CN112275294A - 一种蜂窝式超低温脱硝催化剂及其制备方法 - Google Patents
一种蜂窝式超低温脱硝催化剂及其制备方法 Download PDFInfo
- Publication number
- CN112275294A CN112275294A CN202011222096.8A CN202011222096A CN112275294A CN 112275294 A CN112275294 A CN 112275294A CN 202011222096 A CN202011222096 A CN 202011222096A CN 112275294 A CN112275294 A CN 112275294A
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- China
- Prior art keywords
- ammonium
- honeycomb type
- source
- catalyst
- denitration catalyst
- Prior art date
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000001035 drying Methods 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 9
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 27
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 22
- 239000011863 silicon-based powder Substances 0.000 claims description 22
- 239000004408 titanium dioxide Substances 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 21
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004033 plastic Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 10
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- -1 polyoxyethylene Polymers 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 9
- 239000004310 lactic acid Substances 0.000 claims description 9
- 235000014655 lactic acid Nutrition 0.000 claims description 9
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 8
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 8
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 8
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 7
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 claims description 7
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- AIGRXSNSLVJMEA-FQEVSTJZSA-N ethoxy-(4-nitrophenoxy)-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound O([P@@](=S)(OCC)C=1C=CC=CC=1)C1=CC=C([N+]([O-])=O)C=C1 AIGRXSNSLVJMEA-FQEVSTJZSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 229920001131 Pulp (paper) Polymers 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003546 flue gas Substances 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 12
- 239000012046 mixed solvent Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 4
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 4
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 4
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 3
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 3
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 108091006231 SLC7A2 Proteins 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 108091006230 SLC7A3 Proteins 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- RFRMMZAKBNXNHE-UHFFFAOYSA-N 6-[4,6-dihydroxy-5-(2-hydroxyethoxy)-2-(hydroxymethyl)oxan-3-yl]oxy-2-(hydroxymethyl)-5-(2-hydroxypropoxy)oxane-3,4-diol Chemical compound CC(O)COC1C(O)C(O)C(CO)OC1OC1C(O)C(OCCO)C(O)OC1CO RFRMMZAKBNXNHE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
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Abstract
本发明公开了一种蜂窝式超低温脱硝催化剂及其制备方法,以钛白粉或钛硅粉为原料,通过加入少量的金属盐、结构助剂、造孔剂和粘合剂,通过混炼、陈腐、挤出烘干等步骤获得。该催化剂的各活性组分的质量百分含量为:V2O5 2.5‑5 wt.%,WO3 0.1‑10 wt.%,MoO3 0.1‑10 wt.%,TiO2 76‑96.39 wt.%,及以下组分中的至少一种:SiO2 0.01‑3 wt.%,B2O3 0.01‑2 wt.%,P2O5 0.01‑2 wt.%,F 0.01‑2 wt.%。该催化剂具有使用温度低(120‑160℃)、催化活性好(脱硝效率≥90%),抗SO2、H2O中毒能力强等特点,可应用于超低温条件下烟气脱硝。
Description
技术领域
