CN115364868A - Catalyst for catalytic decomposition of ozone and preparation method thereof - Google Patents
Catalyst for catalytic decomposition of ozone and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000003421 catalytic decomposition reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 41
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 24
- 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 abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000000919 ceramic Substances 0.000 claims abstract description 7
- 239000004480 active ingredient Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 31
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 20
- LBKJNHPKYFYCLL-UHFFFAOYSA-N potassium;trimethyl(oxido)silane Chemical compound [K+].C[Si](C)(C)[O-] LBKJNHPKYFYCLL-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 8
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 8
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000001771 vacuum deposition Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 14
- 239000007789 gas Substances 0.000 abstract description 9
- 238000011282 treatment Methods 0.000 abstract description 8
- 239000010865 sewage Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- 239000006255 coating slurry Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005949 ozonolysis reaction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000010792 warming Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention relates to a catalytic decomposition ozone catalyst and a preparation method thereof, belonging to the technical field of waste gas treatment. The catalyst takes cordierite honeycomb ceramic as a substrate, and a carrier and an active component are coated on the substrate, wherein the carrier is hydrophobic nano K 2 O‑SiO 2 ‑TiO 2 The active ingredient is MnO 2 、V 2 O 5 And Fe 2 O 3 . The catalyst prepared by the invention has excellent catalytic ozone decomposition performance and water poisoning resistance, when the catalyst is used in tail gas of sewage treatment and other industries with the humidity of more than 80%, the ozone removal rate can be stably maintained at more than 95% for a long time, and the service life of the catalyst can reach 3-5 years.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for catalytically decomposing ozone and a preparation method thereof.
Background
The ozone is used as an oxidant to treat pollutants, has the obvious advantages of high efficiency, environmental protection and the like, and has the market occupation ratio of over 50 percent in sewage treatment, sterilization, disinfection, air purification and the like. However, during the use of ozone, the discharge of excess ozone into the environment can have adverse effects such as global warming, oxidation of building materials, and harm to human health. In recent years, SO has been increased with increasing national environmental protection 2 、NO x CO, PM2.5, PM10, etc. have been effectively controlled. Ozone emission control is also becoming an important direction for air pollution control.
Common ozone treatment technologies comprise thermal decomposition, activated carbon decomposition, plasma decomposition, photocatalytic decomposition, catalytic decomposition and the like, wherein the catalytic decomposition technology has the advantages of high decomposition efficiency, small occupied space, good safety and the like, and is the technology which is most researched at home and abroad at present. The tail gas discharged by industries such as sewage treatment and the like has the characteristics of high ozone concentration, low temperature, high humidity and the like, and when the catalyst is used for decomposing ozone in the field, water poisoning is the first difficulty of a catalytic decomposition technology. In the high-humidity exhaust gas, water vapor and ozone compete for adsorption on the surface of the catalyst to cover the active sites of the catalyst, so that the activity of the catalyst is greatly reduced in a short time and cannot be used continuously.
Disclosure of Invention
The invention aims to solve the problem that the catalytic activity of the catalyst is greatly reduced in a short time and the catalyst cannot be used continuously because the existing catalyst for decomposing ozone is easy to generate a catalyst water poisoning phenomenon in the field of water treatment, and provides a catalyst for catalytically decomposing ozone, which has strong water poisoning resistance, high ozone removal rate and long service life, and a preparation method thereof.
The invention adopts the following technical scheme: catalytic decomposition of odorThe catalyst comprises a substrate and a coating layer on the surface of the substrate, wherein the coating layer is formed by loading active components on a carrier, the catalyst substrate is cordierite honeycomb ceramic, and the catalyst carrier is nano-scale K 2 O-SiO 2 -TiO 2 The active component of the catalyst is MnO 2 、V 2 O 5 And Fe 2 O 3 The carrier accounts for 80-88% of the total mass of the coating layer, and the active component accounts for 12-20% of the total mass of the coating layer.
Further, the nanoscale K 2 O-SiO 2 -TiO 2 Middle K 2 O、SiO 2 And TiO 2 The mass ratio is 47.
Further, the nanoscale K 2 O-SiO 2 -TiO 2 The particle size of the carrier is 2-10 nm.
Further, mnO as an active ingredient 2 、V 2 O 5 And Fe 2 O 3 The mass ratio is 2.
