CN116116454B - Supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for cement kiln and preparation method and application thereof - Google Patents
Supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for cement kiln and preparation method and application thereof Download PDFInfo
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- CN116116454B CN116116454B CN202310186430.6A CN202310186430A CN116116454B CN 116116454 B CN116116454 B CN 116116454B CN 202310186430 A CN202310186430 A CN 202310186430A CN 116116454 B CN116116454 B CN 116116454B
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- Prior art keywords
- resistant
- oxide
- scr denitration
- denitration catalyst
- auxiliary agent
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000011593 sulfur Substances 0.000 title claims abstract description 44
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000004568 cement Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 58
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 30
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920002472 Starch Polymers 0.000 claims abstract description 7
- 239000008107 starch Substances 0.000 claims abstract description 7
- 235000019698 starch Nutrition 0.000 claims abstract description 7
- 239000004113 Sepiolite Substances 0.000 claims abstract description 5
- 239000002808 molecular sieve Substances 0.000 claims abstract description 5
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 5
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229960000892 attapulgite Drugs 0.000 claims abstract description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 40
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- 238000001354 calcination Methods 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 16
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 239000000428 dust Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 6
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000013538 functional additive Substances 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002907 Guar gum Polymers 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 208000020584 Polyploidy Diseases 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000007765 extrusion coating Methods 0.000 claims 1
- 238000001771 vacuum deposition Methods 0.000 abstract description 5
- 239000011241 protective layer Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 46
- 238000012360 testing method Methods 0.000 description 11
- 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 8
- 239000010410 layer Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 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 4
- 235000010981 methylcellulose Nutrition 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- 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 2
- 239000000126 substance Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- -1 coking Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002918 waste heat Substances 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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Abstract
The invention relates to a supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for a cement kiln and a preparation method and application thereof, wherein the SCR denitration catalyst comprises a carrier, an active component, a reactive auxiliary agent, a forming auxiliary agent and a functional auxiliary agent, wherein the active component comprises an oxide of Fe and an oxide of V, the reactive auxiliary agent comprises a transition metal oxide and a rare earth metal oxide, the functional auxiliary agent is ZSM-5 and one or a combination of more selected from starch, attapulgite, sepiolite powder, MCM-41, ethylene glycol and a 4A molecular sieve, and the ZSM-5 accounts for more than 15% of the total mass of the functional auxiliary agent; according to the invention, functional auxiliary agents are utilized to form a protective layer rich in pore channels around the transition metal oxide active components which are easy to generate sulfur poisoning in a vacuum coating mode, and then rare earth metal oxide and vanadium oxide are subjected to a step-by-step impregnation mode, so that the phenomenon of mutual coating caused by mixed co-impregnation is avoided, and the synergistic effect among different elements is exerted to the greatest extent.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for a cement kiln, and a preparation method and application thereof.
Background
Nitrogen oxides are one of the atmospheric pollutants, and not only can lead to photochemical smog, but also have great adverse effects on human health. Although the emission concentration limit of nitrogen oxides in the emission standard of the atmospheric pollution of the cement industry (GB 4915-2013) is 400mg/m 3 (the special emission limit of enterprises in important areas should be within 320mg/m 3). In recent years, more strict regulations are provided for emission of nitrogen oxides (NOx) in the cement industry in various places, ultra-low emission standards are continuously put out, and nitrogen oxides are even required to be reduced to 50mg/m 3 in some key areas.
In order to meet the increasingly severe emission index of nitrogen oxides, a plurality of sets of high-temperature and medium-temperature SCR denitration systems are successively arranged in the cement industry in recent years, but the high-temperature SCR denitration project at present has the problems of high dust content and easy blockage, and the medium-temperature SCR denitration project faces the problem that the service time of the catalyst is influenced under the high-sulfur condition.
Chinese patent publication No. CN103585885A discloses a low-temperature denitration catalyst module and a cement kiln low-temperature selective catalytic reduction denitration system, but in its embodiment, SO 2 gas which is easy to deactivate the catalyst is not introduced, and the applicable temperature section of the catalyst is above 170 ℃, and the temperature of the gas after a general dust remover is below 140 ℃ and even lower, SO that the gas needs to be heated, resulting in increased energy consumption; chinese patent publication No. CN109876798A discloses a V-Mn-based low-temperature SCR denitration catalyst and a preparation method thereof, but only a powdery catalyst is prepared for denitration test, when the powdery catalyst is prepared into an integral catalyst, denitration efficiency is affected by different degrees, and the stability test under the condition of sulfur and water is not mentioned in the invention; chinese patent publication No. CN106268784a discloses a low-temperature flat-plate denitration catalyst and a preparation method thereof, but no steam is introduced in the stability test, and the catalyst is deactivated due to the cooperation of steam and SO 2, SO that verification is required. Chinese patent publication No. CN105521777a discloses a preparation method of a low-temperature denitration catalyst, which has higher stability under low-temperature conditions, but the stability test is not performed in the examples. Therefore, the development of the denitration catalyst with wide applicable temperature range and good sulfur and water resistance is of great significance.
