CN106423193A - Honeycomb manganese denitration catalyst and preparation method thereof - Google Patents
Honeycomb manganese denitration catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN106423193A CN106423193A CN201610840300.XA CN201610840300A CN106423193A CN 106423193 A CN106423193 A CN 106423193A CN 201610840300 A CN201610840300 A CN 201610840300A CN 106423193 A CN106423193 A CN 106423193A
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- China
- Prior art keywords
- salt
- manganese
- oxide
- preparation
- denitrating catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 239000011572 manganese Substances 0.000 title claims abstract description 73
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002245 particle Substances 0.000 claims abstract description 65
- 239000010936 titanium Substances 0.000 claims abstract description 59
- 239000007787 solid Substances 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 38
- 229910001868 water Inorganic materials 0.000 claims abstract description 33
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 150000002696 manganese Chemical class 0.000 claims abstract description 18
- 239000008139 complexing agent Substances 0.000 claims abstract description 13
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 150000000703 Cerium Chemical class 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 5
- 230000001413 cellular effect Effects 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 35
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 22
- 239000003365 glass fiber Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 244000068988 Glycine max Species 0.000 claims description 12
- 235000010469 Glycine max Nutrition 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000008107 starch Substances 0.000 claims description 12
- 235000019698 starch Nutrition 0.000 claims description 12
- 239000002383 tung oil Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 10
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 10
- -1 extrusion aid Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 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 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- WBJXZTQXFVDYIZ-UHFFFAOYSA-N [Sb].[N+](=O)(O)[O-] Chemical group [Sb].[N+](=O)(O)[O-] WBJXZTQXFVDYIZ-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 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
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical group [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- PLXQGEWNITUHNB-UHFFFAOYSA-N [La]=O Chemical compound [La]=O PLXQGEWNITUHNB-UHFFFAOYSA-N 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims 1
- 235000003891 ferrous sulphate Nutrition 0.000 claims 1
- 239000011790 ferrous sulphate Substances 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 150000001462 antimony Chemical class 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000005242 forging Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 55
- 229910002651 NO3 Inorganic materials 0.000 description 23
- 238000004898 kneading Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 8
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 description 1
- HTBAHYGLEFPCLK-UHFFFAOYSA-N [Ti].[Ce].[Mn] Chemical compound [Ti].[Ce].[Mn] HTBAHYGLEFPCLK-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- RJIWZDNTCBHXAL-UHFFFAOYSA-N nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical class [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 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
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a honeycomb manganese denitration catalyst and a preparation method thereof. The method includes the following steps that manganese salt and a complexing agent are dissolved in water, titanium dioxide is added and stirred, ultrasonic dipping, drying and grinding are conducted, and Mn-Ti oxide solid particles are obtained, wherein the molar ratio of the manganese salt to the complexing agent is (65-187):1; metal salt and cerium salt are dissolved in water to obtain a mixed metal solution, wherein metal salt is at least one of ferric salt, cobalt salt, lanthanum salt, antimony salt and nickel salt; a pore-forming agent, an adhesive, an extrusion aid, a reinforcing agent, the Mn-Ti oxide solid particles and the mixed metal solution are mixed and formed into a honeycomb blank, and drying and forging are conducted. The catalyst is good in active component dispersity, is not easily sintered, good in pore structure, large in porosity and high in mechanical strength, the axial compressive strength of the catalyst is 4.7-5.1 MPa, and the radial compressive strength of the catalyst is 1.2-1.4 MPa. The porosity of the catalyst is 84-90%. The catalyst prepared through the method has relatively high denitration activity in the range of 120-250 DEG C and is suitable for low-temperature denitration.
Description
Technical field
The present invention relates to a kind of catalyst, particularly relate to a kind of cellular manganese systems denitrating catalyst and preparation method thereof.
Background technology
Nitrogen oxides (NOx) it is one of main atmosphere pollution, before causing the problem such as acid rain, secondary fine particle
Body thing.At present, at NOxIn removing sulfuldioxide, selective catalytic reduction (SCR, Selective Catalytic Reduction)
Denitration, has obtained the most attention of countries in the world, has been to apply the most in the world with the technology of its maturation and good denitration effect
Extensive gas denitrifying technology.
Current widely used commercialized catalyst is mainly V2O5-WO3/TiO2Or V2O5-MoO3/TiO2, but this type of catalysis
It is narrower that agent has Process window, and active temperature is high, only has higher denitration activity at 350～400 DEG C, and vanadium is to human body and ring
The shortcomings such as border is harmful.Therefore, reduce the load capacity of vanadium or prepare novel effective catalyst with other metallic elements replacement vanadium
Significant.Compared to vanadium titanium class catalyst, manganese oxide type catalyst has low temperature, efficient, nontoxic, cheap etc. excellent
Point, the load capacity of manganese is higher simultaneously, typically at about 10%-30%.Active component in manganese cerium titanium system catalysis material is not for
Oxide with valence state, it is desirable in the calcination process of catalysis material, manganese needs oxidized, but catalysis material in existing technology
General calcining under Oxygen Condition, catalysis material is particularly easy to burning, and this is relatively low mainly due to the fusing point of manganese cerium salt, and cerium
Having combustion-supporting effect, the organic additive adding in forming process all very easily burns so that honeycomb catalyst material internal temperature
Spend height and cause its surfaces externally and internally excessive temperature differentials to ftracture.In addition, some conventional manganese presomas, such as manganese nitrate, second
Acid manganese and manganese oxalate, can discharge gas in calcination process, cause the cracking of honeycomb catalysis material, even efflorescence.
