CN113648992A - Preparation method of catalyst for catalyzing ozone to oxidize chlorine-containing volatile organic compounds - Google Patents
Preparation method of catalyst for catalyzing ozone to oxidize chlorine-containing volatile organic compounds Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 239000000460 chlorine Substances 0.000 title claims abstract description 19
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 14
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 12
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000006104 solid solution Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 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 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- -1 transition metal salt Chemical class 0.000 claims description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 6
- 230000000607 poisoning effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 3
- 239000004744 fabric Substances 0.000 abstract 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NEGBOTVLELAPNE-UHFFFAOYSA-N [Ti].[Ce] Chemical compound [Ti].[Ce] NEGBOTVLELAPNE-UHFFFAOYSA-N 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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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
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/0201—Impregnation
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a catalyst for catalyzing ozone to oxidize chlorine-Containing Volatile Organic Compounds (CVOCs). The catalyst mainly comprises MnCeOxIs prepared from active component through template process and vacuum drying process. The preparation process is simple, the raw materials are easy to obtain, and the method can effectively utilize the template agent to enable the manganese-cerium solid solution to form a specific structure and increase the specific surface area of the manganese-cerium solid solution; the surface and even the inner part of the two transition metal oxides can be improvedUniformity of the cloth, more Mn-Ce-O bonds are formed, chlorine species are made to react with HCl and Cl2Is removed in the form of (1). The catalyst prepared by the invention can catalyze ozone to oxidize CVOCs into CO at room temperature2、H2O、HCl、Cl2And the like, has excellent low-temperature redox activity, chlorine poisoning resistance and higher CO2And (4) selectivity.
Description
Technical Field
The invention relates to the technical field of environment, in particular to a preparation method of a catalyst for catalyzing ozone to oxidize chlorine-containing volatile organic compounds.
Background
Volatile Organic Compounds (VOCs) are organic chemical substances with high vapor pressure and volatility at normal temperature and normal pressure, and are important precursors for forming atmospheric pollution such as haze, photochemical smog and the like. chlorine-Containing Volatile Organic Compounds (CVOCs) are a class with a high content of VOCs and are widely used as production raw materials, solvents, refrigerants and the like. Most CVOCs have the characteristics of strong volatility, poor degradability, high toxicity and the like, and partial CVOCs even have the effect of causing three causes, so that the environmental quality is seriously influenced, and the human health is also greatly threatened. Therefore, it is urgent to find a practical and effective technique for controlling CVOCs.
The chlorine-containing volatile organic compounds have chlorine atoms which are difficult to convert in the environment, and are liable to cause catalyst poisoning and deactivation. In order to solve the problem of chlorine poisoning of the catalyst, scholars at home and abroad make a great deal of research work and develop a series of composite metal (or oxide) chlorine-resistant catalysts. CN 112588289A discloses a high CO2The selective CVOCs removing catalyst is prepared with titanium oxide as carrier, transition metal oxide as active component and noble metal Pd as modifying component. CN 101402047A discloses a catalyst for CVOCs catalytic combustion and a preparation method thereof, the cerium titanium nanotube catalyst prepared by the method can effectively remove dichloroethane and has strong chlorine poisoning resistance.
In recent years, the technology of catalyzing ozone to oxidize VOCs has attracted much attention because of the advantages of high purification efficiency, no secondary pollution, no need of auxiliary heating, etc. However, few studies on this technology have been reported to deal with CVOCs. The invention prepares a mesoporous manganese-cerium solid solution catalyst by utilizing a template method and a vacuum drying method. The preparation process is simple, the raw materials are easy to obtain, and the method can effectively utilize the template agent to enable the manganese-cerium solid solution to form a specific structure and increase the specific surface area of the manganese-cerium solid solution; can also improve the uniformity of the surface and even internal distribution of two transition metal oxides, form more Mn-Ce-O bonds, and make chlorine species adopt HCl and Cl2Is removed in the form of (1). Catalyst prepared by the inventionThe oxidant can catalyze ozone to oxidize CVOCs into CO at room temperature2、H2O、HCl、Cl2And the like, has excellent low-temperature redox activity, chlorine poisoning resistance and higher CO2And (4) selectivity.
