CN112958153B - Heteropoly acid-containing denitration catalyst and preparation method and application thereof - Google Patents
Heteropoly acid-containing denitration catalyst and preparation method and application thereof Download PDFInfo
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- CN112958153B CN112958153B CN202110177626.XA CN202110177626A CN112958153B CN 112958153 B CN112958153 B CN 112958153B CN 202110177626 A CN202110177626 A CN 202110177626A CN 112958153 B CN112958153 B CN 112958153B
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- heteropolyacid
- acid
- denitration catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 176
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 41
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003546 flue gas Substances 0.000 claims abstract description 29
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 28
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 25
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 21
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 11
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 11
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 29
- 229910052718 tin Inorganic materials 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 229910052787 antimony Inorganic materials 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 17
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 11
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 9
- 229910000385 transition metal sulfate Inorganic materials 0.000 claims description 9
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 154
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 91
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 150000003839 salts Chemical class 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 21
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 17
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000012216 screening Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000779 smoke Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 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 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 150000004715 keto acids Chemical class 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- WYOIGGSUICKDNZ-UHFFFAOYSA-N 2,3,5,6,7,8-hexahydropyrrolizin-1-one Chemical compound C1CCC2C(=O)CCN21 WYOIGGSUICKDNZ-UHFFFAOYSA-N 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- OSYLPIYJUCCMTQ-UHFFFAOYSA-O azanium;cerium(3+);nitrate Chemical compound [NH4+].[Ce+3].[O-][N+]([O-])=O OSYLPIYJUCCMTQ-UHFFFAOYSA-O 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- DBUHPIKTDUMWTR-UHFFFAOYSA-K erbium(3+);triacetate Chemical compound [Er+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBUHPIKTDUMWTR-UHFFFAOYSA-K 0.000 description 1
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 1
- SYDXSHCNMKOQFW-UHFFFAOYSA-H erbium(3+);trisulfate Chemical compound [Er+3].[Er+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SYDXSHCNMKOQFW-UHFFFAOYSA-H 0.000 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- HWZAHTVZMSRSJE-UHFFFAOYSA-H praseodymium(iii) sulfate Chemical compound [Pr+3].[Pr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HWZAHTVZMSRSJE-UHFFFAOYSA-H 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- -1 transition metal sulphate Chemical class 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of denitration catalysts, and discloses a heteropolyacid-containing denitration catalyst, a preparation method and application thereof, wherein the denitration catalyst contains heteropolyacid, an active component and a modification auxiliary agent; the heteropoly acid is in a keggin cage structure, and hetero atoms in the heteropoly acid are selected from at least one of phosphorus atoms, antimony atoms and tin atoms; the polyatoms in the heteropoly acid are selected from at least one of molybdenum atoms, tungsten atoms, niobium atoms and tantalum atoms; the active component contains at least one of vanadium element, iron element, manganese element and copper element; the modifying auxiliary agent contains at least one of cerium element, lanthanum element, praseodymium element and erbium element. The heteropolyacid-containing denitration catalyst provided by the invention has higher denitration efficiency and stronger H resistance 2 O, NOx and SO 2 The flue gas capacity can meet the denitration requirements of furnace start-up and shut-down and deep peak shaving under the complex flue gas conditions and the operation working conditions of the coal-fired power plant.
Description
Technical Field
The invention relates to the field of denitration catalysts, in particular to a heteropolyacid-containing denitration catalyst, and a preparation method and application thereof.
Background
Nitrogen Oxides (NO) x ) Is one of the main atmospheric pollutants, is an important factor for forming acid rain, is one of important precursors for generating ozone and photochemical smog, and is also an important cause for forming regional ultrafine particle (PM 2.5) pollution and dust haze.
The coal-fired power plant is NO x Is one of the primary sources of emissions. NO in the current power plant of China x The emission adopts the world-wide emission limit value, and the best technical approach meeting the standard is ammonia selective catalytic reduction (NH 3 -SCR). Traditional commercial V is commonly used in flue gas denitration of coal-fired power plants 2 O 5 /WO 3 -TiO 2 The optimal activity temperature range of the catalyst is 300-420 ℃.
In recent years, due to the improvement of environmental protection requirements, the emission requirements on nitrogen oxides of a start-up and shut-down furnace are strict, and the deep peak shaving requirement of thermal power is met, more than 60% of coal-fired units are in a low-load running state, and the flue gas temperature is often lower than 300 ℃. When the smoke temperature is lower than the optimal ammonia spraying temperature, the power plant generally has the conditions of increasing the ammonia spraying amount to different degrees so as to improve the denitration efficiency, so that the problems of increased operation cost, overhigh ammonia escape, shortened catalyst life, frequent blockage of an air preheater and the like are caused, and new problems and challenges are brought to the safe operation of a unit. The prior method for solving the problem is to reduce the heat extraction amount of the economizer in front of the denitration system by engineering modification, so that the temperature of flue gas at the inlet of the denitration system reaches more than 300 ℃ under low load (< 50% THA) to ensure that the traditional catalyst can normally operate, including the segmentation of the economizer, the flue gas bypass, the water side bypass of the economizer, the hot water recirculation of the economizer and the like. However, the methods have the advantages of high modification cost, long construction period, reduced boiler efficiency, increased operation cost of the power plant and significant power plant loss increase.
The wide-temperature denitration catalyst can expand the operating temperature window to 240-420 ℃, effectively reduce the minimum ammonia injection temperature range of the denitration catalyst on the premise of not changing the integral structure and the system of the boiler, realize the condition that a unit is started and stopped and the emission of nitrogen oxides under low load meets the national ultra-low emission environment-friendly requirement, and the transformation cost is only the normal replacement of the catalyst, so that the wide-temperature denitration catalyst has remarkable economic benefit.
Coal accounts for 70% in the energy structure of China, and is obviously different from western countries, the coal quality of China generally has the characteristics of high sulfur and high ash, and under the condition that the unit operation is not fine and reasonable enough, the denitration catalyst has serious invalidation in the use process, and the specific appearance is that: combustion conditions are unstable in the processes of unit start-up and shut-down and deep peak regulation, so that NO is introduced into a denitration system x The concentration is 2-3 times higher than that of the catalyst in stable operationThe denitration efficiency of the chemical agent also provides a serious test, thus providing a method for high-concentration NO x The catalyst with high denitration efficiency is also of great significance.
At the same time, the SO of the boiler under the combustion condition is about 1 percent 2 Conversion to SO 3 When passing through the denitration system, the catalyst can have SO of 1 percent 2 Conversion to SO 3 This is in combination with injected reductant NH 3 The water in the flue gas forms Ammonium Bisulfate (ABS), and when the temperature of the flue gas is lower than 300 ℃, the flue gas can be condensed into sticky substances to cause the blocking of micropores of the catalyst, and the covering of active sites causes the deactivation of the catalyst. Secondly, SO 3 Will also be in contact with V in the catalyst 2 O 5 Chemical reaction occurs to generate VOSO 4 Resulting in slow deactivation of the catalyst. Ammonium Bisulfate (ABS) dew point temperature and SO in flue gas 3 、H 2 O and NH 3 Is generally in the range of 280-300 c depending on the design conditions of the respective project. SO in flue gas 2 、NO x And H 2 The higher the O concentration, the corresponding [ SO ] 3 ]·[H 2 O]·[NH 3 ]The greater the concentration product, the higher the ABS dew point temperature and the greater the risk of catalyst failure at low temperature operation. The method for resisting ABS poisoning commonly used in industrial flue gas denitration at present is to heat the temperature of a catalyst to be above the dew point temperature of ABS, however, the load change of a coal-fired power plant is required to be changed according to a power grid, and the use environment is difficult to provide. Thus, low temperature NH was developed to resist ABS poisoning 3 SCR denitration technology has great scientific significance and practical value in both environmental and energy fields, but faces great challenges.