Disclosure of Invention
Aiming at the problems of higher using temperature and poorer sulfur and water resistance of the existing SCR denitration catalyst, one of the purposes of the invention is to provide a preparation method of a load type wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for a cement kiln, the SCR denitration catalyst adopts a honeycomb or plate type form as a support, and is molded by steps of extrusion, dipping, coating, calcining and the like, and the preparation method is simple, strong in repeatability and easy for large-scale mass production.
The invention further aims to provide the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln, which has a wide denitration temperature window and good sulfur resistance and water resistance.
The invention also aims to provide an application of the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln, and the SCR denitration catalyst can remove NOx in flue gas at a wide temperature of 100-350 ℃.
The invention is realized in this way, a preparation method of a supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for a cement kiln, the SCR denitration catalyst comprises a carrier, an active component, an active auxiliary agent, a forming auxiliary agent and a functional auxiliary agent, wherein the active component comprises an oxide of Fe and an oxide of V, the active auxiliary agent comprises a transition metal oxide and a rare earth metal oxide, the functional auxiliary agent is ZSM-5 and one or a combination of more selected from starch, attapulgite, sepiolite powder, MCM-41, glycol and a 4A molecular sieve, and the ZSM-5 accounts for more than 15% of the total mass of the functional auxiliary agent;
The preparation method of the SCR denitration catalyst comprises the following specific steps:
(1) Uniformly mixing the carrier powder, washing in deionized water for 1-2 times, and drying at 60-80 ℃ to obtain a dried carrier;
(2) Mixing the dried carrier powder in the step (1) with a certain amount of deionized water and a forming additive to prepare a mud-shaped blank, extruding, forming or coating and pressing the mud-shaped blank on a plate-type structural frame, standing for 10-24 h at normal temperature, drying for 5-10 h at 100 ℃, calcining for 2-5 h at 250 ℃, and heating at a speed of 5 ℃/min-10 ℃/min to obtain a formed carrier;
(3) Preparing a precursor of iron oxide in the active component and a precursor of transition metal oxide in the active additive into a solution with a certain concentration, soaking the blank on the molded carrier, standing for 5h at normal temperature, drying at 80 ℃ for 2-5 h, calcining at 300-450 ℃ for 2-5 h, and heating at a speed of 2 ℃/min-5 ℃/min to obtain an intermediate sample of the loaded transition metal oxide;
(4) Uniformly mixing functional auxiliary agents, adding a proper amount of deionized water to prepare a suspension with a certain concentration, and uniformly covering the suspension on the intermediate sample obtained in the step (3) by adopting vacuum polyploid volume excess coating; standing for 5h at normal temperature, drying at 80 ℃ for 2-5 h, calcining at 300-450 ℃ for 2-5 h, and heating at a speed of 2-5 ℃/min to obtain a functional auxiliary agent modified intermediate sample;
(5) Uniformly mixing precursors of rare earth metal oxides in the active auxiliary agent, adding a proper amount of deionized water to prepare a solution with a certain concentration, soaking a haploid product on the intermediate sample obtained in the step (4), standing for 5h at normal temperature, drying at 80 ℃ for 2-5 h, calcining at 300-450 ℃ for 1-2 h, and heating at a speed of 2 ℃/min-5 ℃/min; obtaining an intermediate sample of the supported rare earth metal oxide;
(6) Adding a proper amount of deionized water into a precursor of the oxide of V in the active component to prepare a solution with a certain concentration, soaking the haploid product on the intermediate sample obtained in the step (5), standing for 5h at normal temperature, drying at 80 ℃ for 2-5 h, calcining at 450-550 ℃ for 2-5 h, and heating at a speed of 2 ℃/min-5 ℃/min to obtain the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln.
In the above technical scheme, preferably, the carrier accounts for 85% -88% of the total mass of the catalyst; iron oxide accounts for 1-3% of the total mass of the catalyst; the oxide of vanadium accounts for 0.5 to 5 percent of the total mass of the catalyst; the active auxiliary agent accounts for 0.2 to 3 percent of the total mass of the catalyst; the forming auxiliary agent accounts for 3-10% of the total mass of the catalyst; the functional auxiliary agent accounts for 0.1 to 1 percent of the total mass of the catalyst; the sum of the mass percentages of the carrier, the active component, the active auxiliary agent, the forming auxiliary agent and the functional auxiliary agent is 100 percent.
In the above technical scheme, preferably, the carrier is titanium dioxide and one or a combination of more than one of silicon dioxide, magnesium oxide and aluminum oxide, and the titanium dioxide accounts for 75-82% of the total mass of the catalyst.
