CN108722477B - Anti-alkalosis efficient denitration catalyst and preparation method and application thereof - Google Patents
Anti-alkalosis efficient denitration catalyst and preparation method and application thereof Download PDFInfo
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- CN108722477B CN108722477B CN201810573766.7A CN201810573766A CN108722477B CN 108722477 B CN108722477 B CN 108722477B CN 201810573766 A CN201810573766 A CN 201810573766A CN 108722477 B CN108722477 B CN 108722477B
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- drying
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 208000005223 Alkalosis Diseases 0.000 title claims description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000000607 poisoning effect Effects 0.000 claims abstract description 22
- 239000010936 titanium Substances 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 231100000572 poisoning Toxicity 0.000 claims abstract description 20
- 239000004568 cement Substances 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000010955 niobium Substances 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 239000010937 tungsten Substances 0.000 claims abstract description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims abstract description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 4
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 4
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 86
- 239000000243 solution Substances 0.000 claims description 65
- 238000001035 drying Methods 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000011068 loading method Methods 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000002390 rotary evaporation Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000003929 acidic solution Substances 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 11
- 150000000703 Cerium Chemical class 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 238000000643 oven drying Methods 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 150000002751 molybdenum Chemical class 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 150000002821 niobium Chemical class 0.000 claims description 6
- 150000003657 tungsten Chemical class 0.000 claims description 6
- 150000003681 vanadium Chemical class 0.000 claims description 6
- 150000003754 zirconium Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical group Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical group Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229960001759 cerium oxalate Drugs 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 159000000014 iron salts Chemical class 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 13
- 150000001340 alkali metals Chemical class 0.000 abstract description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 9
- 239000000428 dust Substances 0.000 abstract description 9
- 206010027439 Metal poisoning Diseases 0.000 abstract description 8
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003546 flue gas Substances 0.000 abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000000306 component Substances 0.000 abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 10
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- 239000000377 silicon dioxide Substances 0.000 description 9
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- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 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 description 2
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- 238000000227 grinding Methods 0.000 description 2
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- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
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Abstract
本发明提供了一种抗碱中毒高效脱硝催化剂的制备方法及其应用。本发明的催化剂以钛掺杂的介孔分子筛为载体，以钒、铈、锆、铌、锰为活性组分，以钨、钼、铁、铜为助剂；其中，以钛掺杂的介孔分子筛中Si元素质量为基准，掺杂元素钛的含量为15％～35％；以钛掺杂介孔分子筛载体质量为基准，活性组分钒、铈、锆、铌和锰氧化物质量百分含量为1％～5％，助剂钨、钼、铁和铜氧化物质量百分含量为1％～15％。本发明的催化剂在300℃～400℃范围具有高于90％的NOx转化率，最高活性达到99.7％；具有更强的抗碱金属、碱土金属中毒能力，特别适用于水泥窑炉高粉尘、高碱金属和高碱土金属烟气中NOx的脱除。
The invention provides a preparation method and application of a high-efficiency denitration catalyst against alkali poisoning. The catalyst of the invention uses titanium-doped mesoporous molecular sieve as carrier, vanadium, cerium, zirconium, niobium and manganese as active components, and tungsten, molybdenum, iron and copper as auxiliary agents; Based on the mass of Si element in the porous molecular sieve, the content of titanium doping element is 15% to 35%; based on the mass of the titanium-doped mesoporous molecular sieve carrier, the mass of active components vanadium, cerium, zirconium, niobium and manganese oxides is 100%. The content of the components is 1% to 5%, and the mass percentage content of the auxiliary tungsten, molybdenum, iron and copper oxides is 1% to 15%. The catalyst of the invention has a NOx conversion rate higher than 90% in the range of 300°C to 400°C, and the highest activity reaches 99.7%; it has stronger resistance to alkali metal and alkaline earth metal poisoning, and is especially suitable for cement kilns with high dust, Removal of NOx from overalkali metal and overalkali earth metal flue gas.
Description
Technical Field
The invention belongs to the technical field of catalysts, relates to an anti-alkali poisoning efficient denitration catalyst, and a preparation method and application thereof, and particularly relates to an anti-alkali poisoning efficient denitration catalyst taking a titanium-doped mesoporous molecular sieve as a carrier, and a preparation method and application thereof.
