CN114210330A - Metal titanium-based denitration catalyst and preparation method and application thereof - Google Patents
Metal titanium-based denitration catalyst and preparation method and application thereof Download PDFInfo
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- CN114210330A CN114210330A CN202111640170.2A CN202111640170A CN114210330A CN 114210330 A CN114210330 A CN 114210330A CN 202111640170 A CN202111640170 A CN 202111640170A CN 114210330 A CN114210330 A CN 114210330A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 89
- 239000002184 metal Substances 0.000 title claims abstract description 89
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000010936 titanium Substances 0.000 title claims abstract description 85
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 57
- 238000001035 drying Methods 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000000151 deposition Methods 0.000 claims abstract description 24
- 230000008021 deposition Effects 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004070 electrodeposition Methods 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 9
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims abstract description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 20
- 230000003197 catalytic effect Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000005530 etching Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 7
- 238000005488 sandblasting Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 39
- 239000011248 coating agent Substances 0.000 abstract description 38
- 230000000694 effects Effects 0.000 abstract description 15
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 21
- 229910052761 rare earth metal Inorganic materials 0.000 description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 150000002910 rare earth metals Chemical class 0.000 description 16
- 229910052717 sulfur Inorganic materials 0.000 description 16
- 239000011593 sulfur Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000006056 electrooxidation reaction Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000000866 electrolytic etching Methods 0.000 description 4
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940098458 powder spray Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
- B01J37/0226—Oxidation of the substrate, e.g. anodisation
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Abstract
The invention relates to the technical field of catalyst preparation, in particular to a metal titanium-based denitration catalyst and a preparation method and application thereof, and the following scheme is proposed, wherein the preparation method comprises the steps of dissolving a solute in a solvent, ultrasonically dispersing for 25-35min at 80-90 ℃, then stirring for 30-60min at constant temperature, standing and aging to obtain a deposition solution, stirring the deposition solution for 0.5-4h at 80-90 ℃ to obtain a first mixed solution, placing a metal titanium-based carrier in the first mixed solution for electrodeposition, drying and roasting the electrodeposited metal titanium-based carrier to obtain the metal titanium-based denitration catalyst; each liter of the solvent containsThe solute comprises 1-5g of ammonium metavanadate, 1-5g of ammonium metatungstate, 1-5g of ammonium heptamolybdate and ZrOCl2·8H2O 0.5‑1g、Ce(NO3)30.5-1g, chloroplatinic acid or chloropalladate 0.1-1g and nano TiO20.1-0.5 g. The metal titanium-based carrier prepared by the invention has the characteristics of high mechanical strength, good low-temperature activity and tight combination of the catalyst coating and the metal titanium base, and can quickly conduct and transfer heat.
Description
Technical Field
The invention relates to the field of preparation of catalysts, in particular to a metal titanium-based denitration catalyst and a preparation method and application thereof.
Background
A small amount of reports about research on metal-based SCR denitration catalysts and carriers thereof are reported, and CN102553596A discloses that a high-temperature flame powder spray gun is used for hot spraying on a metal substrate, the spraying temperature is 2500-3500 ℃, so that the surface of the substrate is in a molten state, and an aluminum oxide nano-particle inlaid large-specific-surface is formed to be beneficial to loading a catalytic coating; publication No. CN 102225332B reports that a stainless steel substrate is used as a carrier, surface modification is carried out by adopting an electric arc TiN spraying mode, then acid cleaning and etching are carried out, a specific surface is enlarged, and then loading and roasting are carried out by adopting a nano impregnation liquid coating mode to form an SCR catalyst; the binding force and the loading capacity between the carrier and the catalytic coating are increased by physical means, but the high-temperature treatment is needed, the energy consumption is large, meanwhile, the production equipment consumption is large, and the large-scale production cost is high.
