CN113694918A - Manganese oxide catalyst catalyzed by formaldehyde and preparation method thereof - Google Patents
Manganese oxide catalyst catalyzed by formaldehyde and preparation method thereof Download PDFInfo
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- CN113694918A CN113694918A CN202110997270.4A CN202110997270A CN113694918A CN 113694918 A CN113694918 A CN 113694918A CN 202110997270 A CN202110997270 A CN 202110997270A CN 113694918 A CN113694918 A CN 113694918A
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title abstract description 108
- 230000003197 catalytic effect Effects 0.000 claims abstract description 39
- 229910016978 MnOx Inorganic materials 0.000 claims abstract description 30
- 239000004094 surface-active agent Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 150000002696 manganese Chemical class 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 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 18
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 238000004887 air purification Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 101100293261 Mus musculus Naa15 gene Proteins 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002459 sustained effect Effects 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
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The invention provides a formaldehyde catalytic manganese oxide catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: mixing manganese salt and strong base into a solution in deionized water; adding a surfactant into the mixed solution in the S1, heating and stirring; sealing and heating the solution in the S2; and washing and drying the solid precipitate obtained in the S3, and then calcining to obtain the porous MnOx catalytic material. The invention has the advantages that: the porous MnOx catalytic material is prepared by adopting a surfactant as a template, has a large specific surface area and high formaldehyde adsorption capacity, can efficiently and continuously decompose indoor formaldehyde completely, and does not generate an intermediate product to cause secondary pollution; and the preparation process is simple and easy to operate, and can be used for large-scale production in the field of air purification.
Description
Technical Field
The invention belongs to the field of air purification materials, and particularly relates to a manganese oxide catalyst catalyzed by formaldehyde and a preparation method thereof.
Background
Formaldehyde (HCOOH) is considered to be a major indoor air pollutant emitted by widely used building and decorative materials. Prolonged exposure to room air containing ppb concentrations of formaldehyde can have adverse effects on human health. Catalytic oxidation is one of the most promising technologies for controlling formaldehyde contaminants.
For example, noble metal supported catalysts have been reported to have high activity for complete oxidation of hundreds of ppm of formaldehyde to CO2And H2And O. However, the concentration of indoor formaldehyde emissions is much lower (<1ppm) and the corresponding catalytic treatment is relatively energy-intensive. Therefore, the traditional indoor formaldehyde treatment usually adopts an adsorption method, but the adsorption material needs to be frequently replaced, otherwise, secondary pollution is easily caused.
Therefore, it is important to develop a catalytic material that combines both high capacity adsorption and catalytic oxidation properties.
Disclosure of Invention
The invention provides a formaldehyde catalytic manganese oxide catalyst and a preparation method thereof, aiming at the problems that the catalytic treatment of a noble metal loaded catalyst in the prior art is relatively energy-consuming and the materials of an adsorption treatment method need to be frequently replaced.
The technical scheme of the invention is as follows: a preparation method of a formaldehyde-catalyzed manganese oxide catalyst comprises the following steps:
s1, mixing manganese salt and strong base in deionized water to form a solution;
s2, adding a surfactant into the mixed solution in the S1, and heating and stirring;
sealing and heating the solution in S3 and S2;
s4, washing and drying the solid precipitate obtained in the S3, and then calcining to obtain the porous MnOx catalytic material.
Further, the manganese salt is at least one of manganese acetate, manganese nitrate, manganese sulfate and manganese chloride.
Further, the strong base is at least one of potassium hydroxide and sodium hydroxide.
Further, the surfactant is at least one of polyvinyl alcohol, cetyl trimethyl ammonium bromide and polyethylene glycol.
Further, in step S1, the mass ratio of the manganese salt to the strong base is mMn：mStrong base0.5-2; step S2The mass ratio m of the middle surfactant to the manganese saltActive agent：mMn＝1～10。
Further, in the step S2, the reaction is carried out for 1-4 hours under stirring at 60-100 ℃, and in the step S3, the reaction is heated for 6-24 hours at 75 ℃.
Further, the calcination temperature in step S4 is 400-600 ℃, and the calcination time is 4-12 h.