本发明涉及一种脱硝催化剂及其制备方法,尤其涉及一种蜂窝式超低温脱硝催化剂及其制备方法,属于环保催化剂开发及大气污染物控制领域。
背景技术
工业燃烧过程中所产生的氮氧化物(NOx)是主要的大气污染物之一,也是控制大气污染物的重点。在众多的脱硝技术中,选择性催化还原技术(SCR,selective catalyticreduction)是目前脱硝效率最高,应用最为广泛的一项技术。经过近10年对商业钒钛基脱硝催化剂的技术引进与自主研发,已基本解决燃煤电厂烟气污染物控制问题。
非电行业的烟气污染物处理难度较大,主要在于烟气温度较低,尘含量较高,特别是水泥窑、白灰窑等窑炉中,烟气经过余热锅炉和除尘装置后,温度远低于180℃,现有的低温脱硝催化剂难以正常工作,因此,亟需开发超低温脱硝催化剂(工作温度区间在120-160℃)。
国外学者对于超低温脱硝催化剂研究者众多,主要集中于Mn基脱硝催化剂改性,主要方法有溶胶凝胶法,共沉淀法等,均是使用金属无机盐作为前驱体,采用尿素等作为沉淀剂,制备出粉体催化剂,但是这些粉体催化剂活性组分含量高,很多催化剂并没有载体组分,难以加工成型,且没有经济效益,且未有实际应用报道。
CN 109718767 A公开了一种钌系超低温脱硝催化剂的制备方法,是以氧化钌、二氧化锰和二氧化铈作为活性组分,二氧化钛作为载体,采用分步浸渍和焙烧的方式制备出钌系超低温脱硝催化剂,在135-165℃催化效率在85%以上,但是其抗中毒性能并未说明。
CN 10987699 A公开了一种钌系超低温SCR脱硝催化剂及其制备方法,以二氧化锰为活性组分,三氧化二钕为助剂,二氧化钛作为载体,通过超声浸渍的方式制备出超低温脱硝催化剂,在100-220℃催化效率在95%以上,但是其二氧化锰含量较高,难以加工成型。
CN 105879879 A公开了一种高抗硫超低温SCR脱硝催化剂及其制备方法,以二氧化锰作为活性组分,三氧化二铁和三氧化二钬作为助剂,二氧化钛作为载体,采用分步浸渍方式将硝酸盐前驱体浸渍于载体孔道结构中,制备出锰铁钬钛复合氧化物,在120-200℃催化效率在75%以上,并且表现出较好的抗水、抗硫性能,然而通过大量的硝酸盐浸渍载体,所制备的催化剂难以成型。
综上所述,国内专利关于超低温脱硝催化剂及其制备方法,主要是以二氧化锰作为活性组分,通过加入大量的三氧化二铁和三氧化二钕等作为助剂,通过提高二氧化锰含量提高低温活性。另外,前驱体主要以硝酸盐为主,这类超低温脱硝催化剂尚处于实验室研究阶段,催化剂难以加工成型,无法实现工业生产与应用。
发明内容
本发明的目的是提供一种蜂窝式超低温脱硝催化剂及其制备方法,以解决现有技术中超低温脱硝催化剂催化效率低,难以加工成型的问题。
一、蜂窝式超低温脱硝催化剂的组分设计及制备
本发明蜂窝式超低温脱硝催化剂的活性组分含量为:V2O5 2.5-5 wt.%,WO3 0.1-10wt.%,MoO3 0.1-10 wt.%,TiO2 76-96.39 wt.%,及以下组分中的至少一种:SiO2 0.01-3wt.%,B2O3 0.01-2 wt.%,P2O5 0.01-2 wt.%,F 0.01-2 wt.%。
本发明一种蜂窝式超低温脱硝催化剂的制备方法,包括以下步骤。
(1)用有机碱水溶液分别将钒源、钨源、钼源溶解形成混合溶液A。有机碱为甲胺、乙醇胺、正丁胺和乙二胺中的一种或多种,有机碱水溶液的浓度为5-20wt. %。钒源为硫酸氧钒、偏钒酸铵、草酸氧钒和乙酰丙酮氧钒中的至少一种,钒源的用量以V2O5计量为催化剂总质量的2.5-5 wt.%。钨源为钨酸铵、仲钨酸铵、偏钨酸铵、钨酸亚铁和磷钨酸铵中的至少一种,钨源的用量以WO3计量为催化剂总质量的0.1-10 wt.%。钼源为二钼酸铵、乙酸钼、七钼酸铵和钼酸镁中的至少一种,钼源的用量以MoO3计量为催化剂总质量的0.1-10 wt.%。
(2)将磷源溶解于去离子水中,形成溶液B。磷源为磷酸氢二铵、磷酸二氢铵、六乙基亚磷酸胺和磷酸铵中的至少一种,磷源的用量以P2O5计量为催化剂总质量的0.1-2 wt.%。
