed.
In one embodiment of the present invention, the powder molding may be a honeycomb molding process including mud refining, aging, pre-extrusion and extrusion, drying, and baking. The powder forming specifically comprises the following steps:
dry-mixing the powder and the solid forming auxiliary agent, adding the liquid forming auxiliary agent for wet mixing, and adding water for stirring to obtain a material;
fully mixing the materials (in a vacuum pugging machine), and aging for 6-48 hours to obtain a molded blank;
extruding the formed blank into a honeycomb shape to obtain a honeycomb blank;
and drying and calcining the honeycomb molding blank to obtain honeycomb molding powder.
In one embodiment of the present invention, the drying includes two steps, primary drying and secondary drying. Wherein, the primary drying adopts a constant-humidity constant-temperature mode. Wherein the primary drying temperature is 30-70 ℃, the humidity is 10-95%, and the time is 3-10 days. Wherein the temperature of the secondary drying is 70-110 ℃ and the time is 12-48 h.
In one embodiment of the present invention, the solid forming aid and the liquid forming aid employed are selected from the group consisting of reinforcing agents, inorganic binders, organic binders, pore formers and lubricants as a mixture of two or more thereof;
specifically, the content of the reinforcing agent is 10% -50% of the mass of the powder; the reinforcing agent is glass fiber or titanium dioxide.
Specifically, the content of the inorganic binder is 5-15% of the mass of the powder; the inorganic binder is preferably one or a combination of at least two of pseudo-boehmite, nitric acid, water glass and silica sol; preferably, the inorganic binder has a molar ratio of 2 to 10: pseudo-boehmite according to 1 and nitric acid.
Specifically, the content of the organic binder is 1% -5% of the mass of the powder; the organic binder is preferably one or a combination of at least two of polyvinyl alcohol, hydroxypropyl methylcellulose, methylcellulose and polyethylene oxide.
Specifically, the content of the pore-forming agent is 8% -10% of the mass of the powder; the pore-forming agent is preferably activated carbon or sesbania powder.
Specifically, the content of the lubricant is 10% -15% of the mass of the powder; the lubricant is preferably glycerol.
In one embodiment of the invention, the water-resistant, sulfur-resistant and dust-resistant coating film is realized by immersing powder or integrally formed catalyst (including honeycomb and plate type) in a solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent. The solvent adopted by the solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent is one or a combination of more of cyclohexane, n-heptane and ethanol; the solute adopted by the water-resistant, sulfur-resistant and dust-resistant auxiliary agent solution is one or a combination of more of fluorine-containing polyacrylate, dimethyl cyclosiloxane and silicone oil.
Specifically, the fluorine-containing polyacrylate is selected from the group consisting of hexafluorobutyl polyacrylate, hexafluorobutyl polymethacrylate, poly (2, 2-trifluoroethyl methacrylate), poly (dodecyl methacrylate), poly (tridecyl methacrylate), and poly (perfluoroalkyl ethyl acrylate).
Specifically, the dimethylcyclosiloxane is selected from hexamethylcyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, and dodecamethyl cyclohexasiloxane.
Specifically, the silicone oil is selected from methyl hydrogen silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxyl silicone oil, ethyl hydrogen silicone oil, hydroxyl hydrogen silicone oil and methyl silicone oil.
In the invention, one or a combination of a plurality of fluorine-containing polyacrylate, dimethyl cyclosiloxane and silicone oil is used as a water-resistant, sulfur-resistant and dust-resistant auxiliary agent to prepare a coating liquid, and the coating liquid is coated on the catalyst powder or the integrally formed catalyst to form a water-resistant, sulfur-resistant and dust-resistant coating film, so that the stability of the catalyst under the atmosphere of water and sulfur dioxide at the same time is effectively improved; the method can treat various solid catalysts such as particles, honeycombs, plates and the like, and has a wide application range.
The preparation method of the low-temperature denitration catalyst has the advantages that the adopted raw materials are easy to obtain, the preparation process is simple and suitable for industrial amplification, the raw materials required by the coating liquid are easy to obtain, the preparation is simple, the coating liquid is less in one-time coating loss, the coating liquid can be repeatedly used, the cost is low, the preparation method is suitable for industrial amplification production, and conditions are provided for subsequent industrial application.
