CN111495363A - Preparation method of nanofiber composite filtering membrane for decomposing ozone - Google Patents

Preparation method of nanofiber composite filtering membrane for decomposing ozone Download PDF

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CN111495363A
CN111495363A CN201910089415.3A CN201910089415A CN111495363A CN 111495363 A CN111495363 A CN 111495363A CN 201910089415 A CN201910089415 A CN 201910089415A CN 111495363 A CN111495363 A CN 111495363A
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ozone
manganese
potassium permanganate
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裴小强
郭国良
高婷婷
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Ningbo Fotile Kitchen Ware Co Ltd
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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
    • B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
    • 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
    • B01D53/8675—Ozone
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/39—Electrospinning
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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 preparation method of a nanofiber composite filtering membrane for decomposing ozone, which is characterized by comprising the following steps of: dissolving a precursor manganese salt in deionized water, uniformly stirring to prepare a precursor solution, adding a carrier into the precursor solution, and uniformly stirring the solution to prepare a catalytic solution; dissolving potassium permanganate and a cocatalyst metal salt in deionized water, and uniformly stirring to prepare a potassium permanganate mixed solution; dropwise adding the potassium permanganate mixed solution into the catalytic solution, and stirring; and washing and drying the obtained precipitate with deionized water to obtain ozone catalyst particles, adding the ozone catalyst particles into a polymer solution, carrying out electrostatic spinning, and collecting the obtained nano fibers on the surface of a non-woven fabric to obtain the nano fiber filtering membrane capable of decomposing ozone.

Description

Preparation method of nanofiber composite filtering membrane for decomposing ozone
Technical Field
The invention relates to the field of air purification, in particular to a preparation method of a nanofiber composite filtering membrane capable of decomposing ozone.
Background
The existing method for decomposing ozone in air is generally to load ozone catalyst particles on a substrate of a filter device, and decompose ozone in air by the ozone catalyst particles. For example, CN200910201218.2 discloses a method for preparing a catalyst for rapidly decomposing ozone in air and its application, which comprises preparing manganese dioxide and glycerol into a preparation according to a certain proportion, selecting air filtering materials selected from sponge, mesh and fibrous filter screen as carriers, and impregnating the carriers to adsorb the prepared preparation. The ozone filter is used for decomposing and filtering ozone contained in air, has the effects of simplicity, convenience, low cost, rapidness, high efficiency and durability, and can be widely applied to air purifiers, electrostatic copiers, laser printers, electrostatic dust collectors, sterilization disinfection cabinets and other electrical equipment adopting high-voltage discharge.
However, the filter device has the following defects in the use process: (1) manganese dioxide is directly fixed on material carriers such as sponge in a gluing mode, a large amount of catalyst particles are covered in sol in the gluing process, a large enough specific surface area is not available for contacting pollutants, and in addition, the carriers are filter materials with conventional sizes, so that few active adsorption sites can be provided for the catalyst, and the amount of the supported catalyst is small. (2) The method adopts manganese dioxide powder with simple substance, and the decomposition capability of the manganese dioxide powder to ozone is far lower than that of the prepared MnOx catalytic material; (3) the air resistance of the scheme can sharply rise along with the increase of dust holding capacity in the using process of the filter screen, so that a large amount of energy is consumed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a composite nanofiber composite filtering membrane which has high effective utilization rate and can remove particles in air and decompose ozone in view of the current situation of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a nanofiber composite filtering membrane for decomposing ozone is characterized by comprising the following steps:
1) preparation of catalyst particles
Dissolving a precursor manganese salt in deionized water, uniformly stirring to prepare a precursor solution, slowly adding a carrier into the precursor solution, and stirring at 300-1000 rpm for 0.5-3 h until the solution is uniform to prepare a catalytic solution, dissolving potassium permanganate and cocatalyst metal salt in deionized water, uniformly stirring to prepare a potassium permanganate mixed solution with the concentration of 0.015-0.5 mol/L.