Content of the invention
Present invention is primarily targeted at, a kind of novel cellular manganese systems denitrating catalyst and preparation method thereof is provided,
To be solved technical problem is that makes it have high denitration catalyst activity at low temperatures, thus more suitable for practicality.
The object of the invention to solve the technical problems realizes by the following technical solutions.Propose according to the present invention
The preparation method of a kind of cellular manganese systems denitrating catalyst, it comprises the following steps:
1) by soluble in water to manganese salt and complexing agent, add titanium dioxide, stirring, ultrasonic immersing, dry, grinding, obtain Mn-
Ti oxide solid particle；Wherein, manganese salt and the mol ratio of complexing agent are 65-187:1；
2) slaine is soluble in water with cerium salt, obtain hybrid metal solution；Described slaine is molysite, cobalt salt, lanthanum
At least one in salt, antimonic salt and nickel salt；
3) by pore creating material, binding agent, extrusion aid, reinforcing agent, described Mn-Ti oxide solid particle and described mixing
Metallic solution mixes, and is molded into honeycomb packaging blank, is dried, and calcining obtains cellular manganese systems denitrating catalyst.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Preferably, the preparation method of aforesaid cellular manganese systems denitrating catalyst, wherein said complexing agent be oxalic acid or
Citric acid；Described manganese salt is manganese nitrate, manganese acetate, at least one in manganese oxalate；Described titanium dioxide is Detitanium-ore-type
Nano titanium oxide.
Preferably, the preparation method of aforesaid cellular manganese systems denitrating catalyst, the wherein said Mn element in manganese salt
With the weight of described titanium dioxide than for 0.11-0.45：1.
Preferably, the preparation method of aforesaid cellular manganese systems denitrating catalyst, wherein said Mn-Ti oxide solid
The particle diameter of particle is 300-400 mesh.
Preferably, the preparation method of aforesaid cellular manganese systems denitrating catalyst, wherein said molysite is ferric nitrate, sulphur
At least one in acid ferrous iron, ferric sulfate, iron chloride；Described cobalt salt be cobalt nitrate, cobalt acetate, cobaltous sulfate, in cobalt chloride
At least one；Described lanthanum salt is lanthanum acetate, lanthanum sulfate, at least one in lanthanum chloride；Described antimonic salt is nitric acid antimony；Described
Nickel salt be nickel nitrate, nickel acetate, nickel sulfate, at least one in cobalt chloride；Described cerium salt is cerous nitrate, cerous acetate, sulphur
At least one in acid cerium, cerium chloride.
Preferably, the preparation method of aforesaid cellular manganese systems denitrating catalyst, wherein said pore creating material be activated carbon,
At least one in starch, wood chip, polymethyl methacrylate；Described binding agent is carboxymethylcellulose calcium and/or polyoxygenated
Ethene；Described extrusion aid is glycerine, soya-bean oil, at least one in tung oil；Described reinforcing agent is glass fibre.
Preferably, the preparation method of aforesaid cellular manganese systems denitrating catalyst, in wherein said hybrid metal solution
Metallic element and the weight of water and described Mn-Ti oxide solid particle than for X：Ce：H2O：Mn-Ti oxide=
0.9-4.4：2-4：25-35：100, wherein X is at least one in Fe, Co, La, Sb, Ni.
Preferably, the preparation method of aforesaid cellular manganese systems denitrating catalyst, wherein said pore creating material, binding agent,
The weight of extrusion aid, reinforcing agent and described Mn-Ti oxide solid particle is than for 4-6：1-2：2-4：4-6：100.
Preferably, the preparation method of aforesaid cellular manganese systems denitrating catalyst, the process of wherein said drying is：?
50-70 DEG C is dried 5-7h, is warming up to 100-110 DEG C of dry 11-13h；The temperature of described calcining is 400-600 DEG C, calcining
Time is 2-5h.
The object of the invention to solve the technical problems also uses following technical scheme to realize.Propose according to the present invention
One cellular manganese systems denitrating catalyst, its active component is by ferriferous oxide, cobalt/cobalt oxide, lanthanum-oxides, sb oxide, nickel
At least one in oxide and cerium oxide composition, carrier is Mn-Ti oxide；Wherein metallic element in each oxide
Weight is than for X：Ce：Mn：Ti=0.9-4.4：2-4：13-24：76-87, X are at least one in Fe, Co, La, Sb, Ni.
By technique scheme, the present invention cellular manganese systems denitrating catalyst and preparation method thereof at least has following excellent
Point：
1st, the present invention first carries out single treatment to manganese presoma and titanium dioxide before the forming, obtains Mn-Ti powder.Wherein
Ultrasonic immersing, so that manganese salt and titanium dioxide are fully contacted, dry before shaping and starts to make manganese salt decompose generation manganese oxygen in advance
Compound, and discharge gas, so can reduce the amount of green honeycomb volatile matter during drying and calcining, it is not easy to cause
The cracking of green honeycomb, efflorescence.Generation Mn oxide even dispersion is between titanium dioxide granule simultaneously, increases active component
Load area, improves the contact area of Mn oxide and nitrogen oxides.
2nd, the honeycomb catalyst of the present invention, the good dispersion of active component, not easy-sintering, pore passage structure is excellent, porosity
Greatly, mechanical strength is high, and its axial compression strength is 4.7-5.1Mpa, and radial crushing strength is 1.2-1.4Mpa；The side of the present invention
Catalyst porosity prepared by method is 84-90%.