The low-temperature denitration catalyst of the invention is characterized in that the catalyst is at low temperature<The high water resistance and sulfur resistance and smoke resistance of the 300 ℃ flue gas are realized, and the method is suitable for the selective catalytic reduction of nitrogen oxides in low-temperature flue gas. For example, the catalyst can be used for catalyzing denitration reaction of low-temperature flue gas (flue gas with the temperature lower than 300 ℃), and is particularly suitable for controlling emission of nitrogen oxides of low-temperature flue gas (130 ℃ -300 ℃) of garbage incinerator, glass, steel, coking coke oven, petroleum and petrochemical process heating furnace, kiln in cement industry, alumina clinker kiln and the like. The catalyst has good low-temperature denitration activity by synergistically regulating and controlling the redox and the acid-base, has good low-temperature denitration activity, and can inhibit SO 2 Oxidation to SO 3 The formation of the ammonium sulfate salt is reduced, and the water resistance, sulfur resistance and smoke resistance of the catalyst under a low temperature window are obviously improved.
The low-temperature denitration catalyst has good low-temperature denitration activity by synergistically regulating and controlling the redox and the acid-base, and can inhibit SO 2 Oxidation to SO 3 The formation of the sulfur ammonium salt is reduced, and the water resistance and sulfur resistance of the catalyst are obviously improved at the same time under a low temperature window.
The low-temperature denitration catalyst of the invention has sulfur dioxide and water existing at low temperatureThe activity decrease rate under the condition is obviously slowed down, and the reaction condition is more severe (laboratory simulated NH) 3 :1000ppm，NO x :1000ppm，O 2 :8％，SO 2 :250ppm-1000ppm，H 2 O:20％，N 2 Balance gas at 180 deg.c and 8000 hr volume space velocity -1 -75000h -1 The water resistance and the sulfur resistance of the catalyst can be improved under the condition that the gas flow is 120 mL/min), so that the catalyst is more suitable for industrial application.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The embodiment provides a low-temperature denitration catalyst, which is prepared by the following steps:
0.386g of ammonium metavanadate, 0.368g of ammonium molybdate tetrahydrate, 0.292g of ammonium fluoride, 1.59g of magnesium nitrate hexahydrate and 0.87g of zirconium nitrate pentahydrate are taken and dissolved in 3.5g of deionized water, 0.5g of oxalic acid is added, and the mixture is heated and stirred under the water bath condition of 50 ℃ until the mixture is completely dissolved.
Taking 5g of TiO 2 The (anatase) type carrier is prepared by uniformly adding the impregnating solution to the carrier by adopting an equal volume impregnation method. Standing at room temperature overnight, drying at 110deg.C for 6h, and calcining at 500deg.C for 5h to obtain powder.
Tabletting the powder, crushing and sieving to 20-40 mesh. A40 mL beaker was taken, 5g of hexafluorobutyl polyacrylate and 40g of cyclohexane were added and stirred until well mixed. Placing the powder on an iron wire filter screen with a certain pore, soaking the iron wire filter screen into a hexafluorobutyl polyacrylate solution for 5 hours, taking out the iron wire filter screen, standing the iron wire filter screen at room temperature for 12 hours, drying the iron wire filter screen at 110 ℃ for 3 hours, and roasting the iron wire filter screen at 300 ℃ for 3 hours to obtain the catalyst.
Test method of catalyst performance:
the simulated flue gas composition is NH 3 :1000ppm，NO x :1000ppm，O 2 :8％，SO 2 :500ppm，H 2 O:20％，N 2 Balance gas at 180 deg.C and space velocity of 40000h -1 Gas, gasThe flow rate was 120mL/min.