Dropwise adding the potassium permanganate mixed solution into the catalytic solution at the speed of 2-5 drops/second, and controlling potassium permanganate: the manganese salt is stirred for 0.5-3 hours at 300-1000 rpm with the molar ratio of 1: 1-4; washing the generated precipitate with deionized water for 3-5 times, filtering, drying the obtained precipitate for 4-6 h at 90-110 ℃, preferably, roasting the dried material for 3-5 h at 300-500 ℃; preparing ozone catalyst particles with the particle size of 50-200 nm;
the precursor manganese salt is selected from at least one of manganese nitrate, manganese acetate, manganese sulfate, manganese chloride and manganese carbonate; the carrier is nano gamma-Al2O3Particles;
the catalysis-assisting metal salt can be at least one of silver nitrate, cobalt nitrate, ferric nitrate, silver acetate, cobalt acetate and ferric acetate;
in the preferable catalyst particles, the molar ratio of manganese elements (including precursor manganese salt and potassium permanganate) to metal elements is 2-80: 1; the weight ratio of the manganese element to the carrier is 5-30%.
2) Preparation of nanofiber gel solution
Dissolving a polymer in a solvent, and preparing a polymer solution with the concentration of 5-20 wt% at 40-80 ℃; adding the ozone catalyst particles into the polymer solution, stirring for 3-12 h at the temperature of room temperature-80 ℃, standing or defoaming in vacuum to prepare uniform and transparent nanofiber gel liquid;
the weight ratio of the ozone catalyst particles to the polymer solution is 1-20%;
the polymer is selected from at least one of polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyacrylonitrile, polyvinylpyrrolidone and polyethyleneimine;
the solvent is at least one selected from water, ethanol, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
3) preparation of nanofiber composite filtering membrane for decomposing ozone
And (3) putting the nanofiber gel solution into electrostatic spinning equipment for spinning, and collecting the obtained nanofibers on the surface of a non-woven fabric to obtain the nanofiber filtering membrane capable of decomposing ozone.
Preferably, the molar ratio of the manganese salt to the metal salt is 2-80: 1.
Preferably gamma-Al2O3The particle size of the particles is 10-50 nm.
The electrostatic spinning conditions are as follows:
the electrostatic spinning voltage is 8-30kv, the distance between the needle end of the injector and the collector is 5-25cm, the injection speed is 3-100ul/min, the rotating speed of the collector is 300-;
the non-woven fabric is wrapped on the collector.
The injection speed is 5-20 mu L/min, and the electrostatic spinning voltage is 15-25 KV.
Compared with the prior art, the nanofiber filtering membrane prepared by the method has a high specific surface area, the catalytic performance is greatly improved, ozonolysis and PM2.5 filtering can be efficiently compounded into a whole, and two pollutants can be compositely treated by one filter screen; the preparation method is simple.
Drawings
FIG. 1 is an SEM image of ozone catalyst particles prepared in example 1 of the present invention.
FIG. 2 is an EDS diagram of ozone catalyst particles prepared in example 1 of the present invention; wherein, the upper left part is an electron microscope picture of the sample, the upper right part is a distribution diagram of manganese element, the lower left part is aluminum element, and the lower right part is oxygen element; it can be seen from fig. 2 that the MnOx catalyst particles are uniformly dispersed on the nano alumina support;
fig. 3 is an SEM photograph of the nanofiber composite membrane prepared in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1
(1) Preparation of catalyst particles
Dissolving 0.418g of manganese nitrate tetrahydrate in 50m L of deionized water, uniformly stirring to prepare a manganese nitrate solution with the concentration of 0.033 mol/L, and mixing 2.5g of gamma-Al2O3Slowly adding the manganese nitrate solution into the manganese nitrate solution, and stirring the solution at 500rpm for 0.5h until the solution is uniform to prepare the catalytic solution.