Background
China is the country with the largest cement production and use amount (accounting for more than 50% of the total amount all over the world) in the world, the cement yield is 23.16 hundred million tons in 2017, nitrogen oxides are discharged by the national cement industry about 200 million tons, the nitrogen oxides account for about 10% of the national nitrogen oxide discharge amount, and the cement industry occupies the third position after thermal power generation and automobile exhaust discharge.
The latest emission standard of atmospheric pollutants for cement industry (GB4915-2013) regulates the emission concentration from the original 800mg/Nm3Down to 400mg/Nm3(300 mg/Nm in the area of interest)3) The standards of some regions are more strict, and the environmental protection hall of Jiangsu province in 2017 is about developing NO industry in the whole province and non-electricity industryxThe notification of deep emission reduction requires NO before 2019, 6 months and 1 day in the cement industryxEmission not higher than 100mg/Nm3NO of cement industryxControl is imminent.
The Selective Catalytic Reduction (SCR) technology is used for removing Nitrogen Oxides (NO) in the smoke discharged by a fixed sourcex) An effective means of (1). The cement kiln tail flue gas has the characteristics of high dust content and high alkali metal and alkaline earth metal content, on one hand, the high dust easily causes the pore channel blockage of the SCR denitration catalyst, and on the other hand, the high alkali metal and alkaline earth metal content easily causes the alkali (earth) metal poisoning of the catalyst, so that the catalyst is finally inactivated, the service life of the catalyst is reduced, the operation cost of a system is increased, and the SCR denitration efficiency is reduced.
In order to solve the problem, CN107983354A discloses a preparation method of an alkali poisoning resistant copper-based spinel low-temperature denitration catalyst, which comprises the following steps: dissolving copper salt and metal salt in distilled water, stirring for 2-10 h at 30-80 ℃, slowly adding a mixed acid solution while stirring, wherein the ratio of the copper salt, the metal salt, the distilled water and the mixed acid solution is 0.025-0.4 mol: 0.1 mol: 240mL of: 300-700 mL; step two, putting the solution obtained after the reaction in the step one into an oven, drying for 5-10 hours at 50-100 ℃ to obtain a dried solid, grinding the dried solid, and sieving the ground solid with a sieve of 80-400 meshes; calcining the solid treated in the step two for 2-12 hours under the condition of oxygen-enriched atmosphere, uniformly grinding the obtained solid, and sieving the solid by a sieve of 150-400 meshes; and step four, calcining the solid obtained in the step three for 0.5-2 hours at 400-700 ℃ under the protection of reducing atmosphere, thus obtaining the catalyst. The catalyst prepared by the method has good alkali metal poisoning resistance, the NO removal rate of the prepared potassium poisoning catalyst at 180 ℃ reaches 74%, and the NO removal rate at 120-200 ℃ reaches more than 65%, but the preparation process is complex, the raw materials are expensive, and the catalyst is not suitable for large-scale industrial application.
CN103230813A discloses a preparation method of an alkali poisoning resistant denitration catalyst suitable for cement kilns, which comprises the following preparation steps: adding manganese salt, cerium salt and an auxiliary agent into a titanium source solution, stirring to obtain a mixed solution, sequentially adding a urea solution, ammonia water and hydrogen peroxide into the mixed solution until no precipitate is generated, continuously stirring for 1-5 hours, then sequentially using distilled water and absolute ethyl alcohol for centrifugal washing, drying for 8-24 hours at 70-105 ℃, calcining for 2-6 hours at 450-650 ℃, and preparing into a 40-60-mesh catalyst; wherein, the temperature of the water bath is kept at 65-95 ℃ when the urea solution is added, and the manganese salt is any one of manganese acetate, manganese nitrate, manganese sulfate and manganese chloride in the preparation process of the catalyst; the cerium salt is any one of cerous chloride, cerium nitrate, ammonium ceric nitrate or cerium sulfate; the titanium source solution is any one of titanyl sulfate, titanium sulfate and butyl titanate; the added auxiliary agent is any one of ferric nitrate, cupric nitrate, nickel nitrate and chromium nitrate. The catalyst is prepared by adopting a coprecipitation method, but the utilization rate of active sites is not high, and the highest catalytic efficiency is only 99%.