In the above technical scheme, preferably, the precursor of the iron oxide is one or a combination of several of ferric nitrate, ferric acetate, ferric chloride and ferric sulfate, the iron oxide comprises ferric oxide and ferroferric oxide, and the ferric oxide accounts for more than 70% of the total mass of the iron oxide;
The V oxide is vanadium pentoxide, and the precursor of the vanadium pentoxide is a mixture of ammonium metavanadate and oxalic acid, a mixture of ammonium metavanadate and lactic acid, or a combination of two or more of vanadyl oxalate.
In the above technical solution, preferably, in the active auxiliary agent, according to the mass ratio, the transition metal oxide: rare earth metal oxide=1:2 to 2:1.
In the above technical solution, preferably, the transition metal in the transition metal oxide is cobalt and one or a combination of several selected from manganese, chromium, nickel, copper, zirconium, molybdenum and tungsten, and the precursor of the transition metal oxide is one or a combination of several selected from nitrate, acetate, chloride and sulfate, wherein cobalt oxide accounts for more than 30% of the total mass of the transition metal oxide.
In the above technical solution, preferably, the rare earth metal in the rare earth metal oxide is lanthanum and cerium, and is selected from holmium and/or praseodymium, and the precursor of the rare earth metal oxide is one or a combination of a plurality of nitrate, acetate, chloride or sulfate, wherein the lanthanum-cerium solid solution accounts for more than 40% of the total mass of the rare earth metal oxide.
In the above technical solution, preferably, the forming auxiliary agent is one or a combination of several of deionized water, dilute nitric acid, dilute acetic acid, ammonia water, methylcellulose, PEO, kaolin, polyethylene glycol and guar gum.
The supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln is prepared by adopting the preparation method of the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln.
The application of the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln is characterized in that the SCR denitration catalyst is used for catalyzing and removing NOx, the NOx removal efficiency is more than 85% when the reaction temperature is 100-350 ℃, and the catalyst can be used for flue gas denitration in which SO 2 and water exist and is suitable for flue gas denitration in a high-dust environment.
The principle of the invention is as follows:
the invention adopts the principle of the cooperation of the multifunctional active components to ensure that the SCR denitration catalyst has higher denitration efficiency in a wider temperature range; the vacuum coating method is adopted, and a protective layer and a pore-forming auxiliary agent are added, so that the surface of the low-temperature denitration active component is uniformly covered with the protective layer with rich pore channel structures; the mode of coating the low-temperature denitration active components by the functional auxiliary agent ensures that ammonium sulfate and ammonium nitrate cannot penetrate into the inner layer, is not easy to generate and accumulate on the surfaces of the low-temperature denitration active components, and improves the sulfur resistance of the low-temperature section of the SCR denitration catalyst; the SCR denitration catalyst provided by the invention has two types of honeycomb and plate, wherein the plate denitration catalyst is particularly suitable for flue gas denitration with high dust content, and compared with the honeycomb catalyst, the system resistance can be greatly reduced.
The invention has the advantages and positive effects that:
(1) The supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln can realize the removal of nitrogen oxides in a wider temperature range aiming at the flue gas working condition of the cement kiln, can ensure good denitration efficiency for the low-temperature SCR technology with lower temperature or the working condition with larger flue gas temperature fluctuation, can be used for the removal of nitrogen oxides in a high-sulfur water-containing atmosphere, and has the NOx removal efficiency of more than 85 percent at 100-350 ℃.
(2) According to the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln, a functional auxiliary agent is used for forming a protective layer rich in pore channels around a transition metal oxide active component and the auxiliary agent which are easy to generate sulfur poisoning in a vacuum coating mode, so that substances such as ammonium bisulfate and the like are prevented from being covered on the surface of the active component, and the active sites of the catalyst are reduced; and then the rare earth metal oxide auxiliary agent and the vanadium oxide are immersed step by step, so that the phenomenon of mutual cladding caused by mixed co-immersion is avoided, and the synergistic effect among different elements is exerted to the greatest extent.
(3) The invention adopts a formula of transition metal coupling rare earth metal elements to realize wide-temperature denitration, and takes Fe oxide and V oxide as main active components, wherein the V oxide active components mainly play a role of Wen Duantuo nitrate, and the V oxide active components firstly contact smoke and have better sulfur resistance; the rare earth metal oxide auxiliary agent and the oxide active component of V synergistically play a role in denitration and play a role in hydrophobic; the functional auxiliary agent is positioned in the inner layer of the active component and can protect the inner transition metal oxide active component; the oxidation of Fe and other transition metal oxides are positioned at the innermost layer, are protected and are not easy to poison, and the denitration effect of the low-temperature section is cooperatively exerted, so that the denitration efficiency is high.
(4) The plate-type SCR denitration catalyst product prepared by the invention can be suitable for removing nitrogen oxides in a high-temperature and high-dust environment, and the increase of system resistance is small. The honeycomb SCR denitration catalyst product prepared by the invention can be suitable for removing nitrogen oxides in medium-temperature medium-dust and low-temperature low-dust environments, and can also be used for removing nitrogen oxides in industries such as steel, coking, chemical industry and the like.