The preparation method of the catalyst for catalytically decomposing ozone comprises the following steps:
(1) Matrix pretreatment: completely immersing cordierite honeycomb ceramic into a dilute hydrochloric acid solution with the volume concentration of 5%, taking out the cordierite honeycomb ceramic after 5-6 h, and drying the cordierite honeycomb ceramic for later use;
(2) Nanoscale K 2 O-SiO 2 -TiO 2 Preparing a carrier: weighing potassium trimethylsilanolate and tetrabutyl titanate according to a proportion, dissolving the potassium trimethylsilanolate by using cold water with the solid mass of 10-15 times, slowly adding the tetrabutyl titanate into the potassium trimethylsilanolate solution, and stirring the solution for 2 h; adding ammonia water to adjust the pH value of the solution to 9.5-10.5, then heating the solution to 85 ℃, and keeping stirring for 4 h-6 h; filtering to obtain a precipitated solid, drying the obtained solid at 110 ℃ to obtain 12 h, and roasting at 450 ℃ to obtain 4 h to obtain nano K 2 O-SiO 2 -TiO 2 A carrier;
(3) Preparing coating layer slurry: weighing manganese acetate tetrahydrate, ammonium metavanadate and ferric nitrate nonahydrate according to a proportion, adding ammonium metavanadate into hot water at 95 ℃, slowly adding ethanolamine to completely dissolve ammonium metavanadate, and adding manganese acetate tetrahydrate and ferric nitrate nonahydrateStirring the ferric nitrate till the ferric nitrate is completely dissolved, wherein the water consumption for dissolving the ammonium metavanadate is K 2 O-SiO 2 -TiO 2 1.2 to 1.5 times of the mass of the carrier; the nano-scale K prepared in the step (2) 2 O-SiO 2 -TiO 2 Adding the carrier into the solution, stirring for 30min with a high-speed stirrer, adding sodium carboxymethylcellulose, polyacrylamide and appropriate amount of water under stirring, and stirring to obtain a solution with viscosity of 150 mm 2 /s～210 mm 2 Coating layer slurry/s;
(4) Coating of a catalyst: coating a cordierite honeycomb substrate in a vacuum coating mode;
(5) Roasting the catalyst: and roasting the coated catalyst to obtain the catalytic decomposition ozone catalyst, wherein the roasting temperature rise program is that 1 h is heated to 80 ℃, the temperature is kept for 12 hours, the temperature is heated to 450 ℃ for 6 hours, and the temperature is kept for 6 h.
Further, the addition amount of the sodium carboxymethyl cellulose in the step (3) is nano-scale K 2 O-SiO 2 -TiO 2 5-10% of the carrier, the addition of the polyacrylamide is nano-scale K 2 O-SiO 2 -TiO 2 0.5-1.5% of the carrier.
The advantages of the invention are as follows:
(1) Excellent water resistance: the invention adopts potassium trimethylsilanolate and tetrabutyl titanate as raw materials to prepare the nanoscale K 2 O-SiO 2 -TiO 2 Carriers, during preparation, nanoscale K formed 2 O and SiO 2 Is uniformly dispersed in-TiO 2 Surface while K 2 O and SiO 2 The surface of the formed carrier has extremely strong hydrophobicity, so that the adsorption of water on the surface of the catalyst can be remarkably reduced in high-humidity tail gas, the activity of the catalyst can be kept stable for a long time in the tail gas with the humidity of more than 80%, and the service life of the catalyst can be as long as 3-5 years;
(2) Strong ozone decomposition capacity: at different roasting temperatures, manganese acetate is decomposed to form different products, and when the roasting temperature of the catalyst is 450 ℃, alpha-MnO is formed 2 Active components to make the catalyst have stronger electron transfer capacity and ensureHigh ozonolysis rate, active component V 2 O 5 And Fe 2 O 3 The addition of the catalyst can enhance the oxidation performance of the catalyst, promote the ozonolysis reaction and further improve the ozonolysis rate;
(3) Nanoscale K 2 O-SiO 2 -TiO 2 K in the vector + Can promote lattice defects and generate oxygen vacancies, and the oxygen vacancies can be combined with oxygen atoms in ozone molecules to break chemical bonds among the oxygen atoms in the ozone molecules, promote the decomposition of ozone and improve the activity of the catalyst. Furthermore, K + And the adsorption rate and the adsorption quantity of the ozone can be enhanced through the acting force between the ozone and O atoms in the ozone, the completion of the ozone decomposition reaction is facilitated, and the ozone decomposition capacity is improved.
