CN108212146B - Metal integrally-structured denitration catalyst with core-shell structure and preparation method thereof - Google Patents
Metal integrally-structured denitration catalyst with core-shell structure and preparation method thereof Download PDFInfo
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- CN108212146B CN108212146B CN201810017867.6A CN201810017867A CN108212146B CN 108212146 B CN108212146 B CN 108212146B CN 201810017867 A CN201810017867 A CN 201810017867A CN 108212146 B CN108212146 B CN 108212146B
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- salt
- metal
- core
- catalyst
- coupling agent
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 239000002184 metal Substances 0.000 title claims abstract description 50
- 239000011258 core-shell material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000007822 coupling agent Substances 0.000 claims abstract description 40
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- 238000011068 loading method Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 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
- 150000003839 salts Chemical class 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 150000000703 Cerium Chemical class 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical group [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 150000002471 indium Chemical class 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims 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 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000003657 tungsten Chemical class 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 150000003681 vanadium Chemical class 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 150000003754 zirconium Chemical class 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims 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 claims description 2
- 239000006262 metallic foam Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 50
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 21
- 239000007789 gas Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 230000002457 bidirectional effect Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 24
- 238000012360 testing method Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002131 composite material Substances 0.000 description 12
- 238000010335 hydrothermal treatment Methods 0.000 description 12
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- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000010453 quartz Substances 0.000 description 12
- 239000000779 smoke Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000002791 soaking Methods 0.000 description 11
- 238000009736 wetting Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- -1 diisopropyl titanate Chemical compound 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 239000006260 foam Substances 0.000 description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- ZGMCLEXFYGHRTK-UHFFFAOYSA-N [Fe].[Ce] Chemical compound [Fe].[Ce] ZGMCLEXFYGHRTK-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 238000002525 ultrasonication Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 239000012298 atmosphere Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- NNLJGFCRHBKPPJ-UHFFFAOYSA-N iron lanthanum Chemical compound [Fe].[La] NNLJGFCRHBKPPJ-UHFFFAOYSA-N 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- HZGFMPXURINDAW-UHFFFAOYSA-N iron zirconium Chemical compound [Fe].[Zr].[Zr] HZGFMPXURINDAW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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Abstract
The invention discloses a core-shell structured denitration catalyst with a metal integral structure and a preparation method thereof. The denitration catalyst is a core-shell structure catalyst which is formed by growing hydroxide on a metal monolithic carrier in situ and then self-assembling the hydroxide into a metal monolithic structure by one step under the bidirectional bridging action of a coupling agent, wherein a main active component and an auxiliary agent are used as cores, and metal is oxidized into a shell. The loading capacity of the main active component is 0.01-30 wt%, the loading capacity of the auxiliary agent is 0-30 wt%, the loading capacity of the metal oxide is 0-50 wt%, and the balance is the metal integral material. The catalyst has the advantages of good low-temperature activity, excellent sulfur resistance and water resistance, simple preparation method, no need of molding, good heat conductivity and the like, and is suitable for treating nitrogen oxides in tail gas discharged from coal-fired power plants, garbage incinerators, steel mills and the like.
Description
Technical Field
The invention relates to a denitration catalyst and a preparation method thereof, in particular to a metal integral structured core-shell structure denitration catalyst taking a metal integral carrier as a raw material and a preparation method thereof2And the removal of nitrogen oxides discharged by a fixed source of water vapor, belonging to the technical field of nitrogen oxide control and purification in environmental protection.
Background
With the rapid development of industry and economy, flue gas discharged from coal-fired power plants, steel plants and boiler plants causes great pollution to the atmosphere. Nitrogen Oxides (NO)x) The main atmospheric pollutants are the important sources of acid rain, photochemical smog and haze, and are used for the ecosystem and the human healthConstituting a great threat. Ammonia selective catalytic reduction (NH)3SCR) is the most widely applied flue gas denitration technology at home and abroad, and the catalyst is the core of the reaction. At present V2O5-WO3(MoO3)/TiO2The catalyst has been commercialized, however, the catalyst has a high temperature window of activity (300-400%oC) Therefore, the catalytic device is required to be placed before dust removal and desulfurization SO as to ensure high temperature conditions, but high dust and high SO2The atmosphere is liable to cause catalyst poisoning deactivation. However, if denitration is performed after dedusting and desulfurization, the flue gas temperature is generally low, and the catalyst activity is seriously reduced. Therefore, the development of high-efficiency low-temperature sulfur-resistant SCR catalyst is urgently needed.
Conventional V2O5-WO3(MoO3)/TiO2In practical application, the catalyst generally needs to be extruded or coated on some formed carriers, such as honeycomb ceramics or activated carbon, and the like, but the carriers have slow thermal response, low mass transfer performance, easy influence of dust and the like, and short service life. In recent years, metal carriers have been attracting more and more attention because of their advantages such as low exhaust resistance, high thermal conductivity, and low thermal fusion. Chinese patent CN100455352C and chinese patent CN102166515A disclose honeycomb-shaped wire mesh supported TiO of alumina coating2Or WO3-TiO2The catalyst, but the coating technology relates to secondary loading of active components of the catalyst, has the defects of complicated steps, high treatment cost, uneven coating, easy falling of the catalyst and the like, is difficult to adapt to complex working condition application, and does not fundamentally solve the defect of poor low-temperature sulfur resistance, so that the development of a preparation technology of a novel low-temperature sulfur-resistant metal integral denitration catalyst is urgently needed.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a metal integrally-structured core-shell structure denitration catalyst.