Therefore, the invention provides a metal titanium-based denitration catalyst, and a preparation method and application thereof.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a metal titanium-based denitration catalyst and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a metal titanium-based denitration catalyst and a preparation method and application thereof comprise the following steps: dissolving a solute in a solvent, ultrasonically dispersing for 25-35min at 80-90 ℃, stirring for 30-60min at a constant temperature, standing and aging to obtain a deposition solution, stirring the deposition solution for 0.5-4h at 80-90 ℃ to obtain a first mixed solution, placing a metal titanium-based carrier in the first mixed solution for electrodeposition, drying and roasting the electrodeposited metal titanium-based carrier to obtain the metal titanium-based denitration catalyst(ii) a The solute contained in each liter of the solvent comprises 1-5g of ammonium metavanadate, 1-5g of ammonium metatungstate, 1-5g of ammonium heptamolybdate and ZrOCl2·8H2O 0.5-1g、Ce(NO3)30.5-1g, chloroplatinic acid or chloropalladate 0.1-1g and nano TiO20.1-0.5g。
Further, the preparation method of the metallic titanium-based carrier comprises the following steps:
step 1: placing the metal titanium alloy plate into an electrolytic bath for electrochemical surface etching, wherein the current density is 20-200A/m at 50-100 DEG C2Etching for 6-12h to obtain a first carrier plate, wherein the electrolyte in the electrolytic bath comprises 2-10 wt% of oxalic acid solution;
step 2: roasting the first carrier plate at the temperature of 300-400 ℃ for 1-2h to obtain a second carrier plate, placing the second carrier plate in a nitric acid solution with the temperature of 80-100 ℃ and the weight of 5-10% to react for 1-2h, washing and airing to obtain a third carrier plate, placing the third carrier plate in hydrogen peroxide with the weight of 1-3% for 3-6h, then roasting at the temperature of 550 ℃ for 15-25min, and cooling to obtain the metal titanium-based carrier.
Further, the preparation method of the metal titanium alloy plate comprises the steps of carrying out sand blasting and polishing on the honeycomb titanium alloy plate, then placing the polished honeycomb titanium alloy plate in 5-10 wt% of alkali solution at 80-100 ℃ for 30-120min, drying to obtain a first plate, placing the first plate in 5-10 wt% of acid solution at 80-100 ℃ for 1-2h to obtain a second plate, washing the second plate with water, placing the second plate in ethanol or acetone solution, carrying out ultrasonic treatment, and airing to obtain the metal titanium alloy plate.
Further, the alkali solution comprises NaOH and NaCO3And/or aqueous KOH.
Further, the acid solution includes an aqueous solution of oxalic acid, hydrochloric acid, sulfuric acid, and/or nitric acid.
Further, the time of the electro-deposition is 0.5-2h, and the current density is 30-50A/m2And the electrode spacing is 10-15 mm.
Furthermore, the temperature for drying the metal-based carrier subjected to electrodeposition is 50-100 ℃ and the time is 2-4h, the temperature for roasting is 400-500 ℃ and the time is 1.5-2.5 h.
Further, the solvent comprises ethanol, n-butanol, isopropanol, polyethylene glycol and water, and the weight ratio of each component in each liter of solvent is ethanol: n-butanol: isopropyl alcohol: polyethylene glycol: water-0.2: 1.6:1.6: 0.2: 6.4.
the metal titanium-based denitration catalyst prepared by the preparation method.
The metal titanium-based denitration catalyst prepared by the preparation method is applied to catalytic removal of nitrogen oxides in flue gas.
The invention has the beneficial effects that:
1. the preparation method of the metal titanium-based denitration catalyst provided by the invention is simple and easy to operate, the honeycomb titanium alloy base material is used as the raw material of the metal titanium-based carrier, the metal titanium-based carrier is obtained by processing the honeycomb titanium alloy base material, the denitration catalyst is directly formed by electrodepositing the coating liquid of the catalyst layer and is attached to the surface of the metal titanium-based carrier, and the defects of complex preparation processes of multiple extrusion, mixing, drying and roasting, high energy consumption and high pollution in the process of preparing the denitration catalyst in the traditional process are avoided;
2. the catalytic coating slurry of the metal titanium-based denitration catalyst prepared by the invention is simple in material preparation, the usage amount of titanium dioxide (titanium dioxide) and other raw materials is reduced, the prepared catalytic coating is long in service life, high in catalytic activity and good in stability, and meanwhile, the preparation method provided by the invention is simple and can be industrialized;
3. the metallic titanium-based carrier prepared by the invention has the characteristics of high mechanical strength, good thermal conductivity and close combination of the catalyst coating and the metallic titanium base, can quickly conduct and transfer heat, and has the characteristics of water resistance, sulfur resistance, high temperature resistance, corrosion resistance and good low-temperature activity.
