CN105964284A - Honeycomb low temperature flue gas denitration catalyst and preparation method thereof - Google Patents
Honeycomb low temperature flue gas denitration catalyst and preparation method thereof Download PDFInfo
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- CN105964284A CN105964284A CN201610284318.6A CN201610284318A CN105964284A CN 105964284 A CN105964284 A CN 105964284A CN 201610284318 A CN201610284318 A CN 201610284318A CN 105964284 A CN105964284 A CN 105964284A
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 221
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003546 flue gas Substances 0.000 title claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 274
- 239000000843 powder Substances 0.000 claims abstract description 32
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 30
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000000694 effects Effects 0.000 claims abstract description 23
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 230000002829 reductive effect Effects 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 230000000740 bleeding effect Effects 0.000 claims description 111
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 60
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 51
- 239000008367 deionised water Substances 0.000 claims description 49
- 229910021641 deionized water Inorganic materials 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 38
- 239000012752 auxiliary agent Substances 0.000 claims description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 230000002441 reversible effect Effects 0.000 claims description 32
- 229910021529 ammonia Inorganic materials 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 28
- 230000001413 cellular effect Effects 0.000 claims description 24
- 238000007493 shaping process Methods 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 19
- 229910052681 coesite Inorganic materials 0.000 claims description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims description 17
- 238000005520 cutting process Methods 0.000 claims description 17
- 238000005470 impregnation Methods 0.000 claims description 17
- 235000006408 oxalic acid Nutrition 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- 229910052682 stishovite Inorganic materials 0.000 claims description 17
- 229910052905 tridymite Inorganic materials 0.000 claims description 17
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 9
- 229920001131 Pulp (paper) Polymers 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000006004 Quartz sand Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 235000010980 cellulose Nutrition 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 230000001788 irregular Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 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 description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 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 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 239000011863 silicon-based powder Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims 1
- 235000012216 bentonite Nutrition 0.000 claims 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims 1
- 229910001648 diaspore Inorganic materials 0.000 claims 1
- 238000004898 kneading Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- 239000010881 fly ash Substances 0.000 abstract 2
- 230000003628 erosive effect Effects 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 39
- -1 polyethylene Polymers 0.000 description 30
- 238000005516 engineering process Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 10
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 102000011759 adducin Human genes 0.000 description 4
- 108010076723 adducin Proteins 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 238000013036 cure process Methods 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229910003320 CeOx Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000292525 Titanio Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 238000003911 water pollution Methods 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
- 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a honeycomb low temperature flue gas denitration catalyst and a preparation method thereof, and belongs to the field of atmosphere pollution control and environment catalysis materials. The catalyst adopts TiO2, V2O5, MoO3, WO3 and rare earth (La, Ce, Pr, Nd, Zr and Y) oxides as active components and P2O5 and SO3 as modification assistants, and is prepared through powder preparation, mixing and kneading steps. The catalyst has an excellent removal effect on NOx in low temperature flue gas, and the denitration efficiency at 170-180DEG C can reach 90% or above. The catalyst has high mechanical strength and anti-wear resistance, the vertical compressive strength is greater than 2.4MPa, and the hard end fly ash wear rate is smaller than 0.08%/Kg. The erosion, wearing and etching of fly ash to the catalyst are reduced, so the service life of the catalyst is prolonged. The catalyst has the advantages of simple and easily available production raw materials, simple and easily controllable preparation process, and easy realization of industrial production.
Description
Technical field
The invention belongs to Air Pollution Control and environmental catalysis Material Field, it is specifically related to a kind of cellular low-temperature denitration of flue gas catalyst and preparation method thereof, the NOx emission of low-temperature flue gas or technology waste gas that this catalyst is applicable to the industries such as non-electricity industry boiler, kiln metallurgy, chemical industry, coking and petrochemical industry controls, and the denitrating technique that electric boiler low temperature, low dirt are arranged.
Background technology
Nitrogen oxides (NOx), it has also become continue SO2Another global air pollution thing afterwards, the NOx in air has higher contribution margin to many environmental problems such as global warming, acid rain, photochemical fog, the rising of surface ozone concentration, water pollutions, it has also become the primary pollutant in the air of big city.China is NOx emission big country, it is derived mainly from station boiler, transportation and various industrial process, annual emissions is more than 20,000,000 tons, and present the trend increased year by year, to public health and ecological environment bringing on a disaster property consequence, therefore, the emission control of NOx becomes the top priority of air contaminant treatment.In " 13 planning outlines (draft) ", China is clearly proposed in 2016 to SO2Reduce 3% respectively with the discharge capacity of NOx, and require control stress point area fine particle (PM2.5) concentration.Therefore, China's denitration situation is more acute, and the emission control of NOx becomes the main task that current atmospheric is administered, and the popularization to denitration technology proposes challenge.
In many NOx emission control technology, SCR (SCR) becomes the mainstream technology of denitration industry owing to it is ripe, reliable, efficient and obtains engineering verification, can be harmless N by NOx conversion2And H2The core cell of O, SCR technique is catalyst, directly determines cost and the efficiency of denitrating system.At present, the SCR catalyst that station boiler uses is with V2O5-WO3(MoO3)/TiO2System is main middle high temperature modification, and the operating temperature of catalyst is mostly 310-410 DEG C.But, many Industrial Boilers of non-electricity industry, kiln, metallurgy, chemical industry, coking and petrochemical industry etc., owing to secondary utilizes waste heat or other power-saving technologies supporting, its waste gas or smog discharge temperature relatively low (mostly below 200 DEG C), it is difficult in utilization, high temperature modification (310-410 DEG C) SCR catalyst carries out the emission control of NOx.
Therefore, developing low temperature high activity SCR catalyst, the low-temperature flue gas in non-electricity industry uses SCR technology, or the denitrating technique at the power industry use low dirt of low temperature, has huge Social benefit and economic benefit.Shan etc. (ShanWB, LiuFD, etal., Appl.Catal., B, 2012,115-116:100-106) utilize Co deposited synthesis to have the CeO of low temperature active2-WO3/TiO2Catalyst, the ratio of Ce and W low temperature active, temperature window and N to catalyst2Selectivity has a significant impact, and when the mol ratio of Ce and W is 1:1, can significantly improve intensity and the quantity of catalyst surface acidic site, improve the NH of catalyst3-SCR reactivity.Rooms etc. (Fang Jingrui, Wu Yanxia, etc. environmental project journal, 2014,8 (2): 636-640) are with the TiO of molding2Carrier is prepared for Mn-Ce/TiO by infusion process2Low-temperature SCR catalyst, the denitration efficiency of catalyst is had a significant impact by the content of Mn, when Mn/ (Mn+Ce) mol ratio is that low temperature active when 0.4 and 0.85 is the highest.Yan etc. (Yan Dongjie, beautiful sub-, etc. chemistry of fuel journal, 2016,44 (2): 232-238) utilize sol-gal process to be prepared for Mn-Ce/TiO2Low-temperature SCR catalyst, SO2Activity is had obvious inhibitory action, SO2When concentration is 700ppm, the removal efficiency of NOx is down to 42% from 84% in 2h by catalyst, and activity is irreversible reduces 50%；Active specy MnOx crystal conversion generates SA Mn2O3Species, it is suppressed that gas phase oxygen, to the transformation of Lattice Oxygen, reduces the redox performance of CeOx, additionally, sulfate is attached to catalyst at catalyst surface, are also the key factors causing catalysqt deactivation.Shen etc. (ShenBX, YaoY, etal., Chin.J.Catal, 2011,32 (12): 1803-1811) use ion exchange to be prepared for titanio laminated clay column TiO2-PILC carrier, obtains xMn/TiO by infusion process load Mn active component2-PILC catalyst, CeO2Doping can significantly improve 8%Mn/TiO2Active and the anti-SO of the catalysis of-PILC catalyst2Performance, 8%Mn-2%CeO2/TiO2-PILC reaches 95% 200 DEG C of removal efficiency to NO, CeO2Doping can improve surface acidity and the oxidation-reduction ability of catalyst.Chen etc. (ChenL, LiJH, etal., J.Phys.Chem.C, 2009,113:21177-21184) utilize CeOx to V2O5-WO3/TiO2Catalyst is doped, modified to improve catalyst performance, result shows, Ce doping is favorably improved catalyst surfaceThe intensity of acidic site and quantity, 0.1%V2O5-6%WO3-10%CeO2There is preferable low temperature active, anti-H2O and SO2Performance, is maintained at more than 90% the 200-400 DEG C of removal efficiency to NOx.