Example 2
The embodiment provides a low-temperature denitration catalyst, which is prepared by the following steps:
0.193g of ammonium metavanadate, 0.368g of ammonium molybdate tetrahydrate, 0.929g of ammonium dihydrogen phosphate, 1.59g of magnesium nitrate hexahydrate and 0.41g of manganese sulfate are dissolved in 3.5g of deionized water, 1g of oxalic acid is added, and the mixture is heated and stirred under the water bath condition of 60 ℃ until the mixture is completely dissolved. Taking 5G TiO 2 The (anatase) type carrier is prepared by uniformly adding the impregnating solution to the carrier by adopting an equal volume impregnation method. Standing at room temperature overnight, drying at 110deg.C for 12h, and calcining at 400deg.C for 5h to obtain powder.
Tabletting the powder, crushing and sieving to 20-40 mesh. A40 mL beaker was taken, 10g of polytridecyl methacrylate and 20g of cyclohexane were added and stirred until well mixed. Placing the powder on an iron wire filter screen with a certain pore, soaking the iron wire filter screen into a solution of the poly (tridecafluorooctyl methacrylate) for 12 hours, taking out the iron wire filter screen, standing the iron wire filter screen at room temperature for 12 hours, drying the iron wire filter screen at 110 ℃ for 3 hours, and roasting the iron wire filter screen at 300 ℃ for 3 hours. A catalyst was obtained and the catalyst performance test method was as in example 1.
Example 3
The embodiment provides a low-temperature denitration catalyst, which is prepared by the following steps:
0.193g of ammonium metavanadate, 0.491g of ammonium molybdate tetrahydrate, 0.286g of boric acid, 0.107g of potassium nitrate, 0.146g of calcium nitrate, 0.617g of manganese nitrate (50%), 0.631g of cerium nitrate hexahydrate are dissolved in 5g of deionized water, 1.5g of citric acid is added, and the mixture is heated and stirred under the water bath condition of 60 ℃ until the mixture is completely dissolved.
Taking 5g of TiO 2 (anatase) type carrier, the impregnation liquid is mixed with the carrier by an excess volume impregnation method and stirred into uniform slurry. Standing at room temperature overnight, drying at 110deg.C for 12h, and calcining at 450deg.C for 5h to obtain powder.
Tabletting the powder, crushing and sieving to 20-40 mesh. 10g of silicone oil and 40g of n-heptane were added to a 40mL beaker and stirred until uniformly mixed. Placing the powder on an iron wire filter screen with a certain pore, soaking in the coating liquid for 30min, taking out, standing at room temperature for 20min, drying at 110 ℃ for 1h, soaking in the coating liquid again for 30min, repeating the steps twice, and finally drying at 110 ℃ for 3h to obtain the catalyst. The catalyst performance evaluation conditions were as in example 1.
Example 4
The embodiment provides a low-temperature denitration catalyst, which is prepared by the following steps:
0.386g of ammonium metavanadate and 0.368g of ammonium molybdate tetrahydrate are dissolved in 3.5g of deionized water, 0.4g of oxalic acid is added, and the mixture is heated and stirred under the water bath condition of 60 ℃ until the mixture is completely dissolved.
Taking 5g of TiO 2 The (anatase) type carrier is prepared by uniformly adding the impregnating solution on the carrier by adopting an equal volume impregnation method. Standing at room temperature overnight, drying at 110 ℃ for 12h, and roasting at 450 ℃ for 5h to obtain the catalyst powder.
Tabletting the powder, crushing and sieving to 20-40 mesh. A40 mL beaker was taken, 5g of hexamethylcyclotrisiloxane and 30g of cyclohexane were added and stirred until well mixed. Placing the powder on an iron wire filter screen with a certain pore, soaking the iron wire filter screen in the coating liquid for 30min, taking out the iron wire filter screen, standing the iron wire filter screen at room temperature for 10min, and drying the iron wire filter screen at 110 ℃ for 3h to obtain the catalyst.
The catalyst performance evaluation conditions were as in example 1.
Example 5
The embodiment provides a low-temperature denitration catalyst, which is prepared by the following steps:
7.544g of ammonium metavanadate, 8.832g of ammonium molybdate tetrahydrate, 7.01g of ammonium fluoride, 1.47g of ammonium bromide, 22.075g of aluminum nitrate nonahydrate and 9.84g of manganese sulfate are weighed and dissolved in 68g of deionized water, and 4.6g of oxalic acid is added to prepare a uniform solution through water bath stirring at 60 ℃. 100g of TiO is taken 2 The (anatase) type carrier is prepared by uniformly adding the impregnating solution on the carrier by adopting an equal volume impregnation method. Standing at room temperature for one night, drying at 110 ℃ for 12 hours, and roasting in a muffle furnace at 500 ℃ for 5 hours.