Preferably, the mass ratio of the manganese salt to the strong base in the step S1 is mMn：mStrong base1-1.2; mass ratio m of surfactant to manganese salt in step S2Active agent：mMn4-6 ℃, the temperature is 70-80 ℃, and the stirring time is 2 h; s3, heating in the oven for 12-14 h; in the step S4, the calcining temperature is 500 ℃, and the calcining time is 6-8 h.
Preferably, the surfactant is CTAB, the strong base is sodium hydroxide, the manganese salt is manganese nitrate, and the mass ratio m of the manganese salt to the strong base in the step S1 isMn(NO3)2:mNaOH1.14; mass ratio m of surfactant to manganese salt in step S2CTAB:m Mn(NO3)24.19, the temperature is 75 ℃, and the stirring time is 2 h; the heating time in the oven in the step S3 is 12 h; the calcining temperature in the step S4 is 500 ℃, and the calcining time is 6 h.
The formaldehyde-catalyzed manganese oxide catalyst is prepared by adopting the preparation method of the formaldehyde-catalyzed manganese oxide catalyst.
The invention has the advantages that: the porous MnOx catalytic material is prepared by adopting a surfactant as a template, has a large specific surface area and high formaldehyde adsorption capacity, can efficiently and continuously decompose indoor formaldehyde completely, and does not generate an intermediate product to cause secondary pollution; and the preparation process is simple and easy to operate, and can be used for large-scale production in the field of air purification.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention adopts a template method to prepare a porous MnOx catalytic material, takes a surfactant as a template, and removes the template through high-temperature calcination, so that the prepared MnOx has a loose porous structure and a high specific surface area, and can quickly adsorb formaldehyde gas on the surface of the MnOx and catalytically decompose the formaldehyde gas.
The preparation method comprises the following steps:
s1, manganese salt and strong base according to a certain mass ratio mMn：mStrong baseAdding the powder 0.5-2 into deionized water under the stirring action to form a solution;
s2, adding a certain amount of surfactant into the mixed solution, wherein the mass ratio m of the surfactant to the manganese salt isActive agent：mMnStirring and reacting for 1-4 h at 60-100 ℃;
s3, transferring the stirred solution to a sealed flask, and placing the flask in an oven to be heated for 6-24 hours at the temperature of 75 ℃;
s4, filtering, washing and drying the obtained solid precipitate, and calcining at 400-600 ℃ for 4-12h to obtain the porous MnOx catalytic material.
Wherein the manganese salt is at least one of manganese acetate, manganese nitrate, manganese sulfate and manganese chloride;
wherein the strong base is at least one of potassium hydroxide and sodium hydroxide;
wherein the surfactant is at least one of polyvinyl alcohol, cetyl trimethyl ammonium bromide and polyethylene glycol;
the optimal preparation scheme of the porous MnOx is as follows: the mass ratio of manganese salt to strong base is mMn：mStrong base1-1.2, the mass ratio m of the surfactant to the manganese saltActive agent：mMnThe stirring reaction temperature is 70-80 ℃, the stirring time is 2 hours, the heating time in an oven is 12-14 hours, the calcining temperature is 500 ℃, and the calcining time is 6-8 hours.
The following specific preparation method description and analysis of formaldehyde catalysis test results are carried out by taking a surfactant CTAB (cetyl trimethyl ammonium bromide), strong alkali sodium hydroxide and manganese nitrate as examples:
example 1: dissolving 1.6g of manganese nitrate and 1.4g of sodium hydroxide into 50mL of deionized water, adding 6.7g of a surfactant CTAB, stirring for 2h at 75 ℃, then transferring into a closed flask, placing into an oven, and heating for 12h at 75 ℃; and filtering, washing and drying the obtained solid precipitate, and calcining for 6 hours at 500 ℃ to obtain the porous MnOx catalytic material.
Example 2: dissolving 1.6g of manganese nitrate and 1.4g of sodium hydroxide into 50mL of deionized water, adding 6.7g of a surfactant CTAB, stirring for 1h at 75 ℃, then transferring into a closed flask, putting into an oven, and heating for 6h at 75 ℃; and filtering, washing and drying the obtained solid precipitate, and calcining for 6 hours at 500 ℃ to obtain the porous MnOx catalytic material.