Dissolving 0.132g of potassium permanganate and 0.011g of silver nitrate in 50m L deionized water, and uniformly stirring to obtain a potassium permanganate mixed solution with the concentration of 0.016 mol/L, wherein the molar ratio of potassium permanganate to manganese salt is 1:2.06
Slowly dripping the potassium permanganate mixed solution into a manganese nitrate solution at the speed of 2-5 drops/second, stirring for 0.5h, cleaning the generated precipitate with deionized water for 3-5 times, drying the precipitate obtained by filtering at 105 ℃ for 5h, and roasting at 300 ℃ for 3h to obtain ozone catalytic particles with the particle size of 50-100 nm. The molar ratio of manganese (including precursor manganese salt and potassium permanganate) to silver in the mixed solution in the whole preparation process is 40: 1;
the prepared ozone catalyst particles are subjected to electron microscope scanning, as shown in figures 1 and 2, the prepared ozone catalyst MnOx is uniformly loaded on the surface of alumina and is in a shape of a sphere with the diameter of about 50nm, and is aggregated, rough and uneven in surface and large in specific surface area, so that the adsorption of reactants and the provision of reaction active sites are facilitated, and meanwhile, the catalyst presents a foam pore system with the thickness of 0.1-2 microns, so that the diffusion of pollutants and products is facilitated.
(2) Preparing nanofiber gel liquid: dissolving 15g of polyvinyl alcohol (PVA) in 80g of deionized water, stirring for 3h at 500rpm at 70 ℃ until the solution is transparent, then adding 5g of catalyst particles into the solution, stirring for 5h until the solution is uniform, and defoaming before spinning or standing for defoaming for 12 h.
(3) And (2) preparing the nanofiber composite filtering membrane for decomposing ozone, namely putting the gel solution into an electrostatic spinning device, adjusting spinning parameters, setting the injection speed at 20 mu L/min, setting the distance between a needle and a collector at 15cm, applying a voltage at 15KV, setting the rotating speed of the collector at 500rpm, spinning at the temperature of 25 ℃ and the humidity of 50%, and spinning for 1h to obtain the PVA nanofiber composite membrane taking the non-woven fabric as a supporting layer.
The prepared nanofiber composite filtering membrane for decomposing ozone is subjected to electron microscope scanning, and is shown in figure 3. From the figure, it can be seen that the ozone catalyst particles are embedded on the nanofibers and partially exposed outside the fibers, and the efficiency of the nanofiber ozone catalysis is increased by virtue of the advantage of large specific surface area of the nanofibers.
The nanofiber filtration membranes prepared in the respective examples were subjected to performance tests.
Firstly, the catalytic performance of the nanofiber for ozone decomposition is as follows:
the size of a sample is 15cm × 15cm, the sample is loaded into a testing device, and the air speed is adjusted to 150000h-1The ozone inlet gas concentration is c0Was 10 ppm. Detecting the concentration c of ozone at the outlet of the pipeline by adopting a Model 202 Serial ozone analyzer, detecting the stable concentration of the outlet, and calculating the ozone removal rate according to the following formula:
Figure BDA0001962806550000041
secondly, the filtering performance of the nano-fiber particles is as follows:
the filtering performance of the composite nanofiber membrane is tested by adopting a TSI 8130 type automatic filter material tester, the sample size is 15cm × 15cm, NaCl aerosol with the mass median diameter of particle particles of 0.26um is generated, and the air flow speed is 32L/min.
The filtering efficiency η of the particles is obtained by testing the concentration of the particles at two ends of the membrane
Figure BDA0001962806550000042
C1As outlet aerosol concentration, C2Is the inlet aerosol concentration.
And (3) performance test results: the catalytic ozone decomposition efficiency of the sample is 75%, and the filtering performance of PM0.3 is 99.1%.
Example 2:
(1) preparing catalyst particles, dissolving 7.35g of tetrahydrate manganese acetate in 50m L deionized water, stirring uniformly to prepare 0.6 mol/L manganese acetate solution, and preparing 2.5g of gamma-Al2O3Slowly adding the manganese acetate solution into the manganese acetate solution, and stirring the solution at 500rpm for 0.5h until the solution is uniform to prepare the catalytic solution.