Currently, wide temperature catalyst general operating requirements in the industry require NOx concentrations below 500mg/Nm 3 ，SO 2 Concentration of less than 2000mg/Nm 3 Hereinafter, H 2 The O content is lower than 10 percent, and the device is suitable for wide load operation at the operation temperature of 280-420 ℃; while for higher sulfur (SO 2 ) The operating requirements of high nitrogen (NOx), high water vapor fumes and lower windows have not been addressed.
Therefore, the wide-temperature denitration catalyst technology suitable for the smoke with complex components and the operation condition is still a difficult point of the industry technology.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a denitration catalyst which is suitable for meeting the requirements of furnace startup and shutdown and wide-load operation of a coal-fired power plant under the conditions of high sulfur, high nitrogen and high water vapor in flue gas and a preparation method thereof.
The inventor of the invention creatively researches that by combining specific types and contents of heteropoly acid with active components and modifying auxiliary agents to form a denitration catalyst, the heteropoly acid is complexed with the active substances to form a cage-shaped structure of the heteropoly acid surrounding active center ions, a catalyst structure with the synergistic effect of an active center and an acid center is formed, and the catalyst has a high-activity redox center and an acid center, so that the effective dispersion of the active points and the reaction product molecules NH are promoted 3 And mass transfer and diffusion of NO, improving the catalyst in high NO x And height H 2 Denitration efficiency under O content; meanwhile, the cage structure has a certain protection effect on the active center, inhibits the coverage of ammonium bisulfate ABS on the active site at low temperature, and improves SO of the catalyst at low temperature 2 Is a high-strength steel sheet. The catalyst has higher denitration efficiency and stronger H resistance 2 O，NO x And SO 2 The flue gas capacity can meet the requirements of denitration of furnace start-up and shut-down and deep peak shaving under complex flue gas conditions and operation conditions of the coal-fired power plant, and therefore the invention is provided.
In order to achieve the above object, a first aspect of the present invention provides a heteropolyacid-containing denitration catalyst, which contains a heteropolyacid, an active component and a modifying auxiliary agent;
the heteropoly acid is in a keggin cage structure, and hetero atoms in the heteropoly acid are selected from at least one of phosphorus atoms, antimony atoms and tin atoms; the polyatoms in the heteropoly acid are selected from at least one of molybdenum atoms, tungsten atoms, niobium atoms and tantalum atoms;
the active component contains at least one of vanadium element, iron element, manganese element and copper element;
the modifying auxiliary agent contains at least one of cerium element, lanthanum element, praseodymium element and erbium element;
In the denitration catalyst, the weight ratio of the hetero atom to the polyatoms to the active component to the modifying auxiliary agent is 0.1-5:0.5-10:0.1-5:1-10, wherein the weight of the hetero atom, the polyatoms, the active component and the modifying assistant are calculated by the weight of the oxide containing metal elements.
In a second aspect, the present invention provides a process for preparing a heteropolyacid-containing denitration catalyst, the process comprising:
(1) First mixing a solution I containing an element A with a solution II containing an element B to obtain a solution III, wherein the element A is at least one of an antimony element, a phosphorus element and a tin element, and the element B is at least one of a tungsten element, a molybdenum element, a niobium element and a tantalum element;
(2) Carrying out second mixing on the solution III and a tetraalkylammonium hydroxide solution to obtain a solution IV;
(3) Thirdly mixing the solution IV with a transition metal sulfate solution to obtain a solution V containing heteropolyacid;
(4) Fourth mixing the solution V, a compound I containing an element C and a compound II containing an element D to obtain powder, wherein the element C is at least one of vanadium element, iron element, manganese element and copper element; the element D is at least one of cerium element, lanthanum element, praseodymium element and erbium element;
(5) Sequentially drying and roasting the powder to obtain a denitration catalyst;
the dosages of the solution I, the solution II, the compound I and the compound II are such that the content weight ratio of the element A, the element B, the element C and the element D calculated by metal oxide in the obtained denitration catalyst is 0.1-5:0.5-10:0.1-5:1-10.
In a third aspect, the present invention provides a heteropolyacid-containing denitration catalyst prepared by the foregoing method.
The fourth aspect of the invention provides application of the heteropolyacid-containing denitration catalyst in flue gas denitration.
Compared with the prior art, the invention has at least the following advantages:
the catalyst provided by the invention has high denitration efficiency and SO resistance 2 The poisoning capability is strong, the long-period operation stability is good, and the method is suitable for NO under the conditions of high sulfur, high nitrogen and high water in flue gas, and the conditions of furnace start-up and shutdown and deep peak regulation of a coal-fired power plant x Ultra low emission control requirements.
According to the method provided by the invention, the coupling structure of the heteropolyacid and the metal ions is formed in situ by a water phase ion exchange method, a carrier is not required to be added, and the catalyst with high denitration efficiency can be obtained by low-temperature roasting, so that the flow is short, the energy consumption is low, and the operation process is simple.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an XRD result pattern of the denitration catalyst prepared in example 1;
fig. 2 is a schematic diagram of a double-center structure of the denitration catalyst of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a heteropolyacid-containing denitration catalyst comprising a heteropolyacid, an active component and a modifying auxiliary agent;
the heteropoly acid is in a keggin cage structure, and hetero atoms in the heteropoly acid are selected from at least one of phosphorus atoms, antimony atoms and tin atoms; the polyatoms in the heteropoly acid are selected from at least one of molybdenum atoms, tungsten atoms, niobium atoms and tantalum atoms;
the active component contains at least one of vanadium element, iron element, manganese element and copper element;
The modifying auxiliary agent contains at least one of cerium element, lanthanum element, praseodymium element and erbium element;
in the denitration catalyst, the weight ratio of the hetero atom to the polyatoms to the active component to the modifying auxiliary agent is 0.1-5:0.5-10:0.1-5:1-10, wherein the weight of the hetero atom, the polyatoms, the active component and the modifying assistant are calculated by the weight of the oxide containing metal elements.
According to the invention, the heteropolyacid with a porous cage structure is complexed with the active component and the modifying auxiliary agent to form a structure that the heteropolyacid surrounds an active center (the active component and the modifying auxiliary agent), so that the active component and the modifying auxiliary agent form close contact with hetero atoms/multiple atoms and are fully dispersed, the exposure of the active points is promoted, and the catalyst with the synergistic effect of double centers (double active centers) of an active center and an acid center is obtained. In the double centers of the catalyst, one of the double centers mainly provides denitration active sites, the other one of the double centers improves the oxygen storage capacity of the catalyst, increases active oxygen species and oxygen vacancies on the surface of the catalyst, and is beneficial to NO at low temperature 3 - Is a transition of (2). In addition, the heteropolyacid of the invention has two metal components, one of which can improve the acidity of the catalyst and improve the NH of the catalyst 3 Is used for the adsorption capacity of the catalyst; another can reduce electronegativity of catalyst surface and reduce SO 3 Adsorption on the catalyst surface, reduction of SO 3 Promote SO in ammonium bisulfate 4 2- Is easy to decompose to promote the volatilization of ABS and improve the SO of the catalyst 2 Is a high-strength steel sheet.