(5) The preparation method of the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln has the advantages of high stability, easy operation, strong repeatability and easy realization of large-scale mass production.
Drawings
FIG. 1 is a schematic diagram of an apparatus for vacuum coating in a preparation method of an SCR denitration catalyst provided by an embodiment of the present invention;
fig. 2 is a schematic structural diagram of an SCR denitration catalyst provided by an embodiment of the present invention.
In the figure: 101-vacuum pumping; 102-sealing a cover plate; 103-vacuum dipping kettle; 104-suspension; 105-intermediate sample; 201-a carrier layer; 202-transition metal active component layer; 203-a functional auxiliary layer; 204-vanadium-based active component and rare earth metal active component layer.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a preparation method of a supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for a cement kiln, which comprises a carrier, an active component, an active auxiliary agent, a forming auxiliary agent and a functional auxiliary agent, wherein the active component comprises an oxide of Fe and an oxide of V, the active auxiliary agent comprises a transition metal oxide and a rare earth metal oxide, the functional auxiliary agent is ZSM-5 and one or a combination of more selected from starch, attapulgite, sepiolite powder, MCM-41, ethylene glycol and a 4A molecular sieve, and the ZSM-5 accounts for more than 15% of the total mass of the functional auxiliary agent.
The carrier accounts for 85% -88% of the total mass of the catalyst; iron oxide accounts for 1-3% of the total mass of the catalyst; the oxide of vanadium accounts for 0.5 to 5 percent of the total mass of the catalyst; the active auxiliary agent accounts for 0.2 to 3 percent of the total mass of the catalyst; the forming auxiliary agent accounts for 3-10% of the total mass of the catalyst; the functional auxiliary agent accounts for 0.1 to 1 percent of the total mass of the catalyst; the sum of the mass percentages of the carrier, the active component, the active auxiliary agent, the forming auxiliary agent and the functional auxiliary agent is 100 percent.
The carrier is titanium dioxide and one or a combination of more than one of silicon dioxide, magnesium oxide and aluminum oxide, and the titanium dioxide accounts for 75-82% of the total mass of the catalyst.
The precursor of the iron oxide is one or a combination of more than one of ferric nitrate, ferric acetate, ferric chloride and ferric sulfate, the iron oxide comprises ferric oxide and ferroferric oxide, and the ferric oxide accounts for more than 70% of the total mass of the iron oxide;
The V oxide is vanadium pentoxide, and the precursor of the vanadium pentoxide is a mixture of ammonium metavanadate and oxalic acid, a mixture of ammonium metavanadate and lactic acid, or a combination of two or more of vanadyl oxalate.
In the active auxiliary agent, the transition metal oxide is prepared from the following components in percentage by mass: rare earth metal oxide=1:2 to 2:1.
The transition metal in the transition metal oxide is cobalt and one or a combination of more than one of manganese, chromium, nickel, copper, zirconium, molybdenum and tungsten, and the precursor of the transition metal oxide is one or a combination of more than one of nitrate, acetate, chloride and sulfate, wherein cobalt oxide accounts for more than 30% of the total mass of the transition metal oxide.
The rare earth metal in the rare earth metal oxide is lanthanum and cerium, and is holmium and/or praseodymium, the precursor of the rare earth metal oxide is one or a combination of a plurality of nitrate, acetate, chloride or sulfate, wherein lanthanum cerium solid solution accounts for more than 40% of the total mass of the rare earth metal oxide.
The forming auxiliary agent is one or a combination of more of deionized water, dilute nitric acid, dilute acetic acid, ammonia water, methylcellulose, PEO, kaolin, polyethylene glycol and guar gum.