Dissolving 2.37g of potassium permanganate and 0.153g of silver nitrate in 50m L of deionized water, and uniformly stirring to obtain a mixed solution of potassium permanganate with the concentration of 0.3 mol/L, wherein the molar ratio of potassium permanganate to manganese salt is 1: 2;
slowly dripping the potassium permanganate mixed solution into a catalytic solution at the speed of 2-5 drops/second, stirring for 1h, washing the generated precipitate with deionized water for 3-5 times, and drying the precipitate obtained by filtering at 105 ℃ for 5h to obtain ozone catalytic particles with the particle size of 50-100 nm.
The molar ratio of manganese (including precursor manganese salt and potassium permanganate) to silver in the mixed solution in the whole preparation process is 50: 1;
(2) preparing nanofiber gel liquid: dissolving 12g of polyacrylonitrile PAN in 83g of DMF, stirring for 3h at 40 ℃ and the rotating speed of 500r/min until the solution is transparent, then adding 5g of the ozone catalytic particles into the solution, stirring for 5h until the solution is uniform, and standing and defoaming for 12h before spinning.
(3) And (2) preparing the nanofiber composite filtering membrane for decomposing ozone, namely putting the gel solution into electrostatic spinning equipment, adjusting spinning parameters, setting the injection speed at 8 mu L/min, setting the distance between a needle and a collector at 12cm, applying a voltage at 18KV, setting the rotating speed of the collector at 500rpm, spinning at the temperature of 25 ℃ and the humidity of 50%, and spinning for 1h to obtain the PAN nanofiber composite membrane taking the non-woven fabric as a supporting layer.
(4) And (3) performance testing: the catalytic ozone decomposition efficiency of the sample is 90%, and the filtering performance of PM0.3 is 93.2%.
Example 3:
(1) preparing catalyst particles by dissolving 1.22g of tetrahydrate manganese acetate in 50m L deionized water, stirring uniformly to prepare 0.1 mol/L manganese acetate solution, and preparing 2.5g of gamma-Al2O3Slowly adding the manganese acetate solution into the manganese acetate solution, and stirring the solution at 500rpm for 0.5h until the solution is uniform to prepare the catalytic solution.
Dissolving 0.198g of potassium permanganate and 0.182g of cobalt nitrate hexahydrate in 50m L deionized water, uniformly stirring to obtain a potassium permanganate mixed solution with the concentration of 0.025 mol/L, wherein the molar ratio of potassium permanganate to manganese salt is 1: 4;
slowly dripping the potassium permanganate mixed solution into the catalytic solution at the speed of 2-5 drops/second, stirring for 1h, washing the generated precipitate with deionized water for 3-5 times, drying the precipitate obtained by filtering at 105 ℃ for 5h, and roasting at 450 ℃ for 5h to obtain ozone catalytic particles with the particle size of 50-100 nm.
The molar ratio of manganese (including precursor manganese salt and potassium permanganate) to cobalt in the mixed solution in the whole preparation process is 10: 1;
(2) preparing nanofiber gel liquid: dissolving 18g of polyethylene oxide (PEO) in 72g of deionized water, stirring for 2 hours at the temperature of 60 ℃ at the rotating speed of 300r/min, uniformly and transparently dissolving the solution, then adding 10g of the ozone catalytic particles into the solution, stirring for 5 hours until the solution is uniform, and standing and defoaming for 12 hours before spinning.
(3) And (2) preparing the nanofiber composite filtering membrane for decomposing ozone, namely putting the gel solution into an electrostatic spinning device, adjusting spinning parameters, setting the injection speed at 20 mu L/min, setting the distance between a needle and a collector at 10cm, applying a voltage at 15KV, setting the rotating speed of the collector at 500rpm, spinning at the temperature of 25 ℃ and the humidity of 50%, and spinning for 1h to obtain the PEO nanofiber composite membrane taking the non-woven fabric as a supporting layer.
(4) And (3) performance testing: the catalytic ozone decomposition efficiency of the sample is 83 percent, and the filtering performance of PM0.3 is 98.0 percent.
Example 4:
(1) preparing catalyst particles by dissolving 1.8g of manganese sulfate in 50m L deionized water, stirring uniformly to prepare 0.24 mol/L manganese sulfate solution, and adding 2.5g of gamma-Al2O3Slowly adding the manganese acetate solution into the manganese acetate solution, and stirring the solution at 500rpm for 0.5h until the solution is uniform to prepare the catalytic solution.
