CN112547047A - Method for preparing nano manganese dioxide catalyst by freeze drying method - Google Patents
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- CN112547047A CN112547047A CN201910913585.9A CN201910913585A CN112547047A CN 112547047 A CN112547047 A CN 112547047A CN 201910913585 A CN201910913585 A CN 201910913585A CN 112547047 A CN112547047 A CN 112547047A
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- polyvinyl alcohol
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- permanganate
- manganese
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 19
- 238000004108 freeze drying Methods 0.000 title claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 36
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001868 water Inorganic materials 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 5
- 150000002696 manganese Chemical class 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 24
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- 229940099607 manganese chloride Drugs 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 17
- 239000012855 volatile organic compound Substances 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000002440 industrial waste Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000006385 ozonation reaction Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/16—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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- 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
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/22—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
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Abstract
The invention provides a preparation method and application of a nano manganese dioxide catalyst. The preparation method of the catalyst comprises the steps of firstly preparing a mixed solution of polyvinyl alcohol and permanganate, then dropwise adding a divalent manganese salt solution into the mixed solution at a constant speed to react to obtain sol, then removing water in the sol by using a vacuum freeze drying technology to obtain black foamy solid mixed by the polyvinyl alcohol and the manganese dioxide, and finally calcining the solid to obtain the product of nano manganese dioxide powder. The preparation process is simple, the raw materials are easy to obtain, the catalyst can be used as a catalyst for catalyzing ozone oxidation, the catalytic activity of the catalyst is high, and the catalyst can be used for catalyzing ozone oxidation of industrial waste gas and indoor air volatile organic compounds.
Description
Technical Field
The invention relates to the technical field of environment inorganic nano materials and environment treatment, in particular to a preparation method of a catalyst for catalyzing ozone to oxidize volatile organic compounds.
Background
Volatile Organic Compounds (VOCs) are a common type of atmospheric pollutants, and the emission of VOCs waste gas causes a series of problems of health, environment, production safety and the like. Therefore, exploring the purification treatment method of VOCs, reducing the discharge of VOCs is beneficial to improving the quality of atmospheric environment, protecting ecological environment and guaranteeing human health, and is also an urgent need for sustainable development of social economy.
In the field of waste gas treatment, catalytic ozonation is an effective method for treating VOCs, for example, CN201510377785.9 discloses a catalyst for catalytic ozonation of VOCs, the catalyst is composed of a metal composite oxide containing manganese, tin, cerium and antimony, the preparation cost of the catalyst is low, and the catalytic activity is high. In addition, CN201810389568.5 also discloses a catalyst for catalyzing ozone to oxidize VOCs, which is composed of an aluminum oxide carrier and a metal composite oxide, and has a large specific surface area and good stability.
Cn201410323516.x discloses a preparation method of porous manganese dioxide, which is a spongy three-dimensional porous structure; CN201410472977.3 discloses a method for preparing manganese dioxide with various structures by using permanganate and ethylene glycol to prepare rod-shaped basic manganese oxide under hydrothermal conditions, and then calcining to prepare nano rod-shaped manganese oxide, but the above patent discloses a method for preparing manganese dioxide with various structures. The common manganese dioxide has larger particle size and smaller specific surface area, and the nano manganese dioxide has finer particles and is well applied in many fields. The nano manganese dioxide catalyst prepared by the vacuum freeze-drying method can be applied to catalytic ozonation of VOCs. The vacuum freeze-drying technology is a technology that a substance containing a large amount of moisture is cooled and frozen into a solid in advance, and then water vapor is directly sublimated from the solid under the vacuum condition, so that a dried product is obtained, and the structure of the substance is not damaged. The nano manganese dioxide prepared by the preparation method has large specific surface area and good chemical stability, and can catalyze ozone to oxidize VOCs and degrade the VOCs into H2O and CO2The redundant ozone can be catalytically decomposed into oxygen, and secondary pollution can not be caused.
Disclosure of Invention
The invention discloses a method for preparing a nano manganese dioxide catalyst by utilizing a freeze-drying method, which aims to improve the deep oxidation of ozone to VOCs (volatile organic compounds) and further degrade the VOCs into CO2And H2O and the like.