In patent CN105126922, with kieselguhr, molecular sieve and nano-TiO2For carrier, rare earth oxide is that active center obtains rare earth base SCR catalyst, has higher removal efficiency to NOx, but Catalyst Production raw material type is many under cryogenic conditions, and preparation process and equipment are complicated.Patent CN102962055 reports V2O5-MoO3/TiO2System low-temperature SCR catalyst raw powder's production technology, in model reaction catalyst when 150 DEG C to the removal efficiency of NOx up to 98%.Patent CN103894180 and CN103894181 utilize gel method and infusion process to prepare Pr, La doping V2O5-MoO3/TiO2Low-temperature SCR catalyst, rare earth element Pr, La doping enter TiO2Lattice is formed Lacking oxygen, improves the low temperature active of catalyst, but be not directed to shaping of catalyst.Patent CN102266761 reports the preparation method of a kind of low-temperature SCR catalyst powder, prepares ZrO first with coprecipitation2-TiO2Metal composite oxide carrier, then by infusion process load C eO2、WO3And V2O5Active component, catalyst shows in the range of 150-450 DEG C and is well catalyzed activity, but its preparation process is complicated.Patent CN104841464 discloses a kind of high efficient cryogenic SCR catalyst, the Br of 0.35-0.5wt%-Doping V2O5-WO3/TiO2Catalyst, can improve the catalyst denitration efficiency when low temperature and resistance to SO_2, extends the service life of catalyst further, but reports shaping of catalyst method, and commercial Application has certain limitation.Patent CN105126816 discloses the preparation method of a kind of catalyst for denitrating flue gas, relates generally to the middle high temperature modification SCR catalyst of station boiler denitration, with TiO2Compound Al2O3、SiO2Deng for carrier, glass fibre is skeleton, and gained catalyst has higher mechanical strength and anti-wear performance, and denitration efficiency, up to more than 92.3%, further increases the service life of catalyst.Therefore, for the low-temperature flue gas of the industry such as Industrial Boiler, kiln, chemical industry and coking and the technology waste gas of non-electricity industry, exploitation low-temperature denitration catalyst and molding technology thereof, significant to the popularization of low-temperature denitration technology and the emission control of NOx.
Summary of the invention
For defect and the deficiency of prior art, the invention provides a kind of cellular low-temperature denitration of flue gas catalyst and preparation method thereof, catalyst is made up of carrier, active component and auxiliary agent, has the low temperature active of excellence and wider temperature window.Present invention also offers cellular low-temperature denitration of flue gas method for preparing catalyst, there is the advantages such as efficient, low cost, easily realize industrialization to produce continuously, on the basis of ensureing catalysis activity, improve mechanical strength and the wear resistance of catalyst, extend catalyst life further.
The technical scheme is that cellular low-temperature denitration of flue gas catalyst, including carrier, active component and auxiliary agent, described active component and auxiliary agent are supported on carrier respectively, and described carrier is TiO2Or TiO2Composite oxides, described carrier content in the catalyst is 70～90wt%；Described active component is V2O5And WO3Or MoO3, described active component load capacity on carrier is: V2O5It is 0.3～6wt%, WO3It is 1.0～15wt% or MoO3Being 1.0～15wt%, described auxiliary agent is P2O5, described auxiliary agent load capacity on carrier is: P2O5For 0.1-3wt%.
The invention has the beneficial effects as follows: the cellular low-temperature denitration of flue gas catalyst that invention is provided, catalyst has good low temperature active and wider temperature window.Utilize the preparation method of the present invention, be favorably improved the active component degree of scatter at carrier surface, enhance the interaction between active specy and carrier, it is suppressed that the catalysqt deactivation caused due to sintering under high temperature.Additionally, gained catalyst has higher mechanical strength and abrasion resistant qualities, further increase the service life of catalyst.
On the basis of technique scheme, the present invention can also do and improve as follows:
Further, described active component also includes that rare earth oxide, described rare earth oxide load capacity on carrier are 0～20wt%, and described rare earth oxide is one or more in the oxide of La, Ce, Pr, Nd, Zr, Y.
Further, described auxiliary agent also includes SO3, SO3Load capacity on carrier is 0-3wt%.
Further, described active component is prepared by active component presoma, and described active component presoma is V2O5、WO3、MoO3And one or more in corresponding oxide, inorganic salt or the organic salt of rare earth oxide；Described auxiliary agent is prepared by auxiliary agent presoma, and described auxiliary agent presoma is P2O5、SO3One or more in corresponding oxide, inorganic salt or organic salt.
The technical scheme that the present invention solves another technical problem is as follows: the preparation method of a kind of cellular low-temperature denitration of flue gas catalyst, comprises the steps:
Prepared by S1 catalyst fines:
S101 adds deionized water in a kettle. and is heated to 40-80 DEG C, adds oxalic acid or citric acid stirring to after being completely dissolved, adds active component presoma and auxiliary agent presoma, be sufficiently stirred for obtaining activity component impregnation liquid, wherein, described V2O5Presoma is 1:(0.8-4 with the mol ratio of oxalic acid or citric acid)；
The activity component impregnation liquid that S102 obtains in step S101 adds the carrier of powder, it is sufficiently stirred for obtaining sticky shape serosity, this sticky shape serosity is processed through ultrasonic disperse and obtains catalyst slurry, wherein, the mass ratio of the deionized water added in described carrier and S101 is 1:(0.9-1.4)；
The catalyst slurry obtained in step S102 is dried by S103, carries out roasting after crushing, and naturally cools to room temperature, pulverizes and obtains catalyst fines；
S2 pug processes and shaping of catalyst:
The catalyst fines that S103 is obtained by S201 arranges standby, regulation strength mixing roll air bleeding valve, and in strength mixing roll air bleeding valve, adding the catalyst fines of 225-315 weight portion and powder aggregate, described powder aggregate is 3-20wt% relative to the addition of catalyst fines；It is subsequently adding the stearic acid of 2-9 weight portion, the lactic acid of 2-9 weight portion or oleic acid, the glycerol of 1-10 weight portion, add deionized water and the ammonia that concentration is 15-25% of 24-32 weight portion of 150-210 weight portion, close strength mixing roll air bleeding valve, the mixing 30-80min of high speed；
S202 regulation strength mixing roll air bleeding valve, mixing roll low cruise, add catalyst fines and the 10-35 weight deionized water of 67-105 weight portion, close strength mixing roll air bleeding valve, the mixing 10-40min of high speed；
S203 regulation strength mixing roll air bleeding valve, mixing roll low cruise, add catalyst fines and the ammonia that concentration is 15-25% of 3-6 weight portion of 60-130 weight portion, close strength mixing roll air bleeding valve, the mixing pug temperature to mixing roll of high speed reaches 90-95 DEG C, fully opens the gas produced when air bleeding valve is discharged mixing, continues mixing 30-60min, the moisture content treating pug is 25-29%, end step S203；
S204 adds the glass fibre of 9-27 weight portion, the wood pulp of 2-7 weight portion, the RP-CHOP anti-crack fiber of 2-7 weight portion and the deionized water of 80-128 weight portion, closes strength mixing roll air bleeding valve, the mixing 10-40min of high speed；
S205 regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, and adds the organic binder bond closedown strength mixing roll air bleeding valve of 3-14 weight portion, the mixing 10-30min of high-speed reverse；
S206 regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, and adds organic binder bond and the ammonia that concentration is 15-25% of 2-8 weight portion of 3-14 weight portion, closes strength mixing roll air bleeding valve, the mixing 15-45min of high-speed reverse；
S207 opens strength mixing roll air bleeding valve, regulates plasticity and the moisture content of pug, when the plasticity of pug is 22-26, when moisture content is 28-31%, mixing end with the ammonia of deionized water and 15-20%；
The pug of mixing end is transferred in kneader by S208, carry out wet pinch mixing 1-3h and shaping of catalyst process after obtain catalyst；
Wherein, described regulation strength mixing roll air bleeding valve, strongly mixing roll exhaust valve opening degree is 10-15%, described mixing roll low cruise, and the rotating speed of mixing roll rotor is 250-450rpm；Described mixing roll high-speed cruising, the rotating speed of mixing roll rotor is 650-850rpm.