Dissolving 1.264g of potassium permanganate and 1.61g of ferric nitrate nonahydrate in 50m L of deionized water, and uniformly stirring to obtain a mixed solution of potassium permanganate with the concentration of 0.16 mol/L, wherein the ratio of potassium permanganate to manganese salt is 1: 1.5;
slowly dripping the potassium permanganate mixed solution into the catalytic solution at the speed of 2-5 drops/second, stirring for 2 hours, washing the generated precipitate with deionized water for 3-5 times, drying the precipitate obtained by filtering at 105 ℃ for 5 hours, and roasting at 400 ℃ for 3 hours to obtain ozone catalytic particles with the particle size of 50-100 nm.
The molar ratio of manganese (including precursor manganese salt and potassium permanganate) to iron in the mixed solution in the whole preparation process is 10: 1;
(2) preparing nanofiber gel liquid: dissolving 20g of polyacrylic acid PAA in 72g of deionized water, stirring for 4 hours at the temperature of 80 ℃, rotating at 300r/min, uniformly stirring the solution and being transparent, then adding 8g of the ozone catalytic particles into the solution, stirring for 5 hours until the solution is uniform, and standing and defoaming for 12 hours before spinning.
(3) And (2) preparing the nanofiber composite filtering membrane for decomposing ozone, namely putting the gel solution into electrostatic spinning equipment, adjusting spinning parameters, setting the injection speed at 100 mu L/min, setting the distance between a needle and a collector at 20cm, applying a voltage at 15KV, setting the rotating speed of the collector at 500rpm, spinning at the temperature of 25 ℃ and the humidity of 50%, and spinning for 1h to obtain the PAA nanofiber composite membrane taking the non-woven fabric as a supporting layer.
(4) And (3) performance testing: the catalytic ozone decomposition efficiency of the sample is 88 percent, and the PM0.3 filtering performance is 92.5 percent.

Claims (7)

1. A preparation method of a nanofiber composite filtering membrane for decomposing ozone is characterized by comprising the following steps:
1) preparation of catalyst particles
Dissolving a precursor manganese salt in deionized water, uniformly stirring to prepare a precursor solution, adding a carrier into the precursor solution, and stirring at 300-1000 rpm for 0.5-3 h until the solution is uniform to prepare a catalytic solution, wherein the concentration of the manganese salt in the precursor solution is 0.03-0.6 mol/L;
dissolving potassium permanganate and a cocatalyst metal salt in deionized water, and uniformly stirring to prepare a potassium permanganate mixed solution with the concentration of 0.015-0.5 mol/L;
dropwise adding the potassium permanganate mixed solution into the catalytic solution at the speed of 2-5 drops/second, and controlling potassium permanganate: the manganese salt is stirred for 0.5-3 hours at 300-1000 rpm with the molar ratio of 1: 1-4; washing the generated precipitate for 3-5 times by using deionized water, filtering, and drying the obtained precipitate for 4-6 h at 90-110 ℃ to prepare ozone catalyst particles with the particle size of 50-200 nm;
the precursor manganese salt is selected from at least one of manganese nitrate, manganese acetate, manganese sulfate, manganese chloride and manganese carbonate; the carrier is nano gamma-Al2O3Particles with the particle size of 10-50 nm; the catalysis-assisting metal salt can be at least one of silver nitrate, cobalt nitrate, ferric nitrate, silver acetate, cobalt acetate and ferric acetate;
the molar ratio of manganese (including precursor manganese salt and potassium permanganate) to metal in the mixed solution in the whole preparation process is 2-80: 1; the weight ratio of the carrier to the carrier is 5-30%;
2) preparation of nanofiber gel solution
Dissolving a polymer in a solvent, and preparing a polymer solution with the concentration of 5-20 wt% at 40-80 ℃; adding the ozone catalyst particles into the polymer solution, stirring for 3-12 h at the temperature of room temperature-80 ℃, standing or defoaming in vacuum to prepare uniform and transparent nanofiber gel liquid;
the polymer is selected from at least one of polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyacrylonitrile, polyvinylpyrrolidone and polyethyleneimine;
the solvent is at least one selected from water, ethanol, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
the weight ratio of the ozone catalyst particles to the polymer solution is 1-20%;
3) preparation of nanofiber composite filtering membrane for decomposing ozone
And (3) putting the nanofiber gel solution into electrostatic spinning equipment for spinning, and collecting the obtained nanofibers on the surface of a non-woven fabric to obtain the nanofiber filtering membrane capable of decomposing ozone.