(3)将硼源或/和氟源分步溶解于去离子水中,形成混合溶液C;硼源为硼酸、戊硼烷和硼氢化钠中的至少一种,硼源的用量以B2O3计量,为催化剂总质量的0.01-2 wt.%;氟源为四丁基氟化铵、氢氟酸和氟化铵中的至少一种,氟源的用量以F计量为催化剂总质量的0.01-2 wt.%。
(4)将部分钛白粉或钛硅粉、粘结剂、造孔剂加入混料机中,加入水和氨水溶液,高速搅拌3-30min;再将溶液A或A和B的混合溶液缓慢加入混料机,高速搅拌30-100min;然后加入溶液C或B或B和C的混合溶液及成型助剂,高速搅拌10-60min;再次加入剩余的钛白粉或钛硅粉,高速搅拌30-60min,用氨水调节pH至7.5-8.5,控制水分在29-32%,最后经过滤、真空捏合后获得可塑泥料,然后在温度在10-30℃、湿度在60-70%的环境下陈腐24h-48h。钛硅粉含有SiO2 0.01-3 wt.%;粘结剂为纤维素类如甲基纤维素、羟丙基甲基纤维素、羟乙基纤维素、羧甲基纤维素,用量为钛白粉或钛硅粉干重的0.2-3%;造孔剂为聚氧化乙烯,其用量为钛白粉或钛硅粉干重的0.1-2%;成型助剂为玻璃纤维、纸浆纤维、乳酸,其用量依次为钛白粉或钛硅粉的1-6%、0.1-1.5%、0.1-3%。
(5)将陈腐后的可塑泥料经强力挤出机挤出成蜂窝式胚体,经过干燥和煅烧后按照尺寸要求切割,即得蜂窝式超低温脱硝催化剂。
所述干燥的环境温度为20-60℃,湿度为85-10%,干燥环境由低温高湿逐渐转变为高温低湿,干燥时间为8-9天。煅烧采用连续式网带窑炉,煅烧温度为450-580℃,产品出窑温度为60-80℃,焙烧时间控制在40-48小时。
二、蜂窝式超低温脱硝催化剂的性能
评定条件:取整体蜂窝式脱硝催化剂,反应温度为80~240℃,气体条件为: 1000ppmNH3+1000ppmNO+5 v.%H2O+5%O2,N2平衡,压力为常压,空速为5000 ml mg-1 h-1,以NO的转化率测定催化剂的反应活性,产物用KM9506烟气分析仪进行分析。
评定结果:本发明制备的蜂窝式超低温脱硝催化剂在超低温条件下(120~160℃)催化效率高(≥90%),具有良好的抗水,抗SO2中毒性能。
本发明相对于现有技术具有以下优势:
1、使用商业催化剂常用的原料生产超低温脱硝催化剂,与其他锰基超低温脱硝催化剂相比较更容易实现工业化生产,本专利所生产的超低温脱硝催化剂在120~160℃具有较好催化活性和抗中毒性能。
2、本发明通过两次添加结构助剂大幅度提高的催化剂超低温活性和成型率:第一,在活性溶液配制过程中,加入少量无机物前驱体作为微观结构助剂,可大幅度提高活性组分与助剂之间的相互作用,形成Me1-P-Me2结构,活性组分与助剂之间形成强相互作用,大幅度提高催化剂超低温活性。另外,第二次加入结构助剂SiO2、B2O3、F其中的一种或多种,提高蜂窝式超低温脱硝催化剂成型性能,避免在干燥和煅烧过程,催化剂开裂、破损等问题;
3、所制备的蜂窝式超低温脱硝催化剂脱硝效率高,具有良好的抗水、抗SO2中毒性能,使用寿命长,可大幅度降低生产成本,是我国环境污染治理科技催化剂领域的原始创新。
具体实施方式
下面通过具体实施例对本发明超低温催化剂粉体的制备和脱硝性能做一步说明。
实施例1
取80L的5wt. %甲胺和20L的5wt. %乙醇胺水溶液形成混合溶剂;依次将17.91kg硫酸氧钒、29.14kg乙酰丙酮氧钒、6.43kg偏钒酸铵、1.31kg钨酸亚铁、1.28kg钼酸铵加入到混合溶剂中溶解形成溶液A;
将1.38kg四丁基氟化铵溶解于60L去离子水中,形成混合溶液C;