100g of powder is weighed and added with 6g of pseudo-boehmite, 32.6g of silica sol and 20g of dilute nitric acid (HNO) 3 10% of mass fraction), 8g of sesbania powder, mechanically mixing, sequentially adding 12.5g of glass fiber and 11.6g of glycerol, mechanically mixing until uniform, aging for 24 hours, and usingThe hydroforming machine extrudes the catalyst into a honeycomb of 18mm diameter. Drying in the shade at room temperature for 24 hours, drying for 6 hours at 60 ℃ and 50% humidity, drying for 6 hours at 120 ℃ and roasting for 12 hours at 500 ℃ to obtain the formed honeycomb catalyst.
The solution of the dodecamethyl cyclohexasiloxane and the cyclohexane is prepared according to the mass ratio of 1:5, and the honeycomb catalyst can be completely immersed. Soaking a certain volume of honeycomb catalyst into a dodecamethyl cyclohexasiloxane solution for 30min, taking out, standing at room temperature for 20min, drying at 110 ℃ for 1h, then soaking into the dodecamethyl cyclohexasiloxane solution again for 30min, taking out, standing for 20min, drying at 110 ℃ for 3h, and roasting at 250 ℃ for 12h to obtain the catalyst.
The simulated flue gas composition of the catalyst reaction was: NH (NH) 3 :1000ppm，NO x :1000ppm，O 2 :8％，SO 2 :250ppm，H 2 O:20％，N 2 Balance gas at 180 deg.C and space velocity of 4000h -1 The gas flow rate was 1.89L/min.
Example 6
The catalyst preparation method is the same as in example 5, taking 15g of the formed honeycomb catalyst, taking 450mg of smoke dust collected in flue gas of a coal-fired boiler, dissolving in 5g of deionized water, fully and uniformly stirring, dropwise adding the mixture to the surface of the honeycomb catalyst by using a dropper, uniformly dropwise adding the mixture to the surface of the honeycomb catalyst, drying the honeycomb catalyst in the shade, drying the dried honeycomb catalyst at 120 ℃ for 6 hours, and roasting the dried honeycomb catalyst at 400 ℃ for 12 hours to obtain the catalyst with the smoke dust on the surface.
Comparative example 1
Preparation of powder referring to example 1, the preparation was not followed by treatment with a solution of hexafluorobutyl polyacrylate. The catalyst performance evaluation conditions were as in example 1.
Comparative example 2
Powder preparation method referring to example 2, the powder was directly evaluated without treatment with a solution of polytridecyl methacrylate. The catalyst performance evaluation conditions were as in example 1.
Comparative example 3
Preparation method of powder catalyst referring to example 5, the preparation was carried out without treatment with a solution of dodecylcyclohexasiloxane, and the catalyst performance evaluation conditions were the same as in example 1.
Comparative example 4
Preparation method of powder catalyst referring to example 1, the acid-base properties of the catalyst were not co-modulated with ammonium fluoride and magnesium nitrate hexahydrate, and other preparation methods were the same as in example 1.
Comparative example 5
Preparation method of powder catalyst referring to example 1, the method of preparing the powder catalyst was the same as in example 1, except that ammonium fluoride and zirconium nitrate were not used to co-modulate the acidity and redox properties of the catalyst.
Comparative example 6
Preparation method of powder catalyst referring to example 1, the acid, alkali and redox properties of the catalyst were not subjected to coupling co-modulation by using ammonium fluoride, magnesium nitrate and zirconium nitrate, and other preparation methods were the same as in example 1.
Comparative example 7
Preparation method of powder catalyst referring to example 5, the preparation method was the same as in example 1 except that ammonium fluoride and aluminum nitrate were not used to adjust the acidity and redox properties of the catalyst.