The second object of the present invention is to provide a method for producing the denitration catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
a metal integral structured core-shell structure denitration catalyst is characterized in that the denitration catalyst is a core-shell structure catalyst which takes integral metal as a carrier, a main active component and an auxiliary agent loaded on the surface of the catalyst are taken as cores, metal oxide is taken as a shell, and the particle diameters of the active component and the auxiliary agent are 1-30 nm; the mass ratio of the auxiliary agent to the main active component is 0-0.01; the mass ratio of the core to the shell is 0.1-10.
The monolithic metal support is a wire mesh or a metal foam of aluminum, iron, magnesium, nickel, copper, zinc or an alloy containing aluminum, iron, magnesium, nickel, copper, zinc.
The main active component is one of Fe, Mn and Ce.
The auxiliary agent is at least one of manganese, lanthanum, indium, cobalt, copper, nickel, cerium, tungsten, zirconium and vanadium.
The metal oxide is SiO2、Al2O3、TiO2、ZrO2At least one of (1).
A method for preparing the denitration catalyst with the metal monolithic structure and the core-shell structure is characterized by comprising the following specific steps:
a. carrying out hydrothermal reaction on the metal integral carrier to enable a layer of metal hydroxide to grow on the surface of the metal integral carrier in situ;
b. dissolving the precursor salt of the main active component, the precursor salt of the auxiliary agent and the coupling agent in an organic solution according to the mass ratio of 0.1-10, and fully and uniformly mixing to prepare a uniform and transparent coupling agent chelating solution;
c. and (c) dipping the product obtained in the step (a) into the coupling agent chelating solution obtained in the step (b), standing for 0.5-4 h, dripping deionized water, standing for 0.5-5 h to fully hydrolyze the coupling agent and hydroxyl in hydroxide on the integral carrier, drying, and roasting at the temperature of 300-600 ℃ for 3-5 h to obtain the metal integrally structured core-shell structure catalyst.
The precursor salt of the main active component is ferric salt, manganese salt or cerium salt.
The ferric salt is ferric chloride, ferric acetate, ferric nitrate or ferric acetylacetonate; the manganese salt is manganese chloride, manganese acetate, manganese nitrate or manganese acetylacetonate; the cerium salt is cerium acetate, cerium nitrate or cerium chloride; the loading amount of the main active component relative to the metal monolithic carrier is 0.01-30 wt%.
The precursor salt of the auxiliary agent is at least one of manganese salt, lanthanum salt, indium salt, cobalt salt, copper salt, nickel salt, cerium salt, tungsten salt, zirconium salt and vanadium salt.
The manganese salt is one of manganese chloride, manganese acetate and manganese nitrate; the lanthanum salt is one of lanthanum acetate, lanthanum nitrate and lanthanum chloride; the indium salt is one of indium acetate, indium nitrate and indium chloride; the cobalt salt is one of cobalt chloride, cobalt acetate and cobalt nitrate; the copper salt is one of copper chloride, copper acetate and copper nitrate; the nickel salt is one of nickel chloride, nickel acetate and nickel nitrate; the cerium salt is one of cerium acetate, cerium nitrate and cerium chloride; the tungsten salt is one of ammonium tungstate, ammonium metatungstate and phosphotungstic acid; the zirconium salt is one of zirconium nitrate, zirconium sulfate and zirconium oxychloride; the vanadium salt is ammonium metavanadate; the loading amount of the auxiliary agent relative to the metal monolithic carrier is 0-30 wt%.
The coupling agent is one of silicate coupling agent, aluminate coupling agent, titanate coupling agent and zirconate coupling agent. The loading amount of the shell oxide relative to the metal monolithic carrier is 0-50 wt%.
The temperature of the hydrothermal reaction is 60-180 DEGoAnd C, the hydrothermal time is 1-36 h.
The organic solvent is one of methanol, acetone and ethanol.
The amount of the deionized water is 10-50 wt% of the mass of the metal integral carrier.
Compared with the prior art, the invention has the following advantages:
(1) compared with the traditional coating technology for preparing the monolithic catalyst, the monolithic catalyst is simple to prepare and easy to industrially amplify, and the catalyst layer is not easy to fall off due to in-situ growth. The whole metal is a carrier, so that the pressure is reduced, and the heat conductivity is better.
(2) Compared with the traditional vanadium tungsten titanium catalyst, the monolithic catalyst has the advantages of low environmental toxicity, high low-temperature activity, excellent sulfur resistance and water resistance, and is more suitable for denitration application with complicated working conditions.
Drawings
Fig. 1 is a plot of sulfur activity and sulfur and water stability of the titanium dioxide coated iron cobalt catalyst with the aluminum mesh structure prepared in example four.
Detailed Description
In order to more clearly illustrate the present invention, the following examples are given, but the present invention is not limited to the scope of the examples.