3rd, catalyst prepared by the method for the present invention is respectively provided with higher denitration activity in the range of 120-250 DEG C, is suitable for
In low-temperature denitration.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, after describing in detail such as with presently preferred embodiments of the present invention below.
Detailed description of the invention
By further illustrating the technological means and effect that the present invention taked by reaching predetermined goal of the invention, below in conjunction with
Preferred embodiment, to its detailed description of the invention of cellular manganese systems denitrating catalyst and preparation method thereof proposing according to the present invention,
Feature and effect thereof, after describing in detail such as.In the following description, what different " embodiments " or " embodiment " referred to is not necessarily
Same embodiment.Additionally, special characteristic or feature in one or more embodiment can be combined by any suitable form.
The preparation method of a kind of cellular manganese systems denitrating catalyst that one embodiment of the present of invention proposes, it includes following
Step:
1) by soluble in water to manganese salt and complexing agent, add titanium dioxide, stirring, ultrasonic immersing, dry, grinding, obtain Mn-
Ti oxide solid particle；Wherein, the concentration of described complexing agent is 3-5mol/L, and manganese salt is 65-with the mol ratio of complexing agent
187:1；Wherein, ultrasonic frequency is 10-30KHz, and the time of ultrasonic immersing is 1-2 hour, by ultrasonic immersing so that
Manganese salt and titanium dioxide are fully contacted；The temperature dried is 105-250 DEG C, and drying time is 20-30h, makes manganese salt by drying
Decompose the oxide generating manganese in advance, and discharge gas, so can reduce green honeycomb in drying and calcination process
The amount of volatile matter, it is not easy to cause the cracking of green honeycomb, efflorescence, the oxide even dispersion of the manganese of generation can be made simultaneously
Between titanium dioxide granule, increasing the load area of active component, the Mn oxide in raising catalyst connects with nitrogen oxides
Contacting surface is amassed.
It is also preferred that the left the complexing agent in the preparation method of the cellular manganese systems denitrating catalyst of the present embodiment is oxalic acid or lemon
Acid；Described manganese salt is manganese nitrate, manganese acetate, at least one in manganese oxalate；Described titanium dioxide is anatase type nano
Titanium dioxide；Complexing agent makes TiO2It is tightly combined with the oxide of manganese, interact and strengthen, make the catalytic mechanical intensity of preparation
Height, catalytic performance is good.
It is also preferred that the left Mn element in the manganese salt described in preparation method of the cellular manganese systems denitrating catalyst of the present embodiment with
The weight of described titanium dioxide is than for 0.11-0.45：1.
It is also preferred that the left the Mn-Ti oxide solid described in preparation method of the cellular manganese systems denitrating catalyst of the present embodiment
The particle diameter of particle is 300-400 mesh.
2) slaine is soluble in water with cerium salt, obtain hybrid metal solution；Described slaine is molysite, cobalt salt, lanthanum
At least one in salt, antimonic salt and nickel salt；
It is also preferred that the left the molysite described in preparation method of the cellular manganese systems denitrating catalyst of the present embodiment is ferric nitrate, sulphur
At least one in acid ferrous iron, ferric sulfate, iron chloride；Described cobalt salt be cobalt nitrate, cobalt acetate, cobaltous sulfate, in cobalt chloride
At least one；Described lanthanum salt is lanthanum acetate, lanthanum sulfate, at least one in lanthanum chloride；Described antimonic salt is nitric acid antimony；Described
Nickel salt be nickel nitrate, nickel acetate, nickel sulfate, at least one in cobalt chloride；Described cerium salt is cerous nitrate, cerous acetate, sulphur
At least one in acid cerium, cerium chloride.
It is also preferred that the left in the hybrid metal solution described in preparation method of the cellular manganese systems denitrating catalyst of the present embodiment
The weight of metallic element and water and described Mn-Ti oxide solid particle is than for X：Ce：H2O：Mn-Ti oxide=0.9-
4.4：2-4：25-35：100, wherein X is at least one in Fe, Co, La, Sb, Ni.
3) by pore creating material, binding agent, extrusion aid, reinforcing agent, described Mn-Ti oxide solid particle and described mixing
Metallic solution mixes, and is molded into honeycomb packaging blank, is dried, and calcining obtains cellular manganese systems denitrating catalyst；Wherein, pore creating material
The catalyst pore passage structure making preparation is excellent, and binding agent makes the catalyst of preparation be difficult to division, and extrusion aid makes catalyst easily become
Type, reinforcing agent adds the mechanical strength of catalyst.
It is also preferred that the left the process of the shaping in the preparation method of the cellular manganese systems denitrating catalyst of the present embodiment is：To make
Hole agent, binding agent, extrusion aid, reinforcing agent, Mn-Ti oxide solid particle and the mixing of hybrid metal solution, true in pug mill
Pug after mixing, all over obtaining pug, is sealed old 2-3 days, is then fed in extruder, is extruded into honeycomb ceramics by empty mixing 2-3
Blank.
It is also preferred that the left the pore creating material described in preparation method of the cellular manganese systems denitrating catalyst of the present embodiment be activated carbon,
At least one in starch, wood chip, polymethyl methacrylate；Described binding agent is carboxymethylcellulose calcium and/or polyoxygenated
Ethene；Described extrusion aid is glycerine, soya-bean oil, at least one in tung oil；Described reinforcing agent is glass fibre.