According to the invention, the heteropoly acid is an oxygen-containing polyacid which is formed by coordination and bridging of hetero atoms and polyatoms through oxygen atoms according to a certain structure. The structure of the heteropoly acid is a cage type, and the cage type is a space porous network structure formed by coordination of a plurality of oxo acids around a central oxo acid. The inventor of the invention discovers that the heteropolyacid with a cage structure is selected and cooperated with other components in the catalyst to obtain the catalyst with the cage porous structure of the heteropolyacid reserved, and the space in the cage pore canal is more suitable for reactant molecules NH 3 And mass transfer and diffusion of NO, increase the relative heightNO x And height H 2 Denitration efficiency of O flue gas. Meanwhile, the cage structure has a certain protection effect on active centers (active components and modified auxiliary agents), inhibits the coverage of ammonium bisulfate ABS on active sites at low temperature, and improves SO (sulfur oxide) on the catalyst at low temperature 2 Is a high-strength steel sheet.
According to the invention, the denitration catalyst has a cage-type porous structure.
Preferably, the specific surface area of the denitration catalyst is 5 to 20m 2 ·g -1 Average pore diameter of 10-20nm, bulk density of 0.7-1.3g/cm 3 。
Preferably, the particle diameter of the denitration catalyst is 40 to 60 meshes.
According to the invention, the denitration catalyst provided by the invention has a coupling structure of heteropolyacid and metal ions. As can be seen by XRD, the denitration catalyst of the present invention has a crystal phase structure consistent with that of the heteropolyacid, indicating that the denitration catalyst has a coupled structure of the heteropolyacid and metal ions (active component and modifying aid), instead of solid phase physical mixing of the heteropolyacid, active component and modifying aid.
In order to obtain the denitration catalyst with higher denitration efficiency on high-sulfur, high-nitrogen and high-moisture smoke, stronger adaptability to complex smoke and higher activity at low temperature and wider temperature window, preferably, the weight ratio of the hetero atom, the polyatoms, the active components and the modification auxiliary agent is 0.5-2:1-6:0.5-3:3-5, wherein the weight of the hetero atom, the polyatoms, the active component and the modifying auxiliary agent is calculated by the weight of the oxide containing metal elements.
Preferably, the weight ratio of the active component to the modifying auxiliary agent is 1:1-2, more preferably 1:1-1.5, wherein the weight of the active component and the weight of the modifying auxiliary agent are calculated by the oxide of the contained metal element.
Preferably, the active component contains at least two of vanadium element, iron element, manganese element and copper element.
According to a preferred embodiment of the invention, the active component contains vanadium and manganese elements, and the molar ratio of vanadium to manganese elements is 1:0.2-7 (calculated by metal element).
Thus, the inventors of the present invention found that the content weight ratio of the active component and the modifying assistant is specifically controlled to be 1:1-2, and the active component is especially the preferential condition, the denitration catalyst obtained by being matched with other components in the catalyst has higher tolerance to high-sulfur, high-nitrogen and high-moisture smoke, and particularly has higher denitration efficiency to the high-nitrogen smoke.
According to the present invention, it is preferable that the active component and the modifying aid are both present in the denitration catalyst of the present invention in the form of an oxide of a transition metal element which they contain.
In the invention, the metal oxides of the elements are P respectively when the metal oxidation is performed 2 O 5 (phosphorus element), sb 2 O 3 (antimony element), snO 2 (tin element), moO 3 (molybdenum element), WO 3 (tungsten element), nb 2 O 5 (niobium element), ta 2 O 5 (tantalum element), V 2 O 5 (vanadium element), fe 2 O 3 (iron element), mnO 2 (manganese element), cuO (copper element), ceO 2 (cerium element), la 2 O 3 (lanthanum element), pr 2 O 3 (praseodymium element) and Er 2 O 3 (erbium element).
Preferably, the heteroatom is an antimony atom and/or a tin atom, and the polyatoms are at least one selected from molybdenum atoms, tungsten atoms, niobium atoms, tungsten atoms, and tantalum atoms.
Further preferably, the heteropolyacid is at least one selected from the group consisting of antimony molybdic acid, antimony niobic acid, antimony tantalic acid, antimony tungstic acid, tin molybdic acid, tin niobic acid, tin tungstic acid, and tin tantalic acid.
According to the invention, the antimonomolybdic acid is preferably selected from H 2 Sb 2 Mo 12 O 40 ·nH 2 O、H 2 Sb 2 Mo 6 O 24 ·nH 2 O、HSbMo 6 O 21 ·nH 2 O、H 7 Sb 5 Mo 18 O 66 ·nH 2 O; the antimonic niobic acid is preferablySelected from H 14 Sb 2 Nb 12 O 40 ·nH 2 O、H 8 Sb 2 Nb 6 O 24 ·nH 2 O; the antimony tantalate is preferably selected from H 14 Sb 2 Ta 12 O 40 ·nH 2 O、H 8 Sb 2 Ta 6 O 24 ·nH 2 O; the antimony tungstic acid is preferably selected from H 2 Sb 2 W 12 O 40 ·nH 2 O、H 2 Sb 2 W 6 O 24 ·nH 2 O; the tin molybdic acid is preferably selected from H 4 Sn 2 Mo 6 O 24 ·nH 2 O、H 8 SnMo 6 O 24 ·nH 2 O; the tin niobic acid is preferably selected from H 10 Sn 2 Nb 6 O 24 ·nH 2 O、H 12 Sn 2 Nb 12 O 40 ·nH 2 O; the tin tantalic acid is preferably selected from H 10 Sn 2 Ta 6 O 24 ·nH 2 O、H 12 Sn 2 Ta 12 O 40 ·nH 2 O; the tin tungstic acid is preferably H 4 Sn 2 W 6 O 24 ·nH 2 O、H 8 SnW 6 O 24 ·nH 2 O。
Further preferably, the heteropoly acid is selected from at least one of antimony molybdic acid, tin molybdic acid and tin tungstic acid.
Preferably, the acid of the heteropolyacid is 1-2mmol/g, and the specific surface area is 5-20m 2 ·g -1 The average pore diameter is 10-20nm. According to the invention, the acidity of the heteropolyacid is measured according to the pyridine adsorption method.
The inventors of the present invention have surprisingly found that the heteropoly acids, in particular antimony molybdic acid (preferably H 2 Sb 2 Mo 12 O 40 ·nH 2 O、HSbMo 6 O 21 ·nH 2 O、H 7 Sb 5 Mo 18 O 66 ·nH 2 O), tin molybdic acid (preferably H 8 SnMo 6 O 24 ·nH 2 O) and tin tungstic acid (preferably H 4 Sn 2 W 6 O 24 ·nH 2 O) and other components in the catalyst, the obtained denitration catalyst has higher tolerance to high-sulfur, high-nitrogen and high-moisture flue gas, and particularly has higher denitration efficiency to high-nitrogen flue gas.
According to a particularly preferred embodiment of the present invention, the denitration catalyst contains a heteropolyacid, an active component and a modifying auxiliary agent; the heteropolyacid is antimonomolybdic acid and/or tin tungstic acid, the active component contains vanadium element and manganese element, and the molar ratio of the vanadium element to the manganese element is 1:0.2-7, wherein the modifying auxiliary agent contains cerium element; the weight ratio of the hetero atoms, the polyatoms, the active components and the modifying auxiliary agent is 0.5-2 based on metal oxide: 1-6:0.5-3:3-5, wherein the weight ratio of the active component to the modifying auxiliary agent is 1:1-2.
