CN106423193B - Honeycomb manganese systems denitrating catalyst and preparation method thereof - Google Patents
Honeycomb manganese systems denitrating catalyst and preparation method thereof Download PDFInfo
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- CN106423193B CN106423193B CN201610840300.XA CN201610840300A CN106423193B CN 106423193 B CN106423193 B CN 106423193B CN 201610840300 A CN201610840300 A CN 201610840300A CN 106423193 B CN106423193 B CN 106423193B
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- manganese
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- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 239000011572 manganese Substances 0.000 title claims abstract description 74
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000010936 titanium Substances 0.000 claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002245 particle Substances 0.000 claims abstract description 47
- 239000007787 solid Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 44
- 229910001868 water Inorganic materials 0.000 claims abstract description 33
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 150000002696 manganese Chemical class 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000008139 complexing agent Substances 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- -1 extrusion aid Substances 0.000 claims abstract description 12
- 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 9
- 150000000703 Cerium Chemical class 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 238000002156 mixing Methods 0.000 claims description 55
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 33
- 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
- 238000001035 drying Methods 0.000 claims description 22
- 239000003365 glass fiber Substances 0.000 claims description 20
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 14
- 239000008112 carboxymethyl-cellulose Substances 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
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 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 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 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
- 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
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 229910052742 iron Inorganic materials 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
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 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 compound [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 compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 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
- 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
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 230000006835 compression Effects 0.000 abstract description 5
- 238000007906 compression Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 210000003850 cellular structure Anatomy 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 56
- 229910002651 NO3 Inorganic materials 0.000 description 23
- 230000032683 aging Effects 0.000 description 16
- 238000004898 kneading Methods 0.000 description 13
- 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
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 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
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000010410 dusting Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-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
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 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
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining 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
- 239000002253 acid Substances 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
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 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
- 230000003993 interaction Effects 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
- 238000005259 measurement Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 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
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 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
- 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)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of honeycomb manganese systems denitrating catalysts and preparation method thereof comprising following steps: manganese salt and complexing agent is soluble in water, titanium dioxide, stirring is added, ultrasonic immersing is dried, and grinding obtains Mn-Ti oxide solid particle；Manganese salt and the molar ratio of complexing agent are 65-187:1；Metal salt is soluble in water with cerium salt, mixed metal solution is obtained, metal salt is at least one of molysite, cobalt salt, lanthanum salt, antimonic salt and nickel salt；Pore creating material, binder, extrusion aid, reinforcing agent, Mn-Ti oxide solid particle and mixed metal solution are mixed, honeycomb packaging blank is molded into, dry, calcining.Catalyst of the invention, the good dispersion of active component, not easy-sintering, cellular structure is excellent, porosity is big, high mechanical strength, axial compression strength 4.7-5.1Mpa, radial crushing strength 1.2-1.4Mpa；Catalyst porosity of the invention is 84-90%.The catalyst of method preparation of the invention all has higher denitration activity within the scope of 120-250 DEG C, is suitable for low-temperature denitration.
Description
Technical field
The present invention relates to a kind of catalyst, more particularly to a kind of honeycomb manganese systems denitrating catalyst and preparation method thereof.
Background technique
Nitrogen oxides (NOx) it is one of main atmosphere pollution, it is before leading to acid rain, secondary fine particle
Body object.Currently, in NOxIn removing sulfuldioxide, selective catalytic reduction (SCR, Selective Catalytic Reduction)
Denitration has obtained the most attention of countries in the world with its mature technology and good denitration effect, is in the world using the most
Extensive gas denitrifying technology.
Current widely used commercialized catalyst is mainly V2O5-WO3/TiO2Or V2O5-MoO3/TiO2, but such catalysis
Agent has Process window relatively narrow, and active temperature is high, only the denitration activity with higher at 350~400 DEG C, and vanadium is to human body and ring
The disadvantages of border is harmful.Therefore, it reduces the load capacity of vanadium or substitutes vanadium with other metallic elements to prepare novel effective catalyst
It is of great significance.Compared to vanadium titanium class catalyst, manganese oxide type catalyst has low temperature, efficient, nontoxic, cheap etc. excellent
Point, while the load capacity of manganese is higher, generally in 10%-30% or so.Active component in manganese cerium titanium system catalysis material is not
With the oxide of valence state, it is desirable that manganese needs are oxidized in the calcination process of catalysis material, however catalysis material in existing technology
Generally to be calcined under Oxygen Condition, catalysis material is particularly easy to burn, this is mainly due to the fusing point of manganese cerium salt is lower, and cerium
With combustion-supporting effect, the very easy burning of the organic additive being added in forming process, so that honeycomb catalyst material internal temperature
It spends high and leads to its surfaces externally and internally excessive temperature differentials and crack.In addition to this, some common manganese presomas, such as manganese nitrate, second
Sour manganese and manganese oxalate can release gas in calcination process, cause cracking or even the dusting of honeycomb catalysis material.
Summary of the invention
It is a primary object of the present invention to, a kind of novel honeycomb manganese systems denitrating catalyst and preparation method thereof is provided,
The technical problem to be solved is that making it at low temperature and having high denitration catalyst activity, thus more suitable for practical.