It is also preferred that the left the pore creating material described in preparation method, the binding agent of the cellular manganese systems denitrating catalyst of the present embodiment, help
Squeeze agent, the weight ratio of reinforcing agent and described Mn-Ti oxide solid particle for 4-6：1-2：2-4：4-6：100.
It is also preferred that the left the process of the drying described in preparation method of the cellular manganese systems denitrating catalyst of the present embodiment is：?
50-70 DEG C is dried 5-7h, is warming up to 100-110 DEG C of dry 11-13h；The temperature of described calcining is 400-600 DEG C, calcining
Time is 2-5h.
An alternative embodiment of the invention proposes a kind of cellular manganese systems denitrating catalyst, and its active component is aoxidized by iron
At least one in thing, cobalt/cobalt oxide, lanthanum-oxides, sb oxide, nickel oxide and Mn oxide, cerium oxide composition, carry
Body is Mn-Ti oxide；Wherein the weight of the metallic element in each oxide is than for X：Ce：Mn：Ti=1.5-2.5：2-4：13-
24：76-87, X are at least one in Fe, Co, La, Sb, Ni.
Embodiment 1
50wt% manganese nitrate and the oxalic acid solution that 100ml concentration is 3mol/L of 9.76kg are dissolved in 5000mL deionized water
In, add 10kg titania powder, stir 0.5h, ultrasonic immersing 2h under 25KHz, put into 205 DEG C of drying 24h in baking oven,
Grinding, obtains the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 988gCo (NO3)3·6H2O and 930gCe
(NO3)3·6H2O is dissolved in 3000ml water, obtains hybrid metal solution；10kgMn-Ti oxide solid particle is joined
Hybrid metal solution stirs, continuously adds 500g activated carbon, the carboxymethylcellulose calcium of 100g and 100g polyethylene glycol oxide, 300g
Glycerine, 500g glass fibre, obtain mix walk；Mixing walk is placed in vacuum kneading 3 times in pug mill, after mixing
Pug seals old 2 days, sends in extruder, is extruded into green honeycomb；Green honeycomb is put in 60 DEG C of baking ovens and be dried
Then temperature is increased to 105 DEG C and continues to be dried 12h, finally calcine 3 hours at 500 DEG C in Muffle furnace, obtain cellular by 6h
Manganese systems denitrating catalyst.
Embodiment 2
50wt% manganese nitrate and the oxalic acid solution that 100ml concentration is 4mol/L of 13.02kg are dissolved in 3500mL deionization
In water, add 10kg titania powder, stir 0.5h, ultrasonic immersing 1h under 20KHz, put into 185 DEG C of drying in baking oven
20h, grinding, obtain the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 993gFeSO4·7H2O and 680gCe
(C2H3O2)3It is dissolved in 3000ml water, obtain hybrid metal solution；10kgMn-Ti oxide solid particle is joined mixing
Metallic solution stirs, continuously adds 400g starch, the carboxymethylcellulose calcium of 100g and 100g polyethylene glycol oxide, the beans of 200g
Oil, 400g glass fibre, obtain mixing walk；Mixing walk is placed in vacuum kneading 2 times in pug mill, by the pug after mixing
Seal old 3 days, send in extruder, be extruded into green honeycomb；Green honeycomb is put into 50 DEG C of baking ovens are dried 7h, so
After temperature be increased to 100 DEG C continue to be dried 13h, finally calcine 2 hours at 400 DEG C in Muffle furnace, obtain cellular manganese systems
Denitrating catalyst.
Embodiment 3
50wt% manganese nitrate and the oxalic acid solution that 100ml concentration is 5mol/L of 19.53kg are dissolved in 3500mL deionization
In water, add 10kg titania powder, stir 0.5h, ultrasonic immersing 1h under 30KHz, put into 165 DEG C of drying in baking oven
30h, grinding, obtain the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 1.44kgFe (NO3)3·9H2O and
930gCe(NO3)3·6H2O is dissolved in 2500ml water, obtains hybrid metal solution；By 10kgMn-Ti oxide solid particle
Join in hybrid metal solution and stir, continuously add 600g starch, the carboxymethylcellulose calcium of 100g, the tung oil of 300g, 600g
Glass fibre, obtains mixing walk；Mixing walk is placed in vacuum kneading 2 times in pug mill, the pug after mixing is sealed old
Rotten 3 days, send in extruder, be extruded into green honeycomb；Green honeycomb is put into 70 DEG C of baking ovens are dried 5h, then by temperature
Degree is increased to 110 DEG C and continues to be dried 11h, finally calcines 2 hours at 600 DEG C in Muffle furnace, obtains cellular manganese systems denitration and urge
Agent.
Embodiment 4
It is dissolved in 13.37kg manganese acetate and the citric acid solution that 100ml concentration is 5mol/L in 6000mL deionized water, add
Enter 10kg titania powder, stir 0.5h, ultrasonic immersing 2h under 10KHz, put in baking oven 250 DEG C and dry 30h, grinding,
Obtain the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 845gC4H6O4·Co·4H2O and 680gCe (C2H3O2)3
It is dissolved in 3500ml water, obtain hybrid metal solution；10kgMn-Ti oxide solid particle is joined hybrid metal solution
Middle stirring, continuously adds 500g wood chip, the carboxymethylcellulose calcium of 150g, the tung oil of 400g, and 400g glass fibre obtains mixed soil
Group；Mixing walk is placed in vacuum kneading 2 times in pug mill, the pug after mixing is sealed old 3 days, send in extruder,
It is extruded into green honeycomb；Green honeycomb is put into 70 DEG C of baking ovens are dried 5h, then temperature is increased to 105 DEG C and continues dry
Dry 11h, finally calcines 5 hours at 500 DEG C in Muffle furnace, obtains cellular manganese systems denitrating catalyst.