CN103263913A discloses a preparation method of a high specific surface anti-alkali poisoning denitration catalyst suitable for a cement kiln, which is characterized by comprising the following preparation steps: mixing a titanium source solution with SiO2Uniformly mixing the sol, adding manganese salt, cerium salt and an auxiliary agent, continuously stirring to obtain a mixed solution, sequentially adding a urea solution, ammonia water and hydrogen peroxide into the mixed solution until no precipitate is generated, continuously stirring for 1-3 hours, then sequentially using distilled water and absolute ethyl alcohol for centrifugal washing, and performing centrifugal washing at 75 ℃Drying at 110 ℃ for 6-24 hours, calcining at 450-650 ℃ for 2-6 hours, and preparing into a catalyst with 40-60 meshes; wherein, the temperature of the water bath is kept at 65-95 ℃ when the urea solution is added, and the manganese salt is any one of manganese acetate, manganese nitrate, manganese sulfate and manganese chloride in the preparation process of the catalyst; the cerium salt is any one of cerous chloride, cerium nitrate, ammonium ceric nitrate or cerium sulfate; the titanium source solution is any one of titanyl sulfate, titanium sulfate and butyl titanate; the added auxiliary agent is any one of ferric nitrate, cupric nitrate, nickel nitrate and chromium nitrate; the SiO2The sol is self-made SiO2Sol or 30 wt% silica sol; self-made SiO2The sol is prepared from ethyl orthosilicate, ethanol and water according to a volume ratio of 1: 2-5: 4-8; the molar ratio of Si to Ti is 0.08-0.5: 1, the catalyst is prepared by a coprecipitation method, but the utilization rate of active sites is not high, and the highest catalytic efficiency is only 98%.
In the research of the SCR denitration catalyst in the cement industry, the alkali metal poisoning resistance of the catalyst is improved, the pore channel blockage of the catalyst is avoided according to the characteristic of high dust of the cement kiln tail flue gas, and the service life of the catalyst is prolonged, so that the alkali metal poisoning resistant efficient denitration catalyst aiming at the working condition that the cement kiln flue gas has high dust content and is rich in alkali metal and alkaline earth metal is necessary to be developed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an anti-alkali poisoning efficient denitration catalyst which has excellent pore channel blockage resistance and alkali poisoning resistance, particularly has high denitration efficiency and low cost on cement kiln smoke with high dust content and rich alkali metal and alkaline earth metal, is simple in process, is environment-friendly and does not cause secondary pollution.
In order to achieve the purpose, the invention adopts the following technical scheme:
an anti-alkali poisoning efficient denitration catalyst takes a titanium-doped mesoporous molecular sieve as a carrier, vanadium, cerium, zirconium, niobium and manganese as active components, and tungsten, molybdenum, iron and copper as auxiliaries; wherein, the content of the doping element titanium is 15 to 35 percent based on the mass of Si element in the titanium-doped mesoporous molecular sieve; based on the mass of the titanium-doped mesoporous molecular sieve carrier, the mass percentage of the oxides of vanadium, cerium, zirconium, niobium and manganese as active components is 1-5%, and the mass percentage of the oxides of tungsten, molybdenum, iron and copper as auxiliary agents is 1-15%.
The anti-alkalosis high-efficiency denitration catalyst is prepared by taking a titanium-doped mesoporous molecular sieve as a carrier, vanadium, cerium, zirconium, niobium and manganese as active components and tungsten, molybdenum, iron and copper as auxiliaries and adopting an impregnation method. Compared with the traditional V-W-Ti catalyst, the titanium-doped mesoporous molecular sieve carrier not only keeps the synergistic effect of titanium dioxide in an SCR denitration system, but also can improve the firmness of the active component and auxiliary agent load by utilizing the characteristic of strong adsorption capacity of the molecular sieve, and can strengthen the reaction of reactants on the surface of the catalyst and improve the catalytic efficiency; the catalyst has larger mesoporous size and higher specific surface area, and can better avoid the blockage of catalyst pore channels. The main component of the silicon dioxide of the carrier has stable chemical property, does not react with common acid, is beneficial to acid cleaning regeneration after the catalyst is subjected to alkali poisoning, and prolongs the service life.
Wherein, the content of the doping element titanium is 15 to 35 percent based on the mass of Si element in the titanium doped mesoporous molecular sieve, for example, the content of the doping element titanium is 15 percent, 16 percent, 17 percent, 18 percent, 19 percent, 20 percent, 21 percent, 22 percent, 23 percent, 24 percent, 25 percent, 26 percent, 27 percent, 28 percent, 29 percent, 30 percent, 31 percent, 32 percent, 33 percent, 34 percent and 35 percent; based on the mass of the titanium-doped mesoporous molecular sieve carrier, the mass percentage of the active components vanadium, cerium, zirconium, niobium and manganese oxide is 1-5%, for example, the mass percentage of vanadium, cerium, zirconium, niobium and manganese oxide is 1%, 2%, 3%, 4% and 5%; the mass percentage of the tungsten, molybdenum, iron and copper oxides as the auxiliary agents is 1-15%, for example, the mass percentage of the tungsten, molybdenum, iron and copper oxides is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% and 15%.