The first embodiment is as follows: 1 g of aluminum wire mesh is placed in a hydrothermal reaction kettle containing deionized water, and the hydrothermal reaction kettle is filled with 100 g of aluminum wire meshoC, performing hydrothermal treatment for 12 hours. Washing with deionized water for 3 times, 100 timesoAnd C, drying for 12 h to obtain the aluminum wire mesh structured pseudo-boehmite composite material. 0.1 g of Fe-containing ferric nitrate and 0.03 g of Ce-containing cerous nitrate were weighed and dissolved in 0.8 g of methanol, and 0.416 g of ditriethanolamine diisopropyl titanate was added thereto, and subjected to ultrasonic treatment for 10 minutes. And then, preliminarily wetting and soaking the pseudo-boehmite with the structured aluminum wire mesh in the mixed solution, standing for 2 hours, then dripping 0.08 g of deionized water, and standing for 4 hours to ensure that the coupling agent and the pseudo-boehmite on the integral carrier are fully hydrolyzed. The resulting material 100oC drying for 12 h, 500oCRoasting for 3 h to obtain the titanium dioxide coated iron-cerium catalyst with the aluminum wire mesh structure.
Testing the catalytic activity of the catalyst and simulating the smoke from N2、O2、NO、NH3、SO2Composition of, wherein NO, NH3、SO2The volume concentration is 500 ppm, O2The concentration is 3%, and the balance gas is nitrogen. Taking 0.5 g of the prepared catalyst, putting the catalyst into a fixed bed quartz tube reactor for activity test, and reacting at the temperature of 90-510 DEG CoC, space velocity of 20000 h-1At 250-420oOver 90 percent of NO removal rate can be realized between C, and N2The selectivity was 100%. The catalyst is at 270oC、SO2When the concentration is 500 ppm, the NO conversion rate is 98%, the activity is basically unchanged after 24 hours, 10% of water vapor is introduced, the activity is reduced to about 96% and is kept unchanged for 12 hours, and the activity is improved to the NO removal rate of 98% after the water vapor is turned off.
Practice ofExample two: 1 g of aluminum wire mesh is placed in a hydrothermal reaction kettle containing deionized water, and the hydrothermal reaction kettle is filled with 100 g of aluminum wire meshoC, performing hydrothermal treatment for 12 hours. Washing with deionized water for 3 times, 100 timesoAnd C, drying for 12 h to obtain the aluminum wire mesh structured pseudo-boehmite composite material. 0.1 g of Fe-containing ferric nitrate and 0.03 g of Zr-containing zirconium nitrate were weighed and dissolved in 0.8 g of methanol, and 0.416 g of ditriethanolamine diisopropyl titanate was added thereto, and the mixture was subjected to ultrasonic treatment for 10 minutes. And then, preliminarily wetting and soaking the pseudo-boehmite with the structured aluminum wire mesh in the mixed solution, standing for 2 hours, then dripping 0.08 g of deionized water, and standing for 4 hours to ensure that the coupling agent and the pseudo-boehmite on the integral carrier are fully hydrolyzed. The resulting material 100oC drying for 12 h, 500oCRoasting for 3 h to obtain the titanium dioxide coated iron-zirconium catalyst with the aluminum wire mesh structure.
Testing the catalytic activity of the catalyst and simulating the smoke from N2、O2、NO、NH3、SO2Composition of, wherein NO, NH3、SO2The volume concentration is 500 ppm, O2The concentration is 3%, and the balance gas is nitrogen. Taking 0.5 g of the prepared catalyst, putting the catalyst into a fixed bed quartz tube reactor for activity test, and reacting at the temperature of 90-510 DEG CoC, space velocity of 20000 h-1At the condition of (1), at 300-oOver 90 percent NO removal rate can be realized between C, 300oN below C2The selectivity was 100%. The catalyst is at 270oC、SO2When the concentration is 500 ppm, the NO conversion rate is 99%, the activity is basically unchanged after 24 hours, 10% of water vapor is introduced, the activity is reduced to about 97% and is kept unchanged for 12 hours, and the activity is improved to 99% of NO removal rate after the water vapor is turned off.
Example three: 1 g of aluminum wire mesh is placed in a hydrothermal reaction kettle containing deionized water, and the hydrothermal reaction kettle is filled with 100 g of aluminum wire meshoC, performing hydrothermal treatment for 12 hours. Washing with deionized water for 3 times, 100 timesoAnd C, drying for 12 h to obtain the aluminum wire mesh structured pseudo-boehmite composite material. 0.1 g of Fe-containing ferric nitrate and 0.03 g of La-containing lanthanum nitrate were weighed and dissolved in 0.8 g of methanol, and 0.416 g of bistriethanolamine diisopropyl titanate was added thereto, and the mixture was subjected to ultrasonic treatment for 10 minutes. Then, the pseudo-boehmite with the structured aluminum wire mesh is soaked in the mixed solution in an incipient wetness way, and is added with 0.08 g of deionized water after standing for 2 hours, and is kept standing for 4 hoursh, the coupling agent and the pseudo-boehmite on the monolithic carrier are fully hydrolyzed. The resulting material 100oC drying for 12 h, 500oCRoasting for 3 h to obtain the titanium dioxide coated iron lanthanum catalyst with the aluminum wire mesh structure.