The object of the invention to solve the technical problems adopts the following technical solutions to realize.It proposes according to the present invention
A kind of honeycomb manganese systems denitrating catalyst preparation method comprising following steps:
1) manganese salt and complexing agent is soluble in water, titanium dioxide, stirring is added, ultrasonic immersing is dried, and grinding obtains Mn-
Ti oxide solid particle；Wherein, manganese salt and the molar ratio of complexing agent are 65-187:1；
2) metal salt and cerium salt is soluble in water, obtain mixed metal solution；The metal salt is molysite, cobalt salt, lanthanum
At least one of salt, antimonic salt and nickel salt；
3) by pore creating material, binder, extrusion aid, reinforcing agent, the Mn-Ti oxide solid particle and the mixing
Metallic solution mixing, is molded into honeycomb packaging blank, dry, and calcining obtains honeycomb manganese systems denitrating catalyst.
The object of the invention to solve the technical problems also can be used following technical measures and further realize.
Preferably, the preparation method of honeycomb manganese systems denitrating catalyst above-mentioned, wherein the complexing agent be oxalic acid or
Citric acid；The manganese salt is at least one of manganese nitrate, manganese acetate, manganese oxalate；The titanium dioxide is Detitanium-ore-type
Nano-titanium dioxide.
Preferably, the preparation method of honeycomb manganese systems denitrating catalyst above-mentioned, wherein the Mn element in the manganese salt
Weight ratio with the titanium dioxide is 0.11-0.45:1.
Preferably, the preparation method of honeycomb manganese systems denitrating catalyst above-mentioned, wherein the Mn-Ti oxide solid
The partial size of particle is 300-400 mesh.
Preferably, the preparation method of honeycomb manganese systems denitrating catalyst above-mentioned, wherein the molysite is ferric nitrate, sulphur
At least one of sour ferrous iron, ferric sulfate, iron chloride；The cobalt salt is cobalt nitrate, in cobalt acetate, cobaltous sulfate, cobalt chloride
It is at least one；The lanthanum salt is at least one of lanthanum acetate, lanthanum sulfate, lanthanum chloride；The antimonic salt is nitric acid antimony；It is described
Nickel salt be at least one of nickel nitrate, nickel acetate, nickel sulfate, cobalt chloride；The cerium salt is cerous nitrate, cerous acetate, sulphur
At least one of sour cerium, cerium chloride.
Preferably, the preparation method of honeycomb manganese systems denitrating catalyst above-mentioned, wherein the pore creating material be active carbon,
At least one of starch, sawdust, polymethyl methacrylate；The binder is carboxymethyl cellulose and/or polyoxygenated
Ethylene；The extrusion aid is at least one of glycerol, soya-bean oil, tung oil；The reinforcing agent is glass fibre.
Preferably, the preparation method of honeycomb manganese systems denitrating catalyst above-mentioned, wherein in the mixed metal solution
Metallic element and the weight ratio of water and the Mn-Ti oxide solid particle be X:Ce:H2O:Mn-Ti oxide=
0.9-4.4:2-4:25-35:100, wherein X is at least one of Fe, Co, La, Sb, Ni.
Preferably, the preparation method of honeycomb manganese systems denitrating catalyst above-mentioned, wherein the pore creating material, binder,
The weight ratio of extrusion aid, reinforcing agent and the Mn-Ti oxide solid particle is 4-6:1-2:2-4:4-6:100.
Preferably, the preparation method of honeycomb manganese systems denitrating catalyst above-mentioned, wherein the process of the drying are as follows:
Dry 5-7h, is warming up to 100-110 DEG C of dry 11-13h in 50-70 DEG C；The temperature of the calcining is 400-600 DEG C, calcining
Time is 2-5h.
Also the following technical solution is employed for the object of the invention to solve the technical problems to realize.It proposes according to the present invention
A kind of honeycomb manganese systems denitrating catalyst, active component is by ferriferous oxide, cobalt/cobalt oxide, lanthanum-oxides, sb oxide, nickel
At least one of oxide and cerium oxide form, and carrier is Mn-Ti oxide；Wherein metallic element in each oxide
Weight ratio is X:Ce:Mn:Ti=0.9-4.4:2-4:13-24:76-87, at least one of X Fe, Co, La, Sb, Ni.
By above-mentioned technical proposal, honeycomb manganese systems denitrating catalyst of the present invention and preparation method thereof at least has following excellent
Point:
1, the present invention first carries out single treatment to manganese presoma and titanium dioxide before the forming, obtains Mn-Ti powder.Wherein
Ultrasonic immersing can make manganese salt come into full contact with titanium dioxide, and drying starts that manganese salt is made to decompose generation manganese oxygen in advance before forming
Compound, and gas is released, the amount of green honeycomb volatile matter during drying and calcining can be reduced in this way, it is not easy to be caused
The cracking of green honeycomb, dusting.Mn oxide even dispersion is generated between titanium dioxide granule simultaneously, increases active component
Load area improves the contact area of Mn oxide and nitrogen oxides.
2, honeycomb catalyst of the invention, the good dispersion of active component, not easy-sintering, cellular structure is excellent, porosity
Greatly, high mechanical strength, axial compression strength 4.7-5.1Mpa, radial crushing strength 1.2-1.4Mpa；Side of the invention
The catalyst porosity of method preparation is 84-90%.
3, the catalyst of method of the invention preparation all has higher denitration activity within the scope of 120-250 DEG C, is applicable in
In low-temperature denitration.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, with presently preferred embodiments of the present invention, detailed description is as follows below.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Preferred embodiment, to honeycomb manganese systems denitrating catalyst proposed according to the present invention and preparation method thereof its specific embodiment,
Feature and its effect, detailed description is as follows.In the following description, what different " embodiment " or " embodiment " referred to is not necessarily
The same embodiment.In addition, the special characteristic or feature in one or more embodiments can be combined by any suitable form.