Wherein the molar ratio of V/Ce/Zr/Nb/Mn in the active component is 1 (0.1-10): 0.1-5): 0.1-10.
Wherein the molar ratio of W/Mo/Fe/Cu elements in the additive is 1 (0.1-10): 0.1-5.
The invention also aims to provide a preparation method of the anti-alkali poisoning efficient denitration catalyst, which comprises the following steps:
1) preparing a solution containing a template agent
Dissolving P123 in deionized water, stirring to be homogeneous, adding HCl, and stirring uniformly to obtain a mixed solution;
2) preparation of titanium doped mesoporous molecular sieve carrier
Premixing butyl titanate and tetraethyl silicate to obtain a mixed solution, dropwise adding the mixed solution into the mixed solution obtained in the step 1) under vigorous stirring, continuously stirring to form a gel-like liquid, transferring the gel-like liquid into a self-generated pressure reaction kettle with a polytetrafluoroethylene lining, standing, taking out, carrying out suction filtration, washing, drying, and carrying out air roasting in a muffle furnace to obtain a titanium-doped mesoporous molecular sieve carrier;
3) loading of catalytic promoter
Weighing one or more of soluble tungsten salt, molybdenum salt, ferric salt and cupric salt, dissolving in clean water or acidic solution, and stirring to obtain stable solution; dipping the catalyst carrier obtained in the step 2) into a stable solution, stirring, drying, and roasting in a muffle furnace to obtain a catalyst precursor;
4) loading of catalyst active components
Weighing one or more of soluble vanadium salt, cerium salt, zirconium salt, niobium salt and manganese salt, dissolving in clean water or acidic solution, and stirring to obtain stable solution; dipping the catalyst precursor obtained in the step 3) into a stable solution, stirring, drying, and roasting in a muffle furnace to obtain the anti-alkalosis high-efficiency denitration catalyst.
In the step 1), the molar concentration of the added HCl is 0.1-0.3 mol/L, for example, the molar concentration of the added HCl is 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3 mol/L.
In the step 1), P123 serving as a template agent is a triblock copolymer which is fully called polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and the molecular formula of the triblock copolymer is PEO-PPO-PEO; preferably, the mass of the HCl is 15 to 20 times of the mass of the P123, for example, the mass of the HCl is 15 times, 16 times, 17 times, 18 times, 19 times, or 20 times of the mass of the P123.
Preferably, in the step 1), the stirring temperature of the P123 dissolved in the deionized water is 20 to 30 ℃, for example, the stirring temperature is 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ and 30 ℃; the stirring temperature after the addition of hydrochloric acid is 30 to 50 ℃, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃ and 50 ℃.
In the step 2), the mass of the tetraethyl silicate is 2 to 3 times of the mass of the P123, for example, the mass of the tetraethyl silicate is 2 times, 2.1 times, 2.2 times, 2.3 times, 2.4 times, 2.5 times, 2.6 times, 2.7 times, 2.8 times, 2.9 times, 3 times of the mass of the P123; the addition amount of the butyl titanate and the tetraethyl silicate is 15-35% by mass of Ti/Si, for example, the addition amount of the butyl titanate and the tetraethyl silicate is 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35% by mass of Ti/Si.
Preferably, in the step 2), the temperature for forming the gel liquid by stirring is 30-50 ℃, for example, the temperature is 30 ℃, 35 ℃, 40 ℃, 45 ℃ and 50 ℃; the stirring time is 10-20 h, for example, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h and 20 h.
Preferably, in the step 2), the standing temperature is 90-110 ℃, for example, the standing temperature is 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃; the standing time is 20-40 h, for example, the standing time is 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h and 40 h.
Preferably, in the step 2), the roasting temperature is 500-600 ℃, for example, the roasting temperature is 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃ and 600 ℃; the roasting time is 2-8 h, for example, the roasting time is 2h, 3h, 4h, 5h, 6h, 7h and 8 h; the temperature rising speed is 1-5 ℃/min, for example, the temperature rising speed is 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min and 5 ℃/min.