Further, described S1 catalyst fines preparation process specifically includes following steps:
S101 adds deionized water in a kettle. and is heated to 40-80 DEG C, adds oxalic acid or citric acid stirs to being completely dissolved, be sequentially added into V2O5、WO3Or MoO3Active component presoma, or add rare earth oxide active component presoma；Add P2O5Auxiliary agent presoma, or add SO3Auxiliary agent presoma, stirs 10-60min, obtains activity component impregnation liquid, wherein, described V at 40-80 DEG C2O5Presoma is 1:(0.8-4 with the mol ratio of oxalic acid or citric acid)；
The activity component impregnation liquid that S102 obtains in step S101 adds the carrier of powder, sticky shape serosity is obtained after stirring 10-60min at 40-80 DEG C, this sticky shape serosity ultrasonic disperse process 1-3h is obtained catalyst slurry, wherein, the mass ratio of the deionized water added in described carrier and S101 is 1:(0.9-1.4)；
The catalyst slurry that S103 obtains in step S102, at 200-300 DEG C of dry 2-12h, at 300-600 DEG C of roasting 2-8h after crushing, naturally cools to room temperature, is crushed to 100-300 mesh and obtains catalyst fines.
Further, in described S208, shaping of catalyst process specifically includes following steps:
1) filter, pre-squeeze: described filtration is that pug step S208 obtained is placed in twin screw filter, utilizes mud mouth stainless steel sift net filtration, combing pug, removes impurity in pug；Described pre-crowded, the pug after filtering carries out pre-extrusion forming, obtains square clod；
2) old: by step 1) in pre-squeeze after clod old 12-72h under the conditions of 25-40 DEG C and humidity are 45-90%；
3) extrusion molding: by step 2) in old rear pug obtain honeycombed catalyst base substrate through Powerful extruder molding；
4) be dried: by step 3) in moisture removal in honeycombed catalyst base substrate, to reach roasting requirement, described being dried includes that one-level is dried and secondary drying, and described one-level is dried and is increased to 60-65 DEG C by room temperature, and humidity is reduced to 28-35% by 90-95%；Described secondary drying, is dried 24-72h in 45-60 DEG C of hot-air；
5) roasting, cutting: described roasting is by step 4) in catalyst base substrate after secondary drying be placed in mesh-belt kiln, at 200-650 DEG C of roasting 20-40h, obtain cellular low-temperature SCR catalyst, described cutting is to utilize double end band saw to cut catalyst end face, cuts the irregular part in two ends；
6) front end hardening: by step 5) in cutting rear catalyst end face be placed in hardening bath dipping 2-10min, impregnating depth is 20-40mm.
Further, described powder aggregate includes quartz sand, glass powder with low melting point, Al2O3, silicon powder, white carbon, gas phase SiO2, clay, montmorillonite, attapulgite, aluminum phosphate, aluminium dihydrogen phosphate, boehmite, Kaolin, meerschaum, one or more in bentonite, described powder aggregate is 3-20wt% relative to the addition of catalyst fines.
Further, described organic binder bond includes one or more in methylcellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, ammonium cellulose, sodium cellulosate, polyacrylamide, polyvinyl alcohol, polyethylene glycol oxide, described organic binder bond is 0.5-10wt% relative to the addition of catalyst fines
Further, described hardening bath is the aqueous solution of hardening medium, and described hardening medium is Al2(SO4)3Or AlPO4Or Al (H2PO4)3, the mass concentration of described hardening medium is 10-50wt%.
Above-mentioned further scheme is used to provide the benefit that:
(1) catalyst has higher denitration efficiency at low-temperature range, the NOx emission being suitable for the industry discharge low-temperature flue gas such as non-electricity industry boiler, kiln metallurgy, chemical industry, coking and petrochemical industry or technology waste gas controls, and the catalyst denitration efficiency when 170-180 DEG C is maintained at more than 90%.
(2) catalyst can keep high removal efficiency to NOx within the scope of wider temperature, it is possible to adapts to the wide fluctuations of flue-gas temperature, advantageously reduces operating cost and the energy consumption of denitrating technique.
(3) catalyst of gained of the present invention has higher mechanical strength and wear resistance, and catalyst longitudinal direction comprcssive strength is more than 2.4MPa, and hardening end ash cutting rate is less than 0.08%/Kg.Decrease flying dust catalyst to be washed away, wear and tear and etches, extend the service life of catalyst.
(4) catalyst of the present invention, its raw material is simple and easy to get, and preparation process is simple and easy to control, easily realizes industrialization and produces continuously.
Detailed description of the invention
Being described principle and the feature of the present invention below in conjunction with specific embodiment, example is served only for explaining the present invention, is not intended to limit the scope of the present invention.
Cellular low-temperature denitration of flue gas catalyst, including carrier, active component and auxiliary agent, described active component and auxiliary agent are supported on carrier respectively, and described carrier is TiO2Or TiO2Composite oxides, described carrier content in the catalyst is 70～90wt%；Described active component is V2O5And WO3Or MoO3, described active component load capacity on carrier is: V2O5It is 0.3～6wt%, WO3It is 1.0～15wt% or MoO3Being 1.0～15wt%, described auxiliary agent is P2O5, described auxiliary agent load capacity on carrier is: P2O5For 0.1-3wt%.
Described active component also includes that rare earth oxide, described rare earth oxide load capacity on carrier are 0～20wt%, and described rare earth oxide is one or more in the oxide of La, Ce, Pr, Nd, Zr, Y.
Described auxiliary agent also includes SO3, SO3Load capacity on carrier is 0-3wt%.
Described active component is prepared by active component presoma, and described active component presoma is V2O5、WO3、MoO3And one or more in corresponding oxide, inorganic salt or the organic salt of rare earth oxide；Described auxiliary agent is prepared by auxiliary agent presoma, and described auxiliary agent presoma is P2O5、SO3One or more in corresponding oxide, inorganic salt or organic salt.