Drawings
FIG. 1 is a graph showing the results of comparative tests on the ozonolysis rate and stability of catalysts of examples 1 to 4 of the present invention and comparative examples.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying figures are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be embodied in other specific forms than those described herein, and it will be apparent to those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the present invention.
The catalyst prepared by the invention can be used in various environments such as sewage treatment tail gas, indoor air purifiers and the like.
Example 1:
a preparation method of a catalyst for catalytically decomposing ozone comprises the following steps:
(1) Matrix pretreatment: completely immersing the cordierite honeycomb into a dilute hydrochloric acid solution with the volume concentration of 5%, taking out the cordierite honeycomb after 6 h and drying the cordierite honeycomb for later use;
(2) Nano K 2 O-SiO 2 -TiO 2 Preparation of the carrier: cooling with 120 kgDissolving 12 kg potassium trimethylsilanolate in water, slowly adding 42.6 kg tetrabutyl titanate into potassium trimethylsilanolate solution and stirring 2 h; adding ammonia water to adjust the pH value of the solution to 9.5, then heating the solution to 85 ℃, and keeping stirring 4 h; filtering to obtain a precipitated solid, drying the obtained solid at 110 ℃ to obtain 12 h, and roasting at 450 ℃ to obtain 4 h to obtain nano K 2 O-SiO 2 -TiO 2 A carrier;
(3) Preparation of coating slurry: adding 1.61 kg ammonium metavanadate into 24 kg hot water, slowly adding ethanolamine to completely dissolve the ammonium metavanadate, then adding 7.05 kg manganese acetate tetrahydrate and 6.31 kg ferric nitrate nonahydrate, and stirring until the ammonium metavanadate is completely dissolved; step 2 preparation K 2 O-SiO 2 -TiO 2 Adding the carrier into the solution, stirring for 30min by using a high-speed stirrer, then adding 1 kg sodium carboxymethyl cellulose, 0.3 kg polyacrylamide and 40 kg water, and uniformly stirring to obtain coating slurry;
(4) Catalyst coating and calcination: coating a cordierite honeycomb substrate in a vacuum coating mode;
(5) Roasting the catalyst: and roasting the coated catalyst to obtain the catalytic decomposition ozone catalyst, wherein the roasting temperature rise program is that 1 h is heated to 80 ℃, the temperature is kept for 12 hours, the temperature is heated to 450 ℃ for 6 hours, and the temperature is kept for 6 h.
The catalytic ozone decomposition catalyst prepared by the steps comprises the following components: 10% MnO 2 、5%V 2 O 5 、5%Fe 2 O 3 And 80% of K 2 O-SiO 2 -TiO 2 。
Example 2:
a preparation method of a catalyst for catalytically decomposing ozone comprises the following steps:
(1) Matrix pretreatment: completely immersing the cordierite honeycomb into a dilute hydrochloric acid solution with the volume concentration of 5%, taking out the cordierite honeycomb after 6 h and drying the cordierite honeycomb for later use;
(2) Nano K 2 O-SiO 2 -TiO 2 Preparing a carrier: dissolving 12 kg potassium trimethylsilanolate in 180 kg cold water, slowly adding 42.6 kg tetrabutyl titanate to the potassium trimethylsilanolate solution and stirring 2 h; adding ammonia water to adjust the pH value of the solution to 10.5, then heating the solution to 85 ℃, and keeping stirring for 6 h;filtering to obtain a precipitated solid, drying the obtained solid at 110 ℃ to obtain 12 h, and roasting at 450 ℃ to obtain 4 h to obtain nano K 2 O-SiO 2 -TiO 2 A carrier;
(3) Preparation of coating slurry: adding 0.88 kg ammonium metavanadate into 30 kg hot water, slowly adding ethanolamine to completely dissolve the ammonium metavanadate, then adding 3.85 kg manganese acetate tetrahydrate and 3.44 kg ferric nitrate nonahydrate, and stirring until the ammonium metavanadate is completely dissolved; step 2 preparation K 2 O-SiO 2 -TiO 2 Adding the carrier into the solution, stirring for 30min by using a high-speed stirrer, then adding 2 kg sodium carboxymethyl cellulose, 0.1 kg polyacrylamide and 30 kg water, and uniformly stirring to obtain coating slurry;
(4) Coating of a catalyst: coating the cordierite honeycomb substrate in a vacuum coating mode;
(5) Roasting the catalyst: roasting the coated catalyst to obtain the catalytic decomposition ozone catalyst, wherein the roasting temperature rise program is that 1 h is heated to 80 ℃, the temperature is kept for 12 hours, 6 hours are heated to 450 ℃, and the temperature is kept for 6 h.