In the step 3), the soluble tungsten salt is ammonium tungstate, ammonium paratungstate or ammonium metatungstate; the molybdenum salt is ammonium molybdate; the ferric salt is ferric nitrate, ferric chloride or ferric sulfate; the copper salt is copper chloride, copper nitrate or copper acetate.
Preferably, in step 3), the stirring temperature after dipping is 20 to 30 ℃, for example, the stirring temperature is 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ and 30 ℃; the stirring time is 20-40 h, for example, the stirring time is 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, and 40 h.
Preferably, in the step 3), the drying is spin-drying and then oven-drying.
Preferably, in the step 3), the temperature of the oven drying is 100-120 ℃, for example, the temperature of the oven drying is 100 ℃, 105 ℃, 110 ℃, 115 ℃ and 120 ℃; the drying time of the oven is 10-20 h, for example, the drying time of the oven is 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h and 20 h.
Preferably, in the step 3), the roasting temperature is 500-600 ℃, for example, the roasting temperature is 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃ and 600 ℃; the roasting time is 2-8 h, for example, the roasting time is 2h, 3h, 4h, 5h, 6h, 7h and 8 h; the temperature rising speed is 1-5 ℃/min, for example, the temperature rising speed is 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min and 5 ℃/min.
In the step 4), the soluble vanadium salt is ammonium metavanadate; the cerium salt is cerous nitrate, cerous oxalate, cerous carbonate or cerous chloride; the zirconium salt is zirconium oxychloride; the niobium salt is niobium pentachloride or niobium oxalate; the manganese salt is manganese nitrate.
Preferably, in step 4), the stirring temperature after dipping is 20 to 30 ℃, for example, the stirring temperature is 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ and 30 ℃; the stirring time is 20-40 h, for example, the stirring time is 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, and 40 h.
Preferably, in the step 4), the drying is spin-drying and then oven-drying.
Preferably, in the step 4), the temperature of the oven drying is 100-120 ℃, for example, the temperature of the oven drying is 100 ℃, 105 ℃, 110 ℃, 115 ℃ and 120 ℃; the drying time of the oven is 10-20 h, for example, the drying time of the oven is 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h and 20 h.
Preferably, in the step 4), the roasting temperature is 500-600 ℃, for example, the roasting temperature is 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃ and 600 ℃; the roasting time is 2-8 h, for example, the roasting time is 2h, 3h, 4h, 5h, 6h, 7h and 8 h; the temperature rising speed is 1-5 ℃/min, for example, the temperature rising speed is 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min and 5 ℃/min.
Preferably, the acidic solution in step 3) and step 4) is nitric acid, sulfuric acid or hydrochloric acid.
Preferably, the acidic solution has a mass concentration of 5% to 15%, for example, a mass concentration of 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%.
As a preferable scheme of the invention, the preparation method of the alkali poisoning resistant efficient denitration catalyst comprises the following steps:
1) preparing a solution containing a template agent
Dissolving P123 in deionized water, and stirring at 25 ℃ to be homogeneous; adding HCl with the mass concentration of 0.2mol/L, and fully stirring for 1-4 h at 40 ℃ to obtain a mixed solution;
2) preparation of titanium doped mesoporous molecular sieve carrier
Premixing butyl titanate and tetraethyl silicate to obtain a mixed solution, dropwise adding the mixed solution into the mixed solution obtained in the step 1) under vigorous stirring, and continuously stirring for 10-20 hours at 40 ℃; then transferring the formed gel liquid into a self-generated pressure reaction kettle with a polytetrafluoroethylene lining, standing for 20-40 h at 100 ℃, taking out, carrying out suction filtration, washing with deionized water to be neutral, and drying at room temperature; roasting the mixture for 2 to 8 hours at 550 ℃ in air by using a muffle furnace, wherein the heating rate is 1 to 5 ℃/min; obtaining the titanium-doped mesoporous molecular sieve carrier;
3) loading of catalytic promoter
Weighing one or more of soluble tungsten salt, molybdenum salt, ferric salt and cupric salt, dissolving in clean water or acidic solution, and stirring to obtain stable solution; dipping the catalyst carrier obtained in the step 2) into the solution, stirring at room temperature for 20-40 h, then carrying out rotary evaporation drying, drying at 110 ℃ for 10-20 h by using an oven, and roasting at 550 ℃ by using a muffle furnace for 2-8 h in air at the heating rate of 1-5 ℃/min; obtaining a catalyst precursor;
4) loading of catalyst active components
Weighing one or more of soluble vanadium salt, cerium salt, zirconium salt, niobium salt and manganese salt, dissolving in clean water or acidic solution, and stirring to obtain stable solution; dipping the catalyst precursor obtained in the step 3) into the solution, stirring at room temperature for 20-40 h, then carrying out rotary evaporation drying, drying at 110 ℃ for 10-20 h by using an oven, and roasting at 550 ℃ by using a muffle furnace for 2-8 h in air at the heating rate of 1-5 ℃/min; and obtaining the anti-alkalosis high-efficiency denitration catalyst.