According to another particularly preferred embodiment of the present invention, the denitration catalyst contains a heteropolyacid, an active component and a modifying auxiliary agent; the heteropolyacid is antimonomolybdic acid and/or tin tungstic acid, the active component contains vanadium element, and the modification auxiliary agent contains cerium element; the weight ratio of the hetero atoms, the polyatoms, the active components and the modifying auxiliary agent is 0.5-2 based on metal oxide: 1-6:0.5-3:3-5, wherein the weight ratio of the active component to the modifying auxiliary agent is 1:1-2.
In the invention, the composition of the catalyst can be obtained through calculation of the raw material feeding amount and also through testing by analysis means such as element analysis.
As previously described, the second aspect of the present invention provides a process for preparing a heteropolyacid-containing denitration catalyst, the process comprising:
(1) First mixing a solution I containing an element A with a solution II containing an element B to obtain a solution III, wherein the element A is at least one of an antimony element, a phosphorus element and a tin element, and the element B is at least one of a tungsten element, a molybdenum element, a niobium element and a tantalum element;
(2) Carrying out second mixing on the solution III and a tetraalkylammonium hydroxide solution to obtain a solution IV;
(3) Thirdly mixing the solution IV with a transition metal sulfate solution to obtain a solution V containing heteropolyacid;
(4) Fourth mixing the solution V, a compound I containing an element C and a compound II containing an element D to obtain powder, wherein the element C is at least one of vanadium element, iron element, manganese element and copper element; the element D is at least one of cerium element, lanthanum element, praseodymium element and erbium element;
(5) Sequentially drying and roasting the powder to obtain a denitration catalyst;
The dosages of the solution I, the solution II, the compound I and the compound II are such that the content weight ratio of the element A, the element B, the element C and the element D calculated by metal oxide in the obtained denitration catalyst is 0.1-5:0.5-10:0.1-5:1-10.
Preferably, the solution I: solution II: the compound I: the weight ratio of the compound II is 0.1-5:0.5-10:0.1-5:1-10, wherein the solution I is calculated as the oxide of the contained element a, the solution II is calculated as the oxide of the contained element B, the compound I is calculated as the oxide of the contained element C, and the compound II is calculated as the oxide of the contained element D.
In the present invention, unless otherwise specified, the solution includes a solution, a suspension, an emulsion, a cloudy solution, and the like in a liquid form, and those skilled in the art should not understand the limitation of the present invention.
According to a preferred embodiment of the present invention, the solution I is obtained by dissolving a first compound containing element a in a first solvent.
Preferably, the first compound is selected from at least one of an oxide containing an element a, a sulfide containing an element a, a chloride containing an element a, a nitrate containing an element a, and a sulfate containing an element a.
Preferably, the first solvent is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, and deionized water.
Preferably, the weight ratio of the first compound to the first solvent is 0.01-1g/mL.
According to another preferred embodiment of the present invention, the solution II is obtained by dissolving a second compound containing the element B in a second solvent.
Preferably, the second compound is selected from at least one of an oxide containing an element B, a sulfide containing an element B, a chloride containing an element B, a nitrate containing an element B, and a sulfate containing an element B.
Preferably, the second solvent is selected from at least one of deionized water, hydrochloric acid, sulfuric acid, and nitric acid.
Preferably, the weight ratio of the second compound to the second solvent is 0.01-1g/mL.
According to the present invention, in order to promote dissolution of the first compound and the second compound, each of the processes of preparing the solution I and the solution II may independently further include operations for promoting dissolution, such as heating, stirring, etc., which are known in the art.
Preferably, in step (1), the conditions of the first mixing include: the temperature is 30-80deg.C, and the time is 20-80min.
According to the invention, in step (1), the weight ratio of the amount of the solution I to the amount of the solution II is 0.1-5:0.5-10, the solution I being calculated on the oxide of the element A contained and the solution II being calculated on the oxide of the element B contained.
According to a preferred embodiment of the present invention, in step (1), the first mixing is to drop the solution I into the solution II to obtain a solution III (the solution III is a turbid solution).
Preferably, in step (2), the molar ratio of the amount of said solution III to the amount of said tetraalkylammonium hydroxide solution is 1:0.5-1.5, wherein the amount of the solution III is calculated by the total mole of the element A and the element B contained in the solution III, and the amount of the tetramethylammonium hydroxide solution is calculated by the mole of the tetramethylammonium hydroxide contained in the solution III.
Preferably, in step (2), the concentration of the tetraalkylammonium hydroxide solution is from 0.6 to 1.5mol/L.
Preferably, in step (2), the tetraalkylammonium hydroxide is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide solution, more preferably tetramethylammonium hydroxide.
Preferably, in step (2), the conditions of the second mixing include: the temperature is 50-60deg.C, and the time is 30-60min.
Preferably, the second mixing is carried out at a pH of the system of from 5 to 6.
Preferably, in step (2), the pH of the system is adjusted to 5-6 using NaOH solution.
According to a preferred embodiment of the present invention, step (2) comprises: and (3) contacting the solution III with a tetraalkylammonium hydroxide solution, regulating the pH value of the system to 5-6 by using a NaOH solution, and heating in a water bath at 50-60 ℃ for 30-60min for second mixing.
Preferably, in step (3), the concentration of the transition metal sulfate solution is 0.05 to 0.1mol/L.
Preferably, in step (3), the transition metal sulfate is selected from at least one of ferric sulfate, cupric sulfate and nickel sulfate, more preferably ferric sulfate.
Preferably, in step (3), the molar ratio of the amount of said solution IV to the amount of said transition metal sulphate solution is 1:0.05-0.15, the amount of the solution IV being based on the total molar amount of the element A and the element B contained therein, and the amount of the transition metal sulfate solution being based on the molar amount of the transition metal sulfate contained therein.
Preferably, in step (3), the conditions of the third mixing include: the temperature is 50-60deg.C, and the time is 30-60min.
According to the present invention, preferably, step (3) further comprises subjecting the third mixed product to solid-liquid separation to obtain a solution V containing a heteropolyacid. The present invention is not limited to the operation of the solid-liquid separation, and is carried out by filtration, for example.
According to the present invention, in the step (4), the compound I may be one compound or a mixture of a plurality of compounds, for example, the compound I may be ammonium metavanadate or a mixture of ammonium metavanadate and manganese nitrate, and the compound II is similarly not construed as a limitation of the present invention by those skilled in the art.
According to the present invention, in step (4), preferably, the compound I is selected from at least one of a soluble salt of vanadium, a soluble salt of iron, a soluble salt of manganese, and a soluble salt of copper. The soluble salt of vanadium is preferably at least one selected from ammonium metavanadate, vanadyl sulfate and vanadium chloride; the soluble salt of iron is preferably at least one selected from ferric nitrate, ferrous sulfate, ferrous ammonium sulfate, ferric chloride and ferric acetate; the soluble salt of manganese is preferably at least one selected from manganese nitrate, manganese sulfate, manganous sulfate, manganese chloride and manganese acetate; the soluble salt of copper is preferably at least one selected from copper sulfate, copper nitrate, copper chloride, cuprous chloride and copper acetate.
According to the present invention, in step (4), preferably, the compound II is selected from at least one of a soluble salt of cerium, a soluble salt of lanthanum, a soluble salt of praseodymium, and a soluble salt of erbium. The soluble salt of cerium is preferably at least one selected from cerous nitrate, cerous ammonium nitrate, cerous sulfate, cerous chloride and cerous acetate; the soluble salt of lanthanum is preferably at least one selected from lanthanum nitrate, lanthanum sulfate, lanthanum chloride and lanthanum acetate; the soluble salt of praseodymium is preferably at least one selected from praseodymium nitrate, praseodymium sulfate, praseodymium chloride and praseodymium acetate; the soluble salt of erbium is preferably at least one selected from the group consisting of erbium nitrate, erbium sulfate, erbium chloride and erbium acetate.