Drawings
FIG. 1 is a flow chart of a preparation method of a metallic titanium-based denitration catalyst prepared by the present invention;
FIG. 2 is an electron micrograph of a treated metallic titanium-based carrier prepared according to the present invention of example 2;
FIG. 3 is an electron microscope image of a metallic titanium-based denitration catalyst coating prepared by the present invention in example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
1. Pretreatment of
1) Carrying out sand blasting and polishing treatment on a purchased honeycomb titanium alloy plate (TA1 or TA 2); placing the grinded honeycomb metal titanium carrier in 10 wt% hot alkali solution (NaOH, NaCO)3Mixed solution of KOH) at 90 ℃ for 120min, deoiling, and drying to obtain a first plate;
2) treating the first plate in 10 wt% oxalic acid solution at 90 ℃ for 2h, and carrying out corrosion treatment to obtain a second plate;
3) washing the second plate with deionized water, placing the second plate in an ethanol solution, performing ultrasonic treatment for 30-60min, and drying to obtain a metal titanium alloy plate;
2. preparation process of metal titanium-based carrier
1) Placing the metal titanium alloy plate into a self-made electrolytic tank for electrochemical surface etching, wherein the electroetching solution (electrolyte) is 10 wt% oxalic acid solution with the temperature of 50 ℃, the electrochemical oxidation time is 8h, and the current density is 100A/m2Electrochemically etching to obtain a first carrier plate;
2) roasting the first carrier plate at high temperature for 2 hours at the temperature of 400 ℃ to obtain a second carrier plate;
3) immersing the second carrier plate into 10 wt% nitric acid solution at 80 ℃, reacting for 2h, washing with deionized water, and airing to obtain a third carrier plate;
4) putting the third carrier plate in 3 wt% of hydrogen peroxide for 3 hours to obtain a fourth carrier plate;
5) roasting the fourth carrier plate at the roasting temperature of 500 ℃ for 20min, and cooling to room temperature to obtain the metal titanium-based carrier;
3. preparation of catalytic coating
1) The prepared catalyst layer coating liquid mainly comprises the following components:
5g of ammonium metavanadate, 5g of ammonium metatungstate, 5g of ammonium heptamolybdate and ZrOCl2·8H2O 1g、Ce(NO3)31g of chloroplatinic acid, 1g of nano TiO25g of the solvent is dissolved in 1L of the solvent, and the weight ratio of the components of the solvent is ethanol: n-butanol: isopropyl alcohol: polyethylene glycol: water 0.2:1.6:1.6: 0.2: 6.4; stirring and ultrasonically dispersing for 30min at 90 ℃, transferring to a constant-temperature 90 ℃ water bath, heating and stirring for 60min, and standing and aging for 2h to obtain a deposition solution;
2) placing the prepared deposition liquid in a reactor, stirring in a constant-temperature water bath kettle with electromagnetic stirring at 90 ℃ for 4.0h to obtain a first mixed liquid;
3) the prepared metal titanium-based carrier is put into the first mixed solution for electrodeposition, the deposition time is 2 hours, and the inter-polar distance is 15 mm;
4) drying the metal titanium-based carrier catalyst prepared in the step 2) at the drying temperature of 100 ℃ for 4.0h, and then roasting the metal titanium-based carrier catalyst at the roasting temperature of 450 ℃ for 2h to obtain the metal titanium-based denitration catalyst.
Example 2
1. Pretreatment of
1) Carrying out sand blasting and polishing treatment on a purchased honeycomb titanium alloy plate (TA1 or TA 2); placing the grinded honeycomb metal titanium carrier in 10 wt% hot alkali solution (NaOH, NaCO)3Mixed solution of KOH) at 80 ℃ for 30min, deoiling, and drying to obtain a first plate;
2) treating the first plate in 10 wt% oxalic acid solution at 80 ℃ for 1h, and performing corrosion treatment to obtain a second plate;
3) washing the second plate with deionized water, placing the second plate in an ethanol solution, performing ultrasonic treatment, and airing to obtain a metal titanium alloy plate;
2. preparation process of metal titanium-based carrier
1) Placing the metal titanium alloy plate into a self-made electrolytic tank for electrochemical surface etching, wherein the electroetching solution (electrolyte) is 2 wt% oxalic acid solution with the temperature of 50 ℃, the electrochemical oxidation time is 6h, and the current density is 20A/m2Electrochemical methodChemical etching to obtain a first carrier plate;
2) roasting the first carrier plate at high temperature for 2 hours at the temperature of 300 ℃ to obtain a second carrier plate;