The invention also aims to provide application of the alkali poisoning resistant efficient denitration catalyst, and the alkali poisoning resistant efficient denitration catalyst is used for SCR denitration of cement kiln tail flue gas.
Compared with the prior art, the invention has the beneficial effects that:
(1) the anti-alkalosis efficient denitration catalyst disclosed by the invention has efficient medium-temperature SCR denitration activity at the temperature of 300-400 ℃, and the denitration efficiency is higher than 90%; the components of the catalyst system are environment-friendly.
(2) Compared with commercial vanadium-titanium system denitration catalysts, the alkali poisoning resistant efficient denitration catalyst has stronger alkali metal and alkaline earth metal poisoning resistance, and has the K value2When the load amounts of O and CaO reach certain amounts, the K/V molar ratio and the Ca/V molar ratio are respectively 1.0, the catalyst still keeps higher activity, and the denitration efficiency is still more than 85 percent within the temperature range of 330-400 ℃.
(3) The anti-alkalosis high-efficiency denitration catalyst has low cost and simple preparation process, and is particularly suitable for NO in high-dust, high-alkali metal and high-alkaline earth metal flue gas of a cement kilnxAnd (4) removing.
Drawings
FIG. 1 shows 1V8Mo-15Ti/SiO solid obtained in example 1 of the present invention2A catalytic effect diagram of the catalyst;
FIG. 2 shows 1V8Mo-15Ti/SiO solid obtained in example 1 of the present invention at K/V molar ratios of 0.5, 1.0 and 1.5, respectively2A poisoning effect graph of the catalyst;
FIG. 3 shows 1V8Mo-15Ti/SiO solid obtained in example 1 of the present invention at Ca/V molar ratios of 0.5, 1.0 and 1.5, respectively2The poisoning effect of the catalyst.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached figures 1-3.
Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.
Example 1
1) Preparing a solution containing a template agent
Dissolving 4g of P123 in deionized water, and stirring for 4 hours at 25 ℃ until the mixture is homogeneous; 75g of 0.2mol/L HCl is added, and the mixture is fully stirred for 2 hours at the temperature of 40 ℃ to obtain a mixed solution.
2) Preparation of titanium doped mesoporous molecular sieve
Premixing 1g of butyl titanate and 9g of tetraethyl silicate to obtain a mixed solution, dropwise adding the mixed solution into the solution obtained in the step 1) under vigorous stirring, and continuously stirring for 20 hours at 40 ℃. And then transferring the formed gel liquid into a self-generated pressure reaction kettle with a polytetrafluoroethylene lining, standing for 24 hours at 100 ℃, taking out, carrying out suction filtration, washing with deionized water to be neutral, and drying at room temperature. Roasting the mixture for 4 hours at 550 ℃ in air by using a muffle furnace, wherein the heating rate is 1 ℃/min, and thus obtaining the titanium-doped mesoporous molecular sieve carrier.
3) Loading of catalytic promoter
Ammonium molybdate 1.1g is weighed and dissolved in 50mL deionized water, and a stable solution is obtained by stirring. Soaking 10g of the catalyst carrier obtained in the step 2) into the solution, stirring at room temperature for 24h, then carrying out rotary evaporation drying, drying at 110 ℃ for 10h by using an oven, and roasting at 550 ℃ for 6h by using air in a muffle furnace at the heating rate of 1 ℃/min to obtain a catalyst precursor.
4) Loading of catalyst active components
0.13g of ammonium metavanadate is weighed and dissolved in 50mL of oxalic acid solution, and a stable solution is obtained by stirring. Soaking 10g of the catalyst carrier obtained in the step 2) into the solution, stirring at room temperature for 24h, then carrying out rotary evaporation drying, drying at 110 ℃ for 10h in an oven, roasting at 550 ℃ in a muffle furnace for 6h in air at the heating rate of 1 ℃/min to obtain the catalyst 1V8Mo-15Ti/SiO2。
5) And (3) testing the denitration rate:
the catalytic reaction conditions of the invention are as follows: NO: 400ppm, NH3：400ppm，O2：10％，N2The total gas amount is 400mL/min, and the catalyst dosage is 200 mg. And (3) carrying out denitration evaluation by adopting a gas chromatography, wherein the evaluation range is 100-400 ℃, one temperature point is evaluated at intervals of 25 ℃, and each temperature point stays for 1 hour.