2. The method for producing a nanofiber composite filtration membrane for decomposing ozone as claimed in claim 1, wherein the molar ratio of the manganese salt to the metal salt is 2 to 80: 1.
3. The method for producing a nanofiber composite filtration membrane for decomposing ozone as claimed in claim 1, wherein the particle size of the carrier is 10 to 50 nm.
4. The method of manufacturing a nanofiber composite filtration membrane for decomposing ozone as claimed in claim 1, wherein the weight ratio of manganese element to the carrier in the catalyst particles is 5 to 30%.
5. The method for preparing the nanofiber composite filtering membrane for decomposing ozone according to claim 1, wherein the precipitate obtained in the step 1) is dried and then roasted at 300-500 ℃ for 3-5 h to prepare ozone catalyst particles with the particle size of 50-200 nm.
6. The method for preparing an ozone decomposing nanofiber composite filtering membrane as claimed in any one of claims 1 to 5, characterized in that the conditions of said electrospinning are:
the electrostatic spinning voltage is 8-30kv, the distance between the needle end of the injector and the collector is 5-25cm, the injection speed is 3-100ul/min, the rotating speed of the collector is 300-;
the non-woven fabric is wrapped on the collector.
7. The method for producing a nanofiber composite filtration membrane for decomposing ozone as claimed in claim 6, wherein the injection speed is 5 to 20 μ L/min, and the electrospinning voltage is 15 to 25 KV.
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CN115888751A (en) * 2022-11-18 2023-04-04 佛山市顺德区阿波罗环保器材有限公司 Low-concentration ozone catalyst, preparation method thereof and composite material prepared from low-concentration ozone catalyst

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102600861A (en) * 2012-03-26 2012-07-25 中国科学院生态环境研究中心 Manganese-based composite oxide catalyst for catalytically decomposing ozone, and preparation method of manganese-based composite oxide catalyst
CN103381363A (en) * 2013-07-29 2013-11-06 上海交通大学 Catalyst for removing ozone and harmful organic matter simultaneously and preparation method and application thereof
CN105289585A (en) * 2015-11-30 2016-02-03 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of supported rare earth doped manganese dioxide (MnO2) used in ozone catalyst
CN107983320A (en) * 2017-11-21 2018-05-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of difunctional film removed for formaldehyde and products thereof and application
CN108126654A (en) * 2017-12-08 2018-06-08 北京东方计量测试研究所 A kind of material for air purification, preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102600861A (en) * 2012-03-26 2012-07-25 中国科学院生态环境研究中心 Manganese-based composite oxide catalyst for catalytically decomposing ozone, and preparation method of manganese-based composite oxide catalyst
CN103381363A (en) * 2013-07-29 2013-11-06 上海交通大学 Catalyst for removing ozone and harmful organic matter simultaneously and preparation method and application thereof
CN105289585A (en) * 2015-11-30 2016-02-03 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of supported rare earth doped manganese dioxide (MnO2) used in ozone catalyst
CN107983320A (en) * 2017-11-21 2018-05-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of difunctional film removed for formaldehyde and products thereof and application
CN108126654A (en) * 2017-12-08 2018-06-08 北京东方计量测试研究所 A kind of material for air purification, preparation method and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115888751A (en) * 2022-11-18 2023-04-04 佛山市顺德区阿波罗环保器材有限公司 Low-concentration ozone catalyst, preparation method thereof and composite material prepared from low-concentration ozone catalyst

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