CN114588950A - Preparation method of honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst - Google Patents
Preparation method of honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst Download PDFInfo
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- CN114588950A CN114588950A CN202210330595.1A CN202210330595A CN114588950A CN 114588950 A CN114588950 A CN 114588950A CN 202210330595 A CN202210330595 A CN 202210330595A CN 114588950 A CN114588950 A CN 114588950A
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 150
- 239000003054 catalyst Substances 0.000 title claims abstract description 140
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 title claims abstract description 106
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000011593 sulfur Substances 0.000 title claims abstract description 94
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 65
- 239000011248 coating agent Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000001694 spray drying Methods 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 18
- 230000001804 emulsifying effect Effects 0.000 claims description 17
- 239000010439 graphite Substances 0.000 claims description 15
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 14
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 13
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 13
- 239000011609 ammonium molybdate Substances 0.000 claims description 13
- 229940010552 ammonium molybdate Drugs 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 11
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000004254 Ammonium phosphate Substances 0.000 claims description 7
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 125000005456 glyceride group Chemical group 0.000 claims description 6
- 238000007602 hot air drying Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 claims description 4
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- 235000019438 castor oil Nutrition 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910052863 mullite Inorganic materials 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 4
- 229940117972 triolein Drugs 0.000 claims description 4
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000005696 Diammonium phosphate Substances 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 235000001727 glucose Nutrition 0.000 claims description 3
- 238000007603 infrared drying Methods 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 125000005287 vanadyl group Chemical group 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003546 flue gas Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- 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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
The application relates to a preparation method of a honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst. The preparation method of the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst comprises the following steps: adding hydrophobic TiO2The carrier is prepared into hydrophobic TiO with a surface Keggin structure2And (3) powder. The sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst is prepared by taking the catalyst as a carrier and then prepared into slurry. And (3) placing the honeycomb carrier on an automatic coating machine, adding the slurry into a slurry barrel of the automatic coating machine, and uniformly coating the slurry on the inner wall of the pore channel of the carrier by using a negative pressure suction process to obtain a blank. And then drying and roasting to obtain the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst. Compared with the similar catalyst, the catalyst has better NH performance3SCR reaction activity and sulfur-resistant hydrophobicity, and effectively reduces SO in the practical application process2And H2The adsorption of O on the surface of the catalyst has wider application range and has important value in the field of industrial flue gas denitration.
Description
Technical Field
The application relates to the technical field of SCR catalysts, in particular to a preparation method of a honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst and the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst.
Background
In recent years, most of China areas have frequent haze pollution and Nitrogen Oxides (NO)x) Is one of the main pollution sources causing air pollution. NOxThe most effective NO comes from various aspects such as automobiles, boiler combustion, industrial production and the likexThe treatment mode is SCR denitration technology, the core of the treatment mode is SCR catalyst which mainly comprises V2O5-MoO3(WO3)/TiO2. In the practical application process, the components of the flue gas are complex and often contain SO2、H2O, etc., SO2Will be at V2O5Surface oxidation to SO3Then with NH3And H2Reaction of O to NH4HSO4Occupying the active sites of the catalyst, resulting in catalyst deactivation. Therefore, the method has wide application prospect for improving the sulfur resistance and hydrophobicity of the vanadium-titanium-based SCR catalyst. The surface acidity and the redox of the catalyst are crucial to SCR reaction, the heteropoly acid compound has strong surface acidity and redox, and the heteropoly acid with a Keggin structure can adsorb NO and NH3So that it enters the secondary structure of the catalyst and replaces H2Position of O, with SO2Can not enter, and reduces NO and SO on the surface of the catalyst2Competitive adsorption ofThe sulfur resistance of the catalyst is improved. In addition, the hydrophobic material is doped into the carrier, so that H can be effectively reduced2The adsorption of O on the surface of the catalyst improves the hydrophobicity of the catalyst.
The invention utilizes the high shear technology to dope the hydrophobic material into anatase TiO2The catalyst is used as a carrier, a simple impregnation method is used for synthesizing a vanadium-titanium-based SCR catalyst with a Keggin structure, and the vanadium-titanium-based SCR catalyst is uniformly coated on a honeycomb type carrier to obtain the honeycomb type vanadium-titanium-based SCR catalyst. So far, no documents and patents report that the vanadium titanium-based catalyst is used in SCR reaction.