Disclosure of Invention
The invention discloses a preparation method of a catalyst for catalyzing ozone to oxidize chlorine-containing volatile organic compounds. Aims to degrade CVOCs into CO by improving the deep oxidation of ozone to the CVOCs and the chlorine poisoning resistance of the catalyst2、H2O、HCl、Cl2And the like.
The preparation method of the manganese-cerium solid solution catalyst comprises the following steps:
(1) adding manganese salt and cerium salt into pure water, and stirring and dissolving to obtain manganese-cerium salt mixed solution;
(2) soaking the mesoporous silicon template agent in a manganese-cerium salt mixed solution, and then centrifuging to remove a soaking solution;
(3) drying the impregnated product obtained in the step (2) in vacuum and then calcining to obtain a manganese-cerium solid solution precursor;
(4) adopting an alkali solution to dip the manganese-cerium solid solution precursor obtained in the step (3), dissolving a template agent in the manganese-cerium solid solution precursor, filtering, and washing a filter cake to be neutral by pure water;
(5) and drying the filter cake in vacuum to obtain the mesoporous manganese-cerium solid solution catalyst.
In the preparation method, the manganese salt in the step (1) is one or a mixture of more of manganese chloride, manganese sulfate, manganese acetate and manganese nitrate; the cerium salt is one or a mixture of cerium chloride, cerium sulfate and cerium nitrate; the molar ratio of manganese to cerium is from 1:4 to 4: 1.
In the preparation method, the template agent in the step (2) is one or a mixture of more of SBA-15, SBA-16, KIT-6 and MCM-41, and the mass ratio of the template agent to the transition metal salt is 5:4 to 5: 1; the dipping condition is magnetic stirring for 4-10 hours.
In the step (3), the vacuum drying temperature is 60-100 ℃, and the time is 5-14 hours; the calcination temperature is 200-600 ℃ and the calcination time is 4-10 hours.
The alkali solution in the step (4) of the preparation method is one or two mixed solutions of sodium hydroxide and potassium hydroxide, and the concentration is 1-3 mol/L; the dipping condition is magnetic stirring for 4-10 hours.
In the step (5), the vacuum drying temperature is 60-100 ℃, and the time is 5-14 hours.
Drawings
Fig. 1 is a flowchart of a method for preparing a mesoporous manganese-cerium solid solution catalyst according to an embodiment of the present invention;
FIG. 2 is a transmission electron micrograph of a catalyst made according to an embodiment of the invention.
Detailed Description
Example 1: 20g of 50% manganese nitrate solution and 12g of cerium nitrate hexahydrate were dissolved in 130ml of pure water by thoroughly stirring for 30 min. Adding 6g of SBA-15 template agent into the manganese-cerium salt mixed solution, magnetically stirring and soaking at room temperature for 10 hours, and centrifuging to obtain a white solid. And (3) putting the white solid in a vacuum drying oven, drying for 12 hours at the temperature of 60 ℃, and then calcining for 4 hours in a muffle furnace at the temperature of 400 ℃ to obtain a brown manganese-cerium solid solution precursor. Dissolving the manganese-cerium solid solution precursor in 150ml of 2mol/L sodium hydroxide solution, stirring, soaking for 6 hours, filtering, washing a filter cake to pH 7 with pure water, and drying the filter cake in a vacuum drying oven at 60 ℃ for 12 hours to obtain the mesoporous manganese-cerium solid solution catalyst for catalyzing ozone oxidation CVOCs. Evaluation of catalyst Performance: the mass of the catalyst was 0.5g, the gas flow was 125ml/min, and the inlet concentration of dichloroethane was 150mg/m3The ozone concentration at the inlet is 1000mg/m3When the purification rate of dichloroethane is 85%, the selectivity of carbon dioxide is 70%, no ozone is detected at the outlet, the operation lasts for 15 hours, and the performance of the catalyst is stable.