The preparation method for a kind of honeycomb manganese systems denitrating catalyst that one embodiment of the present of invention proposes comprising following
Step:
1) manganese salt and complexing agent is soluble in water, titanium dioxide, stirring is added, ultrasonic immersing is dried, and grinding obtains Mn-
Ti oxide solid particle；Wherein, the concentration of the complexing agent is 3-5mol/L, and the molar ratio of manganese salt and complexing agent is 65-
187:1；Wherein, ultrasonic frequency is 10-30KHz, and the time of ultrasonic immersing is 1-2 hours, can be made by ultrasonic immersing
Manganese salt and titanium dioxide come into full contact with；The temperature of drying is 105-250 DEG C, drying time 20-30h, makes manganese salt by drying
The oxide for generating manganese is decomposed in advance, and releases gas, can reduce green honeycomb in this way during drying and calcination
The amount of volatile matter, it is not easy to cause the cracking of green honeycomb, dusting, while the oxide even dispersion of the manganese generated can be made
Between titanium dioxide granule, increase the load area of active component, improves connecing for the Mn oxide and nitrogen oxides in catalyst
Contacting surface product.
Preferably, the complexing agent in the preparation method of the honeycomb manganese systems denitrating catalyst of the present embodiment is oxalic acid or lemon
Acid；The manganese salt is at least one of manganese nitrate, manganese acetate, manganese oxalate；The titanium dioxide is anatase type nano
Titanium dioxide；Complexing agent makes TiO2It is tightly combined with the oxide of manganese, interaction is reinforced, and the catalytic mechanical intensity of preparation is made
Height, catalytic performance are good.
Preferably, Mn element in manganese salt described in the preparation method of the honeycomb manganese systems denitrating catalyst of the present embodiment with
The weight ratio of the titanium dioxide is 0.11-0.45:1.
Preferably, Mn-Ti oxide solid described in the preparation method of the honeycomb manganese systems denitrating catalyst of the present embodiment
The partial size of particle is 300-400 mesh.
2) metal salt and cerium salt is soluble in water, obtain mixed metal solution；The metal salt is molysite, cobalt salt, lanthanum
At least one of salt, antimonic salt and nickel salt；
Preferably, molysite described in the preparation method of the honeycomb manganese systems denitrating catalyst of the present embodiment is ferric nitrate, sulphur
At least one of sour ferrous iron, ferric sulfate, iron chloride；The cobalt salt is cobalt nitrate, in cobalt acetate, cobaltous sulfate, cobalt chloride
It is at least one；The lanthanum salt is at least one of lanthanum acetate, lanthanum sulfate, lanthanum chloride；The antimonic salt is nitric acid antimony；It is described
Nickel salt be at least one of nickel nitrate, nickel acetate, nickel sulfate, cobalt chloride；The cerium salt is cerous nitrate, cerous acetate, sulphur
At least one of sour cerium, cerium chloride.
Preferably, in mixed metal solution described in the preparation method of the honeycomb manganese systems denitrating catalyst of the present embodiment
The weight ratio of metallic element and water and the Mn-Ti oxide solid particle is X:Ce:H2O:Mn-Ti oxide=0.9-
4.4:2-4:25-35:100 wherein X is at least one of Fe, Co, La, Sb, Ni.
3) by pore creating material, binder, extrusion aid, reinforcing agent, the Mn-Ti oxide solid particle and the mixing
Metallic solution mixing, is molded into honeycomb packaging blank, dry, and calcining obtains honeycomb manganese systems denitrating catalyst；Wherein, pore creating material
Keep the catalyst cellular structure of preparation excellent, binder makes the catalyst of preparation be not easy to divide, and extrusion aid is easy into catalyst
Type, reinforcing agent increase the mechanical strength of catalyst.
Preferably, the molding process in the preparation method of the honeycomb manganese systems denitrating catalyst of the present embodiment are as follows: will make
Hole agent, binder, extrusion aid, reinforcing agent, Mn-Ti oxide solid particle and the mixing of mixed metal solution, it is true in pug mill
Sky is kneaded 2-3 all over pug is obtained, and the pug after mixing is sealed aging 2-3 days, is then fed into extruder, is extruded into honeycomb ceramics
Blank.
Preferably, pore creating material described in the preparation method of the honeycomb manganese systems denitrating catalyst of the present embodiment be active carbon,
At least one of starch, sawdust, polymethyl methacrylate；The binder is carboxymethyl cellulose and/or polyoxygenated
Ethylene；The extrusion aid is at least one of glycerol, soya-bean oil, tung oil；The reinforcing agent is glass fibre.
Preferably, pore creating material described in the preparation method of the honeycomb manganese systems denitrating catalyst of the present embodiment, binder, helping
The weight ratio for squeezing agent, reinforcing agent and the Mn-Ti oxide solid particle is 4-6:1-2:2-4:4-6:100.
Preferably, the process of drying described in the preparation method of the honeycomb manganese systems denitrating catalyst of the present embodiment are as follows:
Dry 5-7h, is warming up to 100-110 DEG C of dry 11-13h in 50-70 DEG C；The temperature of the calcining is 400-600 DEG C, calcining
Time is 2-5h.
Another embodiment of the invention proposes a kind of honeycomb manganese systems denitrating catalyst, and active component is aoxidized by iron
At least one of object, cobalt/cobalt oxide, lanthanum-oxides, sb oxide, nickel oxide and Mn oxide, cerium oxide composition, carry
Body is Mn-Ti oxide；Wherein the weight ratio of the metallic element in each oxide is X:Ce:Mn:Ti=1.5-2.5:2-4:13-
At least one of 24:76-87, X Fe, Co, La, Sb, Ni.