将763.92kg钛白粉、28.65kg羟丙基甲基纤维素和19.10kg造孔剂聚氧化乙烯加入混料机中,加入100.0L水和30.0L氨水溶液于混料机中,高速搅拌3min;再将溶液A缓慢加入混料机,高速搅拌30min;然后加入溶液C和纸浆纤维14.32kg、玻璃纤维57.29kg、乳酸28.65kg,高速搅拌10min;再次加入190.98kg钛白粉,高速搅拌30min,用氨水调节pH至7.8,控制水分在29%;然后经过滤、真空捏合后获得可塑泥料,最后在温度在10℃、湿度在70%的环境下陈腐48h;
将陈腐后的可塑泥料经强力挤出机挤出成蜂窝式胚体,经过干燥和煅烧步骤,最后,按照尺寸要求切割,即得蜂窝式超低温脱硝催化剂,标记为CAT-1。其中,干燥的环境温度为20-60℃,湿度为85-10%,干燥环境由低温高湿逐渐转变为高温低湿,干燥时间为9天。煅烧采用连续式网带窑炉,煅烧温度为450℃,产品出窑温度为60℃,焙烧时间控制在40小时。CAT-1的物理化学性质见表1;CAT-1的低温烟气的脱硝效率率见表2。
实施例2
取40L的15wt. %甲胺、40L的15wt. %乙醇胺水溶液和60L的15wt. %正丁胺水溶液形成混合溶剂;依次将17.91kg硫酸氧钒、29.14kg乙酰丙酮氧钒、25.71kg偏钒酸铵、26.93kg草酸氧钒、21.88kg钨酸铵、20.00kg仲钨酸铵、21.26kg偏钨酸铵、26.20kg钨酸亚铁、34.42kg磷钨酸铵、47.23kg二钼酸铵、29.74kg乙酸钼、24.53kg七钼酸铵和26.60kg钼酸镁溶解于混合溶剂中形成混合溶液A;
将9.30kg磷酸氢二铵、8.10kg磷酸二氢铵、17.43kg六乙基亚磷酸胺和14.31kg磷酸铵溶解于60L去离子水中,形成混合溶液B;
将17.75kg硼酸、9.07kg戊硼烷、5.43kg硼氢化钠、13.76kg四丁基氟化铵、19.47kg氢氟酸和9.74kg氟化铵溶解于20L去离子水中,形成混合溶液C;
将528.00kg钛硅粉、甲基纤维素1.32kg和造孔剂聚氧化乙烯0.66kg加入混料机中,其中钛硅粉含有SiO2 3 wt.%,加入60.0L水和20.0L氨水溶液,加入混料机中,高速搅拌30min;再将A和B的混合溶液缓慢加入混料机,高速搅拌40min;然后加入溶液C和纸浆纤维0.66kg、玻璃纤维6.60kg、乳酸0.66kg,高速搅拌20min;再次加入剩余的132.0kg钛白粉,高速搅拌40min,用氨水调节pH至8.5,控制水分在32%,最后经过滤、真空捏合后获得可塑泥料,然后在温度在15℃、湿度在60%的环境下陈腐24h;
将陈腐后的可塑泥料经强力挤出机挤出成蜂窝式胚体,经过干燥和煅烧步骤,最后,按照尺寸要求切割,即得蜂窝式超低温脱硝催化剂,标记为CAT-2。其中,干燥的环境温度为20-60℃,湿度为85-10%,干燥环境由低温高湿逐渐转变为高温低湿,干燥时间为8天。煅烧采用连续式网带窑炉,煅烧温度为580℃,产品出窑温度为80℃,焙烧时间控制在48小时。CAT-2的物理化学性质见表1;CAT-2的低温烟气的脱硝效率见表2。
实施例3
30L的10wt. %甲胺、30L的10wt. %乙醇胺水溶液和50L的15wt. %乙二胺水溶液形成混合溶剂分别将35.83kg硫酸氧钒、14.57kg乙酰丙酮氧钒、13.46kg草酸氧钒、10.94kg钨酸铵、40.00kg仲钨酸铵、10.63kg偏钨酸铵、13.10kg钨酸亚铁、17.21kg磷钨酸铵、11.81kg二钼酸铵、14.87kg乙酸钼、61.33kg七钼酸铵和12.80kg钼酸镁溶解形成混合溶液A;
将1.86kg磷酸氢二铵溶解于10L去离子水中,形成混合溶液B;
将3.55kg硼酸、3.63kg戊硼烷、3.26kg硼氢化钠、27.52kg四丁基氟化铵、3.16kg氢氟酸和3.89kg氟化铵溶解于40L去离子水中,形成混合溶液C;