The preparation method of the SCR denitration catalyst comprises the following specific steps:
(1) Uniformly mixing the carrier powder, washing in deionized water for 1-2 times, and drying at 60-80 ℃ to obtain a dried carrier;
(2) Mixing the dried carrier powder in the step (1) with a certain amount of deionized water and a forming additive to prepare a mud-shaped blank, extruding, forming or coating and pressing the mud-shaped blank on a plate-type structural frame, standing for 10-24 h at normal temperature, drying for 5-10 h at 100 ℃, calcining for 2-5 h at 250 ℃, and heating at a speed of 5 ℃/min-10 ℃/min to obtain a formed carrier;
(3) Preparing a precursor of iron oxide in the active component and a precursor of transition metal oxide in the active additive into a solution with a certain concentration, soaking the blank on the molded carrier, standing for 5h at normal temperature, drying at 80 ℃ for 2-5 h, calcining at 300-450 ℃ for 2-5 h, and heating at a speed of 2 ℃/min-5 ℃/min to obtain an intermediate sample of the loaded transition metal oxide;
(4) Uniformly mixing functional auxiliary agents, adding a proper amount of deionized water to prepare a suspension with a certain concentration, and uniformly covering the suspension on the intermediate sample obtained in the step (3) by adopting vacuum polyploid volume excess coating; standing for 5h at normal temperature, drying at 80 ℃ for 2-5 h, calcining at 300-450 ℃ for 2-5 h, and heating at a speed of 2-5 ℃/min to obtain a functional auxiliary agent modified intermediate sample; a schematic view of the vacuum coating apparatus is shown in fig. 1;
(5) Uniformly mixing precursors of rare earth metal oxides in the active auxiliary agent, adding a proper amount of deionized water to prepare a solution with a certain concentration, soaking a haploid product on the intermediate sample obtained in the step (4), standing for 5h at normal temperature, drying at 80 ℃ for 2-5 h, calcining at 300-450 ℃ for 1-2 h, and heating at a speed of 2 ℃/min-5 ℃/min; obtaining an intermediate sample of the supported rare earth metal oxide;
(6) Adding a proper amount of deionized water into a precursor of the oxide of V in the active component to prepare a solution with a certain concentration, soaking the haploid product on the intermediate sample obtained in the step (5), standing for 5h at normal temperature, drying at 80 ℃ for 2-5 h, calcining at 450-550 ℃ for 2-5 h, and heating at a speed of 2 ℃/min-5 ℃/min to obtain the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln. The structure of the SCR denitration catalyst is shown in fig. 2.
The present invention will be described in further detail below.
The preparation method is a conventional method unless otherwise specified, and all raw materials used can be obtained from public commercial sources unless otherwise specified.
Example 1
(1) Mixing a certain amount of titanium dioxide and silicon dioxide powder uniformly, washing in deionized water for 1 time, and drying at 80 ℃ to obtain dried carrier powder;
(2) Uniformly mixing the carrier powder dried in the step (1) with a certain amount of deionized water, dilute nitric acid, PEO and kaolin to prepare a mud-shaped blank, coating and pressing the mud-shaped blank on a plate-type structural frame, standing for 24 hours at normal temperature, drying for 10 hours at 100 ℃, calcining for 5 hours at 250 ℃, and heating at a speed of 5 ℃/min to obtain a molded carrier;
(3) Preparing a certain amount of ferric nitrate, cobalt nitrate and ammonium molybdate into a solution with a certain concentration, immersing a haploid product on a molding carrier, standing for 5h at normal temperature, drying for 2h at 80 ℃, calcining for 2h at 450 ℃, and heating at a speed of 2 ℃/min to obtain an intermediate sample of the supported transition metal oxide;
(4) Uniformly mixing a certain amount of starch, ZSM-5 and ethylene glycol, adding a proper amount of deionized water to prepare a suspension with a certain concentration, and uniformly covering the suspension on the intermediate sample obtained in the step (3) by adopting vacuum multi-volume excessive coating; standing for 5h at normal temperature, drying for 5h at 80 ℃, calcining for 3h at 450 ℃, and obtaining a functional additive modified intermediate sample at a heating rate of 5 ℃/min;
(5) Uniformly mixing lanthanum nitrate, cerium nitrate and praseodymium nitrate, adding a proper amount of deionized water to prepare a solution with a certain concentration, soaking a haploid product on the intermediate sample obtained in the step (4), standing for 5 hours at normal temperature, drying for 5 hours at 80 ℃, calcining for 2 hours at 450 ℃, and heating at a speed of 5 ℃/min; obtaining an intermediate sample of the supported rare earth metal oxide;
(6) Adding a certain amount of vanadyl oxalate, ammonium metavanadate and lactic acid into a proper amount of deionized water to prepare a solution with a certain concentration, soaking a haploid product on the intermediate sample obtained in the step (5), standing for 5 hours at normal temperature, drying for 5 hours at 80 ℃, calcining for 5 hours at 450 ℃, and obtaining a load type wide-temperature sulfur-resistant water-resistant SCR denitration catalyst product for a cement kiln at a heating rate of 2 ℃/min.