1V8Mo-15Ti/SiO prepared in this example2The catalytic effect of the catalyst is shown in figure 1, and the denitration efficiency reaches over 90 percent in a temperature range of 300-400 ℃. FIG. 2 and FIG. 3 show different amounts of K supported by the catalyst2Denitration activity of the O and CaO poisoned catalyst is plotted as a function of temperature. As can be seen from FIGS. 2 and 3, with K2The supported amounts of O and CaO are increased, so that the denitration activity of the catalyst is reduced; at K2When the loading amounts of O and CaO reach certain amounts, and the molar ratio of K to V and the molar ratio of Ca to V are respectively 1.0, the catalyst still keeps higher activityAnd in the temperature range of 330-400 ℃, the denitration efficiency is still over 85 percent.
Example 2
1) Preparing a solution containing a template agent
Dissolving 4g of P123 in deionized water, and stirring for 4 hours at 25 ℃ until the mixture is homogeneous; 65g of 0.2mol/L HCl is added, and the mixture is fully stirred for 2 hours at the temperature of 40 ℃ to obtain a mixed solution.
2) Preparation of titanium doped mesoporous molecular sieve
Premixing 1.35g of butyl titanate and 9g of tetraethyl silicate to obtain a mixed solution, dropwise adding the mixed solution into the solution obtained in the step 1) under vigorous stirring, and continuously stirring for 15 hours at 40 ℃. And then transferring the formed gel liquid into a self-generated pressure reaction kettle with a polytetrafluoroethylene lining, standing for 20 hours at 100 ℃, taking out, carrying out suction filtration, washing with deionized water to be neutral, and drying at room temperature. And roasting the mixture for 6 hours at 550 ℃ in air by using a muffle furnace, wherein the heating rate is 3 ℃/min, and thus the titanium-doped mesoporous molecular sieve carrier is obtained.
3) Loading of catalytic promoter
6.4g of ammonium metatungstate is weighed and dissolved in 120mL of deionized water, and a stable solution is obtained by stirring. Soaking 10g of the catalyst carrier obtained in the step 2) into the solution, stirring at room temperature for 20h, then carrying out rotary evaporation drying, drying at 110 ℃ for 12h by using an oven, and roasting at 550 ℃ for 6h by using air in a muffle furnace at the heating rate of 2 ℃/min to obtain a catalyst precursor.
4) Loading of catalyst active components
0.43g of cerium trichloride and 0.2g of niobium pentachloride were weighed out and dissolved in 100mL of an aqueous solution, and a stable solution was obtained by stirring. Soaking 10g of the catalyst carrier obtained in the step 2) into the solution, stirring at room temperature for 18h, drying by rotary evaporation, drying at 110 ℃ for 14h by using an oven, roasting at 550 ℃ for 8h by using air in a muffle furnace at the temperature of 3 ℃/min to obtain the catalyst 1Nb3Ce5W-20Ti/SiO2。
Example 3
1) Preparing a solution containing a template agent
Dissolving 4g of P123 in deionized water, and stirring for 4 hours at 25 ℃ until the mixture is homogeneous; 80g of 0.2mol/L HCl is added, and the mixture is fully stirred for 1 hour at the temperature of 40 ℃ to obtain a mixed solution.
2) Preparation of titanium doped mesoporous molecular sieve
0.68g of butyl titanate and 9g of tetraethyl silicate are premixed to obtain a mixed solution, the mixed solution is added dropwise into the solution obtained in the step 1) under vigorous stirring, and stirring is continued for 20h at 40 ℃. And then transferring the formed gel liquid into a self-generated pressure reaction kettle with a polytetrafluoroethylene lining, standing for 36 hours at 100 ℃, taking out, carrying out suction filtration, washing with deionized water to be neutral, and drying at room temperature. And roasting the mixture for 6 hours at 550 ℃ in air by using a muffle furnace at the heating rate of 1 ℃/min to obtain the titanium-doped mesoporous molecular sieve carrier.