Embodiment 5
It is dissolved in 8.91kg manganese acetate and the citric acid solution that 100ml concentration is 4mol/L in 7500mL deionized water, add
Enter 10kg anatase-type nanometer titanium dioxide, stir 0.5h, ultrasonic immersing 2h under 18KHz, put into 250 DEG C of drying in baking oven
30h, grinding, obtain the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 455gLa (Ac)3And 680gCe
(C2H3O2)3It is dissolved in 3000ml water, obtain hybrid metal solution；10kgMn-Ti oxide solid particle is joined mixing
Metallic solution stirs, continuously adds 500g polymethyl methacrylate, the polyethylene glycol oxide of 150g, the tung oil of 400g, 500g
Glass fibre, obtains mixing walk；Mixing walk is placed in vacuum kneading 2 times in pug mill, the pug after mixing is sealed old
Rotten 2 days, send in extruder, be extruded into green honeycomb；Green honeycomb is put into 70 DEG C of baking ovens are dried 5h, then by temperature
Degree is increased to 105 DEG C and continues to be dried 11h, finally calcines 5 hours at 550 DEG C in Muffle furnace, obtains cellular manganese systems denitration and urge
Agent.
Embodiment 6
It is dissolved in 6.68kg manganese acetate and the citric acid solution that 100ml concentration is 3mol/L in 7500mL deionized water, add
Enter 10kg anatase-type nanometer titanium dioxide, stir 0.5h, ultrasonic immersing 2h under 10KHz, put into 250 DEG C of drying in baking oven
30h, grinding, obtain the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 506gSb (NO3)3And 930gCe
(NO3)3·6H2O is dissolved in 3000ml water, obtains hybrid metal solution；10kgMn-Ti oxide solid particle is joined
Hybrid metal solution stirs, continuously adds 200g polymethyl methacrylate, 300g starch, the polyethylene glycol oxide of 150g,
The tung oil of 200g, 200g soya-bean oil, 500g glass fibre, obtain mixing walk；Mixing walk is placed in vacuum kneading 3 in pug mill
Time, the pug after mixing is sealed old 2 days, sends in extruder, be extruded into green honeycomb；Green honeycomb is put into 70
DEG C baking oven is dried 5h, then temperature is increased to 105 DEG C and continues to be dried 11h, in Muffle furnace, finally at 580 DEG C, calcine 5 little
When, obtain cellular manganese systems denitrating catalyst.
Embodiment 7
It is dissolved in 9.76kg manganese oxalate and the citric acid solution that 100ml concentration is 5mol/L in 8000mL deionized water, add
Enter 10kg anatase-type nanometer titanium dioxide, stir 0.5h, ultrasonic immersing 2h under 10KHz, put into 215 DEG C of drying in baking oven
24h, grinding, obtain the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 991gNi (NO3)2·6H2O and 930gCe
(NO3)3·6H2O is dissolved in 3000ml water, obtains hybrid metal solution；10kgMn-Ti oxide solid particle is joined
Hybrid metal solution stirs, continuously adds 500g activated carbon, the polyethylene glycol oxide of 150g, the tung oil of 200g, 200g soya-bean oil,
500g glass fibre, obtains mixing walk；Mixing walk is placed in vacuum kneading 3 times in pug mill, and the pug after kneading is close
Seal old 2 days, send in extruder, be extruded into green honeycomb；Green honeycomb is put into 70 DEG C of baking ovens are dried 5h, then
Temperature is increased to 105 DEG C and continues to be dried 11h, finally calcine 3 hours at 500 DEG C in Muffle furnace, obtain cellular manganese systems and take off
Denox catalyst.
Embodiment 8
It is dissolved in 6.51kg manganese oxalate and the citric acid solution that 100ml concentration is 4mol/L in 8500mL deionized water, add
Enter 10kg anatase-type nanometer titanium dioxide, stir 0.6h, ultrasonic immersing 2h under 10KHz, put into 235 DEG C of drying in baking oven
24h, grinding, obtain the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 1839gC4H6O4Ni·4H2O and
1839gC4H6O4Ni·4H2O is dissolved in 3000ml water, obtains hybrid metal solution；By 10kgMn-Ti oxide solid particle
Join in hybrid metal solution and stir, continuously add 500g activated carbon, the polyethylene glycol oxide of 150g, the tung oil of 200g, 200g
Soya-bean oil, 500g glass fibre, obtain mixing walk；Mixing walk is placed in vacuum kneading 3 times in pug mill, by the mud after mixing
Material seals old 2 days, sends in extruder, is extruded into green honeycomb；Green honeycomb is put into 70 DEG C of baking ovens is dried 5h,
Then temperature is increased to 105 DEG C and continues to be dried 11h, finally calcine 3 hours at 500 DEG C in Muffle furnace, obtain cellular manganese
It is denitrating catalyst.