Example 2
(1) Mixing a certain amount of titanium dioxide and magnesia powder uniformly, washing in deionized water for 1 time, and drying at 80 ℃ to obtain dried carrier powder;
(2) Uniformly mixing the carrier powder dried in the step (1) with a certain amount of deionized water, dilute acetic acid, PEO and polyethylene glycol to prepare a mud-shaped blank, adopting a honeycomb ceramic die for extrusion molding, standing at normal temperature for 24 hours, drying at 100 ℃ for 10 hours, calcining at 250 ℃ for 5 hours, and heating at a speed of 5 ℃/min to obtain a molded carrier;
(3) Preparing a certain amount of ferric nitrate, cobalt nitrate and manganese nitrate into a solution with a certain concentration, immersing a haploid product on a molding carrier, standing for 5 hours at normal temperature, drying for 2 hours at 80 ℃, calcining for 2 hours at 450 ℃, and obtaining an intermediate sample of a supported transition metal oxide at a heating rate of 2 ℃/min;
(4) Uniformly mixing a certain amount of starch, MCM-41 and ethylene glycol, adding a proper amount of deionized water to prepare a suspension with a certain concentration, and uniformly covering the suspension on the intermediate sample obtained in the step (3) by adopting vacuum multi-volume excessive coating; standing for 5h at normal temperature, drying for 5h at 80 ℃, calcining for 3h at 450 ℃, and obtaining a functional additive modified intermediate sample at a heating rate of 5 ℃/min;
(5) Uniformly mixing lanthanum nitrate, cerium nitrate, praseodymium nitrate and holmium nitrate, adding a proper amount of deionized water to prepare a solution with a certain concentration, soaking a haploid volume on the intermediate sample obtained in the step (4), standing for 5h at normal temperature, drying for 5h at 80 ℃, calcining for 2h at 450 ℃, and heating at a speed of 5 ℃/min; obtaining an intermediate sample of the supported rare earth metal oxide;
(6) Adding proper deionized water into vanadyl oxalate, ammonium metavanadate and oxalic acid to prepare a solution with a certain concentration, soaking a haploid product on the intermediate sample obtained in the step (5), standing for 5 hours at normal temperature, drying for 5 hours at 80 ℃, calcining for 5 hours at 450 ℃, and heating at a speed of 2 ℃/min to obtain a load type wide-temperature sulfur-resistant water-resistant SCR denitration catalyst product for a cement kiln.
Example 3
(1) Mixing a certain amount of titanium dioxide, magnesium oxide and alumina powder uniformly, washing in deionized water for 1 time, and drying at 80 ℃ to obtain dried carrier powder;
(2) Uniformly mixing the carrier powder dried in the step (1) with a certain amount of deionized water, ammonia water, PEO and methyl cellulose to prepare a mud-shaped blank, adopting a honeycomb ceramic die for extrusion molding, standing at normal temperature for 24 hours, drying at 100 ℃ for 10 hours, calcining at 250 ℃ for 5 hours, and heating at a speed of 5 ℃/min to obtain a molded carrier;
(3) Preparing a certain amount of ferric nitrate, cobalt nitrate, ammonium molybdate and ammonium metatungstate into a solution with a certain concentration, immersing a haploid product on a molding carrier, standing for 5h at normal temperature, drying at 80 ℃ for 2h, calcining at 420 ℃ for 2h, and obtaining an intermediate sample of a supported transition metal oxide at a heating rate of 2 ℃/min;
(4) Uniformly mixing a certain amount of sepiolite powder, a 4A molecular sieve and starch, adding a proper amount of deionized water to prepare a suspension with a certain concentration, and uniformly covering the suspension on the intermediate sample obtained in the step (3) by adopting vacuum multi-volume excessive coating; standing for 5h at normal temperature, drying for 5h at 80 ℃, calcining for 3h at 450 ℃, and obtaining a functional additive modified intermediate sample at a heating rate of 5 ℃/min;
(5) Uniformly mixing lanthanum nitrate, cerium nitrate and holmium nitrate, adding a proper amount of deionized water to prepare a solution with a certain concentration, soaking a haploid product on the intermediate sample obtained in the step (4), standing for 5 hours at normal temperature, drying for 5 hours at 80 ℃, calcining for 2 hours at 450 ℃, and heating at a speed of 5 ℃/min; obtaining an intermediate sample of the supported rare earth metal oxide;
(6) Uniformly mixing a certain amount of ammonium metavanadate, oxalic acid and lactic acid, adding a proper amount of deionized water to prepare a solution with a certain concentration, soaking a haploid product on the intermediate sample obtained in the step (5), standing at normal temperature for 5 hours, drying at 80 ℃ for 5 hours, calcining at 450 ℃ for 5 hours, and heating at a speed of 2 ℃/min to obtain a load type wide-temperature sulfur-resistant water-resistant SCR denitration catalyst product for a cement kiln.
Comparative example 1
Unlike example 1, step (4) was absent.
Comparative example 2
Unlike example 2, step (4) was absent.
Comparative example 3
(1) Mixing a certain amount of titanium dioxide, magnesium oxide and alumina powder uniformly, washing in deionized water for 1 time, and drying at 80 ℃ to obtain dried carrier powder;
(2) Uniformly mixing the carrier powder dried in the step (1) with a certain amount of deionized water, ammonia water, PEO and methyl cellulose to prepare a mud-shaped blank, adopting a honeycomb ceramic die for extrusion molding, standing at normal temperature for 24 hours, drying at 100 ℃ for 10 hours, calcining at 250 ℃ for 5 hours, and heating at a speed of 5 ℃/min to obtain a molded carrier;
(3) Preparing a certain amount of ferric nitrate, cobalt nitrate, ammonium molybdate and ammonium metatungstate into a solution with a certain concentration, immersing a haploid product on a formed catalyst carrier, standing for 5h at normal temperature, drying at 80 ℃ for 2h, calcining at 420 ℃ for 2h, and obtaining an intermediate sample of a supported transition metal oxide at a heating rate of 2 ℃/min;
(5) Uniformly mixing lanthanum nitrate, cerium nitrate, holmium nitrate, ammonium metavanadate and oxalic acid, adding a proper amount of deionized water to prepare a solution with a certain concentration, soaking a haploid volume on the intermediate sample obtained in the step (4), standing for 5h at normal temperature, drying for 5h at 80 ℃, calcining for 2h at 450 ℃, and heating at a speed of 5 ℃/min; obtaining the supported SCR denitration catalyst product for the cement kiln.