Preferably, in step (4), the fourth mixing condition includes: the process is carried out under the condition of rotary evaporation, and the temperature is 70-90 ℃.
According to the present invention, the time of the fourth mixing is not particularly limited, as long as the mixing is such that the product powder is obtained.
Preferably, step (5) further comprises ageing said powder before drying, and then drying.
Preferably, the aging conditions include: the aging time is 12-24 hours.
Preferably, in step (5), the drying conditions include: the drying temperature is 85-95deg.C, and the drying time is 3-12h.
Preferably, the drying is performed in an oven.
Preferably, in step (5), the roasting conditions include: the roasting temperature is 200-250 ℃ and the roasting time is 2-5h.
Preferably, in step (5), the temperature rise rate of the calcination is 0.5 ℃/min to 5 ℃/min.
According to the invention, the method also comprises the steps of tabletting and screening the roasted material to obtain the denitration catalyst. Preferably, the particle diameter of the denitration catalyst is 40 to 60 meshes.
In the second aspect of the present invention, preferably, the element a is an antimony element and/or a tin element, and the element B is at least one selected from molybdenum element, niobium element, tungsten element, and tantalum element.
In the second aspect of the present invention, the heteropolyacid has the same properties as those of the heteropolyacid of the foregoing first aspect, such as optional kinds, composition, acidity, specific surface area, etc., and the present invention is not described herein.
Preferably, the solution I, the solution II, the compound I and the compound II are used in such an amount that the content weight ratio of the element a, the element B, the element C and the element D, calculated as metal oxide, in the obtained denitration catalyst is 0.5 to 2:1-6:0.5-3:3-5, namely, the weight ratio of the hetero atom, the polyatoms, the active component and the modifying auxiliary agent in the obtained denitration catalyst is 0.5-2:1-6:0.5-3:3-5.
Preferably, the amount of the compound I and the compound II is such that the content weight ratio of the element C to the element D, calculated as metal oxide, in the obtained denitration catalyst is 1:1-2.
Preferably, the compound I is selected from at least two of soluble salts of vanadium, soluble salts of iron, soluble salts of manganese and soluble salts of copper.
According to a preferred embodiment of the invention, the compound I is a combination of a soluble salt of vanadium and a soluble salt of manganese, and the molar ratio of the soluble salt of vanadium calculated as element of vanadium to the soluble salt of manganese calculated as element of manganese is 1:0.2-7.
According to the process of the present invention, the individual starting materials can be considered to be fully converted to the catalyst.
A preferred embodiment of the method of the invention is provided below, the method comprising:
(1) Dissolving a first compound containing an element A in a first solvent to obtain a solution I; dissolving a second compound containing an element B in a second solvent to obtain a solution II; adding the solution I into the solution II, and cooling to room temperature to form a solution III;
(2) Adding a tetraalkylammonium hydroxide solution into the solution III, dropwise adding a proper NaOH solution to adjust the pH value of the system to 5-6, and heating the mixed solution at 50-60 ℃ for 30-60min to obtain a solution IV;
(3) Adding a transition metal sulfate solution into the solution IV, heating at 50-60 ℃ for 30-60min, cooling to room temperature, and filtering to obtain a solution V containing heteropolyacid;
(4) Adding a compound I containing an element C and a compound II containing an element D into the solution V, fully mixing, and evaporating to dryness at 70-90 ℃ on a rotary evaporator to obtain powder;
(5) Aging the powder for 12-24h, drying at 85-95deg.C for 3-12h, and roasting at 200-250deg.C for 2-5h at a roasting temperature rising rate of 0.5deg.C/min-5deg.C/min;
(6) Tabletting the roasted product, and screening to obtain 40-60 mesh catalyst particles to obtain the catalyst.
The method provided by the invention forms the coupling structure of the heteropolyacid and the metal ions through in-situ synthesis by a water phase ion exchange method, and can obtain the catalyst with high denitration efficiency through low-temperature roasting without adding a carrier, and has the advantages of short flow, low energy consumption and simple operation process. Hetero atoms/polyatoms in the catalyst and the active components/the modifying auxiliary agent form close contact and are fully dispersed, which is beneficial to NH of a reactant in the denitration reaction process 3 And NO x Adsorption, activation and inhibition of SO 2 The oxidation of the catalyst is carried out to obtain the catalyst with better catalyst performance and stability.
As previously described, the third aspect of the present invention provides a heteropolyacid-containing denitration catalyst produced by the aforementioned method.
As previously described, a fourth aspect of the invention provides the use of the aforementioned heteropolyacid-containing denitration catalyst in flue gas denitration.
The specific operation of the application of the present invention is not particularly limited, and may be performed using existing flue gas denitration operations in the art, which will not be described in detail herein, and the present invention is exemplified in the examples section below as a specific operation, and the person skilled in the art should not understand the limitation of the present invention.
The invention will be described in detail below by way of examples.
In the examples below, all the raw materials used are commercially available, unless otherwise specified.
In the following examples, the composition of the catalyst was calculated from the feed amounts.
Example 1
(1) 1g of Sb 2 O 3 Dissolving in 40mL of HCl aqueous solution (3 mol/L) to obtain solution I; 5.3g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O is dissolved in 100ml of deionized water and heated to 50 ℃ to form solution II; then, dropwise adding the solution I into the solution II at 50 ℃ for first mixing, and cooling the mixed solution to room temperature to form a solution III;
(2) Adding 20mL of 1.1mol/L tetramethylammonium hydroxide solution into the solution III, dropwise adding a proper NaOH solution to adjust the pH value of the mixed solution to 5.5, and then heating the mixed solution in a water bath at 60 ℃ for 30min for secondary mixing to obtain a solution IV;
(3) 16mL of 0.1mol/L FeSO was added to solution IV 4 Heating the solution in water bath at 60deg.C for 30min for third mixing, cooling to room temperature, and filtering to obtain heteropolyacid-containing solution V (wherein the heteropolyacid comprises H) 2 Sb 2 Mo 12 O 40 ·nH 2 O, acidity of 1.5mmol/g, specific surface area of 12m 2 ·g -1 An average pore diameter of 13 nm);
(4) To dissolve3g of NH was added to liquid V 4 VO 3 10g of Ce (NO) 3 ) 3 ·6H 2 O is fully mixed, evaporation is carried out on a rotary evaporator at 80 ℃ for fourth mixing, and powder is obtained;
(5) Aging the powder for 12 hours, drying at 90 ℃ for 5 hours, and roasting at 200 ℃ for 3 hours, wherein the heating rate is 2 ℃/min; tabletting the roasted product, and screening to obtain 40-60 mesh catalyst particles to obtain the catalyst.
In the denitration catalyst, the weight ratio of hetero atoms, polyatoms, active components and modification auxiliary agents is 1 in terms of metal oxide: 4.3:2.3:4. the specific surface area of the denitration catalyst is 15m 2 Per gram, average pore diameter 14nm, bulk density 1.0g/cm 3 。
Comparative example 1-A
This comparative example is the preparation of a catalyst without active components and modifying aids.