Embodiment 1
The oxalic acid solution that the 50wt% manganese nitrate of 9.76kg and 100ml concentration are 3mol/L is dissolved in 5000mL deionized water
In, 10kg titania powder is added, stirs 0.5h, the ultrasonic immersing 2h at 25KHz, is put into baking oven and dries for 24 hours for 205 DEG C,
Grinding obtains the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 988gCo (NO3)3·6H2O and 930gCe
(NO3)3·6H2O is dissolved in 3000ml water, obtains mixed metal solution；10kgMn-Ti oxide solid particle is added to
It is stirred in mixed metal solution, continuously adds 500g active carbon, the carboxymethyl cellulose and 100g polyethylene glycol oxide of 100g, 300g
Glycerol, 500g glass fibre, obtain mixing walk；Mixing walk is placed in vacuum kneading 3 times in pug mill, after mixing
Pug seals aging 2 days, is sent into extruder, is extruded into green honeycomb；Green honeycomb is put into 60 DEG C of baking ovens dry
Then temperature is increased to 105 DEG C and continues dry 12h, finally calcined 3 hours at 500 DEG C in Muffle furnace, obtain honeycomb by 6h
Manganese systems denitrating catalyst.
Embodiment 2
The oxalic acid solution that the 50wt% manganese nitrate of 13.02kg and 100ml concentration are 4mol/L is dissolved in 3500mL deionization
In water, 10kg titania powder is added, stirs 0.5h, the ultrasonic immersing 1h at 20KHz, is put into 185 DEG C of drying in baking oven
20h, grinding obtain the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 993gFeSO4·7H2O and 680gCe
(C2H3O2)3It is dissolved in 3000ml water, obtains mixed metal solution；10kgMn-Ti oxide solid particle is added to mixing
It is stirred in metallic solution, continuously adds 400g starch, the carboxymethyl cellulose and 100g polyethylene glycol oxide of 100g, 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
It seals aging 3 days, is sent into extruder, is extruded into green honeycomb；Green honeycomb is put into 50 DEG C of baking ovens dry 7h, so
Temperature is increased to 100 DEG C afterwards and continues dry 13h, is finally calcined 2 hours at 400 DEG C in Muffle furnace, obtains honeycomb manganese systems
Denitrating catalyst.
Embodiment 3
The oxalic acid solution that the 50wt% manganese nitrate of 19.53kg and 100ml concentration are 5mol/L is dissolved in 3500mL deionization
In water, 10kg titania powder is added, stirs 0.5h, the ultrasonic immersing 1h at 30KHz, is put into 165 DEG C of drying in baking oven
30h, grinding obtain the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 1.44kgFe (NO3)3·9H2O and
930gCe(NO3)3·6H2O is dissolved in 2500ml water, obtains mixed metal solution；By 10kgMn-Ti oxide solid particle
It is added in mixed metal solution and stirs, continuously add 600g starch, the carboxymethyl cellulose 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 sealing after mixing is old
It is 3 days rotten, it is sent into extruder, is extruded into green honeycomb；Green honeycomb is put into 70 DEG C of baking ovens dry 5h, it then will be warm
Degree is increased to 110 DEG C and continues dry 11h, finally calcines 2 hours at 600 DEG C in Muffle furnace, obtains honeycomb manganese systems denitration and urge
Agent.
Embodiment 4
The citric acid solution that 13.37kg manganese acetate and 100ml concentration are 5mol/L is dissolved in 6000mL deionized water, is added
Enter 10kg titania powder, stir 0.5h, the ultrasonic immersing 2h at 10KHz, is put into 250 DEG C of drying 30h in baking oven, grinding,
Obtain the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 845gC4H6O4·Co·4H2O and 680gCe (C2H3O2)3
It is dissolved in 3500ml water, obtains mixed metal solution；10kgMn-Ti oxide solid particle is added to mixed metal solution
Middle stirring, continuously adds 500g sawdust, the carboxymethyl cellulose 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 aging 3 days, is sent into extruder,
It is extruded into green honeycomb；Green honeycomb is put into 70 DEG C of baking ovens dry 5h, temperature is then increased to 105 DEG C and continues to do
Dry 11h finally calcines 5 hours at 500 DEG C in Muffle furnace, obtains honeycomb manganese systems denitrating catalyst.
Embodiment 5
The citric acid solution that 8.91kg manganese acetate and 100ml concentration are 4mol/L is dissolved in 7500mL deionized water, is added
Enter 10kg anatase-type nanometer titanium dioxide, stir 0.5h, the ultrasonic immersing 2h at 18KHz, is put into 250 DEG C of drying in baking oven
30h, grinding obtain the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 455gLa (Ac)3And 680gCe
(C2H3O2)3It is dissolved in 3000ml water, obtains mixed metal solution；10kgMn-Ti oxide solid particle is added to mixing
It is stirred in metallic solution, 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 sealing after mixing is old
It is 2 days rotten, it is sent into extruder, is extruded into green honeycomb；Green honeycomb is put into 70 DEG C of baking ovens dry 5h, it then will be warm
Degree is increased to 105 DEG C and continues dry 11h, finally calcines 5 hours at 550 DEG C in Muffle furnace, obtains honeycomb manganese systems denitration and urge
Agent.