Example 3: dissolving 1.6g of manganese nitrate and 1g of sodium hydroxide into 50mL of deionized water, adding 6.7g of a surfactant CTAB, stirring for 2h at 75 ℃, then transferring into a closed flask, putting into an oven, and heating for 12h at 75 ℃; and filtering, washing and drying the obtained solid precipitate, and calcining for 6 hours at 500 ℃ to obtain the porous MnOx catalytic material.
Example 4: dissolving 1.6g of manganese nitrate and 1.4g of sodium hydroxide into 50mL of deionized water, adding 3g of a surfactant CTAB, stirring for 2h at 75 ℃, then transferring into a closed flask, putting into an oven, and heating for 12h at 75 ℃; and filtering, washing and drying the obtained solid precipitate, and calcining for 6 hours at 500 ℃ to obtain the porous MnOx catalytic material.
Example 5: dissolving 1.6g of manganese nitrate and 1.4g of sodium hydroxide into 50mL of deionized water, adding 6.7g of a surfactant CTAB, stirring for 2h at 75 ℃, then transferring into a closed flask, placing into an oven, and heating for 12h at 75 ℃; and filtering, washing and drying the obtained solid precipitate, and calcining for 3 hours at 500 ℃ to obtain the porous MnOx catalytic material.
Example 6: dissolving 16g of manganese nitrate and 14g of sodium hydroxide into 150mL of deionized water, adding 67g of a surfactant CTAB, stirring for 2h at 75 ℃, then transferring into a closed flask, putting into an oven, and heating for 12h at 75 ℃; and filtering, washing and drying the obtained solid precipitate, and calcining for 6 hours at 500 ℃ to obtain the porous MnOx catalytic material.
The method for testing the catalytic effect of the porous MnOx catalytic material on formaldehyde prepared in the above embodiment is as follows: 0.3g of the porous MnOx material prepared above was placed on quartz wool in a metal tube having a diameter of 5mm to evaluate the catalytic decomposition activity, the bottom of the metal tube was connected to a formaldehyde generator, and the top was connected to an infrared spectrometer. Blowing compressed air into a formaldehyde carrying tank, mixing the air and formaldehyde to obtain air with the formaldehyde concentration of 5ppm, wherein the air flow is 500ml/min, and the humidity is 50%. The formaldehyde-containing air enters the metal tube containing the catalyst from the bottom and then exits the top into an infrared spectrometer for formaldehyde concentration detection.
The determination of the sustained catalytic effect on the porous MnOx catalytic material was made as the duration of the formaldehyde concentration through the catalyst loaded metal tube down to 0.5ppm (formaldehyde conversion at 90%), and the specific test results are shown in table 1.
TABLE 1 catalytic Effect of porous MnOx catalytic Material on Formaldehyde
| Sample (I) | Original formaldehyde concentration | The formaldehyde conversion rate is more than 90 percent and the maintenance time is long |
| Example 1 | 5ppm | 5h |
| Example 2 | 5ppm | 4h |
| Example 3 | 5ppm | 3h |
| Example 4 | 5ppm | 3.5h |
| Example 5 | 5ppm | 2h |
| Example 6 | 5ppm | 4.5h |
The results of the above tests show that the catalytic effect on formaldehyde is better in examples 1 and 6, and the time for maintaining the conversion of 0.3g of porous MnOx to 5ppm of formaldehyde at 90% or more is longer. m isMn(NO3)2:mNaOH＝1.14，mCTAB:m Mn(NO3)2＝4.19。
By comparing example 1 with examples 2 and 3, it can be seen that the reaction time for heating the manganese salt and the strong base to form MnOx and the reduction of the amount of the strong base both affect the catalytic effect of the finally calcined porous MnOx catalytic material, and reduce the duration for maintaining the catalytic conversion rate at 90% or more.
From a comparison of example 1 and example 4, it can be seen that the reduced amount of CTAB surfactant, when other conditions are unchanged, also results in a reduction in the catalytic effect of the final calcined porous MnOx catalytic material, since the amount of CTAB surfactant affects the specific surface area of the resulting porous MnOx catalytic material, affects the adsorption effect of the porous MnOx on formaldehyde, and thus affects the length of time that the catalytic conversion rate is maintained above 90%.
By comparing example 1 with example 5, it can be seen that under the condition of keeping other conditions unchanged, the half reduction of the final high-temperature calcination time seriously affects the catalytic conversion effect of the prepared porous MnOx on formaldehyde, so that the high-temperature calcination process is a key factor affecting the catalytic effect of the porous MnOx catalytic material of the invention, and the process makes MnOx form a porous structure, and the sufficient calcination time length must be ensured.