The preparation method of a kind of cellular low-temperature denitration of flue gas catalyst, comprises the steps:
Prepared by S1 catalyst fines:
S101 adds deionized water in a kettle. and is heated to 40-80 DEG C, adds oxalic acid or citric acid stirring to after being completely dissolved, adds active component presoma and auxiliary agent presoma, be sufficiently stirred for obtaining activity component impregnation liquid, wherein, described V2O5Presoma is 1:(0.8-4 with the mol ratio of oxalic acid or citric acid)；Preferably, S101 adds deionized water in a kettle. and is heated to 40-80 DEG C, adds oxalic acid or citric acid stirs to being completely dissolved, be sequentially added into V2O5、WO3Or MoO3Active component presoma, or add rare earth oxide active component presoma；Add P2O5Auxiliary agent presoma, or add SO3Auxiliary agent presoma, stirs 10-60min, obtains activity component impregnation liquid, wherein, described V at 40-80 DEG C2O5Presoma is 1:(0.8-4 with the mol ratio of oxalic acid or citric acid)；
The activity component impregnation liquid that S102 obtains in step S101 adds the carrier of powder, it is sufficiently stirred for obtaining sticky shape serosity, this sticky shape serosity is processed through ultrasonic disperse and obtains catalyst slurry, wherein, the mass ratio of the deionized water added in described carrier and S101 is 1:(0.9-1.4)；Preferably, the activity component impregnation liquid that S102 obtains in step S101 adds the carrier of powder, sticky shape serosity is obtained after stirring 10-60min at 40-80 DEG C, this sticky shape serosity ultrasonic disperse process 1-3h is obtained catalyst slurry, wherein, the mass ratio of the deionized water added in described carrier and S101 is 1:(0.9-1.4)；
The catalyst slurry obtained in step S102 is dried by S103, carries out roasting after crushing, and naturally cools to room temperature, pulverizes and obtains catalyst fines；Preferably, the catalyst slurry that S103 obtains in step S102, at 200-300 DEG C of dry 2-12h, at 300-600 DEG C of roasting 2-8h after crushing, naturally cools to room temperature, is crushed to 100-300 mesh and obtains catalyst fines.
S2 pug processes and shaping of catalyst:
The catalyst fines that S103 is obtained by S201 arranges standby, regulation strength mixing roll air bleeding valve, and in strength mixing roll air bleeding valve, adding the catalyst fines of 225-315 weight portion and powder aggregate, described powder aggregate is 3-20wt% relative to the addition of catalyst fines；It is subsequently adding the stearic acid of 2-9 weight portion, the lactic acid of 2-9 weight portion or oleic acid, the glycerol of 1-10 weight portion, add deionized water and the ammonia that concentration is 15-25% of 24-32 weight portion of 150-210 weight portion, close strength mixing roll air bleeding valve, the mixing 30-80min of high speed；
S202 regulation strength mixing roll air bleeding valve, mixing roll low cruise, add catalyst fines and the 10-35 weight deionized water of 67-105 weight portion, close strength mixing roll air bleeding valve, the mixing 10-40min of high speed；
S203 regulation strength mixing roll air bleeding valve, mixing roll low cruise, add catalyst fines and the ammonia that concentration is 15-25% of 3-6 weight portion of 60-130 weight portion, close strength mixing roll air bleeding valve, the mixing pug temperature to mixing roll of high speed reaches 90-95 DEG C, fully opens the gas produced when air bleeding valve is discharged mixing, continues mixing 30-60min, the moisture content treating pug is 25-29%, end step S203；
S204 adds the glass fibre of 9-27 weight portion, the wood pulp of 2-7 weight portion, the RP-CHOP anti-crack fiber of 2-7 weight portion and the deionized water of 80-128 weight portion, closes strength mixing roll air bleeding valve, the mixing 10-40min of high speed；
S205 regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, and adds the organic binder bond closedown strength mixing roll air bleeding valve of 3-14 weight portion, the mixing 10-30min of high-speed reverse；
S206 regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, and adds organic binder bond and the ammonia that concentration is 15-25% of 2-8 weight portion of 3-14 weight portion, closes strength mixing roll air bleeding valve, the mixing 15-45min of high-speed reverse；
S207 opens strength mixing roll air bleeding valve, regulates plasticity and the moisture content of pug, when the plasticity of pug is 22-26, when moisture content is 28-31%, mixing end with the ammonia of deionized water and 15-20%；
The pug of mixing end is transferred in kneader by S208, carry out wet pinch mixing 1-3h and shaping of catalyst process after obtain catalyst；
Wherein, described regulation strength mixing roll air bleeding valve, strongly mixing roll exhaust valve opening degree is 10-15%, described mixing roll low cruise, and the rotating speed of mixing roll rotor is 250-450rpm；Described mixing roll high-speed cruising, the rotating speed of mixing roll rotor is 650-850rpm.
Preferably, in described S208, shaping of catalyst process specifically includes following steps: 1) filter, pre-squeeze: described filtration is that pug step S208 obtained is placed in twin screw filter, utilize mud mouth stainless steel sift net filtration, combing pug, remove impurity in pug；Described pre-crowded, the pug after filtering carries out pre-extrusion forming, obtains square clod；
2) old: by step 1) in pre-squeeze after clod old 12-72h under the conditions of 25-40 DEG C and humidity are 45-90%；
3) extrusion molding: by step 2) in old rear pug obtain honeycombed catalyst base substrate through Powerful extruder molding；
4) be dried: by step 3) in moisture removal in honeycombed catalyst base substrate, to reach roasting requirement, described being dried includes that one-level is dried and secondary drying, and described one-level is dried and is increased to 60-65 DEG C by room temperature, and humidity is reduced to 28-35% by 90-95%；Described secondary drying, is dried 24-72h in 45-60 DEG C of hot-air；
5) roasting, cutting: described roasting is by step 4) in catalyst base substrate after secondary drying be placed in mesh-belt kiln, at 200-650 DEG C of roasting 20-40h, obtain cellular low-temperature SCR catalyst, described cutting is to utilize double end band saw to cut catalyst end face, cuts the irregular part in two ends；
6) front end hardening: by step 5) in cutting rear catalyst end face be placed in hardening bath dipping 2-10min, impregnating depth is 20-40mm.
Described powder aggregate includes quartz sand, glass powder with low melting point, Al2O3, silicon powder, white carbon, gas phase SiO2, clay, montmorillonite, attapulgite, aluminum phosphate, aluminium dihydrogen phosphate, boehmite, Kaolin, meerschaum, one or more in bentonite, described powder aggregate is 3-20wt% relative to the addition of catalyst fines.
Described organic binder bond includes one or more in methylcellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, ammonium cellulose, sodium cellulosate, polyacrylamide, polyvinyl alcohol, polyethylene glycol oxide, described organic binder bond is 0.5-10wt% relative to the addition of catalyst fines
Described hardening bath is the aqueous solution of hardening medium, and described hardening medium is Al2(SO4)3Or AlPO4Or Al (H2PO4)3, the mass concentration of described hardening medium is 10-50wt%.
Described powder aggregate, organic bond, hardening bath are that shaping of catalyst process needs.
Below by way of specific embodiment, the present invention is further detailed:
Embodiment 1
Step in all embodiments is all corresponding with step in S1 and S2, and for convenience of describing, step numbers has been changed.
1) prepared by catalyst fines
Step 1, add 750 parts by weight of deionized water in a kettle. and be heated to 50-55 DEG C, add 95 weight portion oxalic acid to stir to being completely dissolved, it is slowly added to 23 weight portion ammonium metavanadates (10-30min adds), after stirring 20-30min, add 44.5 weight portion ammonium molybdates, 8.5 parts by weight of phosphoric acid three ammoniums and 126 parts by weight of cerium nitrate, at 50 DEG C, continue stirring 30min obtain activity component impregnation solution
Step 2, adds 600 weight portion TiO2Powder, 45 DEG C of stirring 20min obtain sticky shape serosity, stirring, ultrasonic disperse 1.5h,
Step 3, by catalyst slurry in reactor at 250 DEG C of dry 3.0h, at 450 DEG C of roasting 3.5h after crushing, is crushed to 200 mesh after naturally cooling to room temperature.