Testing the catalytic activity of the catalyst and simulating the smoke from N2、O2、NO、NH3、SO2Composition of, wherein NO, NH3、SO2The volume concentration is 500 ppm, O2The concentration is 3%, and the balance gas is nitrogen. Taking 0.5 g of the prepared catalyst, putting the catalyst into a fixed bed quartz tube reactor for activity test, and reacting at the temperature of 90-510 DEG CoC, space velocity of 20000 h-1At 270-oOver 90 percent NO removal rate can be realized among C, 350 percentoN below C2The selectivity was 100%. The catalyst is at 270oC、SO2When the concentration is 500 ppm, the NO conversion rate is 95%, the activity is basically unchanged after 24 hours, 10% of water vapor is introduced, the activity is reduced to about 92% and is kept unchanged for 12 hours, and the activity is improved to 95% of NO removal rate after the water vapor is turned off.
Example four:
1 g of aluminum wire mesh is placed in a hydrothermal reaction kettle containing deionized water, and the hydrothermal reaction kettle is filled with 100 g of aluminum wire meshoC, performing hydrothermal treatment for 12 hours. Washing with deionized water for 3 times, 100 timesoAnd C, drying for 12 h to obtain the aluminum wire mesh structured pseudo-boehmite composite material. 0.1 g of Fe-containing ferric nitrate and 0.03 g of Co-containing cobalt nitrate were weighed and dissolved in 0.8 g of methanol, and 0.416 g of ditriethanolamine diisopropyl titanate was added thereto, and the mixture was subjected to ultrasonic treatment for 10 minutes. And then, preliminarily wetting and soaking the pseudo-boehmite with the structured aluminum wire mesh in the mixed solution, standing for 2 hours, and then dripping 0.08 g of deionized water to ensure that the coupling agent and the pseudo-boehmite on the integral carrier are fully hydrolyzed. The resulting material 100oC drying for 12 h, 500 oCRoasting for 3 h to obtain the titanium dioxide coated iron-cobalt catalyst with the aluminum wire mesh structure.
Testing the catalytic activity of the catalyst and simulating the smoke from N2、O2、NO、NH3、SO2Composition of, wherein NO, NH3、SO2The volume concentration is 500 ppm, O2At a concentration of3% and the balance gas is nitrogen. 0.5 g of the prepared catalyst is put into a fixed bed quartz tube reactor for activity test, and the result is shown in the figure I. At a reaction temperature of 90-510 DEG CoC, space velocity of 20000 h-1At 240-oThe removal rate of nitrogen oxides between C can be kept above 90%, and N2The selectivity was 100%. The catalyst is at 240oC、SO2When the concentration is 500 ppm, the NO conversion rate is close to 100%, the activity is basically unchanged after 24 hours, 10% of water vapor is introduced, the activity is reduced to about 97% and is maintained unchanged after 12 hours, and the activity is improved to be close to the NO removal rate of 100% after the water vapor is turned off.
Example five:
1 g of aluminum wire mesh is placed in a hydrothermal reaction kettle containing deionized water, and the hydrothermal reaction kettle is filled with 100 g of aluminum wire meshoC, performing hydrothermal treatment for 12 hours. Washing with deionized water for 3 times, 100 timesoAnd C, drying for 12 h to obtain the aluminum wire mesh structured pseudo-boehmite composite material. 0.1 g of Mn-containing manganese nitrate and 0.03 g of Co-containing cobalt nitrate were weighed and dissolved in 0.8 g of methanol, and 0.416 g of ditriethanolamine diisopropyl titanate was added thereto, and the mixture was subjected to ultrasonic treatment for 10 minutes. And then, preliminarily wetting and soaking the pseudo-boehmite with the structured aluminum wire mesh in the mixed solution, standing for 2 hours, and then dripping 0.08 g of deionized water to ensure that the coupling agent and the pseudo-boehmite on the integral carrier are fully hydrolyzed. The resulting material 100oC drying for 12 h, 500 oCRoasting for 3 h to obtain the titanium dioxide coated manganese cobalt catalyst with the aluminum wire mesh structure.
Testing the catalytic activity of the catalyst and simulating the smoke from N2、O2、NO、NH3、SO2Composition of, wherein NO, NH3、SO2The volume concentration is 500 ppm, O2The concentration is 3%, and the balance gas is nitrogen. Taking 0.5 g of the prepared catalyst, putting the catalyst into a fixed bed quartz tube reactor for activity test, and reacting at the temperature of 90-510 DEG CoC, space velocity of 20000 h-1At 210-oThe removal rate of nitrogen oxides between C can be kept above 90%, and the catalyst has good low-temperature activity and a wide temperature window.