(1) 1g of Sb 2 O 3 Dissolving in 40mL of HCl aqueous solution (3 mol/L) to obtain solution I; 5.3g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O is dissolved in 100mL of deionized water and heated to 50 ℃ to form solution II; then, dropwise adding the solution I into the solution II at 50 ℃ for first mixing, and cooling the mixed solution to room temperature to form a solution III;
(2) Adding 20ml of 1.1mol/L tetramethylammonium hydroxide solution into the solution III, dropwise adding proper NaOH to adjust the pH value of the mixed solution to 5.5, and then heating the mixed solution in a water bath at 60 ℃ for 30min for secondary mixing to obtain a solution IV;
(3) 16ml of 0.1mol/L FeSO are added to the solution IV 4 Heating the solution in water bath at 60deg.C for 30min for third mixing, cooling to room temperature, and filtering to obtain heteropolyacid-containing solution V (wherein the heteropolyacid comprises H) 2 Sb 2 Mo 12 O 40 ·nH 2 O, acidity of 1.5mmol/g, specific surface area of 12m 2 ·g -1 An average pore diameter of 13 nm);
(4) The filtrate was evaporated on a rotary evaporator at 80 ℃ to give a powder. The powder was dried at 90℃for 5h. Tabletting the powder, and screening to obtain 40-60 mesh catalyst particles to obtain the catalyst.
Comparative examples 1-B
The comparative example is the preparation of a catalyst without a modifying aid.
A catalyst was prepared in a similar manner to example 1, except that: in the step (4), ce (NO) is not added 3 ) 3 ·6H 2 O (modifying aid);
the step (4) is specifically as follows: to solution V3 g of NH was added 4 VO 3 Fully mixing, evaporating at 80deg.C on a rotary evaporator to obtain powder,
the rest was the same as in example 1 to obtain a catalyst.
Comparative examples 1 to C
The comparative example was a catalyst prepared using a solid phase mixing method.
1g of Sb was added to 150ml of deionized water 2 O 3 5.3g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 3g NH 4 VO 3 10g of Ce (NO) 3 ) 3 ·6H 2 O, thoroughly mixed and evaporated on a rotary evaporator at 80 ℃ to give a powder. The powder was dried at 90℃for 5h and calcined at 200℃for 3 h at a heating rate of 2℃per minute. Tabletting the roasted catalyst, and screening to obtain 40-60 mesh catalyst particles to obtain the catalyst.
Comparative examples 1 to D
The comparative example differs from example 1 in the process for preparing a heteropolyacid;
The specific process is as follows:
(1) 1g of Sb 2 O 3 Dissolving in 40mL of HCl aqueous solution (3 mol/L) to obtain solution I; 5.3g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O is dissolved in 100mL of deionized water and heated to 50 ℃ to form solution II; then dropwise adding the solution I into the solution II while the solution I is hot, and cooling the mixed solution to room temperature to form a solution III;
(2) Dropwise adding proper NaOH solution into the solution III to adjust the pH value of the mixed solution to 3.1, and heating the mixed solution at 60 ℃ for 30min to obtain a heteropolyacid-containing solution IV (wherein, the heteropolyacid group isHSbMo formation 6 O 21 ·nH 2 O, acidity of 0.8mmol/g, specific surface area of 4m 2 ·g -1 Average pore size of 22 nm);
(3) To solution IV 3g of NH was added 4 VO 3 10g of Ce (NO) 3 ) 3 ·6H 2 O is fully mixed, evaporation is carried out on a rotary evaporator at 80 ℃ for fourth mixing, and powder is obtained;
(4) Aging the powder for 12 hours, drying at 90 ℃ for 5 hours, and roasting at 200 ℃ for 3 hours, wherein the heating rate is 2 ℃/min; tabletting the roasted product, and screening to obtain 40-60 mesh catalyst particles to obtain the catalyst.
Comparative examples 1 to E
Preparing a heteropolyacid according to steps (1) - (3) of example 1, and then preparing a catalyst by a solid phase mixing method;
the specific process is as follows: 3g of NH 4 VO 3 10g of Ce (NO) 3 ) 3 ·6H 2 And calcining O in an air atmosphere at 550 ℃ for 7 hours to obtain vanadium oxide and cerium oxide.
The prepared heteropolyacid, vanadium oxide and cerium oxide were put into a planetary ball mill, milled for 8 hours at a rotation speed of 200rpm, and then the milled powder was calcined at 500 ℃ for 1 hour to obtain a catalyst. The specific surface area of the catalyst is 4m 2 Per gram, average pore diameter 14nm, bulk density 2.0g/cm 3 。
Example 2
(1) 0.8g of SnO 2 Dissolving in 50mL of 3mol/L HCl aqueous solution to obtain solution I; 3.9g (NH) 4 ) 10 W 12 O 41 ·5H 2 O is dissolved in 120mL of deionized water and heated to 50 ℃ to form solution II; then dropwise adding the solution I into the solution II while the solution I is hot, and cooling the mixed solution to room temperature to form a solution III;
(2) 36mL of 1.1mol/L tetramethylammonium hydroxide solution is added into the solution III, proper NaOH is added dropwise to adjust the pH value of the mixed solution to 5.6, and the mixed solution is heated at 60 ℃ for 45min to obtain solution IV;
(3) To the solution IV 30ml of 0.1mol/L FeSO are added dropwise 4 The solution is added in a water bath at 60 DEG CHeating for 40min, cooling to room temperature, and filtering to obtain solution V containing heteropolyacid (wherein the heteropolyacid comprises H 4 Sn 2 W 6 O 24 ·nH 2 O, acidity of 1.8mmol/g, specific surface area of 16m 2 ·g -1 Average pore size 15 nm);
(4) 1.8g of NH was added to solution V 4 VO 3 Mn (NO) 2g 3 ) 2 10g of Ce (NO) 3 ) 3 ·6H 2 O, fully mixing, evaporating at 70 ℃ on a rotary evaporator to obtain powder;
(5) Aging the powder for 24 hours, drying at 90 ℃ for 7 hours, roasting at 250 ℃ for 3 hours, wherein the heating rate is 4 ℃/min, tabletting the roasted catalyst, and screening to obtain 40-60 mesh catalyst particles to obtain the catalyst.
In the denitration catalyst, the weight ratio of the hetero atom, the polyatoms, the active component and the modifying auxiliary agent is 0.8 in terms of metal oxide: 3.5:2.4:4. the specific surface area of the denitration catalyst is 11m 2 Per gram, average pore diameter 16nm, bulk density 1.1g/cm 3 。
Example 2-A
A catalyst was prepared in a similar manner to example 2, except that: in the step (4), mn (NO) is not added 3 ) 2 ；
The step (4) is specifically as follows: 1.8g of NH was added to solution V 4 VO 3 10g of Ce (NO) 3 ) 3 ·6H 2 O, fully mixing, evaporating at 70 ℃ on a rotary evaporator to obtain powder,
the rest was the same as in example 2 to obtain a catalyst.
Example 2-B
A catalyst was prepared in a similar manner to example 2, except that: in step (4), NH is not added 4 VO 3 ；
The step (4) is specifically as follows: to solution V2 g of Mn (NO 3 ) 2 10g of Ce (NO) 3 ) 3 ·6H 2 O, fully mixing, evaporating at 70 ℃ on a rotary evaporator to obtain powder;
the rest was the same as in example 2 to obtain a catalyst.
Comparative example 2-A
The comparative example is the preparation of a heteropolyacid-free catalyst.
To 170ml deionized water was added 1.8g NH 4 VO 3 、2gMn(NO 3 ) 2 、10gCe(NO 3 ) 3 ·6H 2 O, thoroughly mixed and evaporated on a rotary evaporator at 70 ℃ to give a powder. The powder was dried at 90℃for 7h and calcined at 250℃for 3 h at a rate of 2℃per minute. Tabletting the roasted catalyst, and screening to obtain 40-60 mesh catalyst particles to obtain the catalyst.