Embodiment 6
The citric acid solution that 6.68kg manganese acetate and 100ml concentration are 3mol/L is dissolved in 7500mL deionized water, is added
Enter 10kg anatase-type nanometer titanium dioxide, stir 0.5h, the ultrasonic immersing 2h at 10KHz, is put into 250 DEG C of drying in baking oven
30h, grinding obtain the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 506gSb (NO3)3And 930gCe
(NO3)3·6H2O is dissolved in 3000ml water, obtains mixed metal solution；10kgMn-Ti oxide solid particle is added to
It is stirred in mixed metal solution, 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 aging 2 days, is sent into extruder, is extruded into green honeycomb；Green honeycomb is put into 70
Then temperature is increased to 105 DEG C and continues dry 11h by dry 5h in DEG C baking oven, finally calcining 5 is small at 580 DEG C in Muffle furnace
When, obtain honeycomb manganese systems denitrating catalyst.
Embodiment 7
The citric acid solution that 9.76kg manganese oxalate and 100ml concentration are 5mol/L is dissolved in 8000mL deionized water, is added
Enter 10kg anatase-type nanometer titanium dioxide, stir 0.5h, the ultrasonic immersing 2h at 10KHz, is put into 215 DEG C of drying in baking oven
For 24 hours, grinding obtains the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 991gNi (NO3)2·6H2O and 930gCe
(NO3)3·6H2O is dissolved in 3000ml water, obtains mixed metal solution；10kgMn-Ti oxide solid particle is added to
It is stirred in mixed metal solution, continuously adds 500g active 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, the pug after mixing is close
It seals aging 2 days, is sent into extruder, is extruded into green honeycomb；Green honeycomb is put into 70 DEG C of baking ovens dry 5h, then
Temperature is increased to 105 DEG C and continues dry 11h, is finally calcined 3 hours at 500 DEG C in Muffle furnace, it is de- to obtain honeycomb manganese systems
Denox catalyst.
Embodiment 8
The citric acid solution that 6.51kg manganese oxalate and 100ml concentration are 4mol/L is dissolved in 8500mL deionized water, is added
Enter 10kg anatase-type nanometer titanium dioxide, stir 0.6h, the ultrasonic immersing 2h at 10KHz, is put into 235 DEG C of drying in baking oven
For 24 hours, grinding obtains the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 1839gC4H6O4Ni·4H2O and
1839gC4H6O4Ni·4H2O is dissolved in 3000ml water, obtains mixed metal solution；By 10kgMn-Ti oxide solid particle
It is added in mixed metal solution and stirs, continuously add 500g active 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
Aging 2 days of material sealing, is sent into extruder, is extruded into green honeycomb；Green honeycomb is put into 70 DEG C of baking ovens dry 5h,
Then temperature is increased to 105 DEG C and continues dry 11h, finally calcined 3 hours at 500 DEG C in Muffle furnace, obtain honeycomb manganese
It is denitrating catalyst.
Embodiment 9
The oxalic acid solution that 4.88kg manganese oxalate and 100ml concentration are 3mol/L is dissolved in 9000mL deionized water, is added
10kg anatase-type nanometer titanium dioxide stirs 0.6h, the ultrasonic immersing 2h at 25KHz, is put into baking oven and dries for 24 hours for 245 DEG C,
Grinding obtains the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 494gCo (NO3)3·6H2O and 930gCe
(NO3)3.6H2O is dissolved in 2500ml water, obtains mixed metal solution；10kgMn-Ti oxide solid particle is added to mixed
It closes and is stirred in metallic solution, continuously add 500g active carbon, the carboxymethyl cellulose and 100g polyethylene glycol oxide of 100g, 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, it will
Pug after mixing seals aging 2 days, is sent into extruder, is extruded into green honeycomb；Green honeycomb is put into 65 DEG C of bakings
Then temperature is increased to 104 DEG C and continues dry 11h, finally calcined 4 hours at 500 DEG C in Muffle furnace by dry 5.5h in case,
Obtain honeycomb manganese systems denitrating catalyst.
Embodiment 10
The oxalic acid solution that 13.37kg manganese oxalate and 100ml concentration are 5mol/L is dissolved in 6000mL deionized water, is added
10kg anatase-type nanometer titanium dioxide stirs 0.6h, the ultrasonic immersing 2h at 25KHz, is put into baking oven and dries for 24 hours for 245 DEG C,
Grinding obtains the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 423gC4H6O4·Co·4H2O、228gLa
(Ac)3With 680gCe (C2H3O2)3It is dissolved in 3000ml water, obtains mixed metal solution；By 10kgMn-Ti oxide solid
Particle is added in mixed metal solution and stirs, and continuously adds 500g starch, the carboxymethyl cellulose and 100g polyoxygenated of 100g
Ethylene, the tung oil of 200g, 200g soya-bean oil, 550g glass fibre obtain mixing walk；Mixing walk is placed in vacuum in pug mill
It is kneaded 3 times, the pug after mixing is sealed aging 3 days, be sent into extruder, be extruded into green honeycomb；By green honeycomb
It is put into 65 DEG C of baking ovens dry 5.5h, temperature is then increased to 106 DEG C and continues dry 12h, finally in Muffle furnace at 550 DEG C
Calcining 4 hours, obtains honeycomb manganese systems denitrating catalyst.