By comparing example 1 with example 6, the reduction effect of the catalytic effect of the porous MnOx catalytic material prepared under the same preparation conditions is not significant when the mass of each component of example 1 is increased ten times. Therefore, during the production of large-scale production, the formaldehyde conversion rate is slightly reduced, but the formaldehyde conversion rate is still higher, so that the requirement of actual production can be met.
The preparation method has simple process and simple operation, is suitable for industrial scale-up production, and the prepared catalyst has good porous structure, increases the specific surface area of the material, improves the reduction performance, can adsorb and catalytically decompose formaldehyde in indoor air, and is suitable for removing formaldehyde pollutants in closed and semi-closed spaces.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the formaldehyde-catalyzed manganese oxide catalyst is characterized by comprising the following steps:
s1, mixing manganese salt and strong base in deionized water to form a solution;
s2, adding a surfactant into the mixed solution in the S1, and heating and stirring;
sealing and heating the solution in S3 and S2;
s4, washing and drying the solid precipitate obtained in the S3, and then calcining to obtain the porous MnOx catalytic material.
2. The method of claim 1, wherein the formaldehyde-catalyzed manganese oxide catalyst is prepared by: the manganese salt is at least one of manganese acetate, manganese nitrate, manganese sulfate and manganese chloride.
3. The method of claim 1, wherein the formaldehyde-catalyzed manganese oxide catalyst is prepared by: the strong base is at least one of potassium hydroxide and sodium hydroxide.
4. The method of claim 1, wherein the formaldehyde-catalyzed manganese oxide catalyst is prepared by: the surfactant is at least one of polyvinyl alcohol, cetyl trimethyl ammonium bromide and polyethylene glycol.
5. The method of claim 1, wherein the formaldehyde-catalyzed manganese oxide catalyst is prepared by: in step S1, the mass ratio of the manganese salt to the strong base is mMn：mStrong base0.5-2; mass ratio m of surfactant to manganese salt in step S2Active agent：mMn＝1～10。
6. The method of claim 5, wherein the formaldehyde-catalyzed manganese oxide catalyst is prepared by: in the step S2, stirring and reacting for 1-4 h at 60-100 ℃; and step S3, heating for 6-24 h at 75 ℃ in an oven.
7. The method of preparing the formaldehyde-catalyzed manganese oxide catalyst according to any one of claims 5 to 6, wherein: the calcination temperature in the step S4 is 400-600 ℃, and the calcination time is 4-12 h.
8. The method of claim 1, wherein the formaldehyde-catalyzed manganese oxide catalyst is prepared by: the mass ratio of the manganese salt to the strong base in the step S1 ismMn：mStrong base1-1.2; mass ratio m of surfactant to manganese salt in step S2Active agent：mMnHeating at 70-80 ℃ for 4-6 hours, and stirring for 2 hours; s3, heating the mixture in an oven at 75 ℃ for 12-14 h; in the step S4, the calcining temperature is 500 ℃, and the calcining time is 6-8 h.
9. The method of claim 8, wherein the formaldehyde-catalyzed manganese oxide catalyst is prepared by: the surfactant is CTAB, the strong base is sodium hydroxide, and the manganese salt is manganese nitrate; mass ratio m of manganese salt to strong base in step S1Mn(NO3)2:mNaOH1.14; mass ratio m of surfactant to manganese salt in step S2CTAB:mMn(NO3)2Heating at 75 deg.C for 4.19, and stirring for 2 h; s3, heating for 12h at 75 ℃ in an oven; the calcination time in the step S4 is 6 h.
10. The formaldehyde-catalyzed manganese oxide catalyst is characterized by being prepared by the preparation method of the formaldehyde-catalyzed manganese oxide catalyst according to any one of claims 1 to 9.
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| CN117816151A (en) * | 2024-01-29 | 2024-04-05 | 康纳新型材料(杭州)有限公司 | Catalyst for decomposing formaldehyde and preparation method and application thereof |
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| CN1789145A (en) * | 2005-11-07 | 2006-06-21 | 山东师范大学 | Method for synthesizing nano-structure of bunchy manganese dioxide |
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