Example six:
placing 1 g of aluminum wire meshIn a hydrothermal reaction kettle containing deionized water, 100 percentoC, performing hydrothermal treatment for 12 hours. Washing with deionized water for 3 times, 100 timesoAnd C, drying for 12 h to obtain the aluminum wire mesh structured pseudo-boehmite composite material. 0.1 g of Mn-containing manganese nitrate and 0.03 g of Ce-containing cerium nitrate were weighed and dissolved in 0.8 g of methanol, 0.416 g of ditetraethanolamine diisopropyl titanate was added, and the mixture was subjected to ultrasonic treatment for 10 minutes. And then, preliminarily wetting and soaking the pseudo-boehmite with the structured aluminum wire mesh in the mixed solution, standing for 2 hours, and then dripping 0.08 g of deionized water to ensure that the coupling agent and the pseudo-boehmite on the integral carrier are fully hydrolyzed. The resulting material 100oC drying for 12 h, 500 oCRoasting for 3 h to obtain the titanium dioxide coated manganese cerium catalyst with the aluminum wire mesh structure.
Testing the catalytic activity of the catalyst and simulating the smoke from N2、O2、NO、NH3、SO2Composition of, wherein NO, NH3、SO2The volume concentration is 500 ppm, O2The concentration is 3%, and the balance gas is nitrogen. Taking 0.5 g of the prepared catalyst, putting the catalyst into a fixed bed quartz tube reactor for activity test, and reacting at the temperature of 90-510 DEG CoC, space velocity of 20000 h-1At 230-oThe removal rate of nitrogen oxides between C can be kept above 90%, and the catalyst has good low-temperature activity and a wide temperature window.
Example seven: 1 g of aluminum wire mesh is placed in a hydrothermal reaction kettle containing deionized water, and the hydrothermal reaction kettle is filled with 100 g of aluminum wire meshoC, performing hydrothermal treatment for 12 hours. Washing with deionized water for 3 times, 100 timesoAnd C, drying for 12 h to obtain the aluminum wire mesh structured pseudo-boehmite composite material. 0.1 g of Fe-containing iron nitrate and 0.03 g of Ce-containing cerium nitrate were weighed out and dissolved in 0.8 g of methanol, and 0.26 g of zirconate coupling agent (ZCA-N44) was added thereto and subjected to ultrasonication for 10 minutes. And then, preliminarily wetting and soaking the pseudo-boehmite with the structured aluminum wire mesh in the mixed solution, standing for 2 hours, then dripping 0.08 g of deionized water, and standing for 4 hours to ensure that the coupling agent and the pseudo-boehmite on the integral carrier are fully hydrolyzed. The resulting material 100oC drying for 12 h, 500 oCRoasting for 3 h to obtain the aluminum wire mesh structured zirconium dioxide coated iron-cerium catalyst.
Testing the above catalystsCatalytic activity, simulated smoke from N2、O2、NO、NH3、SO2Composition of, wherein NO, NH3、SO2The volume concentration is 500 ppm, O2The concentration is 3%, and the balance gas is nitrogen. Taking 0.5 g of the prepared catalyst, putting the catalyst into a fixed bed quartz tube reactor for activity test, and reacting at the temperature of 90-510 DEG CoC, space velocity of 20000 h-1At 300-oOver 90 percent of NO removal rate can be realized between C, and N2The selectivity was 100%. The catalyst is at 270oC、SO2When the concentration is 500 ppm, the NO conversion rate is 97%, the activity is basically unchanged after 24 hours, 10% of water vapor is introduced, the activity is reduced to about 96% and is kept unchanged for 12 hours, and the activity is improved to 97% of NO removal rate after the water vapor is turned off.
Example eight: 1 g of aluminum wire mesh is placed in a hydrothermal reaction kettle containing deionized water, and the hydrothermal reaction kettle is filled with 100 g of aluminum wire meshoC, performing hydrothermal treatment for 12 hours. Washing with deionized water for 3 times, 100 timesoAnd C, drying for 12 h to obtain the aluminum wire mesh structured pseudo-boehmite composite material. 0.1 g of Fe-containing iron nitrate and 0.03 g of Mn nitrate were weighed out and dissolved in 0.8 g of methanol, and 0.26 g of zirconate coupling agent (ZCA-N44) was added thereto and subjected to ultrasonication for 10 minutes. And then, preliminarily wetting and soaking the pseudo-boehmite with the structured aluminum wire mesh in the mixed solution, standing for 2 hours, then dripping 0.08 g of deionized water, and standing for 4 hours to ensure that the coupling agent and the pseudo-boehmite on the integral carrier are fully hydrolyzed. The resulting material 100oC drying for 12 h, 500 oCRoasting for 3 h to obtain the aluminum wire mesh structured zirconium dioxide coated ferro-manganese catalyst.
Testing the catalytic activity of the catalyst and simulating the smoke from N2、O2、NO、NH3、SO2Composition of, wherein NO, NH3、SO2The volume concentration is 500 ppm, O2The concentration is 3%, and the balance gas is nitrogen. Taking 0.5 g of the prepared catalyst, putting the catalyst into a fixed bed quartz tube reactor for activity test, and reacting at the temperature of 90-510 DEG CoC, space velocity of 20000 h-1At 270-oOver 90 percent of NO removal rate can be realized between C, and N2The selectivity was 100%. The catalyst is in270 oC、SO2When the concentration is 500 ppm, the NO conversion rate is 99%, the activity is basically unchanged after 24 hours, 10% of water vapor is introduced, the activity is reduced to about 98% and is kept unchanged for 12 hours, and the activity is improved to 99% of NO removal rate after the water vapor is turned off.