Comparative example 8
The procedure and method is substantially as in example 6, except that the honeycomb catalyst is prepared without a water-resistant sulfur-resistant smoke-resistant coating, i.e., without treatment with a solution of dodecylcyclohexasiloxane and cyclohexane.
In order to examine the smoke resistance of the catalyst prepared by the invention, smoke dust in the flue gas of a coal-fired boiler is dissolved in water, stirred to form a uniform mixture, then the uniform mixture is dripped on the surface of a formed honeycomb catalyst, and then the honeycomb catalyst is dried and roasted to examine the denitration performance. The result proves that the low-temperature denitration catalyst prepared by the invention has good smoke resistance.
The results of evaluating the catalyst performance are shown in table 1.
TABLE 1 deposition of the catalyst surface sulfur ammonium salt after 100 hours of catalyst reaction
Table 2 examples 5, 6 and comparative example 8 were reacted for 100 hours before NO x Conversion and deposition amount of ammonium sulfate salt
As can be seen from Table 1, the oxidation-reduction property and the acid-base property are used for cooperative regulation and control, and then the water-resistant and sulfur-resistant film is coated on the surface of the catalyst, and the catalyst contains SO at 180 DEG C 2 500mg/Nm 3 In the flue gas with the water vapor content of 20%, the catalysts of the five embodiments not only show excellent conversion rate of nitrogen oxides in the initial reaction>90 percent) and after the reaction is carried out for 100 hours, the conversion rate of the nitrogen oxide is almost unchanged, and is maintained above 90 percent, which shows excellent catalyst stability, and the deposited sulfur ammonium salt on the surface of the catalyst is 0.010 to 0.018 percent. In comparison with examples 1, 2 and 3, comparative examples 1, 2 and 3 were not coated with a water-repellent sulfur-resistant film on the catalyst surface, and although there was no difference in the conversion of nitrogen oxides at the time of the initial reaction, the conversion of nitrogen oxides was reduced from 90% or more to about 60% and the conversion of nitrogen oxides was reduced by about 30% after 100 hours of reaction, and in addition, the deposition of a sulfur ammonium salt on the catalyst surface was significantly increased from 0.010% to 0.016% to 0.061% to 0.083%. The adoption of the water-resistant and sulfur-resistant film can improve the low-temperature water-resistant and sulfur-resistant performance of the catalyst.
As can be seen from Table 1, the conversion of nitrogen oxides at the beginning of the reaction was reduced (82% -87%) and the conversion of nitrogen oxides was further significantly reduced (62% -67%) after 100 hours of reaction time, as well as the ammonium sulfate salt, as in comparative example 4, comparative example 5, comparative example 6 and comparative example 7, were not subjected to the coupling modulation of oxidation reactivity and acidity-basicity. This demonstrates that the redox and acid-base coupling modulation is adopted, and the catalyst has good inhibition effect on the production of the surface sulfur ammonium salt of the catalyst. The method adopts the coupling modulation of oxidation reactivity and acid-base property, and carries out water-resistant and sulfur-resistant film treatment on the surface of the catalyst, thus having key effects on improving the activity of the catalyst and keeping good stability.
As can be seen from Table 2, the catalyst activity of example 6 after soot impregnation is comparable to the activity of example 5 catalyst not poisoned by soot, NO x The conversion rate of (2) was only 5%, the NOx activity was also only 7% after 100 hours of reaction, the deposition amounts of the ammonium sulfate salt on the surfaces of example 5 and example 6 were not much different, and were less than 0.02%, which revealed that the catalyst of example 6 had good water-sulfur resistance and smoke resistance and good stability. In contrast, comparative example 8, which did not employ a water-and sulfur-resistant smoke-resistant protective film, had 89% NO at the initial activity of the reaction x Conversion, but after 100 hours of reaction, NO x The conversion is significantly reduced and the amount of deposition of the ammonium sulfate salt is also significantly increased.