Embodiment 9
It is dissolved in 4.88kg manganese oxalate and the oxalic acid solution that 100ml concentration is 3mol/L in 9000mL deionized water, add
10kg anatase-type nanometer titanium dioxide, stirs 0.6h, ultrasonic immersing 2h under 25KHz, puts into 245 DEG C of drying 24h in baking oven,
Grinding, obtains the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 494gCo (NO3)3·6H2O and 930gCe
(NO3)3.6H2O is dissolved in 2500ml water, obtains hybrid metal solution；10kgMn-Ti oxide solid particle is joined mixed
Close stirring in metallic solution, continuously add 500g activated carbon, the carboxymethylcellulose calcium of 100g and 100g polyethylene glycol oxide, 200g's
Tung oil, 200g soya-bean oil, 500g glass fibre, obtain mixing walk；Mixing walk is placed in vacuum kneading 3 times in pug mill, will
Pug after mixing seals old 2 days, sends in extruder, is extruded into green honeycomb；Green honeycomb is put into 65 DEG C of bakings
Case is dried 5.5h, then temperature is increased to 104 DEG C and continues to be dried 11h, finally calcine 4 hours at 500 DEG C in Muffle furnace,
Obtain cellular manganese systems denitrating catalyst.
Embodiment 10
It is dissolved in 13.37kg manganese oxalate and the oxalic acid solution that 100ml concentration is 5mol/L in 6000mL deionized water, add
10kg anatase-type nanometer titanium dioxide, stirs 0.6h, ultrasonic immersing 2h under 25KHz, puts into 245 DEG C of drying 24h in baking oven,
Grinding, obtains the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 423gC4H6O4·Co·4H2O、228gLa
(Ac)3With 680gCe (C2H3O2)3It is dissolved in 3000ml water, obtain hybrid metal solution；By 10kgMn-Ti oxide solid
Particle joins in hybrid metal solution and stirs, and continuously adds 500g starch, the carboxymethylcellulose calcium of 100g and 100g polyoxygenated
Ethene, the tung oil of 200g, 200g soya-bean oil, 550g glass fibre, obtain mixing walk；Mixing walk is placed in vacuum in pug mill
Knead 3 times, the pug after mixing is sealed old 3 days, sends in extruder, be extruded into green honeycomb；By green honeycomb
Put into and 65 DEG C of baking ovens are dried 5.5h, then temperature is increased to 106 DEG C and continues to be dried 12h, finally in Muffle furnace at 550 DEG C
Calcine 4 hours, obtain cellular manganese systems denitrating catalyst.
Embodiment 11
It is dissolved in 6.51kg manganese oxalate and the oxalic acid solution that 100ml concentration is 4mol/L in 6000mL deionized water, add
10kg anatase-type nanometer titanium dioxide, stirs 0.6h, ultrasonic immersing 2h under 25KHz, puts into 245 DEG C of drying 24h in baking oven,
Grinding, obtains the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 720gFe (NO3)3·9H2O、253gSb(NO3)3
With 930gCe (NO3)3·6H2O is dissolved in 3000ml water, obtains hybrid metal solution；By 10kgMn-Ti oxide solid
Grain joins in hybrid metal solution and stirs, and continuously adds 500g starch, the carboxymethylcellulose calcium of 100g and 100g polyoxyethylene
Alkene, the tung oil of 200g, 200g glycerine, 550g glass fibre, obtain mixing walk；Mixing walk is placed in vacuum in pug mill mix
Refine 3 times, the pug after mixing is sealed old 3 days, sends in extruder, be extruded into green honeycomb；Green honeycomb is put
Enter and 65 DEG C of baking ovens are dried 5.5h, then temperature is increased to 106 DEG C and continues to be dried 12h, finally forge at 580 DEG C in Muffle furnace
Burn 4 hours, obtain cellular manganese systems denitrating catalyst.
Embodiment 12
50wt% manganese nitrate and the oxalic acid solution that 100ml concentration is 3mol/L of 9.76kg are dissolved in 6000mL deionized water
In, add 10kg anatase-type nanometer titanium dioxide, stir 0.6h, ultrasonic immersing 2h under 25KHz, put in baking oven 245 DEG C
Dry 24h, grinding, obtain the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 720gFe (NO3)3·9H2O、
496gNi(NO3)2·6H2O and 930gCe (NO3)3·6H2O is dissolved in 2800ml water, obtains hybrid metal solution；Will
10kgMn-Ti oxide solid particle joins in hybrid metal solution and stirs, and continuously adds 500g starch, the carboxymethyl of 100g
Cellulose and 100g polyethylene glycol oxide, the soya-bean oil of 200g, 200g glycerine, 550g glass fibre, obtain mixing walk；By mixed soil
Group is placed in vacuum kneading 3 times in pug mill, seals the pug after mixing old 3 days, sends in extruder, be extruded into honeycomb ceramics
Blank；Green honeycomb is put into 65 DEG C of baking ovens are dried 5.5h, then temperature is increased to 106 DEG C and continues to be dried 12h, finally
Muffle furnace is calcined 4 hours at 580 DEG C, obtains cellular manganese systems denitrating catalyst.
Embodiment 13
50wt% manganese nitrate and the oxalic acid solution that 100ml concentration is 5mol/L of 19.53kg are dissolved in 6000mL deionization
In water, add 10kg anatase-type nanometer titanium dioxide, stir 0.6h, ultrasonic immersing 2h under 25KHz, put in baking oven 245
DEG C dry 24h, grinding, obtain the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 423gC4H6O4·Co·
4H2O、920gC4H6O4Ni·4H2O and 680gCe (C2H3O2)3It is dissolved in 2800ml water, obtain hybrid metal solution；Will
10kgMn-Ti oxide solid particle joins in hybrid metal solution and stirs, and continuously adds 500g starch, the carboxymethyl of 100g
Cellulose and 100g polyethylene glycol oxide, the soya-bean oil of 200g, 200g glycerine, 550g glass fibre, obtain mixing walk；By mixed soil
Group is placed in vacuum kneading 3 times in pug mill, seals the pug after mixing old 3 days, sends in extruder, be extruded into honeycomb ceramics
Blank；Green honeycomb is put into 65 DEG C of baking ovens are dried 5.5h, then temperature is increased to 106 DEG C and continues to be dried 12h, finally
Muffle furnace is calcined 4 hours at 570 DEG C, obtains cellular manganese systems denitrating catalyst.