Example nine: 1 g of aluminum wire mesh is placed in a hydrothermal reaction kettle containing deionized water, and the hydrothermal reaction kettle is filled with 100 g of aluminum wire meshoC, performing hydrothermal treatment for 12 hours. Washing with deionized water for 3 times, 100 timesoAnd C, drying for 12 h to obtain the aluminum wire mesh structured pseudo-boehmite composite material. 0.1 g of Fe-containing iron nitrate and 0.03 g of La-containing lanthanum nitrate were weighed and dissolved in 0.8 g of methanol, and 0.26 g of zirconate coupling agent (ZCA-N44) was added thereto and subjected to ultrasonication for 10 minutes. And then, preliminarily wetting and soaking the pseudo-boehmite with the structured aluminum wire mesh in the mixed solution, standing for 2 hours, then dripping 0.08 g of deionized water, and standing for 4 hours to ensure that the coupling agent and the pseudo-boehmite on the integral carrier are fully hydrolyzed. The resulting material 100oC drying for 12 h, 500 oCRoasting for 3 h to obtain the aluminum wire mesh structured zirconium dioxide coated iron lanthanum catalyst.
Testing the catalytic activity of the catalyst and simulating the smoke from N2、O2、NO、NH3、SO2Composition of, wherein NO, NH3、SO2The volume concentration is 500 ppm, O2The concentration is 3%, and the balance gas is nitrogen. Taking 0.5 g of the prepared catalyst, putting the catalyst into a fixed bed quartz tube reactor for activity test, and reacting at the temperature of 90-510 DEG CoC, space velocity of 20000 h-1At 270-oOver 90 percent of NO removal rate can be realized between C, and N2The selectivity was 100%. The catalyst is at 270oC、SO2When the concentration is 500 ppm, the NO conversion rate is 98%, the activity is basically unchanged after 24 hours, 10% of water vapor is introduced, the activity is reduced to about 96% and is kept unchanged for 12 hours, and the activity is improved to the NO removal rate of 98% after the water vapor is turned off.
Example ten: 1 g of aluminum wire mesh is placed in a hydrothermal reaction kettle containing deionized water, and the hydrothermal reaction kettle is filled with 100 g of aluminum wire meshoC, performing hydrothermal treatment for 12 hours. Washing with deionized water for 3 times, 100 timesoAnd C, drying for 12 h to obtain the aluminum wire mesh structured pseudo-boehmite composite material. Iron nitrate containing 0.1 g of Fe and 0.03 g of Co nitrate were weighed outThe cobalt acid was dissolved in 0.8 g of methanol, and 0.26 g of zirconate coupling agent (ZCA-N44) was added thereto, followed by sonication for 10 minutes. And then, preliminarily wetting and soaking the pseudo-boehmite with the structured aluminum wire mesh in the mixed solution, standing for 2 hours, then dripping 0.08 g of deionized water, and standing for 4 hours to ensure that the coupling agent and the pseudo-boehmite on the integral carrier are fully hydrolyzed. The resulting material 100oC drying for 12 h, 500 oCRoasting for 3 h to obtain the aluminum wire mesh structured zirconium dioxide coated iron-cobalt catalyst.
Testing the catalytic activity of the catalyst and simulating the smoke from N2、O2、NO、NH3、SO2Composition of, wherein NO, NH3、SO2The volume concentration is 500 ppm, O2The concentration is 3%, and the balance gas is nitrogen. Taking 0.5 g of the prepared catalyst, putting the catalyst into a fixed bed quartz tube reactor for activity test, and reacting at the temperature of 90-510 DEG CoC, space velocity of 20000 h-1At 270-oOver 90 percent of NO removal rate can be realized between C, and N2The selectivity was 100%. The catalyst is at 270oC、SO2When the concentration is 500 ppm, the NO conversion rate is 99%, the activity is basically unchanged after 24 hours, 10% of water vapor is introduced, the activity is reduced to about 97% and is kept unchanged for 12 hours, and the activity is improved to 99% of NO removal rate after the water vapor is turned off.
Example eleven: 1 g of foamed nickel is put into a hydrothermal reaction kettle containing deionized water, 0.01M of nickel nitrate and 0.04M of ammonium chloride are added, and 100 parts of nickel nitrate and ammonium chloride are addedoC, carrying out hydrothermal treatment for 3 h. Washing with deionized water for 3 times, 100 timesoAnd C, drying for 12 h to obtain the nickel hydroxide composite material with the foam nickel structure. 0.1 g of Fe-containing iron nitrate and 0.03 g of Ce-containing cerium nitrate were weighed out and dissolved in 0.8 g of methanol, and 0.26 g of zirconate coupling agent (ZCA-N44) was added thereto and subjected to ultrasonication for 10 minutes. And then, soaking the nickel hydroxide with the foam nickel structure in the mixed solution in an incipient wetness manner, standing for 2 hours, then, dripping 0.08 g of deionized water, and standing for 4 hours to ensure that the coupling agent and the hydroxyl of the strong nickel oxide on the integral carrier are subjected to full hydrolysis. The resulting material 100oC drying for 12 h, 500 oCRoasting for 3 h to obtain the foam nickel structured zirconium dioxide coated iron-cerium catalyst.