Performance testing
The laboratory adopts a tubular fixed reaction bed to test the activity and the denitration stability of the SCR denitration catalyst, the SCR denitration catalysts prepared in examples 1-3 and comparative examples 1-3 are respectively tested for eliminating nitrogen oxides under the condition of introducing sulfur dioxide and water, the denitration efficiency is tested after the stability test is compared by a common 7-day life test (168 h) for the catalyst test, and the catalyst is tested by using a honeycomb catalyst to be broken into particles or a plate-type catalyst coating to be broken into particles, wherein the particle size is 2-3 mm.
Test conditions: the test temperatures are 100 ℃,200 ℃ and 300 ℃ respectively, and correspond to the positions of the outlet of the cement kiln preheater C1, the outlet of the waste heat boiler and the outlet of the kiln tail dust collector respectively, the NO inlet concentration is 500mg/Nm 3,NH3, the inlet concentration is 500mg/Nm 3、O2 and 5% (v/v), N 2 is balance gas, and the gas volume airspeed is 4000h -1. The concentration of NO at the inlet and outlet of the monolithic catalyst is detected by a nitrogen oxide detector, and the analysis results are shown in tables 1, 2 and 3.
TABLE 1 test results (100 ℃ C.)
TABLE 2 test results (200 ℃ C.)
TABLE 3 test results (300 ℃ C.)
As shown in the test results of tables 1 to 3, the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln prepared by the method has higher denitration efficiency at low temperature, medium temperature and high temperature and effectively improves the sulfur resistance and water resistance compared with the catalyst prepared by the conventional method.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments may be modified or some or all of the technical features may be replaced equivalently, and these modifications or replacements do not make the essence of the corresponding technical scheme deviate from the scope of the technical scheme of the embodiments of the present invention.
Claims (10)
1. A preparation method of a supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for a cement kiln is characterized by comprising the following steps of: the SCR denitration catalyst comprises a carrier, an active component, a coagent, a forming coagent and a functional coagent, wherein the active component comprises an oxide of Fe and an oxide of V, the coagent comprises a transition metal oxide and a rare earth metal oxide, the transition metal in the transition metal oxide is cobalt and one or more selected from manganese, chromium, nickel, copper, zirconium, molybdenum and tungsten, the functional coagent is ZSM-5 and one or more selected from starch, attapulgite, sepiolite powder, MCM-41, ethylene glycol and 4A molecular sieve, and the ZSM-5 accounts for more than 15% of the total mass of the functional coagent;
The preparation method of the SCR denitration catalyst comprises the following specific steps:
(1) Uniformly mixing the carrier powder, washing in deionized water for 1-2 times, and drying at 60-80 ℃ to obtain a dried carrier;
(2) Mixing the dried carrier powder in the step (1) with a certain amount of deionized water and a forming additive to prepare a mud-shaped blank, performing extrusion molding or coating pressing on a plate-type structural frame, standing at normal temperature for 10-24 hours, drying at 100 ℃ for 5-10 hours, calcining at 250 ℃ for 2-5 hours, and heating at a speed of 5 ℃/min-10 ℃/min to obtain a formed carrier;
(3) Preparing a precursor of iron oxide in the active component and a precursor of transition metal oxide in the active additive into a solution with a certain concentration, soaking the blank on the molded carrier, standing for 5h at normal temperature, drying for 2-5 h at 80 ℃, calcining for 2-5 h at 300-450 ℃, and heating at a speed of 2 ℃/min-5 ℃/min to obtain an intermediate sample of the loaded transition metal oxide;
(4) Uniformly mixing functional auxiliary agents, adding a proper amount of deionized water to prepare a suspension with a certain concentration, and uniformly covering the suspension on the intermediate sample obtained in the step (3) by adopting vacuum polyploid volume excess coating; standing for 5h at normal temperature, drying for 2-5 h at 80 ℃, calcining for 2-5 h at 300-450 ℃, and obtaining a functional additive modified intermediate sample at a heating rate of 2-5 ℃/min;
(5) Uniformly mixing precursors of rare earth metal oxides in the active auxiliary agent, adding a proper amount of deionized water to prepare a solution with a certain concentration, soaking a haploid product on the intermediate sample obtained in the step (4), standing for 5h at normal temperature, drying at 80 ℃ for 2-5 h, calcining at 300-450 ℃ for 1-2 h, and heating at a speed of 2 ℃/min-5 ℃/min; obtaining an intermediate sample of the supported rare earth metal oxide;
(6) Adding a proper amount of deionized water into a precursor of the oxide of V in the active component to prepare a solution with a certain concentration, soaking the haploid product on the intermediate sample obtained in the step (5), standing for 5h at normal temperature, drying at 80 ℃ for 2-5 h, calcining at 450-550 ℃ for 2-5 h, and heating at a speed of 2 ℃/min-5 ℃/min to obtain the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln.