Through the catalyst fines prepared by step 1-3, active component and auxiliary agent load capacity it is: V2O5For 3wt%, MoO3For 6wt%, CeO2For 8wt%, P2O5For 0.5wt%；
2) pug processes and shaping of catalyst
Step 1, regulation strength mixing roll air bleeding valve, by 280 weight portions 1) in the catalyst fines of preparation, 6.7 weight portion quartz sands, 4.5 weight portion glass powder with low melting point join in mixing roll, add 4.5 weight portion stearic acid, 4.5 weight portion oleic acid, 5.4 parts by weight of glycerin, 188.5 parts by weight of deionized water and the ammonia of 32 weight portions 15%, close strength mixing roll air bleeding valve, the mixing 40min of high speed；
Step 2, regulation strength mixing roll air bleeding valve, mixing roll low cruise, adds 77 weight portions 1) in the catalyst fines of preparation and the deionized water of 16.5 weight portions, close air bleeding valve, the mixing 25min of high speed；
Step 3, regulation strength mixing roll air bleeding valve, mixing roll low cruise, adds 93 weight portions 1) in preparation catalyst fines and the ammonia of 6 weight portions 15%, close air bleeding valve, the mixing pug temperature to mixing roll of high speed reaches 95 DEG C, fully opening the gas produced when air bleeding valve is discharged mixing, continue mixing 35min, pug moisture content is 28.0%, end step 3
Step 4, adds 13.5 parts by weight of glass fiber, 3.6 weight portion wood pulps, 3.2 weight portion RP-CHOP fiber and 85.5 parts by weight of deionized water, closes air bleeding valve, the mixing 15min of high speed,
Step 5, regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, and adds 3.5 weight portion hydroxypropyl celluloses, 3.5 weight account polyethylene alcohol and 1.9 weight portion poly(ethylene oxide), closes air bleeding valve, the mixing 10min of high-speed reverse；
Step 6, regulation strength mixing roll air bleeding valve mixing roll low-speed reverse is run, and adds 2.3 weight portion hydroxypropyl celluloses, 2.3 weight account polyethylene alcohol, 1.3 poly(ethylene oxide) and the ammonia of 3 weight portions 15%, closes air bleeding valve, the mixing 25min of high-speed reverse；
Step 7, fully opens strength mixing roll air bleeding valve, regulates moisture content and the plasticity of pug with the ammonia of deionized water and 15-20%, and the moisture content of pug is 29.2%, and plasticity is 24.7, mixing end；
Step 8, transfers in kneader by the pug of mixing end, carry out wet pinch mixing 1.5h and shaping of catalyst process after obtain catalyst；
In step 1-step 7,
Regulation strength mixing roll air bleeding valve, strongly the exhaust valve opening degree of mixing roll is 10-15%,
Mixing roll low cruise, when mixing roll runs, the rotating speed of rotor is 300rpm,
Mixing roll high-speed cruising, when mixing roll runs, the rotating speed of rotor is 750rpm,
3) pre-squeezing is filtered
Mixing kneading process gained pug is placed in twin screw filter, utilizes mud mouth stainless steel sift net filtration, combing pug, remove impurity in pug；After filtration, pug is through pre-extrusion forming, obtains square clod；
4) old
Pre-crowded rear pug is placed in 25-40 DEG C and humidity is old 12-72h under the conditions of 45-90%；
5) extrusion molding
Old rear pug obtains honeycombed catalyst base substrate, catalyst appearance length and internal gutter size through Powerful extruder molding and determines according to engine request；
6) it is dried
At hothouse, catalyst base substrate is dried, removes the moisture in base substrate, to reach roasting requirement；Being dried and include that one-level is dried and secondary drying, one-level is dried and is increased to 65 DEG C by room temperature, and humidity is reduced to 35% by 95%；Secondary drying, is dried 24-72h in 45-60 DEG C of hot-air,
7) roasting cutting
Roasting, the catalyst base substrate after secondary drying is placed in mesh-belt kiln, at 200-650 DEG C of roasting 20-40h, obtains cellular low-temperature SCR catalyst,
Cutting, utilizes double end band saw to cut catalyst end face, cuts the irregular part in two ends,
8) front end hardening
Cutting rear catalyst end face is placed in the AlPO of 35wt%4Solution impregnates 5min, impregnating depth 20-40mm.
The catalyst of embodiment 1 preparation is under the conditions of test case, and denitration efficiency when 170 DEG C reaches 91.7%, and longitudinal comprcssive strength of catalyst is 2.48MPa, and horizontal comprcssive strength is 0.84MPa, and hardening end wear strength is 0.073%/Kg.
Embodiment 2
1) prepared by catalyst fines
Step 1, add 750 parts by weight of deionized water in a kettle. and be heated to 50-55 DEG C, add 95 weight portion oxalic acid to stir to being completely dissolved, it is slowly added to 23 weight portion ammonium metavanadates (10-30min adds) and stirs 20-30min, add 32.8 weight portion ammonium tungstates, 8.5 parts by weight of phosphoric acid three ammonium 2.5 parts sulfuric acid ammonium and 126 parts by weight of cerium nitrate, at 50 DEG C, continue stirring 30min obtain activity component impregnation solution；
Step 2, adds 600 weight portion TiO2Powder, 45 DEG C of stirring 20min obtain sticky shape serosity, then stirring, ultrasonic disperse 1.5h；
Step 3, by catalyst slurry in reactor at 250 DEG C of dry 3.0h, at 450 DEG C of roasting 3.5h after crushing, is crushed to 200 mesh after naturally cooling to room temperature.
Through the catalyst fines prepared by step 1-3, active component and auxiliary agent load capacity it is: V2O5For 3wt%, WO3For 6wt%, CeO2For 8wt%, P2O5For 0.5wt%, SO3For 0.25wt%；
2) mixing kneading
Step 1, regulation strength mixing roll air bleeding valve, add 300 weight portions 1) in preparation catalyst fines, the quartz sand of 9 weight portions join in mixing roll, add 3.6 weight portion stearic acid, 4.5 weight portion lactic acid, 4.5 parts by weight of glycerin, 174 parts by weight of deionized water and the ammonia of 30 weight portions 15%, close air bleeding valve, the mixing 40min of high speed；
Step 2, regulation strength mixing roll air bleeding valve, mixing roll low cruise, adds 75 weight portions 1) in the catalyst fines of preparation and 20 parts by weight of deionized water, close air bleeding valve, the mixing 25min of high speed；
Step 3, regulation strength mixing roll air bleeding valve, mixing roll low cruise, adds 75 weight portions 1) in preparation catalyst fines and the ammonia of 6 weight portions 15%, close air bleeding valve, the mixing pug temperature to mixing roll of high speed reaches 95 DEG C, fully opening the gas produced when air bleeding valve is discharged mixing, continue mixing 35min, pug moisture content is 27.5%, end step 3
Step 4, adds 13.5 parts by weight of glass fiber, 3.2 weight portion wood pulps, 3.6 weight portion RP-CHOP anti-peacekeeping 96 parts by weight of deionized water, closes strength mixing roll air bleeding valve, the mixing 15min of high speed；
Step 5, regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, and adds 2.3 weight portion hydroxypropyl celluloses, 2.3 weight account polyethylene alcohol and 1.8 weight portion poly(ethylene oxide), closes strength mixing roll air bleeding valve, the mixing 10min of high-speed reverse；
Step 6, regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, 2.3 weight portion hydroxypropyl celluloses, 2.3 weight account polyethylene alcohol, 1.8 weight portion poly(ethylene oxide) and the ammonia of 4 weight portions 15%, close strength mixing roll air bleeding valve, the mixing 25min of high-speed reverse
Step 7, fully opens strength mixing roll air bleeding valve, regulates moisture content and the plasticity of pug with the ammonia of deionized water and 15-20%, and the moisture content of pug is 28.9%, and plasticity is 25.5, mixing end；
Step 8, transfers in kneader by the pug of mixing end, carry out wet pinch mixing 2h and shaping of catalyst process after obtain catalyst；
In step 1-step 7,
Regulation strength mixing roll air bleeding valve, strongly the exhaust valve opening degree of mixing roll is 10-15%,
Mixing roll low cruise, when mixing roll runs, the rotating speed of rotor is 300rpm,
Mixing roll high-speed cruising, when mixing roll runs, the rotating speed of rotor is 750rpm,
The follow-up shaping of catalyst carried out, i.e. filter pre-crowded, old, extrusion molding, be dried, roasting cutting and front end cure process process be with embodiment 1.