Embodiment 14
It is dissolved in 8.91kg manganese acetate and the citric acid solution that 100ml concentration is 4mol/L in 6000mL deionized water, add
Enter 10kg anatase-type nanometer titanium dioxide, stir 0.6h, ultrasonic immersing 2h under 25KHz, put into 245 DEG C of drying in baking oven
24h, grinding, obtain the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 228gLa (Ac)3、253gSb(NO3)3With
930gCe(NO3)3·6H2O is dissolved in 2800ml water, obtains hybrid metal solution；By 10kgMn-Ti oxide solid particle
Join in hybrid metal solution and stir, continuously add 500g starch, the carboxymethylcellulose calcium of 100g and 100g polyethylene glycol oxide,
The soya-bean oil of 200g, 200g glycerine, 550g glass fibre, obtain mixing walk；Mixing walk is placed in vacuum kneading 3 in pug mill
Time, the pug after mixing is sealed old 3 days, sends in extruder, be extruded into green honeycomb；Green honeycomb is put into 65
DEG C baking oven is dried 5.5h, then temperature is increased to 107 DEG C and continues to be dried 11h, in Muffle furnace, finally at 570 DEG C, calcine 5
Hour, obtain cellular manganese systems denitrating catalyst.
Embodiment 15
It is dissolved in 4.88kg manganese oxalate and the citric acid solution that 100ml concentration is 3mol/L in 6000mL deionized water, add
Enter 10kg anatase-type nanometer titanium dioxide, stir 0.6h, ultrasonic immersing 2h under 25KHz, put into 245 DEG C of drying in baking oven
24h, grinding, obtain the Mn-Ti oxide solid particle that particle diameter is 300-400 mesh；By 228gLa (Ac)3、920gC4H6O4Ni·
4H2O and 930gCe (NO3)3·6H2O is dissolved in 2800ml water, obtains hybrid metal solution；10kgMn-Ti oxide is solid
Body particle joins in hybrid metal solution and stirs, and continuously adds 500g starch, the carboxymethylcellulose calcium of 100g and 100g polyoxy
Change ethene, the soya-bean oil of 200g, 200g glycerine, 550g glass fibre, obtain mixing walk；Mixing walk is placed in pug mill very
Pug after mixing is sealed old 3 days, sends in extruder, be extruded into green honeycomb by empty mixing 3 times；By honeycomb ceramics base
Material is put into and is dried 5.5h in 65 DEG C of baking ovens, then temperature is increased to 107 DEG C and continues to be dried 11h, finally in Muffle furnace 570 DEG C
Lower calcining 5 hours, obtains cellular manganese systems denitrating catalyst.
Comparative example 1
By 988gCo (NO3)3·6H2O、930gCe(NO3)3·6H2O, 10kg titanium dioxide, 500g activated carbon, 100g's
Carboxymethylcellulose calcium and 100g polyethylene glycol oxide, the glycerine of 500g, 500g glass fibre joins stirring 0.3h in batch mixer, adds
Entering 9.76kg 50wt% manganese nitrate solution, mixing obtains plasticity walk, vacuum kneading 2 times in pug mill by walk, will mixing
After pug seal old 3 days, then send into pug in extruder, be extruded into green honeycomb；By above-mentioned green honeycomb
Put in 60 DEG C of baking ovens 6 hours, then temperature is increased to 105 DEG C and continues to be dried 12 hours；It is finally putting in Muffle furnace 500 DEG C
Lower roasting 3 hours, obtains honeycomb catalyst.
Comparative example 2
By 6.68kgMn (CH3COO)2·4H2O、988gCo(NO3)3·6H2O、930gCe(NO3)3·6H2O, 10kg dioxy
Changing titanium, 500g activated carbon, the carboxymethylcellulose calcium of 100g and 100g polyethylene glycol oxide, the glycerine of 400g, 500g glass fibre adds
Entering in batch mixer stirring 0.5h, being subsequently adding 3000ml water, mixing obtains plasticity walk, and by walk, in pug mill, vacuum is mixed
Refine 3 times, the pug after mixing is sealed old 2 days, then sends into pug in extruder, be extruded into green honeycomb；By upper
State green honeycomb to put in 60 DEG C of baking ovens 6 hours, then temperature is increased to 105 DEG C and continues to be dried 12 hours；It is finally putting into
In Muffle furnace, roasting 3 hours at 500 DEG C, obtain honeycomb catalyst.
The method of evaluating performance of catalyst：By the Catalyst packing of preparation in stainless steel fixed bed reactors, loadings
For 18cm3, ammonia nitrogen ratio is 1:1, oxygen concentration is 6% (V/V), GHSV (gas space velocity per hour)=5000h-1Flue gas, point
Ce Ding the NO conversion ratio of 120 DEG C, 150 DEG C, 200 DEG C, 250 DEG C etc. 4 temperature spots.When reactor is stabilized to a certain temperature spot
When, start to be passed through simulated flue gas, after reacting 10 minutes, use flue gas analyzer (Testo350, Germany) to measure gas before and after reaction
NO concentration in body, it is 15 minutes that each temperature spot continues minute, averages, calculates NO conversion ratio according to formula 1, i.e. de-
Efficiency.The Activity Results recording is as shown in appendix 1.