Testing the catalytic activity of the catalyst and simulating the smoke from N2、O2、NO、NH3、SO2Composition of, wherein NO, NH3、SO2The volume concentration is 500 ppm, O2The concentration is 3%, and the balance gas is nitrogen. Taking 0.5 g of the prepared catalyst, putting the catalyst into a fixed bed quartz tube reactor for activity test, and reacting at the temperature of 90-510 DEG CoC, space velocity of 20000 h-1At 300-350oOver 90 percent of NO removal rate can be realized between C, and N2 The selectivity was 100%. The catalyst is at 270oC、SO2When the concentration is 500 ppm, the NO conversion rate is 95%, the activity is basically unchanged after 24 hours, 10% of water vapor is introduced, the activity is reduced to about 92% and is kept unchanged for 12 hours, and the activity is improved to 95% of NO removal rate after the water vapor is turned off.
Example twelve: 1 g of foamed nickel is put into a hydrothermal reaction kettle containing deionized water, 0.01M of nickel nitrate and 0.04M of ammonium chloride are added, and 100 parts of nickel nitrate and ammonium chloride are addedoC, carrying out hydrothermal treatment for 3 h. Washing with deionized water for 3 times, 100 timesoAnd C, drying for 12 h to obtain the nickel hydroxide composite material with the foam nickel structure. 0.1 g of Fe-containing ferric nitrate and 0.03 g of Ce-containing cerous nitrate were weighed and dissolved in 0.8 g of methanol, and 0.416 g of ditriethanolamine diisopropyl titanate was added thereto, and subjected to ultrasonic treatment for 10 minutes. And then, soaking the nickel hydroxide with the foam nickel structure in the mixed solution in an incipient wetness manner, standing for 2 hours, then, dripping 0.08 g of deionized water, and standing for 4 hours to ensure that the coupling agent and the hydroxyl of the nickel hydroxide on the integral carrier are fully hydrolyzed. The resulting material 100oC drying for 12 h, 500 oCRoasting for 3 h to obtain the foam nickel structured titanium dioxide coated iron-cerium catalyst.
Testing the catalytic activity of the catalyst and simulating the smoke from N2、O2、NO、NH3、SO2Composition of, wherein NO, NH3、SO2The volume concentration is 500 ppm, O2The concentration is 3%, and the balance gas is nitrogen. Taking 0.5 g of the prepared catalyst, putting the catalyst into a fixed bed quartz tube reactor for activity test, and reacting at the temperature of 90-510 DEG CoC, space velocity of 20000 h-1At 270-oAll can be found between CThe NO removal rate is more than 90 percent, and N2 The selectivity was 100%. The catalyst is at 270oC、SO2When the concentration is 500 ppm, the NO conversion rate is 96%, the activity is basically unchanged after 24 hours, 10% of water vapor is introduced, the activity is reduced to about 93% and is kept unchanged for 12 hours, and the activity is improved to 96% of NO removal rate after the water vapor is turned off.
The foregoing description of the exemplary embodiment should not be construed as limiting the present invention. Although exemplary embodiments have been disclosed, any changes or substitutions that may be easily made by one skilled in the art within the technical scope of the disclosure should be covered by the protection scope of the present invention. Therefore, the preparation method of the monolithic denitration catalyst using the same or similar steps and structures as those of the above-described embodiment of the present invention and the denitration catalyst prepared by the method are within the scope of the present invention.
Claims (12)
1. A denitration catalyst with a metal integral structure and a core-shell structure is characterized in that: the denitration catalyst is a catalyst with a core-shell structure, wherein an integral metal is used as a carrier, a main active component and an auxiliary agent are loaded on the surface of the catalyst as a core, a metal oxide is used as a shell, and the particle sizes of the active component and the auxiliary agent are 1-30 nm; the mass ratio of the auxiliary agent to the main active component is 0-0.01; the mass ratio of the core to the shell is 0.1-10;
the main active component is one of Fe, Mn and Ce;
the metal oxide is SiO2、Al2O3、TiO2、ZrO2At least one of;
the denitration catalyst with the metal integral structure and the core-shell structure is prepared by the following steps:
a. carrying out hydrothermal reaction on the metal integral carrier to enable a layer of metal hydroxide to grow on the surface of the metal integral carrier in situ;
b. dissolving a main active component precursor salt, an auxiliary agent precursor salt and a coupling agent in an organic solvent according to the mass ratio of 0.1-10, and fully and uniformly mixing to prepare a uniform and transparent coupling agent chelating solution;
c. and (c) dipping the product obtained in the step (a) into the coupling agent chelating solution obtained in the step (b), standing for 0.5-4 h, dripping deionized water, standing for 0.5-5 h to fully hydrolyze the coupling agent and hydroxyl in hydroxide on the monolithic carrier, drying, and roasting at the temperature of 300-600 ℃ for 3-5 h to obtain the metal integrally structured core-shell structure catalyst.
2. The metal monolithic structured core-shell structured denitration catalyst according to claim 1, characterized in that: the monolithic metal support is a wire mesh or a metal foam of aluminum, iron, magnesium, nickel, copper, zinc or an alloy containing aluminum, iron, magnesium, nickel, copper, zinc.