Therefore, in view of the above deficiencies, there is a need to provide a technical solution to overcome or at least alleviate at least one of the above-mentioned drawbacks of the prior art.
Disclosure of Invention
The technical problem that this application will be solved lies in, to the defect among the prior art, provides a road laying dirt load detection device.
In order to solve the technical problem, the application provides a preparation method of a honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst, which comprises the following steps:
preparing a hydrophobic TiO2 carrier by deionized water, ethanol and expanded graphite;
preparing a first liquid from deionized water, ammonium molybdate and ammonium phosphate;
mixing the first liquid with the hydrophobic TiO2 carrier, thereby obtaining a second liquid;
treating the second liquid to obtain hydrophobic TiO2 powder with a surface Keggin structure;
mixing vanadyl oxalate solution with the hydrophobic TiO2 powder with the surface Keggin structure to obtain third liquid;
treating the third liquid to obtain a sulfur-resistant hydrophobic vanadium-titanium-based SCR catalyst;
dispersing and emulsifying the deionized water, the sulfur-resistant hydrophobic vanadium titanium based SCR catalyst powder, a dispersing agent, a pore-expanding agent and a binder, and adjusting the pH of the solution to 8-10 by using NH 3H 2O to obtain sulfur-resistant hydrophobic vanadium titanium based SCR catalyst slurry;
coating the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry on a honeycomb carrier to obtain a sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank;
and drying and roasting the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank to obtain the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst.
Optionally, the preparing the hydrophobic TiO2 carrier from deionized water, ethanol, and expanded graphite comprises:
adding deionized water, ethanol and expanded graphite into a high-speed dispersion emulsifying machine for dispersion and emulsification treatment, adding TiO2, stirring, adding fatty glyceride and stirring;
and (3) spray-drying the stirred slurry, and then placing the slurry in a tunnel kiln for roasting to obtain the hydrophobic TiO2 carrier.
Optionally, the preparing the first liquid by deionized water, ammonium molybdate and ammonium phosphate salt comprises:
adding deionized water, ammonium molybdate and ammonium phosphate into a reaction kettle, stirring, heating the stirred solution to 40-80 ℃, continuing stirring, and then adjusting the pH of the solution to 1-2 by using HNO3 to obtain a first liquid.
Optionally, processing the second liquid to obtain the hydrophobic TiO2 powder with the surface Keggin structure includes:
and carrying out spray drying on the second liquid, and roasting the spray-dried second liquid to obtain the hydrophobic TiO2 powder with a Keggin structure on the surface.
Optionally, the treating the third liquid to obtain the sulfur-tolerant hydrophobic vanadium-titanium-based SCR catalyst comprises:
and carrying out spray drying on the third liquid, and roasting the spray-dried third liquid to obtain the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst.
Optionally, the coating the sulfur-tolerant hydrophobic vanadium titanium-based SCR catalyst slurry on a honeycomb carrier to obtain a sulfur-tolerant hydrophobic vanadium titanium-based SCR catalyst blank comprises:
obtaining a honeycomb carrier;
placing the honeycomb carrier on an automatic coating machine;
and coating the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry on the inner wall of the pore channel of the carrier by using a negative pressure suction process, thereby obtaining a sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank.
Optionally, the ammonium phosphate salt is triammonium phosphate, diammonium phosphate, or monoammonium phosphate;
the solid content of the vanadium titanium-based SCR catalyst slurry is 5-20 wt%;
the mass fraction of the dispersing agent in the slurry is 0.02-0.5 wt%;
the dispersant comprises polyacrylic acid, triolein, castor oil or ammonium polymethacrylate;
the weight percentage of the pore-expanding agent in the slurry is 0.2-2 wt%;
the pore-expanding agent comprises malonic acid, stearic acid, glucose or starch;
the mass fraction of the binder in the slurry is 0.1-2 wt%;
the binder comprises silica sol or aluminum sol;
the honeycomb carrier comprises cordierite, mullite, aluminum titanate, silicon carbide, activated alumina, zirconia or silicon nitride;
the coating amount of the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst is 100-300 g/L;
the drying method comprises hot air drying, infrared drying or microwave drying.
Optionally, the vanadyl oxalate solution is obtained by the following method:
adding deionized water and oxalic acid into a reaction kettle, adjusting the stirring speed to be 30-150 r/min, heating to 40-80 ℃, stirring for 0.1-0.5 h, then adding quantitative ammonium metavanadate, stirring for 0.1-0.5 h, and completely dissolving the ammonium metavanadate, thereby obtaining vanadyl oxalate.