3) immersing the second carrier plate into a 5 wt% nitric acid solution at 80 ℃, reacting for 1h, washing with deionized water, and airing to obtain a third carrier plate;
4) putting the third carrier plate in 1 wt% of hydrogen peroxide for 3 hours to obtain a fourth carrier plate;
5) roasting the fourth carrier plate at the roasting temperature of 450 ℃ for 20min, and cooling to room temperature to obtain the metal titanium-based carrier;
3. preparation of catalytic coating
1) The prepared catalyst layer coating liquid mainly comprises the following components:
1g of ammonium metavanadate, 1g of ammonium metatungstate, 1g of ammonium heptamolybdate and ZrOCl2·8H2O 0.5g、Ce(NO3)30.5g, chloropalladate 0.1g, nano TiO20.1g of the solvent is dissolved in 1L of the solvent, and the weight ratio of the components of the solvent is ethanol: n-butanol: isopropyl alcohol: polyethylene glycol: water 0.2:1.6:1.6: 0.2: 6.4; stirring and ultrasonically dispersing for 30min at 80 ℃, transferring to a constant-temperature 80 ℃ water bath, heating and stirring for 30min, and standing and aging for 1h to obtain a deposition solution;
2) placing the prepared deposition liquid in a reactor, stirring in a constant-temperature water bath kettle with electromagnetic stirring at the temperature of 80 ℃ for 0.5h to obtain a first mixed liquid;
3) the prepared metal titanium-based carrier is put into the first mixed solution for electrodeposition, the deposition time is 0.5h, and the inter-polar distance is 10 mm;
4) drying the metal titanium-based carrier catalyst prepared in the step 2) at the drying temperature of 50 ℃ for 0.5h, and then roasting the metal titanium-based carrier catalyst at the roasting temperature of 450 ℃ for 2h to obtain the metal titanium-based denitration catalyst.
Example 3
1. Pretreatment of
1) Carrying out sand blasting and polishing treatment on a purchased honeycomb titanium alloy plate (TA1 or TA 2); placing the grinded honeycomb metal titanium carrier in 10 wt% hot alkali solution (NaOH, NaCO)3And KOH mixed solution) at 90 ℃ for 90min, deoiling, and drying to obtain a first plate;
2) treating the first plate in 10 wt% oxalic acid solution at 90 ℃ for 1.5h, and carrying out corrosion treatment to obtain a second plate;
3) washing the second plate with deionized water, placing the second plate in an ethanol solution, performing ultrasonic treatment for 30-60min, and drying to obtain a metal titanium alloy plate;
2. preparation process of metal titanium-based carrier
1) Placing the metal titanium alloy plate into a self-made electrolytic tank for electrochemical surface etching, wherein the electroetching solution (electrolyte) is 5 wt% oxalic acid solution with the temperature of 80 ℃, the electrochemical oxidation time is 9h, and the current density is 150A/m2Electrochemically etching to obtain a first carrier plate;
2) roasting the first carrier plate at high temperature for 1.5 hours at the temperature of 350 ℃ to obtain a second carrier plate;
3) immersing the second carrier plate into 8 wt% nitric acid solution at 80 ℃, reacting for 1.5h, washing with deionized water, and airing to obtain a third carrier plate;
4) putting the third carrier plate in 2 wt% of hydrogen peroxide for 5 hours to obtain a fourth carrier plate;
5) roasting the fourth carrier plate at the roasting temperature of 500 ℃ for 20min, and cooling to room temperature to obtain the metal titanium-based carrier;
3. preparation of catalytic coating
1) The prepared catalyst layer coating liquid mainly comprises the following components:
2.5g of ammonium metavanadate, 2.5g of ammonium metatungstate, 2.5g of ammonium heptamolybdate and ZrOCl2·8H2O0.8g、Ce(NO3)30.8g, chloroplatinic acid 0.8g, nano TiO20.3g of the solvent is dissolved in 1L of the solvent, and the weight ratio of the components of the solvent is ethanol: n-butanol: isopropyl alcohol: polyethylene glycol: water 0.2:1.6:1.6: 0.2: 6.4; stirring and ultrasonically dispersing for 30min at 90 ℃, transferring to a constant-temperature 90 ℃ water bath, heating and stirring for 45min, and standing and aging for 1.5h to obtain a deposition solution;
2) placing the prepared deposition liquid in a reactor, stirring in a constant-temperature water bath kettle with electromagnetic stirring at 90 ℃ for 2.0h to obtain a first mixed liquid;
3) putting the prepared metal titanium-based carrier into the first mixed solution for electrodeposition, wherein the deposition time is 1h, and the inter-electrode distance is 15 mm;
4) drying the metal titanium-based carrier catalyst prepared in the step 2) at the drying temperature of 80 ℃ for 3.0h, and then roasting the metal titanium-based carrier catalyst at the roasting temperature of 450 ℃ for 2h to obtain the metal titanium-based denitration catalyst.