The catalytic decomposition ozone catalyst prepared by the steps comprises the following components: 6% MnO 2 、3%V 2 O 5 、3%Fe 2 O 3 And 88% of K 2 O-SiO 2 -TiO 2 。
Example 3:
a preparation method of a catalyst for catalytically decomposing ozone comprises the following steps:
(1) Matrix pretreatment: completely immersing the cordierite honeycomb into a dilute hydrochloric acid solution with the volume concentration of 5%, taking out the cordierite honeycomb after 6 h and drying the cordierite honeycomb for later use;
(2) Nano K 2 O-SiO 2 -TiO 2 Preparing a carrier: dissolving 12 kg potassium trimethylsilanolate in 140 kg cold water, slowly adding 42.6 kg tetrabutyl titanate to the potassium trimethylsilanolate solution and stirring 2 h; adding ammonia water to adjust the pH value of the solution to 10, then heating the solution to 85 ℃, and keeping stirring for 4 h; filtering to obtain a precipitated solid, drying the obtained solid at 110 ℃ to obtain 12 h, and roasting at 450 ℃ to obtain 4 h to obtain the nano K 2 O-SiO 2 -TiO 2 A carrier;
(3) Preparation of coating slurry:adding 1.23 kg ammonium metavanadate into 26 kg hot water, slowly adding ethanolamine to completely dissolve the ammonium metavanadate, then adding 5.37 kg manganese acetate tetrahydrate and 4.81 kg ferric nitrate nonahydrate, and stirring until the ammonium metavanadate is completely dissolved; step 2 preparation K 2 O-SiO 2 -TiO 2 Adding the carrier into the solution, stirring for 30min by using a high-speed stirrer, then adding 1.5 kg sodium carboxymethyl cellulose, 0.2 kg polyacrylamide and 36 kg water, and uniformly stirring to obtain coating slurry;
(4) Coating of a catalyst: coating a cordierite honeycomb substrate in a vacuum coating mode;
(5) Roasting the catalyst: roasting the coated catalyst to obtain the catalytic decomposition ozone catalyst, wherein the roasting temperature rise program is that 1 h is heated to 80 ℃, the temperature is kept for 12 hours, 6 hours are heated to 450 ℃, and the temperature is kept for 6 h.
The catalytic decomposition ozone catalyst prepared by the steps comprises the following components: 8% MnO 2 、4%V 2 O 5 、4%Fe 2 O 3 And 84% of K 2 O-SiO 2 -TiO 2 。
Example 4:
a preparation method of a catalyst for catalytically decomposing ozone comprises the following steps:
(1) Matrix pretreatment: completely immersing the cordierite honeycomb into a dilute hydrochloric acid solution with the volume concentration of 5%, taking out and drying the cordierite honeycomb after 6 h for later use;
(2) Nano K 2 O-SiO 2 -TiO 2 Preparing a carrier: dissolving 12 kg potassium trimethylsilanolate in 160 kg cold water, slowly adding 42.6 kg tetrabutyl titanate to the potassium trimethylsilanolate solution and stirring 2 h; adding ammonia water to adjust the pH value of the solution to 9.5, then heating the solution to 85 ℃, and keeping stirring 4 h; filtering to obtain a precipitated solid, drying the obtained solid at 110 ℃ to obtain 12 h, and roasting at 450 ℃ to obtain 4 h to obtain the nano K 2 O-SiO 2 -TiO 2 A carrier;
(3) Preparation of coating slurry: adding 1.41 kg ammonium metavanadate into 27 kg hot water, slowly adding ethanolamine to completely dissolve the ammonium metavanadate, then adding 6.19 kg manganese acetate tetrahydrate and 5.54 kg ferric nitrate nonahydrate, and stirring until the ammonium metavanadate is completely dissolved; step 2 preparation K 2 O-SiO 2 -TiO 2 Adding the carrier into the solution, stirring for 30min by using a high-speed stirrer, then adding 1.8 kg sodium carboxymethyl cellulose, 0.25 kg polyacrylamide and 41 kg water, and stirring to obtain coating slurry;
(4) Coating of a catalyst: coating a cordierite honeycomb substrate in a vacuum coating mode;
(5) Roasting the catalyst: and roasting the coated catalyst to obtain the catalytic decomposition ozone catalyst.