Optionally, the molar ratio of oxalic acid to ammonium metavanadate is 2:1 to 5: 1.
The application also provides a honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst, which is prepared by adopting the preparation method of the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst.
Compared with the similar catalyst, the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst prepared by the preparation method of the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst has better NH3-SCR reaction activity and sulfur-resistant hydrophobicity, effectively reduces the adsorption of SO2 and H2O on the surface of the catalyst in the practical application process, has wider application range, and has important value in the field of industrial flue gas denitration.
Drawings
Fig. 1 shows the SCR activity evaluation results of catalyst samples # 1 in example 1, # 2 in example 2, and # 3 in example 3.
Fig. 2 shows the results of the sulfur-resistant water-resistant life test of catalyst samples # 1 in example 1 and # 2 in example 2 and # 3 in example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The preparation method of the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst comprises the following steps:
step 1: preparation of hydrophobic TiO by deionized water, ethanol and expanded graphite2A carrier;
step 2: preparing a first liquid from deionized water, ammonium molybdate and ammonium phosphate;
and step 3: will be firstA liquid and the hydrophobic TiO2Mixing the carriers to obtain a second liquid;
and 4, step 4: treating the second liquid to obtain hydrophobic TiO with a surface Keggin structure2Powder;
and 5: mixing vanadyl oxalate solution with the hydrophobic TiO with the surface Keggin structure2Mixing the powder to obtain a third liquid;
step 6: treating the third liquid to obtain a sulfur-resistant hydrophobic vanadium-titanium-based SCR catalyst;
and 7: dispersing and emulsifying deionized water, sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst powder, a dispersing agent, a pore-expanding agent and a binder, and then using
Adjusting the pH value of the solution to 8-10 to obtain sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry;
and 8: coating the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry on a honeycomb carrier to obtain a sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank;
and step 9: and drying and roasting the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank to obtain the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst.
Compared with the similar catalyst, the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst prepared by the preparation method of the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst has better NH3-SCR reaction activity and sulfur-resistant hydrophobicity, effectively reduces the adsorption of SO2 and H2O on the surface of the catalyst in the practical application process, has wider application range, and has important value in the field of industrial flue gas denitration.
Specifically, the method has the following advantages:
1. the expanded graphite added in the step 1 has a hydrophobic effect, and can increase the hydrophobic property of the catalyst
2. Through the steps 4-5, the Keggin structure (ammonium phosphomolybdate) prepared on the surface is a strong solid acid, so that the sulfur resistance effect is greatly improved
3. Existing SCR catalysts rarely use coating technology and do not have Keggin structures and expanded graphite.
In this example, hydrophobic TiO was prepared from deionized water, ethanol, and expanded graphite2The carrier comprises:
adding deionized water, ethanol and expanded graphite into a high-speed dispersion emulsifying machine for dispersion and emulsification treatment, and adding TiO2Stirring, and adding fatty glyceride for stirring;
spray drying the stirred slurry, and then placing the slurry in a tunnel kiln for roasting to obtain the hydrophobic TiO2And (3) a carrier.
Specifically, 150L of deionized water, 45kg of ethanol and 3kg of expanded graphite are added into a high-speed dispersion emulsifying machine, the rotating speed is adjusted to 10000rpm, the linear speed is 30m/s, and the stirring is carried out for 0.5 h. 30kg of TiO are added2And stirring for 0.5 h. Then 2.3kg of fatty glyceride was added and stirred for 2 hours. Spray drying the slurry, placing in a tunnel kiln, and roasting at 500 deg.C for 2 hr to obtain hydrophobic TiO2And (3) a carrier.
In this example, the preparation of the first liquid by deionized water, ammonium molybdate and ammonium phosphate salt comprises:
adding deionized water, ammonium molybdate and ammonium phosphate into a reaction kettle, stirring, heating the stirred solution to 40-80 ℃, continuing stirring, and then using HNO3Adjusting the pH value of the solution to 1-2 to obtain a first liquid.
Specifically, in the embodiment, a certain amount of deionized water, ammonium molybdate and ammonium phosphate are added into a reaction kettle, the stirring speed is adjusted to be 30-150 r/min, the mixture is heated to 40-80 ℃, stirred for 0.1-0.5 h, and then HNO is used3And adjusting the pH value of the solution to 1-2 to obtain a first liquid.