Embodiment 11
The oxalic acid solution that 6.51kg manganese oxalate and 100ml concentration are 4mol/L is dissolved in 6000mL deionized water, is added
10kg anatase-type nanometer titanium dioxide stirs 0.6h, the ultrasonic immersing 2h at 25KHz, is put into baking oven and dries for 24 hours for 245 DEG C,
Grinding obtains the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 720gFe (NO3)3·9H2O、253gSb(NO3)3
With 930gCe (NO3)3·6H2O is dissolved in 3000ml water, obtains mixed metal solution；By 10kgMn-Ti oxide solid
Grain, which is added in mixed metal solution, to be stirred, and 500g starch, the carboxymethyl cellulose and 100g polyoxyethylene of 100g are continuously added
Alkene, the tung oil of 200g, 200g glycerol, 550g glass fibre obtain mixing walk；Mixing walk is placed in vacuum in pug mill to mix
Refining 3 times seals the pug after mixing aging 3 days, is sent into extruder, is extruded into green honeycomb；Green honeycomb is put
Enter dry 5.5h in 65 DEG C of baking ovens, temperature is then increased to 106 DEG C and continues dry 12h, is finally forged at 580 DEG C in Muffle furnace
It burns 4 hours, obtains honeycomb manganese systems denitrating catalyst.
Embodiment 12
The oxalic acid solution that the 50wt% manganese nitrate of 9.76kg and 100ml concentration are 3mol/L is dissolved in 6000mL deionized water
In, 10kg anatase-type nanometer titanium dioxide is added, stirs 0.6h, the ultrasonic immersing 2h at 25KHz is put into baking oven 245 DEG C
For 24 hours, grinding obtains the Mn-Ti oxide solid particle that partial size is 300-400 mesh for drying；By 720gFe (NO3)3·9H2O、
496gNi(NO3)2·6H2O and 930gCe (NO3)3·6H2O is dissolved in 2800ml water, obtains mixed metal solution；It will
10kgMn-Ti oxide solid particle, which is added in mixed metal solution, to be stirred, and 500g starch, the carboxymethyl of 100g are continuously added
Cellulose and 100g polyethylene glycol oxide, the soya-bean oil of 200g, 200g glycerol, 550g glass fibre obtain mixing walk；By mixed soil
Group is placed in vacuum kneading 3 times in pug mill, and the pug after mixing is sealed aging 3 days, is sent into extruder, is extruded into honeycomb ceramics
Blank；Green honeycomb is put into 65 DEG C of baking ovens dry 5.5h, temperature is then increased to 106 DEG C and continues dry 12h, finally
It is calcined 4 hours at 580 DEG C in Muffle furnace, obtains honeycomb manganese systems denitrating catalyst.
Embodiment 13
The oxalic acid solution that the 50wt% manganese nitrate of 19.53kg and 100ml concentration are 5mol/L is dissolved in 6000mL deionization
In water, 10kg anatase-type nanometer titanium dioxide is added, stirs 0.6h, the ultrasonic immersing 2h at 25KHz is put into 245 in baking oven
DEG C drying for 24 hours, grinding, obtain partial size be 300-400 mesh Mn-Ti oxide solid particle；By 423gC4H6O4·Co·
4H2O、920gC4H6O4Ni·4H2O and 680gCe (C2H3O2)3It is dissolved in 2800ml water, obtains mixed metal solution；It will
10kgMn-Ti oxide solid particle, which is added in mixed metal solution, to be stirred, and 500g starch, the carboxymethyl of 100g are continuously added
Cellulose and 100g polyethylene glycol oxide, the soya-bean oil of 200g, 200g glycerol, 550g glass fibre obtain mixing walk；By mixed soil
Group is placed in vacuum kneading 3 times in pug mill, and the pug after mixing is sealed aging 3 days, is sent into extruder, is extruded into honeycomb ceramics
Blank；Green honeycomb is put into 65 DEG C of baking ovens dry 5.5h, temperature is then increased to 106 DEG C and continues dry 12h, finally
It is calcined 4 hours at 570 DEG C in Muffle furnace, obtains honeycomb manganese systems denitrating catalyst.
Embodiment 14
The citric acid solution that 8.91kg manganese acetate and 100ml concentration are 4mol/L is dissolved in 6000mL deionized water, is added
Enter 10kg anatase-type nanometer titanium dioxide, stir 0.6h, the ultrasonic immersing 2h at 25KHz, is put into 245 DEG C of drying in baking oven
For 24 hours, grinding obtains the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 228gLa (Ac)3、253gSb(NO3)3With
930gCe(NO3)3·6H2O is dissolved in 2800ml water, obtains mixed metal solution；By 10kgMn-Ti oxide solid particle
It is added in mixed metal solution and stirs, continuously add 500g starch, the carboxymethyl cellulose and 100g polyethylene glycol oxide of 100g,
The soya-bean oil of 200g, 200g glycerol, 550g glass fibre obtain mixing walk；Mixing walk is placed in vacuum kneading 3 in pug mill
Time, the pug after mixing is sealed aging 3 days, is sent into extruder, is extruded into green honeycomb；Green honeycomb is put into 65
Then temperature is increased to 107 DEG C and continues dry 11h, finally calcines 5 at 570 DEG C in Muffle furnace by dry 5.5h in DEG C baking oven
Hour, obtain honeycomb manganese systems denitrating catalyst.