The metal titanium-based denitration catalysts prepared in the above examples 1 to 3 were tested at different temperatures under the same homemade working condition environment, and the test results are shown in table 1; the self-control working condition environment is as follows: test airspeed 20000h-1，NO:600ppm，NH3：600ppm，O：6％，SO230ppm, Ar is balance gas.
Table 1 catalytic efficiency of metallic titanium-based denitration catalysts prepared in examples 1 to 3 of the present invention at different temperatures
| 120℃ | 130℃ | 140℃ | 150℃ | 160℃ | 170℃ | 180℃ | |
| Example 1 | 8.12 | 12.86 | 16.36 | 22.34 | 55.83 | 82.87 | 96.74 |
| Example 2 | 9.22 | 13.32 | 18.65 | 26.51 | 60.11 | 85.33 | 96.13 |
| Example 3 | 10.36 | 13.23 | 17.55 | 23.86 | 57.99 | 86.89 | 96.34 |
Comparative example 1
1. Pretreatment of
Same pretreatment as in example 1:
1) carrying out sand blasting and polishing treatment on a purchased honeycomb titanium alloy plate (TA1 or TA 2); placing the grinded honeycomb metal titanium carrier in 10 wt% hot alkali solution (NaOH, NaCO)3And KOH mixed solution) at 90 ℃ for 120min, deoiling,drying to obtain a first plate;
2) treating the first plate in 10 wt% oxalic acid solution at 90 ℃ for 2h, and carrying out corrosion treatment to obtain a second plate;
3) washing the second plate with deionized water, placing the second plate in an ethanol solution, performing ultrasonic treatment for 30-60min, and drying to obtain a metal titanium alloy plate;
2. preparation process of metal titanium-based carrier
The procedure was the same as in example 1, except that no electro-oxide etching was performed:
1) roasting the metal titanium alloy plate at high temperature for 2 hours at the temperature of 400 ℃ to obtain a second carrier plate;
2) immersing the second carrier plate into 10 wt% nitric acid solution at 80 ℃, reacting for 2h, washing with deionized water, and airing to obtain a third carrier plate;
3) putting the third carrier plate in 3 wt% of hydrogen peroxide for 3 hours to obtain a fourth carrier plate;
4) roasting the fourth carrier plate at the roasting temperature of 500 ℃ for 20min, and cooling to room temperature to obtain the metal titanium-based carrier;
3. preparation of catalytic coating
The catalytic coating preparation was the same as that of example 1:
1) the prepared catalyst layer coating liquid mainly comprises the following components:
5g of ammonium metavanadate, 5g of ammonium metatungstate, 5g of ammonium heptamolybdate and ZrOCl2·8H2O 1g、Ce(NO3)31g of chloroplatinic acid, 1g of nano TiO25g of the solvent is dissolved in 1L of the solvent, and the weight ratio of the components of the solvent is ethanol: n-butanol: isopropyl alcohol: polyethylene glycol: water 0.2:1.6:1.6: 0.2: 6.4; stirring and ultrasonically dispersing for 30min at 90 ℃, transferring to a constant-temperature 90 ℃ water bath, heating and stirring for 60min, and standing and aging for 2h to obtain a deposition solution;
2) placing the prepared deposition liquid in a reactor, stirring in a constant-temperature water bath kettle with electromagnetic stirring at 90 ℃ for 4.0h to obtain a first mixed liquid;
3) the prepared metal titanium-based carrier is put into the first mixed solution for electrodeposition, the deposition time is 2 hours, and the inter-polar distance is 15 mm;
4) drying the metal titanium-based carrier catalyst prepared in the step 2) at the drying temperature of 100 ℃ for 4.0h, and then roasting the metal titanium-based carrier catalyst at the roasting temperature of 450 ℃ for 2h to obtain the metal titanium-based denitration catalyst.