In this embodiment, a first liquid is mixed with the hydrophobic TiO2The carriers are mixed so as to obtain a second liquid, in particular:
adding a measured amount of hydrophobic TiO to the first liquid2And stirring the carrier for 2-6 h, for example, 80-90% of the mass fraction.
In this example, the second liquid was treated to obtain hydrophobic TiO having a surface Keggin structure2The powder comprises:
spray drying the second liquid, and roasting the spray dried second liquid to obtain the hydrophobic TiO with a Keggin structure on the surface2And (3) powder.
Specifically, the temperature of an atomizing disc of a spray dryer is adjusted to be 100-300 ℃, the rotating speed is 100-300 r/min, the second liquid is subjected to spray drying, and then the second liquid is placed in a tunnel kiln, the atmosphere is air, the temperature is 250-500 ℃, roasting is carried out for 2-6 hours, and the hydrophobic TiO with the surface Keggin structure is obtained2And (3) powder.
In this embodiment, a vanadyl oxalate solution is mixed with the hydrophobic TiO having the surface Keggin structure2Mixing the powder to obtain a third liquid, which is specifically:
adding a certain amount of hydrophobic TiO with a surface Keggin structure into vanadyl oxalate solution2And stirring the powder for 2-6 hours to obtain a third liquid.
In this embodiment, treating the third liquid to obtain the sulfur tolerant hydrophobic vanadyl-based SCR catalyst comprises:
and carrying out spray drying on the third liquid, and roasting the spray-dried third liquid to obtain the sulfur-resistant hydrophobic vanadium-titanium-based SCR catalyst.
Specifically, the temperature of an atomizing disc of a spray dryer is adjusted to be 100-300 ℃, the rotating speed is 100-300 r/min, the third liquid is subjected to spray drying, and then the third liquid is placed in a tunnel kiln, the atmosphere is air, the temperature is 250-500 ℃, and the third liquid is roasted for 2-6 hours, so that the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst is obtained.
In this example, deionized water, sulfur-tolerant hydrophobic vanadium-titanium based SCR catalyst powder, dispersant, pore-expanding agent and binder were subjected to dispersion and emulsification treatment, and then used
Adjusting the pH value of the solution to 8-10 to obtain the sulfur-resistant hydrophobic vanadium-titanium-based SCR catalyst slurryThe method specifically comprises the following steps:
adding a certain amount of deionized water, sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst powder, a dispersing agent, a pore-expanding agent and a binder into a high-speed dispersion emulsifying machine, adjusting the rotating speed of the high-speed dispersion emulsifying machine to 1100-14000 rpm and the linear speed of the high-speed dispersion emulsifying machine to 23-44 m/s, and then using the high-speed dispersion emulsifying machine
And adjusting the pH value of the solution to 8-10, stirring for 2-4 h, and measuring the average particle size of the solution to be 0.5-5 mu m to obtain the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry.
In this embodiment, coating the sulfur-tolerant hydrophobic vanadium titanium based SCR catalyst slurry on a honeycomb carrier to obtain a sulfur-tolerant hydrophobic vanadium titanium based SCR catalyst green body comprises:
obtaining a honeycomb carrier;
placing the honeycomb carrier on an automatic coating machine;
and coating the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry on the inner wall of the pore channel of the carrier by using a negative pressure suction process, thereby obtaining a sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank.
The method specifically comprises the following steps: placing a cuboid honeycomb carrier with the length of 100-200 mm, the width of 100-200 mm and the height of 100-1000 mm on an automatic coating machine, then adding the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry into a slurry barrel of the automatic coating machine, adjusting the pressure of the automatic coating machine to be less than or equal to-90 kPa, and uniformly coating the slurry on the inner wall of a pore channel of the carrier by utilizing a negative pressure suction process to obtain a sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank.
In this embodiment, the drying and roasting treatment is performed on the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank, so as to obtain the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst, which specifically comprises:
and (3) placing the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank in drying equipment, drying at the temperature of 90-120 ℃ for 0.5-1 h, and then placing in a tunnel kiln, wherein the atmosphere is air, and the temperature is 350-550 ℃ for 2-6 h, so as to obtain the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst.