Embodiment 15
The citric acid solution that 4.88kg manganese oxalate and 100ml concentration are 3mol/L is dissolved in 6000mL deionized water, is added
Enter 10kg anatase-type nanometer titanium dioxide, stir 0.6h, the ultrasonic immersing 2h at 25KHz, is put into 245 DEG C of drying in baking oven
For 24 hours, grinding obtains the Mn-Ti oxide solid particle that partial size is 300-400 mesh；By 228gLa (Ac)3、920gC4H6O4Ni·
4H2O and 930gCe (NO3)3·6H2O is dissolved in 2800ml water, obtains mixed metal solution；10kgMn-Ti oxide is consolidated
Body particle is added in mixed metal solution and stirs, and continuously adds 500g starch, the carboxymethyl cellulose and 100g polyoxy of 100g
Change ethylene, the soya-bean oil of 200g, 200g glycerol, 550g glass fibre obtain mixing walk；Mixing walk is placed in pug mill very
Sky is kneaded 3 times, and the pug after mixing is sealed aging 3 days, is sent into extruder, is extruded into green honeycomb；By honeycomb ceramics base
Material is put into 65 DEG C of baking ovens dry 5.5h, and temperature is then increased to 107 DEG C and continues dry 11h, finally 570 DEG C in Muffle furnace
Lower calcining 5 hours, obtains honeycomb manganese systems denitrating catalyst.
Comparative example 1
By 988gCo (NO3)3·6H2O、930gCe(NO3)3·6H2O, 10kg titanium dioxide, 500g active carbon, 100g's
Carboxymethyl cellulose and 100g polyethylene glycol oxide, the glycerol of 500g, 500g glass fibre, which is added in batch mixer, stirs 0.3h, adds
Enter 9.76kg 50wt% manganese nitrate solution, mixing obtains plasticity walk, and vacuum kneading 2 times in pug mill, will be kneaded by walk
Pug afterwards seals aging 3 days, and then pug is sent into extruder, is extruded into green honeycomb；By above-mentioned green honeycomb
It is put into 60 DEG C of baking ovens 6 hours, temperature is then increased to 105 DEG C and continues drying 12 hours；500 DEG C are finally putting into Muffle furnace
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
Change titanium, 500g active carbon, the carboxymethyl cellulose and 100g polyethylene glycol oxide of 100g, the glycerol of 400g, 500g glass fibre add
Enter and stir 0.5h into batch mixer, 3000ml water is then added, mixing obtains plasticity walk, and vacuum is mixed in pug mill by walk
Pug after mixing is sealed aging 2 days, then pug is sent into extruder, is extruded into green honeycomb by refining 3 times；It will be upper
It states green honeycomb to be put into 60 DEG C of baking ovens 6 hours, temperature is then increased to 105 DEG C and continues drying 12 hours；It is finally putting into
It is roasted 3 hours at 500 DEG C in Muffle furnace, obtains 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, and oxygen concentration is 6% (V/V), GHSV (gas space velocity per hour)=5000h-1Flue gas, point
Not Ce Ding 4 temperature spots such as 120 DEG C, 150 DEG C, 200 DEG C, 250 DEG C NO conversion ratio.When reactor is stabilized to a certain temperature spot
When, start to be passed through simulated flue gas, reaction after ten minutes, uses flue gas analyzer (Testo350, Germany) measurement reaction front and back gas
NO concentration in body, it is 15 minutes that each temperature spot, which continues minute, is averaged, and calculates NO conversion ratio according to formula 1, i.e., de-
Efficiency.The Activity Results measured are 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, having a size of 200mm*200mm*200mm；
With pressure testing machine test, axially and radially compression strength, test result are as shown in table 1.
The porosity of catalyst is tested on Mercury-injection test instrument, and the results are shown in Table 1.
1 catalyst low temperature SCR denitration reaction test Activity Results of table and physical property characterization result
As shown in Table 1, the catalyst of method of the invention preparation denitration catalyst activity in a low temperature of 120-250 DEG C is high；
The catalyst compression strength prepared through the invention is big, axial compression strength 4.7-5.1Mpa, radial crushing strength 1.2-
1.4Mpa；The catalyst porosity of method preparation of the invention is 84-90%.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, according to
According to technical spirit any simple modification, equivalent change and modification to the above embodiments of the invention, this hair is still fallen within
In the range of bright technical solution.
Claims (10)
1. a kind of preparation method of honeycomb manganese systems denitrating catalyst, it is characterised in that: itself the following steps are included:
1) manganese salt and complexing agent is soluble in water, titanium dioxide, stirring is added, ultrasonic immersing is dried, and grinding obtains Mn-Ti oxygen
Compound solid particle；Wherein, manganese salt and the molar ratio of complexing agent are 65-187:1；
2) metal salt and cerium salt is soluble in water, obtain mixed metal solution；The metal salt is molysite, cobalt salt, lanthanum salt, antimony
At least one of salt and nickel salt；
3) by pore creating material, binder, extrusion aid, reinforcing agent, the Mn-Ti oxide solid particle and the mixed metal
Solution mixing, is molded into honeycomb blank, dry, and calcining obtains honeycomb manganese systems denitrating catalyst.
2. the preparation method of honeycomb manganese systems denitrating catalyst according to claim 1, which is characterized in that the complexing
Agent is oxalic acid or citric acid；The manganese salt is at least one of manganese nitrate, manganese acetate, manganese oxalate；The titanium dioxide
For anatase-type nanometer titanium dioxide.
3. the preparation method of honeycomb manganese systems denitrating catalyst according to claim 1, which is characterized in that the manganese salt
In Mn element and the weight ratio of the titanium dioxide be 0.11-0.45:1.
4. the preparation method of honeycomb manganese systems denitrating catalyst according to claim 1, which is characterized in that the Mn-
The partial size of Ti oxide solid particle is 300-400 mesh.