将631.2kg钛硅粉、羟乙基纤维素7.43kg和造孔剂聚氧化乙烯3.25kg加入混料机中,其中钛硅粉含有SiO2 1 wt.%,加入80.0L水和20.0L氨水溶液,加入混料机中,高速搅拌10min;再将溶液A缓慢加入混料机,高速搅拌50min;然后加入B和C的混合溶液和纸浆纤维3.60kg、玻璃纤维31.00kg、乳酸7.21kg,高速搅拌30min;再次加入剩余的157.8kg钛白粉,高速搅拌50min,用氨水调节pH至8.0,控制水分在30%,最后经过滤、真空捏合后获得可塑泥料,然后在温度在15℃、湿度在60%的环境下陈腐24h;
将陈腐后的可塑泥料经强力挤出机挤出成蜂窝式胚体,经过干燥和煅烧步骤,最后,按照尺寸要求切割,即得蜂窝式超低温脱硝催化剂,标记为CAT-1。其中,干燥的环境温度为20-60℃,湿度为85-10%,干燥环境由低温高湿逐渐转变为高温低湿,干燥时间为8天。煅烧采用连续式网带窑炉,煅烧温度为520℃,产品出窑温度为60℃,焙烧时间控制在36小时。CAT-3的物理化学性质见表1;CAT-3的低温烟气的脱硝效率见表2。
实施例4
60L的10wt. %乙醇胺水溶液和50L的10wt. %乙二胺水溶液形成混合溶剂,分别将35.83kg硫酸氧钒、43.71kg乙酰丙酮氧钒、21.88kg钨酸铵、20.00kg仲钨酸铵、26.20kg钨酸亚铁、23.62kg二钼酸铵、29.74kg乙酸钼、54.53kg七钼酸铵溶解形成混合溶液A;
将3.72kg磷酸氢二铵和10.46kg六乙基亚磷酸胺和溶解于10L去离子水中,形成混合溶液B;
将664.00kg钛硅粉、羧甲基纤维素5.86kg和造孔剂聚氧化乙烯4.12kg加入混料机中,其中钛硅粉含有SiO2 1 wt.%,加入100.0L水和20.0L氨水溶液,加入混料机中,高速搅拌15min;再将溶液A缓慢加入混料机,高速搅拌40min;然后加入B溶液和纸浆纤维3.8kg、玻璃纤维33.0kg、乳酸6.32kg,高速搅拌40min;再次加入剩余的166.00kg钛白粉,高速搅拌50min,用氨水调节pH至8.2,控制水分在31%,最后经过滤、真空捏合后获得可塑泥料,然后在温度在15℃、湿度在70%的环境下陈腐26h;
将陈腐后的可塑泥料经强力挤出机挤出成蜂窝式胚体,经过干燥和煅烧步骤,最后,按照尺寸要求切割,即得蜂窝式超低温脱硝催化剂,标记为CAT-4。其中,干燥的环境温度为20-60℃,湿度为85-10%,干燥环境由低温高湿逐渐转变为高温低湿,干燥时间为9天。煅烧采用连续式网带窑炉,煅烧温度为540℃,产品出窑温度为70℃,焙烧时间控制在36小时。CAT-4的物理化学性质见表1;CAT-4的低温烟气的脱硝效率见表2。
实施例5
50L的5wt. %乙醇胺水溶液和60L的20wt. %正丁胺水溶液形成混合溶剂分别将17.91kg硫酸氧钒、29.14kg乙酰丙酮氧钒、12.85kg偏钒酸铵、26.93kg草酸氧钒、10.94kg钨酸铵、10.00kg仲钨酸铵、10.63kg偏钨酸铵、13.10kg钨酸亚铁、11.81kg二钼酸铵、14.87kg乙酸钼、12.27kg七钼酸铵和12.80kg钼酸镁溶解形成混合溶液A;
将7.44kg磷酸氢二铵、6.48kg磷酸二氢铵和6.97kg六乙基亚磷酸胺溶解于20L去离子水中,形成混合溶液B;
将8.88kg硼酸、9.07kg戊硼烷、68.81kg四丁基氟化铵和19.47kg氢氟酸溶解于60L去离子水中,形成混合溶液C;
将664.00kg钛硅粉、羟丙基甲基纤维素8.21kg和造孔剂聚氧化乙烯3.66kg加入混料机中,其中钛硅粉含有SiO2 2 wt.%,加入80.0L水和40.0L氨水溶液,加入混料机中,高速搅拌15min;再将A和B的混合溶液缓慢加入混料机,高速搅拌35min;然后加入溶液C和纸浆纤维4.20kg、玻璃纤维35.00kg、乳酸7.65kg,高速搅拌35min;再次加入剩余的166.00kg钛白粉,高速搅拌60min,用氨水调节pH至8.3,控制水分在30.5%,最后经过滤、真空捏合后获得可塑泥料,然后在温度在20℃、湿度在70%的环境下陈腐30h;