The preparation method of the nano manganese dioxide comprises the following steps:
(1) mixing polyvinyl alcohol and deionized water according to a certain mass ratio, heating and stirring to obtain a polyvinyl alcohol aqueous solution;
(2) adding permanganate with certain quality into the polyvinyl alcohol aqueous solution obtained in the step (1) to obtain a mixed solution of polyvinyl alcohol and permanganate;
(3) preparing a manganous salt solution, and dropwise adding the manganous salt solution into the mixed solution of the polyvinyl alcohol and the permanganate in the step (2) at a constant speed to react to obtain sol;
(4) fully pre-freezing the sol obtained in the step (3), and then putting the sol into a vacuum freeze dryer for freeze drying to obtain black foam-like solid mixed by polyvinyl alcohol and manganese dioxide;
(5) and (4) calcining the solid obtained in the step (4) to obtain the nano manganese oxide powder.
In the step (1), the mass ratio of polyvinyl alcohol to water is 0.1-10%.
In the step (2), the permanganate solution is one or a mixture of potassium permanganate solution and sodium permanganate solution, and the mass ratio of the polyvinyl alcohol to the permanganate is 4: 1-1: 2.
In the step (3), the manganous salt solution is one or a mixture of more of a manganese chloride solution, a manganese sulfate solution, a manganese nitrate solution and a manganese acetate solution, and the concentration of the manganous salt solution is 0.01-0.6 mol/L.
In the step (4) of the preparation method, the drying process is a vacuum freeze drying technology.
In the step (5) of the preparation method, the calcining temperature is 200-600 ℃, and the calcining time is 4-10 hours.
Detailed Description
The following will further illustrate the application of the freeze-drying method of the present invention to prepare nano manganese dioxide catalyst and catalyze ozone to oxidize VOCs by specific examples.
Example 1: 6g of polyvinyl alcohol is weighed into a beakerAdding 100ml of pure water, and then putting the beaker into a water bath heating pot at 70 ℃ to heat and stir for 30min to obtain a clear and transparent polyvinyl alcohol aqueous solution. 3.16g of potassium permanganate solid was added to the polyvinyl alcohol solution cooled to room temperature to form a mixed solution of polyvinyl alcohol and potassium permanganate. Weighing 10.74g of a 50% manganese nitrate solution by mass fraction, and fixing the volume to a 100ml volumetric flask to prepare 0.3mol/L manganese nitrate solution. 100ml of manganese nitrate solution is dropwise added into a mixed solution of polyvinyl alcohol and potassium permanganate at a constant speed by using a peristaltic pump to form sol, the sol is fully pre-frozen at a low temperature, and then the sol is placed in a freeze dryer with a cold trap temperature of-50 ℃ and a working pressure of 10 Pa for freeze drying for 12 hours to obtain black foam-shaped solid of the polyvinyl alcohol and the manganese dioxide. And putting the solid into a muffle furnace, and calcining for 4 hours at 400 ℃ to obtain the nano manganese dioxide powder. Evaluation of catalyst Performance: the volume of the catalyst was 0.7mL, the gas flow rate was 125mL/min, and the inlet concentration of toluene was 60mg/m3The inlet concentration of ozone is 1000 mg/m3The measured toluene removal rate is 97%, the carbon dioxide selectivity is 60%, ozone is detected at an outlet, the ozone degradation efficiency is 98%, the operation is carried out for 40 hours, and the catalyst performance is stable.
Example 2: weighing 7g of polyvinyl alcohol and adding 100ml of pure water into a beaker, and then putting the beaker into a 70 ℃ water bath heating pot to heat and stir for 30min to obtain a clear and transparent polyvinyl alcohol aqueous solution. 3.16g of potassium permanganate solid was added to the polyvinyl alcohol solution cooled to room temperature to form a mixed solution of polyvinyl alcohol and potassium permanganate. 4.53g of anhydrous manganese sulfate solid is weighed and dissolved in pure water to prepare 100ml of 0.3mol/L manganese sulfate solution. 100ml of manganese sulfate solution is dropwise added into a mixed solution of polyvinyl alcohol and potassium permanganate at a constant speed by using a peristaltic pump to form sol, the sol is fully pre-frozen at a low temperature, and then the sol is placed in a freeze dryer with a cold trap temperature of-50 ℃ and a working pressure of 10 Pa for freeze drying for 12 hours to obtain black foam-shaped solid of the polyvinyl alcohol and the manganese dioxide. And putting the solid into a muffle furnace, and calcining for 4 hours at 300 ℃ to obtain the nano manganese dioxide powder. Evaluation of catalyst Performance: the volume of the catalyst was 0.7mL, the gas flow rate was 125mL/min, and the inlet concentration of toluene was 60mg/m3The inlet concentration of ozone is 1000 mg/m3The measured toluene purification rate is 94%, the carbon dioxide selectivity is 63%, ozone is detected at an outlet, the ozone degradation efficiency is 97%, the operation is carried out for 40 hours, and the catalyst performance is stable.