Claims (26)
1. The low temperature denitration catalyst consists of a carrier, an active component, an acidic modulation auxiliary agent, an alkaline modulation auxiliary agent, a redox modulation auxiliary agent and a water-resistant, sulfur-resistant and dust-resistant coating film; wherein,
taking the mass of the carrier as a reference, the active component accounts for 1-30% of the mass of the carrier, the acidic modulation auxiliary accounts for 0.01-10% of the mass of the carrier, the alkaline modulation auxiliary accounts for 0.01-10% of the mass of the carrier, the redox modulation auxiliary accounts for 0.01-20% of the mass of the carrier, and the water-resistant, sulfur-resistant and dust-resistant coating film accounts for 0.01-10% of the mass of the carrier; wherein:
the active components are molybdenum oxide and vanadium oxide;
the acid modulation auxiliary agent is one or a combination of a plurality of oxides of F, B, br, P;
the alkaline modulation auxiliary agent is one or a combination of a plurality of oxides of Mg, K, ca, al;
the redox modulation auxiliary agent is one or a combination of more of oxides of Ce, mn and Zr;
the catalyst is a particle, honeycomb or plate catalyst;
the water-resistant, sulfur-resistant and dust-resistant coating film is obtained by coating a solution of a water-resistant, sulfur-resistant and dust-resistant auxiliary agent on a carrier; the solute of the solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent is fluorine-containing polyacrylate; the fluorine-containing polyacrylate is selected from the group consisting of poly (hexafluorobutyl acrylate), poly (hexafluorobutyl methacrylate), poly (2, 2-trifluoroethyl methacrylate), poly (dodecafluoroheptyl acrylate), poly (tridecyl methacrylate) and poly (perfluoroalkyl ethyl acrylate).
2. The low temperature denitration catalyst according to claim 1, wherein the carrier is titanium dioxide.
3. The low-temperature denitration catalyst according to claim 2, wherein the carrier is anatase titania, and the specific surface area of the anatase titania is 60m 2 /g-200m 2 /g。
4. The low temperature denitration catalyst according to claim 1, wherein the molar ratio of molybdenum oxide to vanadium oxide is 1: (0.1-5).
5. The low temperature denitration catalyst according to claim 1, wherein the molar ratio of F, B, br, P in the acidic modulation auxiliary is (0.01 to 10): (0.01-10): (0.01-10): (0.01-5).
6. The low temperature denitration catalyst according to claim 1, wherein the molar ratio of Mg, K, ca, al in the basic modulation auxiliary agent is (0.01 to 10): (0.01-10): (0.01-10): (0.01-5).
7. The low-temperature denitration catalyst according to claim 1, wherein the molar ratio of Ce, mn, zr in the redox modulation auxiliary is (0.01 to 10): (0.01-10): (0.01-10).
8. A method for preparing the low temperature denitration catalyst as claimed in any one of claims 1 to 7, which comprises the steps of:
dissolving a precursor of an active component, a precursor of an acidic modulation auxiliary agent, a precursor of an alkaline modulation auxiliary agent and a precursor of a redox modulation auxiliary agent in water, adding oxalic acid or citric acid, and stirring and dispersing in a water bath at 25-70 ℃ to form a mixed solution; wherein the mass ratio of oxalic acid or citric acid to the active components is 0.1-3:1, a step of;
adding a carrier into the mixed solution, drying at 60-120 ℃ for 6-24 h, and roasting at 200-700 ℃ for 1-12 h to obtain powder;
the powder is directly or after being molded, the powder or the molded powder is coated in a solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent in a complete soaking mode, the soaking time is 0.01h-24h, and the volume ratio of the powder or the molded powder to the solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent is 1: drying at 110 ℃ for 3h and roasting at 200-500 ℃ for 3h-12h to obtain the low-temperature denitration catalyst.
9. The preparation method of claim 8, wherein the precursors of the active component are a molybdenum salt precursor and a vanadium salt precursor;
the molybdenum salt precursor is one or a combination of at least two of ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate and ammonium octamolybdate; the vanadium salt precursor is one or a combination of at least two of ammonium metavanadate, vanadyl oxalate and vanadyl sulfate.
10. The preparation method of claim 8, wherein the precursor of the acid modulation auxiliary is one or a combination of a plurality of fluorine precursors, bromine precursors, boron precursors and phosphorus precursors.