5. the preparation method of honeycomb manganese systems denitrating catalyst according to claim 1, which is characterized in that the molysite
For at least one of ferric nitrate, ferrous sulfate, ferric sulfate, iron chloride；The cobalt salt be cobalt nitrate, cobalt acetate, cobaltous sulfate,
At least one of cobalt chloride；The lanthanum salt is at least one of lanthanum acetate, lanthanum sulfate, lanthanum chloride；The antimonic salt is
Nitric acid antimony；The nickel salt is at least one of nickel nitrate, nickel acetate, nickel sulfate；The cerium salt is cerous nitrate, acetic acid
At least one of cerium, cerous sulfate, cerium chloride.
6. the preparation method of honeycomb manganese systems denitrating catalyst according to claim 1, which is characterized in that the pore-creating
Agent is at least one of active carbon, starch, sawdust, polymethyl methacrylate；The binder is carboxymethyl cellulose
And/or polyethylene glycol oxide；The extrusion aid is at least one of glycerol, soya-bean oil, tung oil；The reinforcing agent is glass fibers
Dimension.
7. the preparation method of honeycomb manganese systems denitrating catalyst according to claim 1, which is characterized in that the mixing
The weight ratio of metallic element and water and the Mn-Ti oxide solid particle in metallic solution is X:Ce:H2O:Mn-Ti
Oxide=0.9-4.4:2-4:25-35:100, wherein X is at least one of Fe, Co, La, Sb, Ni.
8. the preparation method of honeycomb manganese systems denitrating catalyst according to claim 1, which is characterized in that the pore-creating
Agent, binder, extrusion aid, reinforcing agent and the Mn-Ti oxide solid particle weight ratio be 4-6:1-2:2-4:4-6:
100。
9. the preparation method of honeycomb manganese systems denitrating catalyst according to claim 1, which is characterized in that the drying
Process are as follows: the dry 5-7h in 50-70 DEG C is warming up to 100-110 DEG C of dry 11-13h；The temperature of the calcining is 400-
600 DEG C, calcination time 2-5h.
10. a kind of honeycomb manganese systems denitrating catalyst, it is characterised in that: its active component is by ferriferous oxide, cobalt/cobalt oxide, lanthanum oxygen
At least one of compound, sb oxide, nickel oxide and cerium oxide composition, carrier are Mn-Ti oxide；Wherein each oxidation
The weight ratio of metallic element in object is X:Ce:Mn:Ti=0.9-4.4:2-4:13-24:76-87, X Fe, Co, La, Sb, Ni
At least one of, the honeycomb manganese systems denitrating catalyst is made by preparation method of any of claims 1-9.
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| CN106975493A (en) * | 2017-04-20 | 2017-07-25 | 宁波钛安新材料科技有限公司 | A kind of honeycomb catalyst materials and its forming method |
| CN107469811A (en) * | 2017-08-16 | 2017-12-15 | 浙江浙能富兴燃料有限公司 | A kind of wide temperature window denitrating catalyst and its preparation method and application |
| CN108097238B (en) * | 2017-12-12 | 2021-05-14 | 广西大学 | Preparation method of Mn-Ce-Ti-O composite metal oxide catalyst |
| CN107999088A (en) * | 2018-01-09 | 2018-05-08 | 广东电网有限责任公司电力科学研究院 | A kind of cobalt manganese cerium based titanium dioxide catalyst and preparation method thereof |
| CN108525707A (en) * | 2018-04-02 | 2018-09-14 | 北京水木星源环保科技有限公司 | A kind of honeycomb type denitrification catalyst and preparation method |
| CN110339831A (en) * | 2018-04-03 | 2019-10-18 | 中化近代环保化工(西安)有限公司 | A kind of novel manganese-based low-temperature denitration catalyst |
| CN108837823B (en) * | 2018-06-15 | 2022-04-22 | 万华化学集团股份有限公司 | Perovskite type catalyst and integral forming method and application thereof |
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| CN111375445B (en) * | 2018-12-29 | 2023-09-05 | 中化近代环保化工(西安)有限公司 | Preparation method and application of molecular sieve supported manganese-based denitration catalyst |
| CN110270326A (en) * | 2019-07-19 | 2019-09-24 | 西安热工研究院有限公司 | A kind of preparation method of honeycomb manganese class demercuration catalyst |
| CN110773191B (en) * | 2019-09-18 | 2022-09-13 | 上海瀚昱环保材料有限公司 | Catalyst for dioxin removal and cooperative denitration and preparation method thereof |
| CN112023908B (en) * | 2020-08-04 | 2023-03-17 | 华北电力大学 | Nitrogen oxide removing catalyst and preparation method thereof |
| CN114433123B (en) * | 2020-11-05 | 2024-02-20 | 中国石油化工股份有限公司 | Integral honeycomb catalyst for low-temperature SCR denitration and preparation method and application thereof |
| CN114713243B (en) * | 2022-04-29 | 2024-05-31 | 辽宁科隆精细化工股份有限公司 | Low-temperature high-efficiency high-sulfur-resistance long-time stable SCR denitration catalyst and preparation method thereof |
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| JPH03154637A (en) * | 1989-11-10 | 1991-07-02 | Babcock Hitachi Kk | Flat catalyst |
| CN101947443B (en) * | 2010-09-03 | 2013-07-31 | 浙江省环境保护科学设计研究院 | Cellular Mn-Ti-based catalyst for low-temperature selective catalytic reduction denitration reaction and preparation method and using method |
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