Comparative example 2
1. Pretreatment of
Same pretreatment as in example 2:
1) carrying out sand blasting and polishing treatment on a purchased honeycomb titanium alloy plate (TA1 or TA 2); placing the grinded honeycomb metal titanium carrier in 10 wt% hot alkali solution (NaOH, NaCO)3Mixed solution of KOH) at 80 ℃ for 30min, deoiling, and drying to obtain a first plate;
2) treating the first plate in 10 wt% oxalic acid solution at 80 ℃ for 1h, and performing corrosion treatment to obtain a second plate;
3) washing the second plate with deionized water, placing the second plate in an ethanol solution, performing ultrasonic treatment, and airing to obtain a metal titanium alloy plate;
2. preparation process of metal titanium-based carrier
The procedure was the same as for the preparation of example 2:
1) placing the metal titanium alloy plate into a self-made electrolytic tank for electrochemical surface etching, wherein the electroetching solution (electrolyte) is 2 wt% oxalic acid solution with the temperature of 50 ℃, the electrochemical oxidation time is 6h, and the current density is 20A/m2Electrochemically etching to obtain a first carrier plate;
2) roasting the first carrier plate at high temperature for 2 hours at the temperature of 300 ℃ to obtain a second carrier plate;
3) immersing the second carrier plate into a 5 wt% nitric acid solution at 80 ℃, reacting for 1h, washing with deionized water, and airing to obtain a third carrier plate;
4) putting the third carrier plate in 1 wt% of hydrogen peroxide for 3 hours to obtain a fourth carrier plate;
5) roasting the fourth carrier plate at the roasting temperature of 450 ℃ for 20min, and cooling to room temperature to obtain the metal titanium-based carrier;
3. preparation of catalytic coating
Ce (NO) is not contained in the catalyst coating liquid3)3,ZrOCl2·8H2Rare earth element O, otherwise prepared in the same manner as in example 2:
1) the prepared catalyst layer coating liquid mainly comprises the following components:
1g of ammonium metavanadate, 1g of ammonium metatungstate, 1g of ammonium heptamolybdate, 0.1g of chloropalladite and nano TiO20.1g of the solvent is dissolved in 1L of the solvent, and the weight ratio of the components of the solvent is ethanol: n-butanol: isopropyl alcohol: polyethylene glycol: water 0.2:1.6:1.6: 0.2: 6.4; stirring and ultrasonically dispersing for 30min at 80 ℃, transferring to a constant-temperature 80 ℃ water bath, heating and stirring for 30min, and standing and aging for 1h to obtain a deposition solution;
2) placing the prepared deposition liquid in a reactor, stirring in a constant-temperature water bath kettle with electromagnetic stirring at the temperature of 80 ℃ for 0.5h to obtain a first mixed liquid;
3) the prepared metal titanium-based carrier is put into the first mixed solution for electrodeposition, the deposition time is 0.5h, and the inter-polar distance is 10 mm;
4) drying the metal titanium-based carrier catalyst prepared in the step 2) at the drying temperature of 50 ℃ for 0.5h, and then roasting the metal titanium-based carrier catalyst at the roasting temperature of 450 ℃ for 2h to obtain the metal titanium-based denitration catalyst.
Comparative example 3
1. Pretreatment of
The support preparation was prepared following the pretreatment of example 3.
2. The procedure of the preparation of the metallic titanium-based carrier was the same as that of example 3.
3. Preparation of catalytic coating
The catalyst coating solution was prepared in the same manner as in example 3, except that chloroplatinic acid was not contained:
1) the prepared catalyst layer coating liquid mainly comprises the following components:
2.5g of ammonium metavanadate, 2.5g of ammonium metatungstate, 2.5g of ammonium heptamolybdate and ZrOCl2·8H2O0.8g、Ce(NO3)30.8g of nano TiO20.3g solutionDissolving in 1L solvent, wherein the weight ratio of the components of the solvent is ethanol: n-butanol: isopropyl alcohol: polyethylene glycol: water 0.2:1.6:1.6: 0.2: 6.4; stirring and ultrasonically dispersing for 30min at 90 ℃, transferring to a constant-temperature 90 ℃ water bath, heating and stirring for 45min, and standing and aging for 1.5h to obtain a deposition solution;
2) placing the prepared deposition liquid in a reactor, stirring in a constant-temperature water bath kettle with electromagnetic stirring at 90 ℃ for 2.0h to obtain a first mixed liquid;
3) putting the prepared metal titanium-based carrier into the first mixed solution for electrodeposition, wherein the deposition time is 1h, and the inter-electrode distance is 15 mm;
4) drying the metal titanium-based carrier catalyst prepared in the step 2) at the drying temperature of 80 ℃ for 3.0h, and then roasting the metal titanium-based carrier catalyst at the roasting temperature of 450 ℃ for 2h to obtain the metal titanium-based denitration catalyst.
The metal titanium-based denitration catalysts prepared in the comparative examples 1-3 are respectively tested under the same self-made working condition environment at different temperatures, and the test results are shown in a table 2; the self-control working condition environment is as follows: test airspeed 20000h-1，NO:600ppm，NH3：600ppm，O：6％，SO230ppm, Ar is balance gas.