Example 3: weighing 8g of polyvinyl alcohol and adding 100ml of pure water into a beaker, and then putting the beaker into a 70 ℃ water bath heating pot to heat and stir for 30min to obtain a clear and transparent polyvinyl alcohol aqueous solution. 3.16g of potassium permanganate solid was added to the polyvinyl alcohol solution cooled to room temperature to form a mixed solution of polyvinyl alcohol and potassium permanganate. 3.78g of anhydrous manganese chloride solid is weighed and dissolved in pure water to prepare 100ml of 0.3mol/L manganese chloride solution. 100ml of manganese chloride solution is dropwise added into a mixed solution of polyvinyl alcohol and potassium permanganate at a constant speed by using a peristaltic pump to form sol, the sol is fully pre-frozen at a low temperature, and then the sol is placed in a freeze dryer with a cold trap temperature of-50 ℃ and a working pressure of 10 Pa for freeze drying for 12 hours to obtain black foam-shaped solid of the polyvinyl alcohol and the manganese dioxide. And putting the solid into a muffle furnace, and calcining for 4 hours at 300 ℃ to obtain the nano manganese dioxide powder. Evaluation of catalyst Performance: the volume of the catalyst was 0.7mL, the gas flow rate was 125mL/min, and the inlet concentration of toluene was 60mg/m3The inlet concentration of ozone is 1000 mg/m3And the measured toluene purification rate is 92%, the carbon dioxide selectivity is 65%, ozone is detected at an outlet, the ozone degradation efficiency is 95%, the operation lasts for 40 hours, and the catalyst performance is stable.
Claims (6)
1. A method for preparing nano manganese dioxide catalyst by utilizing freeze drying method comprises the following steps:
mixing polyvinyl alcohol and deionized water according to a certain mass ratio, heating and stirring to obtain a polyvinyl alcohol aqueous solution;
adding permanganate with certain quality into the polyvinyl alcohol aqueous solution obtained in the step (1) to obtain a mixed solution of polyvinyl alcohol and permanganate;
preparing a divalent manganese salt solution, and dropwise adding the divalent manganese salt solution into the mixed solution of the polyvinyl alcohol and the permanganate in the step (2) at a constant speed to react to obtain sol;
fully pre-freezing the sol obtained in the step (3), and then putting the sol into a vacuum freeze dryer for freeze drying to obtain black foam-like solid mixed by polyvinyl alcohol and manganese dioxide;
and (4) calcining the solid obtained in the step (4) to obtain the nano manganese oxide powder.
2. The method for preparing the catalyst according to claim 1, wherein the mass ratio of the polyvinyl alcohol to the water in the step (1) is 0.1% to 10%.
3. The preparation method of the catalyst according to claim 1, wherein the permanganate solution in step (2) is one or a mixture of potassium permanganate solution and sodium permanganate solution, and the mass ratio of the polyvinyl alcohol to the permanganate is 4: 1-1: 2.
4. The method for preparing the catalyst according to claim 1, wherein the manganous salt solution in the step (3) is one or more of a manganese chloride solution, a manganese sulfate solution, a manganese nitrate solution and a manganese acetate solution, and the concentration of the manganous salt solution is 0.01-0.6 mol/L.
5. The method for preparing a catalyst according to claim 1, wherein the drying process used in step (4) is a vacuum freeze-drying technique.
6. The method of preparing a catalyst according to claim 1, wherein the calcination temperature in the step (5) is 200 to 600 ℃ and the calcination time is 4 to 10 hours.
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| CN113648992A (en) * | 2021-09-09 | 2021-11-16 | 北京化工大学 | Preparation method of catalyst for catalyzing ozone to oxidize chlorine-containing volatile organic compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113648992A (en) * | 2021-09-09 | 2021-11-16 | 北京化工大学 | Preparation method of catalyst for catalyzing ozone to oxidize chlorine-containing volatile organic compounds |
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