Example 3
In a similar manner to example 1, except that the hetero atom contained in the heteropoly acid was phosphorus.
The specific process is as follows:
(1) 0.72g of P 2 O 5 Dissolving in 40mL of HCl aqueous solution (3 mol/L) to obtain solution I; 5.3g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O is dissolved in 100mL of deionized water and heated to 50 ℃ to form solution II; then, dropwise adding the solution I into the solution II at 50 ℃, and cooling the mixed solution to room temperature to form a solution III;
(2) Adding 20mL of 1.1mol/L tetramethylammonium hydroxide solution into the solution III, dropwise adding a proper NaOH solution to adjust the pH value of the mixed solution to 5.5, and then heating the mixed solution at 60 ℃ for 30min to obtain a solution IV;
(3) 16mL of 0.1mol/L FeSO was added to solution IV 4 Heating the solution at 60deg.C for 30min, cooling to room temperature, and filtering to obtain solution V containing heteropoly acid (wherein the heteropoly acid comprises H) 2 P 2 Mo 6 O 24 ·nH 2 O, acidity of 1.0mmol/g, specific surface area of 8m 2 ·g -1 Average pore size of 18 nm);
(4) To solution V3 g of NH was added 4 VO 3 10g of Ce (NO) 3 ) 3 ·6H 2 O is fully mixed and evaporated on a rotary evaporator at 80 ℃ to obtain powder;
(5) Aging the powder for 12 hours, drying at 90 ℃ for 5 hours, and roasting at 200 ℃ for 3 hours, wherein the heating rate is 2 ℃/min; tabletting the roasted product, and screening to obtain 40-60 mesh catalyst particles to obtain the catalyst.
In the denitration catalyst, the weight ratio of the hetero atom, the polyatoms, the active component and the modifying auxiliary agent is 0.72 in terms of metal oxide: 4.3:2.3:4. the specific surface area of the denitration catalyst is 14m 2 Per gram, average pore diameter 15nm, bulk density 0.9g/cm 3 。
Example 4
In a similar manner to example 1, except that the amounts of the respective raw materials used were different.
The specific process is as follows:
(1) 1.6g of Sb 2 O 3 Dissolving in 40mL of HCl aqueous solution (3 mol/L) to obtain solution I; 8.5g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O is dissolved in 100mL of deionized water and heated to 50 ℃ to form solution II; then dropwise adding the solution I into the solution II while the solution I is hot, and cooling the mixed solution to room temperature to form a solution III;
(2) 45mL of 1.1mol/L tetramethylammonium hydroxide solution was added to the solution III, and an appropriate NaOH was added dropwise to adjust the pH of the mixture to 5.5, followed by heating the mixture at 60℃for 30 minutes to give a solution IV (wherein the heteropolyacid composition H 2 Sb 2 Mo 12 O 40 ·nH 2 O, acidity of 1.6mmol/g, specific surface area of 11m 2 ·g -1 Average pore size 15 nm);
(3) 36ml of 0.1mol/L FeSO are added to the solution IV 4 Heating the solution at 60 ℃ for 30min, cooling to room temperature, and filtering to obtain a solution V containing heteropolyacid;
(4) To solution V5 g of NH was added 4 VO 3 4g of Ce (NO) 3 ) 3 ·6H 2 O, fully mixing, evaporating at 80 ℃ on a rotary evaporator to obtain powder;
(5) Aging the powder for 12 hours, drying at 90 ℃ for 5 hours, and roasting at 200 ℃ for 3 hours, wherein the heating rate is 2 ℃/min; tabletting the roasted product, and screening to obtain 40-60 mesh catalyst particles to obtain the catalyst.
In the denitration catalyst, the weight ratio of the hetero atom, the polyatoms, the active component and the modifying auxiliary agent is 1.6 in terms of metal oxide: 6.9:3.9:1.6. the specific surface area of the denitration catalyst is 16m 2 Per gram, average pore diameter 12nm, bulk density 1.0g/cm 3 。
Example 5
In a similar manner to example 1, except that in step (4), 3g of NH was added to the solution V 4 VO 3 3g of Ce (NO) 3 ) 3 ·6H 2 O is fully mixed and evaporated on a rotary evaporator at 80 ℃ to obtain powder;
the rest was the same as in example 1 to obtain a catalyst.
In the denitration catalyst, the weight ratio of the hetero atom, the polyatoms, the active component and the modifying auxiliary agent is 1 in terms of metal oxide: 4.3:2.3:1.2. the specific surface area of the denitration catalyst is 15m 2 Per gram, average pore diameter 14nm, bulk density 1.1g/cm 3 。
Test case
(1) The present invention tests XRD of the denitration catalysts prepared in the above examples and comparative examples, and exemplarily provides an XRD result pattern of the catalyst of example 1 and an XRD result pattern of the heteropolyacid prepared in comparative example 1-a, as shown in fig. 1. As can be seen from fig. 1, the denitration catalyst of the present invention has a crystal phase structure consistent with that of the heteropoly acid, which illustrates that the denitration catalyst provided by the present invention is a coupled structure of the heteropoly acid and metal ions (active component and modifying assistant), rather than a solid phase physical mixture of the heteropoly acid, the active component and the modifying assistant.
The heteropoly acid-containing denitration catalyst provided by the invention has a porous cage-shaped structure, hetero atoms and polyatoms form a porous space network structure, metals in the active component and the modification auxiliary agent are used as active centers to carry out coordination complexing with the heteropoly acid, so that a double-center catalyst structure with an active center and an acid center is formed, and a structural schematic diagram is shown in figure 2.
(2) The denitration catalysts prepared in the above examples and comparative examples were tested for activity.
Denitration efficiency is obtained by testing a small honeycomb test block in a fixed bed reactor under the flue gas condition simulating the working condition of a power plant, and specifically:
Filling 0.6g of the denitration catalyst into a fixed tubular reactor, and introducing simulated flue gas (600-1200 mg/Nm) 3 300-600ppm NH of NO 3 ，NH 3 The molar ratio of/NO is 1:1,3000-10000 mg/Nm 3 SO of (2) 2 5 vol% O 2 12-20 vol.% H 2 O，N 2 As balance gas), space velocity of 150000h -1 The denitration efficiency of the catalyst was measured at temperatures of 200℃and 420℃respectively, and the test results are shown in tables 1 to 3 below, respectively.
The denitration efficiency is calculated by adopting the following formula:
denitration efficiency/% = (C in -C out )/C in ×100
C in Concentration of NO in mg/Nm expressed in a fixed tubular reactor 3 ；
C out The concentration of NO in the fixed tubular reactor, mg/Nm 3 。
Table 1: catalysts at different temperatures with different H 2 Denitration efficiency of O (12%, 20%) content
Note that: table 1 simulates SO in flue gas 2 ＝6500mg/Nm 3 ，NO＝900mg/Nm 3 ，NH 3 The molar ratio of/NO is 1:1..