3) Loading of catalytic promoter
0.3g of ferric nitrate is weighed and dissolved in 80mL of deionized water, and a stable solution is obtained by stirring. Soaking 10g of the catalyst carrier obtained in the step 2) into the solution, stirring at room temperature for 40h, then carrying out rotary evaporation drying, drying at 110 ℃ for 20h by using an oven, and roasting at 550 ℃ for 3h by using air in a muffle furnace at the heating rate of 1 ℃/min to obtain a catalyst precursor.
4) Loading of catalyst active components
0.5g of a nitric acid solution of 50% manganese nitrate and 0.76g of cerium nitrate were weighed and dissolved in 120mL of an oxalic acid solution, and a stable solution was obtained by stirring. Soaking 10g of the catalyst carrier obtained in the step 2) into the solution, stirring the solution at room temperature for 24 hours, then carrying out rotary evaporation drying, drying the solution at the temperature of 110 ℃ for 18 hours in an oven, roasting the solution at the temperature of 550 ℃ in a muffle furnace for 4 hours at the heating rate of 2 ℃/min to obtain the catalyst 1Mn3Ce10Fe-10Ti/SiO2。
Example 4
1) Preparing a solution containing a template agent
Dissolving 4g of P123 in deionized water, and stirring for 2 hours at 25 ℃ until the mixture is homogeneous; 80g of 0.2mol/L HCl is added, and the mixture is fully stirred for 1 hour at the temperature of 40 ℃ to obtain a mixed solution.
2) Preparation of titanium doped mesoporous molecular sieve
Premixing 1.1g of butyl titanate and 9g of tetraethyl silicate to obtain a mixed solution, dropwise adding the mixed solution into the solution obtained in the step 1) under vigorous stirring, and continuously stirring for 10 hours at 40 ℃. And then transferring the formed gel liquid into a self-generated pressure reaction kettle with a polytetrafluoroethylene lining, standing for 24 hours at 100 ℃, taking out, carrying out suction filtration, washing with deionized water to be neutral, and drying at room temperature. And roasting the mixture for 8 hours at 550 ℃ in air by using a muffle furnace at the heating rate of 1 ℃/min to obtain the titanium-doped mesoporous molecular sieve carrier.
3) Loading of catalytic promoter
1.9g of copper nitrate is weighed and dissolved in 120mL of deionized water, and a stable solution is obtained by stirring. Soaking 10g of the catalyst carrier obtained in the step 2) into the solution, stirring at room temperature for 20h, then carrying out rotary evaporation drying, drying at 110 ℃ for 16h by using an oven, and roasting at 550 ℃ for 4h by using air in a muffle furnace at the heating rate of 1 ℃/min to obtain a catalyst precursor.
4) Loading of catalyst active components
0.79g of zirconium oxychloride was dissolved in 100mL of the aqueous solution, and the solution was stirred to obtain a stable solution. Soaking 10g of the catalyst carrier obtained in the step 2) into the solution, stirring the solution at room temperature for 24 hours, then carrying out rotary evaporation drying, drying the solution at the temperature of 110 ℃ for 20 hours in an oven, roasting the dried solution at the temperature of 550 ℃ in a muffle furnace for 6 hours at the temperature rise rate of 2 ℃/min to obtain the catalyst 3Zr8Cu-16Ti/SiO2。
Comparative example
According to the literature report (potassium salt to V)2O5/TiO2Catalyst NH3Influence of selective catalytic reduction NO reaction, chinese electro-mechanical engineering, 2008: 28, 21-26), when the molar ratio of K/V is 1.0, the catalytic activity at 350 ℃ is about 88%, when the molar ratio of K/V is 1.0, the catalytic activity at 350 ℃ is 93.1%, the catalyst still has higher catalytic activity, and the catalyst has stronger alkali metal poisoning resistance.
The active component used in the anti-alkalosis high-efficiency denitration catalyst is low in cost and non-toxic, and can effectively remove NO under the conditions of high-concentration calcium oxide, high dust content and high humidity smokexConversion to N2. The catalyst can have NO higher than 90% in the range of 300-400 DEG CxThe conversion rate and the highest activity reach 99.7 percent; has stronger alkali metal and alkaline earth metal poisoning resistance; can be lengthenedThe time is effectively operated under the condition of high calcium oxide smoke, and the method is particularly suitable for NO in high-dust, high-alkali metal and high-alkaline earth metal smoke of a cement kilnxAnd (4) removing.
The above examples are only intended to illustrate the detailed process of the present invention, and the present invention is not limited to the above detailed process, i.e., it is not intended that the present invention necessarily depends on the above detailed process for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
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