In this embodiment, the ammonium phosphate salt is triammonium phosphate, diammonium phosphate, or monoammonium phosphate;
in the embodiment, the solid content of the vanadium-titanium-based SCR catalyst slurry is 5-20 wt%;
in the embodiment, the mass fraction of the dispersant in the slurry is 0.02-0.5 wt%;
in this embodiment, the dispersant comprises polyacrylic acid, triolein, castor oil, or ammonium polymethacrylate;
in the embodiment, the weight fraction of the pore-expanding agent in the slurry is 0.2-2 wt%;
in this embodiment, the pore-enlarging agent comprises malonic acid, stearic acid, glucose or starch;
in the embodiment, the mass fraction of the binder in the slurry is 0.1-2 wt%;
in the present embodiment, the binder includes silica sol or aluminum sol;
in the present embodiment, the honeycomb carrier comprises cordierite, mullite, aluminum titanate, silicon carbide, activated alumina, zirconia, or silicon nitride;
in the embodiment, the coating amount of the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst is 100-300 g/L;
in the present embodiment, the drying method includes hot air drying, infrared drying, or microwave drying.
In this example, the vanadyl oxalate solution was obtained as follows:
adding deionized water and oxalic acid into a reaction kettle, adjusting the stirring speed to be 30-150 r/min, heating to 40-80 ℃, stirring for 0.1-0.5 h, then adding quantitative ammonium metavanadate, and stirring for 0.1-0.5 h to completely dissolve the ammonium metavanadate, thereby obtaining vanadyl oxalate.
Specifically, a certain amount of deionized water and oxalic acid are added into a reaction kettle, the stirring speed is adjusted to be 30-150 r/min, the mixture is heated to 40-80 ℃, stirred for 0.1-0.5 h, then a certain amount of ammonium metavanadate is added, the mixture is stirred for 0.1-0.5 h, the ammonium metavanadate is completely dissolved, the solution is blue, and the chemical component of the solution is vanadyl oxalate.
In the embodiment, the molar ratio of oxalic acid to ammonium metavanadate is 2:1 to 5: 1.
Example 1:
adding 150L of deionized water, 45kg of ethanol and 3kg of expanded graphite into a high-speed dispersion emulsifying machine, adjusting the rotating speed to 10000rpm and the linear speed to 30m/s, and stirring for 0.5 h. 30kg of TiO are added2And stirring for 0.5 h. Then 2.3kg of fatty glyceride was added and stirred for 2 hours. Spray drying the slurry, placing in a tunnel kiln, and roasting at 500 deg.C for 2 hr to obtain hydrophobic TiO2And (3) a carrier. Adding 100L deionized water, 2.26kg ammonium molybdate and 0.16kg triammonium phosphate into a reaction kettle, heating to 60 deg.C, stirring at 100r/min for 0.2h, and adding HNO3The pH of the solution was adjusted to 1 and 18kg of hydrophobic TiO was added2The carrier was stirred for 2 h. Spray drying the slurry at the atomizing disc temperature of 150 deg.C and rotation speed of 200r/min, and calcining in tunnel kiln at 500 deg.C in air atmosphere for 2 hr to obtain hydrophobic TiO with Keggin structure2And (3) powder. Adding 100L of deionized water and 2.97kg of oxalic acid into a reaction kettle, heating to 60 ℃, stirring for 0.2h, then adding 0.77kg of ammonium metavanadate, stirring for 0.5h, and then adding 18.2kg of hydrophobic TiO with Keggin structure2Stirring the powder for 2 hours. And (3) carrying out spray drying on the slurry, wherein the temperature of an atomizing disc of a spray dryer is 150 ℃, the rotating speed is 200r/min, then placing the slurry in a tunnel kiln, and roasting at 250 ℃ for 2h and at 500 ℃ for 2h in an air atmosphere to obtain the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst powder. Adding 20L of deionized water, 2kg of sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst powder, 0.03kg of polyacrylic acid, 0.1kg of malonic acid and 0.05kg of silica sol into a high-speed dispersion emulsifying machine, adjusting the rotating speed to 10000rpm and the linear speed to 30m/s, and then using
And adjusting the pH value of the solution to 10, stirring for 3h, and obtaining the sulfur-resistant hydrophobic vanadium-titanium-based SCR catalyst slurry with the average particle size of 1 mu m. Placing a cuboid cordierite honeycomb carrier with the length of 150mm, the width of 150mm and the height of 100mm on an automatic coating machine, then adding sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry into a slurry barrel of the automatic coating machine, and uniformly coating the slurry on the pores of the carrier by utilizing the negative pressure (less than or equal to-90 kPa) of the automatic coating machineOn the inner wall, the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst embryo is obtained. And (3) placing the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank in hot air drying equipment, adjusting the temperature of the drying equipment to be 100 ℃, drying for 1h, and then roasting for 2h in a tunnel kiln at 500 ℃ to obtain the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst.