Table 2: the catalyst at different temperatures was different from NO (600 mg/Nm) 3 ，1200mg/Nm 3 ) Denitration efficiency of content
Note that: table 2 simulates H in flue gas 2 O=15 vol%, SO 2 ＝6500mg/Nm 3 ，NH 3 The molar ratio of/NO is 1:1.
table 3: catalyst at different temperatures with different SO' s 2 Content (3000 mg/Nm) 3 、10000mg/Nm 3 ) Is not limited by the denitration efficiency of (a)
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Note that: table 3 simulates H in flue gas 2 O=15 vol%, no=900 mg/Nm 3 ，NH 3 The molar ratio of/NO is 1:1.
from the above results, it can be seen that comparative example 1-a has low catalyst activity without the active component and the modifying assistant, i.e., the catalyst is a heteropolyacid alone, compared with example 1. Comparative example 1-B showed a decrease in catalyst activity compared to example 1, with only the active component in the catalyst and no modifying aid. Comparative examples 1-C compared with example 1, the catalyst had the same composition but no cage type heteropolyacid structure, and the catalyst was 20% H 2 O，1200mg/Nm 3 NO and 10000mg/Nm of (F) 3 SO of (2) 2 At this concentration, the catalytic activity decreases significantly.
The catalyst activity was higher in the presence of the dual active components (V and Mn) in examples 2-A, 2-B and 2; comparative example 2-A compared with example 2, the catalyst had the same active material but no cage-type heteropolyacid, and the catalyst was at 20% H 2 O、1200mg/Nm 3 NO and 10000mg/Nm of (F) 3 SO of (2) 2 At this concentration, the catalytic activity decreases significantly.
In conclusion, the heteropolyacid-containing denitration catalyst provided by the invention is prepared by reacting H with a catalyst at 200-420 DEG C 2 The fluctuation of O concentration is 12-20%, and the fluctuation of NO concentration is 600-1200mg/Nm 3 ，SO 2 Concentration fluctuation is 3000-10000mg/Nm 3 Under the condition, has higher denitration efficiency and stronger H resistance 2 O, NOx and SO 2 The flue gas capacity has higher stability, can meet the requirements of denitration of start-up and shut-down and deep peak shaving under the complex flue gas condition and the operation working condition of the coal-fired power plant, and has wide industrial application prospect.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A heteropoly acid-containing denitration catalyst is characterized in that the denitration catalyst contains heteropoly acid, an active component and a modification auxiliary agent;
the heteropoly acid is in a keggin cage structure, and hetero atoms in the heteropoly acid are antimony atoms and/or tin atoms; the polyatoms in the heteropoly acid are selected from at least one of molybdenum atoms, tungsten atoms, niobium atoms and tantalum atoms;
the active component contains at least one of vanadium element, iron element, manganese element and copper element;
the modifying auxiliary agent contains at least one of cerium element, lanthanum element, praseodymium element and erbium element;
in the denitration catalyst, the weight ratio of the hetero atom to the polyatoms to the active component to the modifying auxiliary agent is 0.1-5:0.5-10:0.1-5:1-10, wherein the weight of the hetero atom, the polyatoms, the active component and the modifying auxiliary agent is calculated by the weight of oxide containing metal elements;
and the preparation method of the heteropolyacid-containing denitration catalyst comprises the following steps:
(1) First mixing a solution I containing an element A with a solution II containing an element B to obtain a solution III, wherein the element A is an antimony element and/or a tin element, and the element B is at least one of a molybdenum element, a niobium element, a tungsten element and a tantalum element;
(2) Carrying out second mixing on the solution III and a tetraalkylammonium hydroxide solution to obtain a solution IV;
(3) Thirdly mixing the solution IV with a transition metal sulfate solution to obtain a solution V containing heteropolyacid;
(4) Fourth mixing the solution V, a compound I containing an element C and a compound II containing an element D to obtain powder, wherein the element C is at least one of vanadium element, iron element, manganese element and copper element; the element D is at least one of cerium element, lanthanum element, praseodymium element and erbium element;
(5) And (3) drying and roasting the powder in sequence to obtain the denitration catalyst.
2. The heteropoly acid-containing denitration catalyst according to claim 1, wherein the weight ratio of the hetero atom, the multi atom, the active component, and the modifying auxiliary agent is 0.5 to 2:1-6:0.5-3:3-5, wherein the weight of the hetero atom, the polyatoms, the active component and the modifying auxiliary agent is calculated by the weight of the oxide containing metal elements.
3. The heteropolyacid-containing denitration catalyst according to claim 1, wherein the weight ratio of the active component to the modifying auxiliary agent is 1:1-2, the weight of the active component and the weight of the modifying auxiliary agent are calculated by the oxide of the contained metal element;
And/or the active component contains at least two of vanadium element, iron element, manganese element and copper element;
and/or, the denitration catalyst has a cage-type porous structure;
and/or the specific surface area of the denitration catalyst is 5-20m 2 •g -1 Average pore diameter of 10-20nm, bulk density of 0.7-1.3g/cm 3 。
4. The heteropolyacid-containing denitration catalyst according to any one of claims 1 to 3, wherein the active component contains vanadium element and manganese element, and the molar ratio of vanadium element and manganese element is 1:0.2-7.
5. The heteropolyacid-containing denitration catalyst according to claim 4, wherein the heteropolyacid is at least one selected from the group consisting of antimony molybdic acid, antimony niobic acid, antimony tantalic acid, antimony tungstic acid, tin molybdic acid, tin niobic acid, tin tungstic acid and tin tantalic acid;
and/or the acid of the heteropolyacid is 1-2mmol/g, and the specific surface area is 5-20m 2 •g -1 The average pore diameter is 10-20nm.
6. A process for preparing the heteropolyacid-containing denitration catalyst as claimed in any one of claims 1 to 5, characterized by comprising:
(1) First mixing a solution I containing an element A with a solution II containing an element B to obtain a solution III, wherein the element A is an antimony element and/or a tin element, and the element B is at least one of a molybdenum element, a niobium element, a tungsten element and a tantalum element;
(2) Carrying out second mixing on the solution III and a tetraalkylammonium hydroxide solution to obtain a solution IV;
(3) Thirdly mixing the solution IV with a transition metal sulfate solution to obtain a solution V containing heteropolyacid;
(4) Fourth mixing the solution V, a compound I containing an element C and a compound II containing an element D to obtain powder, wherein the element C is at least one of vanadium element, iron element, manganese element and copper element; the element D is at least one of cerium element, lanthanum element, praseodymium element and erbium element;
(5) Sequentially drying and roasting the powder to obtain a denitration catalyst;
the dosages of the solution I, the solution II, the compound I and the compound II are such that the content weight ratio of the element A, the element B, the element C and the element D calculated by metal oxide in the obtained denitration catalyst is 0.1-5:0.5-10:0.1-5:1-10.
7. The method of claim 6, wherein in step (1), the first mixing conditions comprise: the temperature is 30-80 ℃;
and/or, in step (2), the conditions of the second mixing include: the temperature is 50-60 ℃ and the time is 30-60min;
And/or, in step (3), the conditions of the third mixing include: the temperature is 50-60 ℃ and the time is 30-60min;
and/or, in step (4), the fourth mixing conditions include: the process is carried out under the condition of rotary evaporation, and the temperature is 70-90 ℃.
8. The method of claim 6, wherein in step (5), the drying conditions include: the drying temperature is 85-95 ℃ and the drying time is 3-12h;
and/or, in step (5), the firing conditions include: the roasting temperature is 200-250 ℃ and the roasting time is 2-5h.
9. The method of any of claims 6-8, wherein the heteropolyacid is selected from at least one of antimony molybdic acid, antimony niobic acid, antimony tantalic acid, antimony tungstic acid, tin molybdic acid, tin niobic acid, tin tungstic acid, and tin tantalic acid.
10. A heteropolyacid-containing denitration catalyst produced by the method according to any one of claims 6 to 9.
11. Use of the heteropolyacid-containing denitration catalyst as claimed in any one of claims 1 to 5 and 10 in flue gas denitration.
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