The catalytic ozone decomposition catalyst prepared by the steps comprises the following components: 9% MnO 2 、4.5%V 2 O 5 、4.5%Fe 2 O 3 And 82% of K 2 O-SiO 2 -TiO 2 。
Comparative example: the catalyst used for removing ozone from tail gas in sewage treatment industry is used as a comparative example, and the catalyst is Pd-Mn/ZSM-5, wherein the content of Pd is 0.75 percent, and MnO is used 2 The content was 13.7%.
Comparative example 1 and examples 1-4 were tested for ozone removal and stability: wherein: the simulated gas has a moisture content of 85%, an ozone concentration of 900 ppm, a gas temperature of 45 ℃ and an airspeed of 6000 h -1 The test results are shown in FIG. 1.
As can be seen from fig. 1, the catalysts of the comparative example and the example both have a high ozone decomposition rate at the beginning of the test, but the activity of the catalyst of the comparative example gradually decreases with the increase of the test time, and the ozone decomposition rate finally stabilizes at about 66% during the test time. In the embodiment, the activity of the catalyst only fluctuates slightly, and the ozone decomposition rate is always kept above 95%. The test results show that the catalytic decomposition ozone catalyst provided by the invention has stronger water resistance and is obviously superior to the commercial catalyst of the comparative example.
Claims (7)
1. A catalyst for catalytically decomposing ozone, characterized by: the catalyst comprises a substrate and a coating layer on the surface of the substrate, wherein the coating layer is formed by loading active components on a carrier, the substrate of the catalyst is cordierite honeycomb ceramic, and the carrier of the catalyst is nano-scale K 2 O-SiO 2 -TiO 2 The active component of the catalyst is MnO 2 、V 2 O 5 And Fe 2 O 3 The carrier accounts for 80-88% of the total mass of the coating layer, and the active component accounts for 12-20% of the total mass of the coating layer.
2. The catalyst for catalytic decomposition of ozone according to claim 1, wherein: the nanoscale K 2 O-SiO 2 -TiO 2 Middle K 2 O、SiO 2 And TiO 2 The mass ratio is 47.
3. The catalyst for catalytic decomposition of ozone according to claim 1, wherein: the nanoscale K 2 O-SiO 2 -TiO 2 The particle size of (A) is 2-10 nm.
4. The catalyst for catalytic decomposition of ozone according to claim 1, wherein: the active ingredient MnO 2 、V 2 O 5 And Fe 2 O 3 The mass ratio is 2.