11. The method of preparation of claim 10, wherein the fluorine precursor is ammonium fluoride; the boron precursor is boric acid or ammonium borate; the bromine precursor is ammonium bromide; the phosphorus precursor is one or a combination of more of phosphoric acid, monoammonium phosphate and diammonium phosphate.
12. The preparation method of claim 8, wherein the precursor of the alkaline modulation auxiliary agent is one or a combination of a plurality of magnesium salt precursors, potassium salt precursors, calcium salt precursors and aluminum salt precursors.
13. The method of preparation of claim 12, wherein the magnesium salt precursor is one or a combination of at least two of magnesium nitrate, magnesium chloride, magnesium sulfate, and magnesium acetate; the potassium salt precursor is one or the combination of two of potassium nitrate and potassium chloride; the calcium salt is one or a combination of at least two of calcium nitrate, calcium sulfate and calcium chloride; the aluminum salt is one or a combination of at least two of aluminum nitrate, aluminum chloride and aluminum sulfate.
14. The preparation method of claim 8, wherein the precursor of the redox modulation auxiliary is one or a combination of several of cerium salt precursor, manganese salt precursor and zirconium salt precursor.
15. The preparation method according to claim 14, wherein the cerium salt precursor is one or a combination of at least two of cerium nitrate, cerium sulfate and cerium chloride; the manganese salt precursor is one or a combination of at least two of manganese nitrate, manganous sulfate, manganous chloride, manganous acetate and manganous chloride; the zirconium salt precursor is one or a combination of at least two of zirconium nitrate, zirconium sulfate, zirconium chloride and zirconium oxychloride.
16. The preparation method of claim 8, wherein the water-resistant, sulfur-resistant and dust-resistant auxiliary agent has a solute mass content of 0.5% -80%;
the solvent adopted by the solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent is cyclohexane, n-heptane or ethanol.
17. The production method according to claim 8, wherein the powder molding comprises the steps of:
dry-mixing the powder and the solid forming auxiliary agent, adding the liquid forming auxiliary agent for wet mixing, and adding water for stirring to obtain a material;
fully mixing the materials, and aging for 6-48 hours to obtain a molded blank;
extruding the formed blank body into a honeycomb shape to obtain a honeycomb blank body;
and drying and calcining the honeycomb molding blank to obtain honeycomb molding powder.
18. The production method according to claim 17, wherein the drying comprises two steps of primary drying and secondary drying; the primary drying temperature is 30-70 ℃, the humidity is 10-95%, and the time is 3-10 days; the temperature of the secondary drying is 70-110 ℃ and the time is 12-48 h.
19. The production method according to claim 17, wherein the solid molding aid and the liquid molding aid are selected from a mixture of two or more of a reinforcing agent, an inorganic binder, an organic binder, a pore-forming agent, and a lubricant.
20. The preparation method of claim 19, wherein the content of the reinforcing agent is 10% -50% of the mass of the powder; the reinforcing agent is glass fiber or titanium dioxide.
21. The preparation method of claim 19, wherein the content of the inorganic binder is 5% -15% of the mass of the powder; the inorganic binder is one or a combination of at least two of pseudo-boehmite, nitric acid, water glass and silica sol.
22. The preparation method of claim 19, wherein the content of the organic binder is 1% -5% of the mass of the powder; the organic binder is one or a combination of at least two of polyvinyl alcohol, hydroxypropyl methyl cellulose, methyl cellulose and polyethylene oxide.
23. The preparation method of claim 19, wherein the content of the pore-forming agent is 8% -10% of the mass of the powder; the pore-forming agent is activated carbon or sesbania powder.
24. The preparation method of claim 19, wherein the content of the lubricant is 10% -15% of the mass of the powder; the lubricant is glycerol.
25. Use of a low temperature denitration catalyst as claimed in any one of claims 1 to 7, which is suitable for the selective catalytic reduction of nitrogen oxides in low temperature flue gas.
26. The use of claim 25, wherein the low temperature denitration catalyst is suitable for nitrogen oxide emission control of low temperature flue gas of garbage incinerators, glass, steel, coker ovens, petrochemical process heating ovens, cement industry kilns, and alumina clinker kilns.
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