Table 2 catalytic efficiency of metallic titanium-based denitration catalysts prepared in comparative examples 1 to 3 at different temperatures
| 120℃ | 130℃ | 140℃ | 150℃ | 160℃ | 170℃ | 180℃ | |
| Comparative example 1 | 5.23 | 8.16 | 10.33 | 15.36 | 38.96 | 62.78 | 75.74 |
| Comparative example 2 | 5.34 | 8.64 | 10.56 | 13.22 | 35.51 | 65.63 | 75.13 |
| Comparative example 3 | 5.12 | 9.34 | 10.35 | 14.86 | 33.86 | 63.98 | 74.34 |
TABLE 3 results of different catalyst Performance experiments
According to Table 3
Passing the strength test: ultrasonic oscillation frequency is 50Hz, oscillation duration is 120min, the residual mass is dried and weighed, and the coating falling effect is verified;
and (4) conclusion: 1. the coating falling degree of the embodiment subjected to the surface treatment and the rare earth doping is obviously lower than that of the comparative example, which shows that the coating subjected to the surface treatment and the rare earth doping is well combined with the carrier firmly;
2. the firmness degree of the carrier electrooxidation treatment is obviously better than that of the untreated carrier and higher than the effect of single rare earth doping, which shows that the bonding strength of the coating and the carrier can be obviously improved by electrooxidation and rare earth doping;
passing the sulfur tolerance test: measured at 220 ℃ in an air atmosphere for 96h with 300ppm of SO2,1000ppm of NO, 1000ppm of NH3, Ar as equilibrium gas, O210% (volume fraction), GHSV of 20000 h-1;
and (4) conclusion: 1. the sulfur resistance result of the embodiment doped with rare earth and added with noble metal elements is obviously better than that of the comparative example;
2. the coating without rare earth doping has lower sulfur resistance effect
3. The coating without chloroplatinic (palladium) acid doping has lower sulfur resistance effect but higher sulfur resistance effect than the coating with rare earth doping;
4. the sulfur-resistant efficiency of the catalyst can be obviously improved by multi-component doping.
Pass the water resistance test: the measurement was carried out in an air atmosphere at 220 ℃ for 96h with 1000ppm NO, 1000ppm NH3, Ar as equilibrium gas, O210% (volume fraction), water content 20% (volume fraction), GHSV 20000 h-1;
and (4) conclusion: 1. the water-resistant effect of the embodiment doped with the rare earth and added with the noble metal element is obviously better than that of the comparative example;
2. the coating without rare earth doping has lower water-resistant effect;
3. the coating without chloroplatinic (palladium) acid doping has lower water-resistant effect but higher water-resistant effect than that of the coating with rare earth doping;
4. the multi-component doping can obviously improve the water-resistant efficiency of the catalyst.
Passing a water-resistant and sulfur-resistant synergistic test: the measurement was carried out in an air atmosphere at 250 ℃ for 96h by 300ppm SO2, water content 20% (volume fraction), 1000ppm NO, 1000ppm NH3, Ar as equilibrium gas, O210% (volume fraction), GHSV 20000 h-1;
and (4) conclusion:
1. the water resistance and sulfur resistance result of the embodiment doped with rare earth and added with noble metal elements is obviously better than that of the comparative example;
2. the coating without rare earth doping has lower water-resistant and sulfur-resistant synergistic effect;
3. the coating without chloroplatinic (palladium) acid doping has lower water-resistant and sulfur-resistant effects, but is higher than the sulfur-resistant effect only with rare earth doping;
4. the multi-component doping can obviously improve the water-resistant and sulfur-resistant efficiency of the catalyst.
Passing the load capacity test: drying the carrier before loading at 150 ℃, cooling and weighing, coating the carrier according to the methods in the embodiment and the comparative example, and then weighing correspondingly, and calculating the loading capacity of unit mass;
and (4) conclusion:
1. the load capacity of the embodiment which is subjected to carrier electrooxidation treatment, rare earth doping and noble metal element addition is obviously higher than that of the comparative example;
2. the catalyst without carrying out the electro-oxidation treatment on the surface of the carrier has poor load capacity and is lower than catalysts only doped with rare earth and noble metals;
3. the coating without rare earth doping has a lower loading, but higher than the catalyst with noble metal doping only;
4. coatings without noble metal doping have lower loadings, but are higher than catalysts without supported electrooxidation treatment;
5. the multi-component doping and carrier electro-oxidation treatment can obviously improve the carrier loading capacity.