2. The method for preparing the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln, which is disclosed by claim 1, is characterized in that: the carrier accounts for 85% -88% of the total mass of the catalyst; iron oxide accounts for 1-3% of the total mass of the catalyst; the vanadium oxide accounts for 0.5% -5% of the total mass of the catalyst; the active auxiliary agent accounts for 0.2% -3% of the total mass of the catalyst; the forming auxiliary agent accounts for 3% -10% of the total mass of the catalyst; the functional auxiliary agent accounts for 0.1% -1% of the total mass of the catalyst; the sum of the mass percentages of the carrier, the active component, the active auxiliary agent, the forming auxiliary agent and the functional auxiliary agent is 100 percent.
3. The method for preparing the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln, which is disclosed by claim 1, is characterized in that: the carrier is titanium dioxide and one or a combination of more than one of silicon dioxide, magnesium oxide and aluminum oxide, wherein the titanium dioxide accounts for 75% -82% of the total mass of the catalyst.
4. The method for preparing the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln, which is disclosed by claim 1, is characterized in that: the precursor of the iron oxide is one or a combination of more than one of ferric nitrate, ferric acetate, ferric chloride and ferric sulfate, the iron oxide comprises ferric oxide and ferroferric oxide, and the ferric oxide accounts for more than 70% of the total mass of the iron oxide;
The V oxide is vanadium pentoxide, and the precursor of the vanadium pentoxide is a mixture of ammonium metavanadate and oxalic acid, a mixture of ammonium metavanadate and lactic acid, or a combination of two or more of vanadyl oxalate.
5. The method for preparing the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln, which is disclosed by claim 1, is characterized in that: in the active auxiliary agent, the transition metal oxide is prepared from the following components in percentage by mass: rare earth metal oxide=1:2 to 2:1.
6. The method for preparing the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln, which is disclosed by claim 1, is characterized in that: the precursor of the transition metal oxide is one or a combination of a plurality of nitrate, acetate, chloride and sulfate, wherein cobalt oxide accounts for more than 30% of the total mass of the transition metal oxide.
7. The method for preparing the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln, which is disclosed by claim 1, is characterized in that: the rare earth metal in the rare earth metal oxide is lanthanum and cerium, and is holmium and/or praseodymium, the precursor of the rare earth metal oxide is one or a combination of a plurality of nitrate, acetate, chloride or sulfate, wherein lanthanum cerium solid solution accounts for more than 40% of the total mass of the rare earth metal oxide.
8. The method for preparing the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln, which is disclosed by claim 1, is characterized in that: the forming auxiliary agent is one or a combination of more of deionized water, dilute nitric acid, dilute acetic acid, ammonia water, methylcellulose, PEO, kaolin, polyethylene glycol and guar gum.
9. A load type wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for a cement kiln is characterized in that: the SCR denitration catalyst is prepared by adopting the preparation method of the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for the cement kiln according to any one of claims 1 to 8.
10. The use of the supported wide-temperature sulfur-resistant water-resistant SCR denitration catalyst for a cement kiln according to claim 9, wherein: the SCR denitration catalyst is used for catalyzing and removing NOx, the NOx removal efficiency is more than 85% when the reaction temperature is 100-350 ℃, and the SCR denitration catalyst can be used for flue gas denitration in which SO 2 and water exist and is suitable for flue gas denitration in a high-dust environment.
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| CN106268784A (en) * | 2016-07-21 | 2017-01-04 | 大唐南京环保科技有限责任公司 | A kind of low temperature Plate-type denitration catalyst and preparation method thereof |
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| CN109967069A (en) * | 2019-05-05 | 2019-07-05 | 天津中材工程研究中心有限公司 | A kind of low-temperature SCR catalyst and preparation method thereof for cement kiln flue gas denitration |
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| CN112495365B (en) * | 2020-11-22 | 2022-07-29 | 浙江盛旺环境工程有限公司 | Medium-low temperature vanadium titanium-based SCR denitration catalyst and preparation method thereof |
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| CN106268784A (en) * | 2016-07-21 | 2017-01-04 | 大唐南京环保科技有限责任公司 | A kind of low temperature Plate-type denitration catalyst and preparation method thereof |
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