将陈腐后的可塑泥料经强力挤出机挤出成蜂窝式胚体,经过干燥和煅烧步骤,最后,按照尺寸要求切割,即得蜂窝式超低温脱硝催化剂,标记为CAT-5。其中,干燥的环境温度为20-60℃,湿度为85-10%,干燥环境由低温高湿逐渐转变为高温低湿,干燥时间为8天。煅烧采用连续式网带窑炉,煅烧温度为560℃,产品出窑温度为70℃,焙烧时间控制在40小时。CAT-5的物理化学性质见表1;CAT-5的低温烟气的脱硝效率见表2。
实施例6
50L的5wt. %乙二胺、10L的20wt. %乙醇胺水溶液和20L的5wt. %正丁胺水溶液形成混合溶剂分别将26.87kg硫酸氧钒、43.71kg乙酰丙酮氧钒、40.39kg草酸氧钒、20.00kg仲钨酸铵、14.87kg乙酸钼和12.27kg七钼酸铵溶解形成混合溶液A;
将9.30kg磷酸二氢铵、17.43kg六乙基亚磷酸胺和14.31kg磷酸铵溶解于30L去离子水中,形成混合溶液B;
将8.88kg硼酸、9.07kg戊硼烷、5.43kg硼氢化钠、68.81kg四丁基氟化铵、5.26kg氢氟酸和9.74kg氟化铵溶解于70L去离子水中,形成混合溶液C;
将672.00kg钛硅粉、羧甲基纤维素9.33kg和造孔剂聚氧化乙烯2.12kg加入混料机中,其中钛硅粉含有SiO2 3 wt.%,加入100.0L水和30.0L氨水溶液,加入混料机中,高速搅拌20min;再将溶液A缓慢加入混料机,高速搅拌40min;然后加入B和C混合溶液、纸浆纤维4.40kg、玻璃纤维39.00kg、乳酸4.22kg,高速搅拌40min;再次加入剩余的168.00kg钛白粉,高速搅拌50min,用氨水调节pH至8.4,控制水分在30.2%,最后经过滤、真空捏合后获得可塑泥料,然后在温度在25℃、湿度在60%的环境下陈腐48h;
将陈腐后的可塑泥料经强力挤出机挤出成蜂窝式胚体,经过干燥和煅烧步骤,最后,按照尺寸要求切割,即得蜂窝式超低温脱硝催化剂,标记为CAT-6。其中,干燥的环境温度为20-60℃,湿度为85-10%,干燥环境由低温高湿逐渐转变为高温低湿,干燥时间为9天。煅烧采用连续式网带窑炉,煅烧温度为580℃,产品出窑温度为80℃,焙烧时间控制在48小时。CAT-6的物理化学性质见表1;CAT-6的低温烟气的脱硝效率见表2。
对比例1
140L的4wt. %乙醇胺水溶液分别将64.27kg偏钒酸铵、73.59kg钼酸铵溶解形成活性溶液;
将712.00kg钛白粉、羟丙基甲基纤维素8.66kg和造孔剂聚氧化乙烯3.12kg加入混料机中,再加入60.0L水和30.0L氨水溶液,高速搅拌20min;将活性溶液缓慢加入混料机,高速搅拌40min;然后加入纸浆纤维4.40kg、玻璃纤维39.00kg、乳酸4.22kg,高速搅拌40min;然后加入剩余的178.00kg钛白粉,高速搅拌50min,用氨水调节pH至8.4,控制水分在30.2%,最后经过滤、真空捏合后获得可塑泥料,然后在温度在25℃、湿度在60%的环境下陈腐48h;
将陈腐后的可塑泥料经强力挤出机挤出成蜂窝式胚体,经过干燥和煅烧步骤,最后,按照尺寸要求切割,即得蜂窝式超低温脱硝催化剂,标记为DB-1。其中,干燥的环境温度为20-60℃,湿度为85-10%,干燥环境由低温高湿逐渐转变为高温低湿,干燥时间为9天。煅烧采用连续式网带窑炉,煅烧温度为580℃,产品出窑温度为80℃,焙烧时间控制在48小时。DB1的物理化学性质见表1;DB-1的低温烟气的脱硝效率见表2。
从表1中可以看出,实施例1-6所制备的催化剂比表面积远大于对比例1,整体式超低温脱硝催化剂具有很好的机械强度和耐磨损性能。
从表2中实施例1-6所制备的整体式超低温脱硝催化剂脱硝性能优于对比例1,在120-160℃内,脱硝率大于90%,在200-240℃内,脱硝率大于98%,具有很好的超低温SCR性能。