NO conversion ratio=[(NOin-NOout)/NOin] × 100% (formula 1)
The intensity test of catalyst：Every kind of catalyst intercepts three test blocks, a size of 200mm*200mm*200mm；
Testing axially and radially compression strength with pressure testing machine, test result is as shown in table 1.
The porosity of catalyst is tested on Mercury-injection test instrument, and result is as shown in table 1.
Table 1 catalyst low temperature SCR denitration reaction test Activity Results and physical property characterization result
As shown in Table 1, the catalyst that prepared by the method for present invention denitration catalyst activity in a low temperature of 120-250 DEG C is high；
The catalyst compression strength prepared by the present invention is big, and axial compression strength is 4.7-5.1Mpa, and radial crushing strength is 1.2-
1.4Mpa；Catalyst porosity prepared by the method for the present invention is 84-90%.
The above, be only presently preferred embodiments of the present invention, not makees any pro forma restriction to the present invention, depends on
Any simple modification, equivalent variations and the modification made above example according to the technical spirit of the present invention, all still falls within this
In the range of bright technical scheme.
Claims (10)
1. the preparation method of a cellular manganese systems denitrating catalyst, it is characterised in that：It comprises the following steps:
1) by soluble in water to manganese salt and complexing agent, add titanium dioxide, stirring, ultrasonic immersing, dry, grinding, obtain Mn-Ti oxygen
Compound solid particle；Wherein, manganese salt and the mol ratio of complexing agent are 65-187:1；
2) slaine is soluble in water with cerium salt, obtain hybrid metal solution；Described slaine is molysite, cobalt salt, lanthanum salt, antimony
At least one in salt and nickel salt；
3) by pore creating material, binding agent, extrusion aid, reinforcing agent, described Mn-Ti oxide solid particle and described hybrid metal
Solution mixes, and is molded into honeycomb packaging blank, is dried, and calcining obtains cellular manganese systems denitrating catalyst.
2. the preparation method of cellular manganese systems denitrating catalyst according to claim 1, it is characterised in that described complexing
Agent is oxalic acid or citric acid；Described manganese salt is manganese nitrate, manganese acetate, at least one in manganese oxalate；Described titanium dioxide
For anatase-type nanometer titanium dioxide.
3. the preparation method of cellular manganese systems denitrating catalyst according to claim 1, it is characterised in that described manganese salt
In the weight of Mn element and described titanium dioxide than for 0.11-0.45：1.
4. the preparation method of cellular manganese systems denitrating catalyst according to claim 1, it is characterised in that described Mn-
The particle diameter of Ti oxide solid particle is 300-400 mesh.
5. the preparation method of cellular manganese systems denitrating catalyst according to claim 1, it is characterised in that described molysite
For at least one in ferric nitrate, ferrous sulfate, ferric sulfate, iron chloride；Described cobalt salt be cobalt nitrate, cobalt acetate, cobaltous sulfate,
At least one in cobalt chloride；Described lanthanum salt is lanthanum acetate, lanthanum sulfate, at least one in lanthanum chloride；Described antimonic salt is
Nitric acid antimony；Described nickel salt is nickel nitrate, nickel acetate, nickel sulfate, at least one in cobalt chloride；Described cerium salt is nitric acid
At least one in cerium, cerous acetate, cerous sulfate, cerium chloride.
6. the preparation method of cellular manganese systems denitrating catalyst according to claim 1, it is characterised in that described pore-creating
Agent is activated carbon, starch, wood chip, at least one in polymethyl methacrylate；Described binding agent is carboxymethylcellulose calcium
And/or polyethylene glycol oxide；Described extrusion aid is glycerine, soya-bean oil, at least one in tung oil；Described reinforcing agent is glass fibers
Dimension.
7. the preparation method of cellular manganese systems denitrating catalyst according to claim 1, it is characterised in that described mixing
The weight of the metallic element in metallic solution and water and described Mn-Ti oxide solid particle is than for X：Ce：H2O：Mn-Ti
Oxide=0.9-4.4：2-4：25-35：100, wherein X is at least one in Fe, Co, La, Sb, Ni.
8. the preparation method of cellular manganese systems denitrating catalyst according to claim 1, it is characterised in that described pore-creating
The weight of agent, binding agent, extrusion aid, reinforcing agent and described Mn-Ti oxide solid particle is than for 4-6：1-2：2-4：4-6：
100.
9. the preparation method of cellular manganese systems denitrating catalyst according to claim 1, it is characterised in that described drying
Process be：It is dried 5-7h in 50-70 DEG C, be warming up to 100-110 DEG C of dry 11-13h；The temperature of described calcining is 400-
600 DEG C, calcination time is 2-5h.
10. a cellular manganese systems denitrating catalyst, it is characterised in that：Its active component is by ferriferous oxide, cobalt/cobalt oxide, lanthanum oxygen
At least one in compound, sb oxide, nickel oxide and cerium oxide composition, carrier is Mn-Ti oxide；Wherein respectively aoxidize
The weight of the metallic element in thing is than for X：Ce：Mn：Ti=0.9-4.4：2-4：13-24：76-87, X are Fe, Co, La, Sb, Ni
In at least one.
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