Example 2: 10g of 50% manganese nitrate solution and 24g of cerium nitrate hexahydrate were dissolved in 130ml of pure water by thoroughly stirring for 30 min. Soaking 6g of SBA-15 template agent in the manganese-cerium salt mixed solution, magnetically stirring and soaking at room temperature for 10 hours, and centrifuging to obtain a white solid. The white solid was dried in a vacuum oven at 60 ℃ for 12 hours and then calcined in a muffle furnace at 400 ℃ for 4 hours to give a brown colorThe precursor of manganese-cerium solid solution. Dissolving the manganese-cerium solid solution precursor in 150ml of 2mol/L sodium hydroxide solution, stirring, soaking for 6 hours, filtering, washing a filter cake to pH 7 with pure water, and drying the filter cake in a vacuum drying oven at 60 ℃ for 12 hours to obtain the mesoporous manganese-cerium solid solution catalyst for catalyzing ozone oxidation CVOCs. Evaluation of catalyst Performance: the mass of the catalyst was 0.5g, the gas flow was 125ml/min, and the inlet concentration of dichloroethane was 150mg/m3The ozone concentration at the inlet is 1000mg/m3The measured dichloroethane purification rate is 96%, the carbon dioxide selectivity is 82%, no ozone is detected at the outlet, the operation is carried out for 15 hours, and the catalyst performance is stable.
Claims (6)
1. A preparation method of a catalyst for catalyzing ozone oxidation of chlorine-containing volatile organic compounds is characterized in that the catalyst is of a mesoporous manganese-cerium solid solution structure and is prepared by adopting a template method-vacuum drying method, and the preparation method comprises the following steps:
(1) adding manganese salt and cerium salt into pure water, and stirring and dissolving to obtain manganese-cerium salt mixed solution;
(2) soaking the mesoporous silicon template agent in a manganese-cerium salt mixed solution, and then centrifuging to remove a soaking solution;
(3) drying the impregnated product obtained in the step (2) in vacuum and then calcining to obtain a manganese-cerium solid solution precursor;
(4) adopting an alkali solution to dip the manganese-cerium solid solution precursor obtained in the step (3), dissolving a template agent in the manganese-cerium solid solution precursor, filtering, and washing a filter cake to be neutral by pure water;
(5) and drying the filter cake in vacuum to obtain the mesoporous manganese-cerium solid solution catalyst.
2. The preparation method of the catalyst according to claim 1, wherein the manganese salt in the step (1) is one or more of manganese chloride, manganese sulfate, manganese acetate and manganese nitrate; the cerium salt is one or a mixture of cerium chloride, cerium sulfate and cerium nitrate; the molar ratio of manganese to cerium is from 1:4 to 4: 1.
3. The method for preparing the catalyst according to claim 1, wherein the template in the step (2) is one or more of SBA-15, SBA-16, KIT-6 and MCM-41, and the mass ratio of the template to the transition metal salt is 5:4 to 5: 1; the dipping condition is magnetic stirring for 4-10 hours.
4. The method for preparing a catalyst according to claim 1, wherein the vacuum drying temperature in the step (3) is 60 to 100 ℃ for 5 to 14 hours; the calcination temperature is 200-600 ℃ and the calcination time is 4-10 hours.
5. The method for preparing the catalyst according to claim 1, wherein the alkali solution in the step (4) is one or a mixture of sodium hydroxide and potassium hydroxide, and the concentration is 1-3 mol/L; the dipping condition is magnetic stirring for 4-10 hours.
6. The method for preparing a catalyst according to claim 1, wherein the vacuum drying temperature in the step (5) is 60 to 100 ℃ for 5 to 14 hours.
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|---|---|---|---|---|
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| CN112495371A (en) * | 2019-09-16 | 2021-03-16 | 北京化工大学 | Preparation method of catalyst for catalyzing ozone to oxidize volatile organic compounds |
| CN112547047A (en) * | 2019-09-25 | 2021-03-26 | 北京化工大学 | Method for preparing nano manganese dioxide catalyst by freeze drying method |
-
2021
- 2021-09-09 CN CN202111056682.4A patent/CN113648992A/en active Pending
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Application publication date: 20211116 |