Example 2:
adding 150L of deionized water, 45kg of ethanol and 3kg of expanded graphite into a high-speed dispersion emulsifying machine, adjusting the rotating speed to 10000rpm and the linear speed to 30m/s, and stirring for 0.5 h. 30kg of TiO are added2And stirring for 0.5 h. Then, 2.3kg of fatty acid glyceride was added and stirred for 2 hours. Spray drying the slurry, placing in a tunnel kiln, and roasting at 500 deg.C for 2 hr to obtain hydrophobic TiO2And (3) a carrier. Adding 100L of deionized water, 2.26kg of ammonium molybdate and 0.16kg of diammonium hydrogen phosphate into a reaction kettle, heating to 60 ℃, stirring at the rotating speed of 100r/min for 0.2h, and then using HNO3The pH of the solution was adjusted to 1 and 18kg of hydrophobic TiO was added2The carrier was stirred for 2 h. Spray drying the slurry at the atomizing disc temperature of 150 deg.C and rotation speed of 200r/min, and calcining in tunnel kiln at 500 deg.C in air atmosphere for 2 hr to obtain hydrophobic TiO with Keggin structure2And (3) powder. Adding 100L of deionized water and 5.56kg of oxalic acid into a reaction kettle, heating to 60 ℃, stirring for 0.2h, then adding 1.44kg of ammonium metavanadate, stirring for 0.5h, and then adding 20kg of hydrophobic TiO with Keggin structure2Stirring the powder for 2 hours. And (3) spray-drying the slurry, wherein the temperature of an atomizing disc of a spray dryer is 150 ℃, the rotating speed is 200r/min, then placing the slurry in a tunnel kiln, and roasting the slurry for 2h at 250 ℃ and 2h at 500 ℃ in an air atmosphere to obtain the sulfur-resistant hydrophobic vanadium-titanium-based SCR catalyst powder. Adding 20L of deionized water, 3kg of sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst powder, 0.04kg of triolein, 0.12kg of stearic acid and 0.06kg of silica sol into a high-speed dispersion emulsifying machine, adjusting the rotating speed to 10000rpm and the linear speed to 30m/s, and then using
Adjusting pH of the solution to 10, stirring for 3 hr to obtain a solution with average particle size of 1.5 μmA sulfur hydrophobic vanadium titanium based SCR catalyst slurry. Placing a cuboid mullite honeycomb carrier with the length of 150mm, the width of 150mm and the height of 200mm on an automatic coating machine, then adding the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry into a slurry barrel of the automatic coating machine, and uniformly coating the slurry on the inner wall of a pore channel of the carrier by using the negative pressure (less than or equal to-90 kPa) of the automatic coating machine to obtain a sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank. And (3) placing the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank in hot air drying equipment, adjusting the temperature of the drying equipment to be 100 ℃, drying for 1h, and then roasting for 2h in a tunnel kiln at 500 ℃ to obtain the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst.