Claims (10)
1.一种蜂窝式超低温脱硝催化剂,其活性组分含量为:V2O5 2.5-5 wt.%,WO3 0.1-10wt.%,MoO3 0.1-10 wt.%,TiO2 76-96.39 wt.%,及以下组分中的至少一种:SiO2 0.01-3wt.%,B2O3 0.01-2 wt.%,P2O5 0.01-2 wt.%,F 0.01-2 wt.%。
2.如权利要求1所述一种蜂窝式超低温脱硝催化剂的制备方法,包括以下步骤:
(1)用有机碱水溶液分别将钒源、钨源、钼源溶解形成混合溶液A;
(2)将磷源溶解于去离子水中,形成溶液B;
(3)将硼源或/和氟源分步溶解于去离子水中,形成溶液或混合溶液C;
(4)将钛白粉或钛硅粉、粘结剂、造孔剂加入混料机中,加入水和氨水溶液,高速搅拌3-30min;再将溶液A或A和B的混合溶液缓慢加入混料机,高速搅拌30-100min;然后加入溶液C或B或B和C的混合溶液及成型助剂,高速搅拌10-60min;再次加入钛白粉或钛硅粉,高速搅拌30-60min,用氨水调节pH至7.5-8.5,控制水分在29-32%,最后经过滤、真空捏合后获得可塑泥料,然后在温度在10-30℃、湿度在60-70%的环境下陈腐24h-48h;
(5)将陈腐后的可塑泥料经强力挤出机挤出成蜂窝式胚体,经过干燥和煅烧后按照尺寸要求切割,即得蜂窝式超低温脱硝催化剂。
3.如权利要求2所述一种蜂窝式超低温脱硝催化剂的制备方法,其特征在于:步骤(1)中,有机碱为甲胺、乙醇胺、正丁胺和乙二胺中的一种或多种,有机碱水溶液的浓度为5-20wt. %。
4.如权利要求2所述一种蜂窝式超低温脱硝催化剂的制备方法,其特征在于:步骤(1)中,钒源为硫酸氧钒、偏钒酸铵、草酸氧钒和乙酰丙酮氧钒中的至少一种,钒源的用量以V2O5计量为催化剂总质量的2.5-5 wt.%;钨源为钨酸铵、仲钨酸铵、偏钨酸铵、钨酸亚铁和磷钨酸铵中的至少一种,钨源的用量以WO3计量为催化剂总质量的0.1-10 wt.%;钼源为二钼酸铵、乙酸钼、七钼酸铵和钼酸镁中的至少一种,钼源的用量以MoO3计量为催化剂总质量的0.1-10 wt.%。
5.如权利要求2所述一种蜂窝式超低温脱硝催化剂的制备方法,其特征在于:步骤(2)中,磷源为磷酸氢二铵、磷酸二氢铵、六乙基亚磷酸胺和磷酸铵中的至少一种,磷源的用量以P2O5计量为催化剂总质量的0.1-2 wt.%。
6.如权利要求2所述一种蜂窝式超低温脱硝催化剂的制备方法,其特征在于:步骤(3)中,硼源为硼酸、戊硼烷和硼氢化钠中的至少一种,硼源的用量以B2O3计量,为催化剂总质量的0.01-2 wt.%;氟源为四丁基氟化铵、氢氟酸和氟化铵中的至少一种,氟源的用量以F计量为催化剂总质量的0.01-2 wt.%。
7.如权利要求2所述一种蜂窝式超低温脱硝催化剂的制备方法,其特征在于:步骤(4)中,钛硅粉含有SiO2 0.01-3 wt.%。
8.如权利要求2所述一种蜂窝式超低温脱硝催化剂的制备方法,其特征在于:步骤(4)中,粘结剂为纤维素类,其用量为钛白粉或钛硅粉干重的0.2-3%;造孔剂为聚氧化乙烯,其用量为钛白粉或钛硅粉干重的0.1-2%;成型助剂为玻璃纤维、纸浆纤维、乳酸,其用量依次为钛白粉或钛硅粉的1-6%、0.1-1.5%、0.1-3%。
9.如权利要求2所述一种蜂窝式超低温脱硝催化剂的制备方法,其特征在于:步骤(5)中,所述干燥的环境温度为20-60℃,湿度为85-10%,干燥环境由低温高湿逐渐转变为高温低湿,干燥时间为8-9天。
10.如权利要求2所述一种蜂窝式超低温脱硝催化剂的制备方法,其特征在于:步骤(5)中,所述煅烧采用连续式网带窑炉,煅烧温度为450-580℃,产品出窑温度为60-80℃,焙烧时间控制在40-48小时。
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