The catalyst of embodiment 2 preparation is under the conditions of test case, and denitration efficiency when 170 DEG C reaches 90.8%, and longitudinal comprcssive strength of catalyst is 2.52MPa, and horizontal comprcssive strength is 0.89MPa, and hardening end wear strength is 0.068%/Kg.
Embodiment 3
1) prepared by catalyst fines
Step 1, add 750 parts by weight of deionized water in a kettle. and be heated to 50-55 DEG C, add 95 weight portion oxalic acid to stir to being completely dissolved, it is slowly added to 23 weight portion ammonium metavanadates (10-30min adds), stirring 20-30min, add 44.5 weight portion ammonium molybdates and 8.5 parts by weight of phosphoric acid three ammoniums, at 50 DEG C, continue stirring 30min obtain activity component impregnation solution；
Step 2, adds 600 weight portion TiO2Powder, 45 DEG C of stirring 20min obtain sticky shape serosity, stirring, ultrasonic disperse 1.5h；
Step 3, in reactor, catalyst slurry is at 250 DEG C of dry 3.0h, at 450 DEG C of roasting 3.5h after crushing, is crushed to 200 mesh after naturally cooling to room temperature；
Through the catalyst fines prepared by step 1-3, active component is negative and auxiliary agent load capacity is: V2O5For 3wt%, MoO3For 6wt%, P2O5For 0.5wt%；
2) mixing kneading
Step 1, regulation strength mixing roll air bleeding valve, by 248 weight portions 1) in preparation catalyst fines and 9 weight portion aerosils join in mixing roll, add 3.6 weight portion stearic acid, 4.5 weight portion oleic acid, 5.0 parts by weight of glycerin, 174 parts by weight of deionized water and the ammonia of 27.5 weight portions 15%, close air bleeding valve, the mixing 40min of high speed；
Step 2, regulation strength mixing roll air bleeding valve, mixing roll low cruise, adds 90 weight portions 1) in the catalyst fines of preparation and the deionized water of 17.5 weight portions, close strength mixing roll air bleeding valve, the mixing 25min of high speed；
Step 3, regulation strength mixing roll air bleeding valve, mixing roll low cruise, add 112.5 weight portions 1) in preparation catalyst fines and the ammonia of 7.5 weight portions 15%, closing strength mixing roll air bleeding valve, the mixing pug temperature to mixing roll of high speed reaches 95 DEG C, fully opens the gas produced when air bleeding valve is discharged mixing, continuing mixing 35min, pug moisture content is26.9 %, end step 3；
Step 4, adds 13.5 parts by weight of glass fiber, 3.6 weight portion wood pulps and 98.5 parts by weight of deionized water, closes strength mixing roll air bleeding valve, the mixing 15min of high speed；
Step 5, regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, is added 2.7 weight portion hydroxypropyl celluloses, 1.8 weight account polyethylene alcohol, 1.8 weight portion RP-CHOP fibers and 1.8 weight portion poly(ethylene oxide), close strength mixing roll air bleeding valve, the mixing 10min of high-speed reverse；
Step 6, regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, is added 2.7 weight portion hydroxypropyl celluloses, 1.8 weight account polyethylene alcohol, 1.8 weight portion RP-CHOP fibers and 1.8 weight portion poly(ethylene oxide), close strength mixing roll air bleeding valve, the mixing 25min of high-speed reverse；
Step 7, fully opens strength mixing roll air bleeding valve, regulates moisture content and the plasticity of pug with the ammonia of deionized water and 15-20%, and the moisture content of pug is 29.4%, and plasticity is 24.7, mixing end；
Step 8, transfers in kneader by the pug of mixing end, carry out wet pinch mixing 1.5h and shaping of catalyst process after obtain catalyst；
Regulation strength mixing roll air bleeding valve, strongly the exhaust valve opening degree of mixing roll is 10-15%,
Mixing roll low cruise, when mixing roll runs, the rotating speed of rotor is 300rpm,
Mixing roll high-speed cruising, when mixing roll runs, the rotating speed of rotor is 750rpm,
The follow-up shaping of catalyst that carries out, i.e. filter pre-crowded, old, extrusion molding, be dried, roasting cutting and front end cure process process be with embodiment 1.
The catalyst of embodiment 3 preparation is under the conditions of test case, and denitration efficiency when 170 DEG C reaches 92.5%, and longitudinal comprcssive strength of catalyst is 2.50MPa, and horizontal comprcssive strength is 0.85MPa, and hardening end wear strength is 0.065%/Kg.
Embodiment 4
1) prepared by catalyst fines
Step 1, add 750 parts by weight of deionized water in a kettle. and be heated to 50-55 DEG C, add 79 weight portion oxalic acid to stir to being completely dissolved, it is slowly added to 19.2 weight portion ammonium metavanadates (10-30min adds), stirring 20-30min, add 44.5 weight portion ammonium molybdates, 8.5 parts by weight of phosphoric acid three ammoniums and 126 parts by weight of cerium nitrate, under the conditions of 50 DEG C, continue stirring 30min obtain activity component impregnation liquid；
Step 2, adds 600 weight portion TiO2Powder, 45 DEG C of stirring 20min obtain sticky shape serosity, stirring, ultrasonic disperse 1.5h；
Step 3, by catalyst slurry in reactor at 250 DEG C of dry 3.0h, at 450 DEG C of roasting 3.5h after crushing, is crushed to 200 mesh after naturally cooling to room temperature；
Through catalyst fines prepared by step 1-3, active component is negative and auxiliary agent load capacity is: V2O5For 2.5wt%, MoO3For 6wt%, CeO2For 8wt%, P2O5For 0.5wt%；
2) mixing kneading
Step 1, regulation strength mixing roll air bleeding valve, by 270 weight portions 1) in the catalyst fines of preparation, 6.8 weight portion aerosils, 20 parts by weight of activated aluminium oxidies join in mixing roll, add 4.7 weight portion stearic acid, 4.7 weight portion lactic acid, 5.6 parts by weight of glycerin, 180 parts by weight of deionized water and the ammonia of 28 weight portions 15%, close strength mixing roll air bleeding valve, the mixing 40min of high speed；
Step 2, regulation strength mixing roll air bleeding valve, mixing roll low cruise, adds 81 weight portions 1) in the catalyst fines of preparation and 18 parts by weight of deionized water, close strength mixing roll air bleeding valve, the mixing 25min of high speed；
Step 3, regulation strength mixing roll air bleeding valve, mixing roll low cruise, add 99 weight portions 1) in preparation catalyst fines and the ammonia of 5 weight portions 15%, close strength mixing roll air bleeding valve, the mixing pug temperature to mixing roll of high speed reaches 95 DEG C, fully open the gas produced when air bleeding valve is discharged mixing, continuing mixing 35min, pug moisture content is 26.2%, end step 3；
Step 4, adds 14 parts by weight of glass fiber, 3.7 weight portion wood pulps, 3.7 weight portion RP-CHOP fiber and 102 parts by weight of deionized water, closes strength mixing roll air bleeding valve, the mixing 15min of high speed；
Step 5, regulation strength mixed connection runs in air valve, and mixing roll low-speed reverse is run, and adds 3.1 weight portion hydroxypropyl celluloses, 2.4 weight account polyethylene alcohol and 2.0 weight portion poly(ethylene oxide), closes strength mixing roll air bleeding valve, the mixing 10min of high-speed reverse；
Step 6, regulation strength mixed connection is run in air valve, and mixing roll low-speed reverse is run, and adds 2.5 weight portion hydroxypropyl celluloses, 2.3 weight account polyethylene alcohol, 1.7 poly(ethylene oxide) and the ammonia of 7 weight portions 15%, close strength mixing roll air bleeding valve, the mixing 25min of high-speed reverse；
Step 7, fully opens strength mixing roll air bleeding valve, regulates moisture content and the plasticity of pug with the ammonia of deionized water and 15-20%, and the moisture content of pug is 29.2%, and plasticity is 23.8, mixing end；
Step 8, transfers in kneader by the pug of mixing end, and the pug of mixing end is transferred in kneader by step 8, carry out wet pinch mixing 2.5h and shaping of catalyst process after obtain catalyst；
In step 1-step 7,
Regulation strength mixing roll air bleeding valve, strongly the exhaust valve opening degree of mixing roll is 10-15%,
Mixing roll low cruise, when mixing roll runs, the rotating speed of rotor is 300rpm, mixing roll high-speed cruising, and when mixing roll runs, the rotating speed of rotor is 750rpm,
The follow-up shaping of catalyst that carries out, i.e. filter pre-crowded, old, extrusion molding, be dried, roasting cutting and front end cure process process be with embodiment 1；
The catalyst of embodiment 4 preparation is under the conditions of test case, and denitration efficiency when 180 DEG C reaches 95.7%, and longitudinal comprcssive strength of catalyst is 2.47MPa, and horizontal comprcssive strength is 0.85MPa, and hardening end wear strength is 0.073%/Kg.