Example 3:
adding 150L of deionized water, 45kg of ethanol and 3kg of expanded graphite into a high-speed dispersion emulsifying machine, adjusting the rotating speed to 10000rpm and the linear speed to 30m/s, and stirring for 0.5 h. 30kg of TiO are added2And stirring for 0.5 h. Then 2.3kg of fatty glyceride was added and stirred for 2 hours. Spray drying the slurry, placing in a tunnel kiln, and roasting at 500 deg.C for 2 hr to obtain hydrophobic TiO2And (3) a carrier. Adding 100L deionized water, 2.26kg ammonium molybdate and 0.16kg ammonium dihydrogen phosphate into a reaction kettle, heating to 60 deg.C, stirring at 100r/min for 0.2h, and adding HNO3The pH of the solution was adjusted to 1 and 18kg of hydrophobic TiO was added2The carrier was stirred for 2 h. Spray drying the slurry at the atomizing disc temperature of 150 deg.C and rotation speed of 200r/min, and calcining in tunnel kiln at 500 deg.C in air atmosphere for 2 hr to obtain hydrophobic TiO with Keggin structure2And (3) powder. Adding 100L of deionized water and 2.97kg of oxalic acid into a reaction kettle, heating to 60 ℃, stirring for 0.2h, then adding 0.77kg of ammonium metavanadate, stirring for 0.5h, and then adding 16kg of hydrophobic TiO with Keggin structure2Stirring the powder for 2 hours. And (3) spray-drying the slurry, wherein the temperature of an atomizing disc of a spray dryer is 150 ℃, the rotating speed is 200r/min, then placing the slurry in a tunnel kiln, and roasting the slurry for 2h at 250 ℃ and 2h at 500 ℃ in an air atmosphere to obtain the sulfur-resistant hydrophobic vanadium-titanium-based SCR catalyst powder. 20L of deionized water, 4kg of sulfur-resistant hydrophobic vanadium titanium based SCR catalyst powder, 0.05kg of castor oil, 0.14kg of glucose and 0.07kg of siliconAdding the sol into a high-speed dispersion emulsifying machine, adjusting the rotation speed to 10000rpm and the linear speed to 30m/s, and then using
And adjusting the pH value of the solution to 10, stirring for 3h, and obtaining the sulfur-resistant hydrophobic vanadium-titanium-based SCR catalyst slurry with the average particle size of 0.5 mu m. Placing a cuboid silicon carbide honeycomb carrier with the length of 150mm, the width of 150mm and the height of 300mm on an automatic coating machine, then adding the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry into a slurry barrel of the automatic coating machine, and uniformly coating the slurry on the inner wall of a pore channel of the carrier by using the negative pressure (less than or equal to-90 kPa) of the automatic coating machine to obtain a sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank. And (3) placing the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank in hot air drying equipment, adjusting the temperature of the drying equipment to be 100 ℃, drying for 1h, and then roasting for 2h in a tunnel kiln at 500 ℃ to obtain the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst.
Test example 1:
the SCR activity test was performed on the catalyst samples # 1 in example 1, # 2 in example 2 and # 3 in example 3, respectively, under the following test conditions: 1000ppm NH3，1000ppm NO，6％O2，N2For balancing gas, the space velocity is 3,000h-1. The test results (fig. 1) show that: the 1#, 2# and 3# catalyst samples all had higher NH3SCR reaction activity, NO conversion can reach 100% at a temperature of 200 ℃, wherein the SCR activity of the 2# catalyst sample is optimal.
Test example 2:
the sulfur-resistant and water-resistant life test was carried out on the catalyst samples # 1 in example 1, # 2 in example 2 and # 3 in example 3, respectively, under the following test conditions: 1000ppm NH3，1000ppm NO，6％O2，50ppm SO2，10％H2O，N2For balancing gas, the space velocity is 3,000h-1The reaction temperature was constant at 200 ℃. The test results (fig. 2) show that: when 50ppm SO was fed into the reaction system2And 10% of H2After O, the NO conversion rates of the No. 1, No. 2 and No. 3 catalyst samples are reduced to be small, and after 20h, the NO conversion rates are reduced to be about 90%, and the No. 1, No. 2 and No. 3 catalysts can be foundThe agent samples all have better sulfur-resistant and water-resistant performances, wherein the sulfur-resistant and water-resistant performances of the No. 2 catalyst sample are the best.
The application also provides a honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst, which is prepared by adopting the preparation method of the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.
Claims (10)
1. A preparation method of a honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst is characterized by comprising the following steps of:
preparation of hydrophobic TiO by deionized water, ethanol and expanded graphite2A carrier;
preparing a first liquid from deionized water, ammonium molybdate and ammonium phosphate;
mixing the first liquid with the hydrophobic TiO2Mixing the carriers to obtain a second liquid;
treating the second liquid to obtain hydrophobic TiO with a surface Keggin structure2Powder;
mixing vanadyl oxalate solution with the hydrophobic TiO with the surface Keggin structure2Mixing the powder to obtain a third liquid;
treating the third liquid to obtain a sulfur-resistant hydrophobic vanadium-titanium-based SCR catalyst;
dispersing and emulsifying the deionized water, the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst powder, the dispersant, the pore-enlarging agent and the binder, and then using
Adjusting the pH value of the solution to 8-10 to obtain sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry;
coating the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry on a honeycomb carrier to obtain a sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank;
and drying and roasting the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank to obtain the honeycomb type sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst.