In conclusion, the preparation method provided by the invention is simple and easy to operate, and avoids the defects of complex preparation processes of multiple extrusion, mixing, drying and roasting, high energy consumption and high pollution in the process of preparing the denitration catalyst by the traditional process;
the prepared metal titanium-based denitration catalyst has high low-temperature catalytic activity and high catalytic efficiency, and the catalyst coating is tightly and firmly combined with the titanium-based carrier; the catalyst has good water resistance and sulfur resistance effects and low consumption of active powder, can be used for catalytically removing nitrogen oxides in industrial waste gas treatment, and has high activity in sulfur-containing nitrogen oxide waste gas and high catalytic efficiency due to the sulfur resistance.
In the description of the present invention, it is to be understood that the terms "first", "second", "third", "fourth", "fifth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of a metal titanium-based denitration catalyst is characterized by comprising the following steps: the method comprises the following steps: dissolving a solute in a solvent, performing ultrasonic dispersion for 25-35min at 80-90 ℃, then stirring for 30-60min at a constant temperature, standing and aging to obtain a deposition solution, stirring the deposition solution for 0.5-4h at 80-90 ℃ to obtain a first mixed solution, placing a metal titanium-based carrier in the first mixed solution for electrodeposition, drying and roasting the electrodeposited metal titanium-based carrier to obtain a metal titanium-based denitration catalyst; the solute contained in each liter of the solvent comprises 1-5g of ammonium metavanadate, 1-5g of ammonium metatungstate, 1-5g of ammonium heptamolybdate and ZrOCl2·8H2O 0.5-1g、Ce(NO3)30.5-1g, chloroplatinic acid or chloropalladate 0.1-1g and nano TiO2 0.1-0.5g。
2. The method of claim 1, wherein the method of preparing the metallic titanium-based denitration catalyst comprises the steps of:
step 1: placing the metal titanium alloy plate into an electrolytic bath for electrochemical surface etching, wherein the current density is 20-200A/m at 50-100 DEG C2Etching for 6-12h to obtain a first carrier plate, wherein the electrolyte in the electrolytic bath comprises 2-10 wt% of oxalic acid solution;
step 2: roasting the first carrier plate at the temperature of 300-400 ℃ for 1-2h to obtain a second carrier plate, placing the second carrier plate in a nitric acid solution with the temperature of 80-100 ℃ and the weight of 5-10% to react for 1-2h, washing and airing to obtain a third carrier plate, placing the third carrier plate in hydrogen peroxide with the weight of 1-3% for 3-6h, then roasting at the temperature of 550 ℃ for 15-25min, and cooling to obtain the metal titanium-based carrier.
3. The preparation method of the metallic titanium-based denitration catalyst according to claim 2, wherein the preparation method of the metallic titanium alloy plate comprises the steps of carrying out sand blasting and polishing on the honeycomb titanium alloy plate, then placing the polished honeycomb titanium alloy plate in 5-10 wt% of alkali solution at 80-100 ℃ for 30-120min, drying to obtain a first plate, placing the first plate in 5-10 wt% of acid solution at 80-100 ℃ for 1-2h to obtain a second plate, washing the second plate with water, placing the second plate in ethanol or acetone solution, carrying out ultrasonic treatment, and airing to obtain the metallic titanium alloy plate.
4. The method of claim 3, wherein the alkali solution comprises NaOH and NaCO3And/or aqueous KOH.
5. The method of claim 3, wherein the acid solution comprises an aqueous solution of oxalic acid, hydrochloric acid, sulfuric acid and/or nitric acid.
6. The method of claim 1, wherein the electrodeposition time is 0.5-2 hours, and the current density is 30-50A/m2And the electrode spacing is 10-15 mm.
7. The method as claimed in claim 1, wherein the step of drying the electrodeposited metal-based support is carried out at a temperature of 50-100 ℃ for 2-4h, and the step of calcining is carried out at a temperature of 400-500 ℃ for 1.5-2.5 h.
8. The method for preparing a metallic titanium-based denitration catalyst according to claim 1, wherein the solvent comprises ethanol, n-butanol, isopropanol, polyethylene glycol and water, and the weight ratio of each component in each liter of solvent is ethanol: n-butanol: isopropyl alcohol: polyethylene glycol: water 0.2:1.6:1.6: 0.2: 6.4.
9. the metallic titanium-based denitration catalyst prepared by the preparation method according to any one of claims 1 to 8.
10. The metal titanium-based denitration catalyst prepared by the preparation method according to any one of claims 1 to 8 is applied to catalytic removal of nitrogen oxides in flue gas.
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| CN117816188A (en) * | 2023-11-14 | 2024-04-05 | 国能龙源催化剂江苏有限公司 | Low-temperature denitration catalyst and preparation method and application thereof |
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