Embodiment 5
1) prepared by catalyst fines
Step 1, add 750 parts by weight of deionized water in a kettle. and be heated to 50-55 DEG C, add 95 weight portion oxalic acid to stir to being completely dissolved, it is slowly added to 23 weight portion ammonium metavanadates (10-30min adds), stirring 20-30min, add 44.5 weight portion ammonium molybdates and 8.5 parts by weight of phosphoric acid three ammoniums, at 50 DEG C, continue stirring 30min obtain activity component impregnation liquid；
Step 2, adds 582 weight portion TiO2Powder and 18 weight portion aerosils, 45 DEG C of stirring 20min obtain sticky shape serosity, stirring, ultrasonic disperse 1.5h；
Step 3, in reactor, catalyst slurry is at 250 DEG C of dry 3.0h, at 450 DEG C of roasting 3.5h after crushing, is crushed to 200 mesh after naturally cooling to room temperature；
Through the catalyst fines prepared by step 1-3, active component is negative and auxiliary agent load capacity is: V2O5For 3wt%, MoO3For 6wt%, P2O5For 0.5wt%；SiO2For 3wt%；
2) mixing kneading
Step 1, regulation strength mixing roll air bleeding valve, by 261 weight portions 1) in preparation catalyst fines join in mixing roll, add 4.5 weight portion stearic acid, 4.5 weight portion oleic acid, 5.4 parts by weight of glycerin, 180 parts by weight of deionized water and the ammonia of 28 weight portions 15%, close air bleeding valve, the mixing 40min of high speed；
Step 2, regulation strength mixing roll air bleeding valve, mixing roll low cruise, adds 81 weight portions 1) in the catalyst fines of preparation and the deionized water of 20 weight portions, close strength mixing roll air bleeding valve, the mixing 25min of high speed；
Step 3, regulation strength mixing roll air bleeding valve, mixing roll low cruise, add 108 weight portions 1) in preparation catalyst fines and the ammonia of 6.2 weight portions 15%, close strength mixing roll air bleeding valve, the mixing pug temperature to mixing roll of high speed reaches 95 DEG C, fully open the gas produced when air bleeding valve is discharged mixing, continuing mixing 35min, pug moisture content is 27.8%, end step 3；
Step 4, adds 15.8 parts by weight of glass fiber, 3.6 weight portion wood pulps, 3.2 weight portion RP-CHOP fiber and 90 parts by weight of deionized water, closes strength mixing roll air bleeding valve, the mixing 15min of high speed；
Step 5, regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, and adds 2.7 weight portion hydroxypropyl celluloses, 2.3 weight account polyethylene alcohol and 1.6 weight portion poly(ethylene oxide), closes strength mixing roll air bleeding valve, the mixing 10min of high-speed reverse；
Step 6, regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, and adds 2.7 weight portion hydroxypropyl celluloses, 2.3 weight account polyethylene alcohol and 1.6 weight portion poly(ethylene oxide), closes strength mixing roll air bleeding valve, the mixing 25min of high-speed reverse；
Step 7, fully opens strength mixing roll air bleeding valve, regulates moisture content and the plasticity of pug with the ammonia of deionized water and 15-20%, and the moisture content of pug is 28.9%, and plasticity is 24.9, mixing end；
Step 8, transfers in kneader by the pug of mixing end, carry out wet pinch mixing 1.5h and shaping of catalyst process after obtain catalyst；
In step 1-step 7,
Regulation strength mixing roll air bleeding valve, strongly the exhaust valve opening degree of mixing roll is 10-15%,
Mixing roll low cruise, when mixing roll runs, the rotating speed of rotor is 300rpm,
Mixing roll high-speed cruising, when mixing roll runs, the rotating speed of rotor is 750rpm,
The follow-up shaping of catalyst that carries out, i.e. filter pre-crowded, old, extrusion molding, be dried, roasting cutting and front end cure process process be with embodiment 1；
The catalyst of embodiment 5 preparation is under the conditions of test case, and denitration efficiency when 180 DEG C reaches 92.7%, and longitudinal comprcssive strength of catalyst is 2.55MPa, and horizontal comprcssive strength is 0.91MPa, and hardening end wear strength is 0.062%/Kg.
Test case
Evaluate the catalysis activity of catalyst in fixed bed SCR reactor using simulated flue gas as reaction gas, reacting gas composition NOx is 1000mg/m3, SO2For 200mg/m3, O2Being 6.0% (v/v), ammonia nitrogen mol ratio MR is 1.0, N2As Balance Air, reaction velocity SV=4000h-1。
Embodiment of the present invention is only that embodiment and preparation method are described in detail and are illustrated; but protection scope of the present invention is not limited to the operating process described in embodiment and step; the values such as cited raw material, raw material bound interval value and technological parameter can realize the present invention, does not i.e. mean that the present invention is necessarily dependent upon above-mentioned preparation process and step could be implemented.The technical staff in described field it should be understood that; any improvement in the present invention; to raw material, material, size equivalence replacement and the interpolation of auxiliary element or change, the selection etc. of detailed description of the invention selected by the present invention, within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
- The most cellular low-temperature denitration of flue gas catalyst, it is characterised in that include carrier, active component and help Agent, described active component and auxiliary agent be supported on carrier respectively, and described carrier is TiO2Or TiO2Answer Closing oxide, described carrier content in the catalyst is 70～90wt%；Described active component is V2O5 And WO3Or MoO3, described active component load capacity on carrier is: V2O5It is 0.3～6wt%, WO3It is 1.0～15wt% or MoO3Being 1.0～15wt%, described auxiliary agent is P2O5, described auxiliary agent is carrying Load capacity on body is: P2O5For 0.1-3wt%.
- The most cellular low-temperature denitration of flue gas catalyst, it is characterised in that described Active component also includes that rare earth oxide, described rare earth oxide load capacity on carrier are 0～20wt%, described rare earth oxide is the one in the oxide of La, Ce, Pr, Nd, Zr, Y Or it is multiple.
- The most cellular low-temperature denitration of flue gas catalyst, it is characterised in that described Auxiliary agent also includes SO3, SO3Load capacity on carrier is 0-3wt%.
- The most cellular low-temperature denitration of flue gas catalyst, it is characterised in that described Active component is prepared by active component presoma, and described active component presoma is V2O5、WO3、MoO3 And one or more in corresponding oxide, inorganic salt or the organic salt of rare earth oxide；Described auxiliary agent by Prepared by auxiliary agent presoma, described auxiliary agent presoma is P2O5、SO3Corresponding oxide, inorganic salt or One or more in organic salt.