3. The metal monolithic structured core-shell structured denitration catalyst according to claim 1, characterized in that: the auxiliary agent is at least one of manganese, lanthanum, indium, cobalt, copper, nickel, cerium, tungsten, zirconium and vanadium.
4. A method for preparing the metal integrally-structured core-shell structure denitration catalyst as described in any one of claims 1 to 3, which comprises the following specific steps:
a. carrying out hydrothermal reaction on the metal integral carrier to enable a layer of metal hydroxide to grow on the surface of the metal integral carrier in situ;
b. dissolving a main active component precursor salt, an auxiliary agent precursor salt and a coupling agent in an organic solvent according to the mass ratio of 0.1-10, and fully and uniformly mixing to prepare a uniform and transparent coupling agent chelating solution;
c. and (c) dipping the product obtained in the step (a) into the coupling agent chelating solution obtained in the step (b), standing for 0.5-4 h, dripping deionized water, standing for 0.5-5 h to fully hydrolyze the coupling agent and hydroxyl in hydroxide on the monolithic carrier, drying, and roasting at the temperature of 300-600 ℃ for 3-5 h to obtain the metal integrally structured core-shell structure catalyst.
5. The method for preparing the denitration catalyst with the metal monolithic structure and the core-shell structure according to claim 4, wherein the method comprises the following steps: the precursor salt of the main active component is ferric salt, manganese salt or cerium salt.
6. The method for preparing the denitration catalyst with the metal monolithic structure and the core-shell structure according to claim 5, wherein the method comprises the following steps: the ferric salt is ferric chloride, ferric acetate, ferric nitrate or ferric acetylacetonate; the manganese salt is manganese chloride, manganese acetate, manganese nitrate or manganese acetylacetonate; the cerium salt is cerium acetate, cerium nitrate or cerium chloride; the loading amount of the main active component relative to the metal monolithic carrier is 0.01-30 wt%.
7. The method for preparing the denitration catalyst with the metal monolithic structure and the core-shell structure according to claim 4, wherein the method comprises the following steps: the precursor salt of the auxiliary agent is at least one of manganese salt, lanthanum salt, indium salt, cobalt salt, copper salt, nickel salt, cerium salt, tungsten salt, zirconium salt and vanadium salt.
8. The metal monolithic structured core-shell structured denitration catalyst according to claim 7, characterized in that: the manganese salt is one of manganese chloride, manganese acetate and manganese nitrate; the lanthanum salt is one of lanthanum acetate, lanthanum nitrate and lanthanum chloride; the indium salt is one of indium acetate, indium nitrate and indium chloride; the cobalt salt is one of cobalt chloride, cobalt acetate and cobalt nitrate; the copper salt is one of copper chloride, copper acetate and copper nitrate; the nickel salt is one of nickel chloride, nickel acetate and nickel nitrate; the cerium salt is one of cerium acetate, cerium nitrate and cerium chloride; the tungsten salt is one of ammonium tungstate, ammonium metatungstate and phosphotungstic acid; the zirconium salt is one of zirconium nitrate, zirconium sulfate and zirconium oxychloride; the vanadium salt is ammonium metavanadate; the loading amount of the auxiliary agent relative to the metal monolithic carrier is 0-30 wt%.
9. The metal monolithic structured core-shell structured denitration catalyst according to claim 4, characterized in that: the coupling agent is one of silicate coupling agent, aluminate coupling agent, titanate coupling agent and zirconate coupling agent; the supported amount of the shell oxide with respect to the metal monolithic carrier is 0 to 50 wt%, and the supported amount of the shell oxide with respect to the metal monolithic carrier is not 0.
10. The method for preparing the denitration catalyst with the metal monolithic structure and the core-shell structure according to claim 4, wherein the method comprises the following steps: the temperature of the hydrothermal reaction is 60-180 ℃, and the hydrothermal time is 1-36 h.
11. The method for preparing the denitration catalyst with the metal monolithic structure and the core-shell structure according to claim 4, wherein the method comprises the following steps: the organic solvent is one of methanol, acetone and ethanol.
12. The method for preparing the denitration catalyst with the metal monolithic structure and the core-shell structure according to claim 4, wherein the method comprises the following steps: the amount of the deionized water is 10-50 wt% of the mass of the metal integral carrier.
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| CN110479296B (en) * | 2019-08-19 | 2022-04-12 | 华能国际电力股份有限公司 | Catalyst capable of reducing escape of denitrated ammonia and preparation method thereof |
| CN111905716B (en) * | 2020-07-31 | 2021-09-24 | 江苏龙净科杰环保技术有限公司 | Thallium poisoning resistant core-shell honeycomb catalyst for cement kiln flue gas denitration and preparation method thereof |
| CN112958127B (en) * | 2021-02-26 | 2023-03-31 | 上海大学材料基因组工程(萍乡)研究院 | Method for loading catalyst on ceramic fiber |
| CN113117666B (en) * | 2021-04-11 | 2024-01-23 | 安徽省中易环保新材料有限公司 | Water-resistant sulfur-resistant denitration catalyst |
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