2. The method of preparing the honeycomb sulfur-tolerant hydrophobic vanadium titanium-based SCR catalyst of claim 1, wherein the preparation of the hydrophobic TiO by deionized water, ethanol, and expanded graphite2The carrier comprises:
adding deionized water, ethanol and expanded graphite into a high-speed dispersion emulsifying machine for dispersion and emulsification treatment, and adding TiO2Stirring, and adding fatty glyceride for stirring;
spray drying the stirred slurry, and then placing the slurry in a tunnel kiln for roasting to obtain the hydrophobic TiO2And (3) a carrier.
3. The method of preparing a honeycomb sulfur-tolerant hydrophobic vanadyl-based SCR catalyst of claim 2, wherein the preparing the first liquid with deionized water, ammonium molybdate, and ammonium phosphate salt comprises:
adding deionized water, ammonium molybdate and ammonium phosphate into a reaction kettle, stirring, heating the stirred solution to 40-80 ℃, continuing stirring, and then using HNO3Adjusting the pH value of the solution to 1-2 to obtain a first liquid.
4. The method of preparing the honeycomb sulfur-tolerant hydrophobic vanadium titanium-based SCR catalyst of claim 3, wherein the second liquid is treated to obtain hydrophobic TiO with surface Keggin structure2The powder comprises:
spray drying the second liquid, and roasting the spray dried second liquid to obtain the hydrophobic TiO with a surface Keggin structure2And (3) powder.
5. The method of preparing a honeycomb-type sulfur-tolerant hydrophobic vanadium titanium-based SCR catalyst of claim 4, wherein the treating the third liquid to obtain the sulfur-tolerant hydrophobic vanadium titanium-based SCR catalyst comprises:
and carrying out spray drying on the third liquid, and roasting the spray-dried third liquid to obtain the sulfur-resistant hydrophobic vanadium-titanium-based SCR catalyst.
6. The method of preparing the honeycomb-type sulfur-tolerant hydrophobic vanadium-titanium-based SCR catalyst of claim 5, wherein the step of coating the sulfur-tolerant hydrophobic vanadium-titanium-based SCR catalyst slurry on the honeycomb carrier to obtain the sulfur-tolerant hydrophobic vanadium-titanium-based SCR catalyst green body comprises the steps of:
obtaining a honeycomb carrier;
placing the honeycomb carrier on an automatic coating machine;
and coating the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst slurry on the inner wall of the pore channel of the carrier by using a negative pressure suction process, thereby obtaining a sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst blank.
7. The method of preparing the honeycomb sulfur-tolerant hydrophobic vanadium titanium based SCR catalyst of claim 6, wherein the ammonium phosphate salt is triammonium phosphate, diammonium phosphate or monoammonium phosphate;
the solid content of the vanadium titanium-based SCR catalyst slurry is 5-20 wt%;
the mass fraction of the dispersant in the slurry is 0.02-0.5 wt%;
the dispersant comprises polyacrylic acid, triolein, castor oil or ammonium polymethacrylate;
the weight percentage of the pore-expanding agent in the slurry is 0.2-2 wt%;
the pore-expanding agent comprises malonic acid, stearic acid, glucose or starch;
the mass fraction of the binder in the slurry is 0.1-2 wt%;
the binder comprises silica sol or aluminum sol;
the honeycomb carrier comprises cordierite, mullite, aluminum titanate, silicon carbide, activated alumina, zirconia or silicon nitride;
the coating amount of the sulfur-resistant hydrophobic vanadium titanium-based SCR catalyst is 100-300 g/L;
the drying method comprises hot air drying, infrared drying or microwave drying.
8. The method for preparing the honeycomb type sulfur-tolerant hydrophobic vanadyl-based SCR catalyst of any one of claims 1 to 7, wherein the vanadyl oxalate solution is obtained by the following method:
adding deionized water and oxalic acid into a reaction kettle, adjusting the stirring speed to be 30-150 r/min, heating to 40-80 ℃, stirring for 0.1-0.5 h, then adding quantitative ammonium metavanadate, stirring for 0.1-0.5 h, and completely dissolving the ammonium metavanadate, thereby obtaining vanadyl oxalate.
9. The preparation method of the honeycomb type sulfur-tolerant hydrophobic vanadium titanium-based SCR catalyst according to claim 8, wherein the molar ratio of oxalic acid to ammonium metavanadate is 2:1 to 5: 1.
10. A honeycomb-type sulfur-tolerant hydrophobic vanadyl-SCR catalyst, characterized in that it is made by the method of any one of claims 1 to 9.
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