- 5. the preparation of cellular low-temperature denitration of flue gas catalyst as described in any one of Claims 1-4 Method, comprises the steps:Prepared by S1 catalyst fines:S101 adds deionized water in a kettle. and is heated to 40-80 DEG C, adds oxalic acid or citric acid stirs Mix to after being completely dissolved, add active component presoma and auxiliary agent presoma, be sufficiently stirred for obtaining activity group Divide impregnation liquid, wherein, described V2O5Presoma is 1:(0.8-4 with the mol ratio of oxalic acid or citric acid)；The activity component impregnation liquid that S102 obtains in step S101 adds the carrier of powder, fully stirs Mix and obtain sticky shape serosity, this sticky shape serosity is processed through ultrasonic disperse and obtains catalyst slurry, its In, the mass ratio of the deionized water added in described carrier and S101 is 1:(0.9-1.4)；The catalyst slurry obtained in step S102 is dried by S103, carries out roasting after crushing, from So it is cooled to room temperature, pulverizes and obtain catalyst fines；S2 pug processes and shaping of catalyst:The catalyst fines that S103 is obtained by S201 arranges standby, regulation strength mixing roll air bleeding valve, and Catalyst fines and powder aggregate, the institute of 225-315 weight portion is added in strength mixing roll air bleeding valve Stating powder aggregate relative to the addition of catalyst fines is 3-20wt%；It is subsequently adding 2-9 weight portion Stearic acid, the lactic acid of 2-9 weight portion or oleic acid, the glycerol of 1-10 weight portion, add 150-210 weight The deionized water of amount part and the ammonia that concentration is 15-25% of 24-32 weight portion, close strength mixing roll row Air valve, the mixing 30-80min of high speed；S202 regulation strength mixing roll air bleeding valve, mixing roll low cruise, add 67-105 weight portion Catalyst fines and 10-35 weight deionized water, close strength mixing roll air bleeding valve, and high speed is mixing 10-40min；S203 regulation strength mixing roll air bleeding valve, mixing roll low cruise, add 60-130 weight portion The concentration of catalyst fines and 3-6 weight portion is the ammonia of 15-25%, closes strength mixing roll air bleeding valve, The mixing pug temperature to mixing roll of high speed reaches 90-95 DEG C, fully open air bleeding valve discharge mixing time The gas produced, continues mixing 30-60min, treats that the moisture content of pug is 25-29%, end step S203；S204 adds the glass fibre of 9-27 weight portion, the wood pulp of 2-7 weight portion, 2-7 weight portion RP-CHOP anti-crack fiber and the deionized water of 80-128 weight portion, close strength mixing roll air bleeding valve, The mixing 10-40min of high speed；S205 regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, and adds 3-14 weight portion Organic binder bond close strength mixing roll air bleeding valve, the mixing 10-30min of high-speed reverse；S206 regulation strength mixing roll air bleeding valve, mixing roll low-speed reverse is run, and adds 3-14 weight portion Organic binder bond and the ammonia that concentration is 15-25% of 2-8 weight portion, close strength mixing roll aerofluxus Valve, the mixing 15-45min of high-speed reverse；S207 opens strength mixing roll air bleeding valve, regulates pug with the ammonia of deionized water and 15-20% Plasticity and moisture content, when the plasticity of pug is 22-26, when moisture content is 28-31%, mixing end；The pug of mixing end is transferred in kneader by S208, carries out wet pinching and mixes 1-3h and catalyst Catalyst is obtained after forming process；Wherein, described regulation strength mixing roll air bleeding valve, strongly mixing roll exhaust valve opening degree is 10-15%, Described mixing roll low cruise, the rotating speed of mixing roll rotor is 250-450rpm；Described mixing roll fortune at a high speed OK, the rotating speed of mixing roll rotor is 650-850rpm.
- 6. the preparation method of cellular low-temperature denitration of flue gas catalyst described in claim 5, it is characterised in that Described S1 catalyst fines preparation process specifically includes following steps:S101 adds deionized water in a kettle. and is heated to 40-80 DEG C, adds oxalic acid or citric acid stirs Mix to being completely dissolved, be sequentially added into V2O5、WO3Or MoO3Active component presoma, or add again Enter rare earth oxide active component presoma；Add P2O5Auxiliary agent presoma, or add SO3Help Agent presoma, stirs 10-60min, obtains activity component impregnation liquid, wherein, described V at 40-80 DEG C2O5 Presoma is 1:(0.8-4 with the mol ratio of oxalic acid or citric acid)；The activity component impregnation liquid that S102 obtains in step S101 adds the carrier of powder, Obtain sticky shape serosity after stirring 10-60min at 40-80 DEG C, this sticky shape serosity ultrasonic disperse is processed 1-3h obtains catalyst slurry, wherein, and the mass ratio of the deionized water added in described carrier and S101 For 1:(0.9-1.4)；The catalyst slurry that S103 obtains in step S102 is at 200-300 DEG C of dry 2-12h, after crushing At 300-600 DEG C of roasting 2-8h, naturally cool to room temperature, be crushed to 100-300 mesh and obtain catalyst powder End.
- 7. the preparation method of cellular low-temperature denitration of flue gas catalyst described in claim 5, it is characterised in that In described S208, shaping of catalyst process specifically includes following steps:1) filter, pre-squeeze: described filtration is that pug step S208 obtained is placed in twin screw filter In, utilize mud mouth stainless steel sift net filtration, combing pug, remove impurity in pug；It is described pre-crowded, Pug after filtering carries out pre-extrusion forming, obtains square clod；2) old: by step 1) in pre-squeeze after clod under the conditions of 25-40 DEG C and humidity are 45-90% Old 12-72h；3) extrusion molding: by step 2) in old rear pug obtain cellular urging through Powerful extruder molding Agent base substrate；4) be dried: by step 3) in moisture removal in honeycombed catalyst base substrate, want reaching roasting Asking, described being dried includes that one-level is dried and secondary drying, and described one-level is dried and is increased to by room temperature 60-65 DEG C, humidity is reduced to 28-35% by 90-95%；Described secondary drying, at 45-60 DEG C of hot-air In be dried 24-72h；5) roasting, cutting: described roasting is by step 4) in catalyst base substrate after secondary drying put In mesh-belt kiln, at 200-650 DEG C of roasting 20-40h, obtain cellular low-temperature SCR catalyst, described in cut Cutting is to utilize double end band saw to cut catalyst end face, cuts the irregular part in two ends；6) front end hardening: by step 5) in cutting rear catalyst end face be placed in hardening bath dipping 2-10min, Impregnating depth is 20-40mm.
- 8. the preparation method of cellular low-temperature denitration of flue gas catalyst described in any one of claim 5 to 7, It is characterized in that, described powder aggregate includes quartz sand, glass powder with low melting point, Al2O3, silicon powder, White carbon, gas phase SiO2, clay, montmorillonite, attapulgite, aluminum phosphate, aluminium dihydrogen phosphate, plan thin One or more in diaspore, Kaolin, meerschaum, bentonite, described powder aggregate relative to The addition of catalyst fines is 3-20wt%.
- 9. the preparation method of cellular low-temperature denitration of flue gas catalyst described in any one of claim 5 to 7, It is characterized in that, described organic binder bond includes methylcellulose, hydroxypropyl methyl cellulose, carboxymethyl In cellulose, ammonium cellulose, sodium cellulosate, polyacrylamide, polyvinyl alcohol, polyethylene glycol oxide one Planting or multiple, described organic binder bond is 0.5-10wt% relative to the addition of catalyst fines.
- 10. the preparation method of cellular low-temperature denitration of flue gas catalyst described in any one of claim 5 to 7, It is characterized in that, described hardening bath is the aqueous solution of hardening medium, and described hardening medium is Al2(SO4)3 Or AlPO4Or Al (H2PO4)3, the mass concentration of described hardening medium is 10-50wt%.
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