5. The method for preparing a catalyst for catalytic decomposition of ozone as claimed in any one of claims 1 to 4, wherein: the method comprises the following steps:
(1) Matrix pretreatment: completely immersing cordierite honeycomb ceramic into a dilute hydrochloric acid solution with the volume concentration of 5%, taking out and drying after 5-6 h for later use;
(2) Nanoscale K 2 O-SiO 2 -TiO 2 Preparing a carrier: weighing potassium trimethylsilanolate and tetrabutyl titanate according to a proportion, dissolving the potassium trimethylsilanolate by using cold water with the solid mass of 10-15 times, slowly adding the tetrabutyl titanate into the potassium trimethylsilanolate solution, and stirring the solution for 2 h; adding ammonia water to adjust the pH value of the solution to 9.5-10.5, then heating the solution to 85 ℃, and keeping stirring for 4 h-6 h; filtering to obtain a precipitated solid, drying the obtained solid at 110 ℃ to obtain 12 h, and roasting at 450 ℃ to obtain 4 h to obtain nano K 2 O-SiO 2 -TiO 2 A carrier;
（3）preparing coating layer slurry: weighing manganese acetate tetrahydrate, ammonium metavanadate and ferric nitrate nonahydrate according to a proportion, adding ammonium metavanadate into hot water at 95 ℃, slowly adding ethanolamine to completely dissolve ammonium metavanadate, adding manganese acetate tetrahydrate and ferric nitrate nonahydrate, stirring until completely dissolving, wherein the water consumption for dissolving ammonium metavanadate is K 2 O-SiO 2 -TiO 2 1.2-1.5 times of the carrier; the nano-scale K prepared in the step (2) 2 O-SiO 2 -TiO 2 Adding the carrier into the solution, stirring for 30min with a high-speed stirrer, adding sodium carboxymethylcellulose, polyacrylamide and appropriate amount of water under stirring, and stirring to obtain a solution with viscosity of 150 mm 2 /s～210 mm 2 Coating layer slurry/s;
(4) Coating of a catalyst: coating a cordierite honeycomb substrate in a vacuum coating mode;
(5) Roasting the catalyst: and roasting the coated catalyst to obtain the catalytic decomposition ozone catalyst.
6. The method of preparing a catalyst for catalytic decomposition of ozone according to claim 5, wherein: the addition amount of the sodium carboxymethylcellulose in the step (3) is nano-scale K 2 O-SiO 2 -TiO 2 5-10% of the carrier, the addition of the polyacrylamide is nano-scale K 2 O-SiO 2 -TiO 2 0.5-1.5% of the carrier.
7. The method of producing a catalyst for catalytic decomposition of ozone according to claim 5, wherein: the roasting temperature-raising program in the step (5) is divided into two stages: the temperature is raised to 80 ℃ in 1 h in the first stage, the temperature is kept for 12 h, and the temperature is raised to 450 ℃ in 6 h in the second stage, and the temperature is kept for 6 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116408067A (en) * | 2023-04-10 | 2023-07-11 | 陕煤集团榆林化学有限责任公司 | Organic matter removal catalyst and preparation method and application thereof |
| RU2811231C1 (en) * | 2023-11-14 | 2024-01-11 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" | Catalytic block material for ozone decomposition based on cordierite ceramics, method for purifying air from ozone using it |
| CN117816253A (en) * | 2024-03-06 | 2024-04-05 | 无锡威孚环保催化剂有限公司 | Ozone decomposition catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101612575A (en) * | 2009-07-10 | 2009-12-30 | 天津大学 | Fe 2O 3And V 2O 5The use for diesel engine Catalysts and its preparation method of double activity component |
| CN103769080A (en) * | 2014-01-22 | 2014-05-07 | 东风商用车有限公司 | Diesel vehicle tail gas purification SCR catalyst and preparation method thereof |
| CN106861675A (en) * | 2016-12-30 | 2017-06-20 | 大连瑞克科技有限公司 | Cordierite honeycomb ceramic is integrated low temperature denitrating catalyst of matrix and preparation method thereof |
-
2022
- 2022-08-30 CN CN202211050876.8A patent/CN115364868B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101612575A (en) * | 2009-07-10 | 2009-12-30 | 天津大学 | Fe 2O 3And V 2O 5The use for diesel engine Catalysts and its preparation method of double activity component |
| CN103769080A (en) * | 2014-01-22 | 2014-05-07 | 东风商用车有限公司 | Diesel vehicle tail gas purification SCR catalyst and preparation method thereof |
| CN106861675A (en) * | 2016-12-30 | 2017-06-20 | 大连瑞克科技有限公司 | Cordierite honeycomb ceramic is integrated low temperature denitrating catalyst of matrix and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116408067A (en) * | 2023-04-10 | 2023-07-11 | 陕煤集团榆林化学有限责任公司 | Organic matter removal catalyst and preparation method and application thereof |
| RU2811231C1 (en) * | 2023-11-14 | 2024-01-11 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" | Catalytic block material for ozone decomposition based on cordierite ceramics, method for purifying air from ozone using it |
| CN117816253A (en) * | 2024-03-06 | 2024-04-05 | 无锡威孚环保催化剂有限公司 | Ozone decomposition catalyst and preparation method thereof |
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