CN114343273B - Antibacterial active carbon mask and preparation method thereof - Google Patents
Antibacterial active carbon mask and preparation method thereof Download PDFInfo
- Publication number
- CN114343273B CN114343273B CN202210118065.0A CN202210118065A CN114343273B CN 114343273 B CN114343273 B CN 114343273B CN 202210118065 A CN202210118065 A CN 202210118065A CN 114343273 B CN114343273 B CN 114343273B
- Authority
- CN
- China
- Prior art keywords
- woven fabric
- melt
- activated carbon
- blown non
- antibacterial
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Respiratory Apparatuses And Protective Means (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an antibacterial active carbon mask and a preparation method thereof. The antibacterial active carbon mask comprises a photocatalyst melt-blown non-woven fabric outer layer, an active carbon melt-blown non-woven fabric inner layer and a pure cotton spun-laced non-woven fabric surface layer from outside to inside; the photocatalyst melt-blown non-woven fabric layer is also provided with an ear strap and a nose bridge strap, and titanium dioxide doped with metallic nickel and an antibacterial agent prepared from graphene oxide, ferric chloride and bacterial cellulose are added into the photocatalyst melt-blown non-woven fabric layer. The invention combines the outer layer with photocatalytic degradation, the copper-doped activated carbon filtration inner layer and the skin-friendly spunlaced non-woven fabric surface layer to prepare the antibacterial activated carbon mask, and has the advantages of simple preparation process, good coordination of each functional layer, good antibacterial performance, high filtering efficiency on particles and stable long-term use performance.
Description
Technical Field
The invention belongs to the technical field of masks, and particularly relates to an antibacterial active carbon mask and a preparation method thereof.
Background
With the continuous development of science and technology, the continuous improvement of the living standard of people and the gradual and severe environmental pollution, the protection consciousness of people is enhanced, and the mask becomes a living necessity. A mask generally refers to an appliance worn on the mouth and nose for filtering air entering the mouth and nose to block harmful gases, odors, and droplets from leaching out of the mouth and nose of a wearer. The mask has a certain filtering effect on air entering the lung, has a very good effect when working in polluted environments such as dust and the like during the flow of respiratory infectious diseases, and particularly has a good effect in cities with serious haze, so that the mask becomes an article which people must wear when going out.
The gauze or non-woven fabrics are overlapped to make into the gauze mask on the market, the gauze can cover nose and mouth when using, in order to reach the tiny particle in the filtered air, or when the dust degree in the air is very big, just need increase the number of layers of gauze or non-woven fabrics, or increase the weaving density of gauze or non-woven fabrics, can lead to the air permeability of gauze like this and will reduce, carbon dioxide that the people breathe to produce, heat, gaseous moisture can not go out, people can produce the feeling of stuffy, even cause inside moisture condensation of material, produce wet cold sense, because the steam of exhaling is difficult to be discharged in the gauze mask, become the warm bed of bacterium, therefore it is very necessary to develop an antibiotic formula gauze mask.
CN 112826162A discloses a method for preparing a biomass-based nitrogen-doped active carbon mask, which uses triazine ring cross-linked cellulose as a biomass carbon source, uses triazine ring as a nitrogen source, and obtains biomass-based nitrogen-doped active carbon through high-temperature carbonization and zinc chloride pore formation, wherein the biomass-based nitrogen-doped active carbon has a rich pore structure and larger specific surface area, provides huge adsorption space for fine particles such as PM2.5 and the like, nitrogen doping forms a large number of nitrogen-containing functional groups such as pyridine nitrogen and graphite nitrogen in an active carbon layer structure, and lone pair electrons of the nitrogen-containing functional groups have strong adsorption effect on formaldehyde and can be used as active adsorption sites of formaldehyde, and meanwhile, the graphite nitrogen structure increases the electron cloud density around the carbon layer, so that the biomass-based nitrogen-doped active carbon mask has excellent adsorption effect on toxic gases such as formaldehyde and PM2.5 through electrostatic attraction on carbonyl positive ions in the carbon layer. Although the mask prepared by the method has excellent adsorption effect on formaldehyde gas and PM2.5, the preparation of the raw material triazine ring crosslinked cellulose for preparing the biomass-based nitrogen-doped active carbon is very complex, and the triazine ring is taken as a nitrogen source, so that the mask has the advantages of severe reaction conditions, high cost and weak antibacterial effect.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an antibacterial active carbon mask and a preparation method thereof.
In order to achieve the above purpose, the invention provides an antibacterial active carbon mask, which sequentially stacks a photocatalyst melt-blown non-woven fabric outer layer, an active carbon melt-blown non-woven fabric inner layer and a pure cotton spun-laced non-woven fabric surface layer from top to bottom; the nose bridge strip is arranged in the middle of the upper end of the outer layer of the photocatalyst melt-blown non-woven fabric, and the nose bridge strip is covered by the non-woven fabric; respectively placing two ear belts at the left and right ends of the outer layer of the photocatalyst melt-blown non-woven fabric; and then hot-pressing to obtain the product; the photocatalyst melt-blown non-woven fabric is characterized in that a composite nano antibacterial agent prepared from graphene oxide, ferric chloride and bacterial cellulose is added into the outer layer of the photocatalyst melt-blown non-woven fabric. The non-woven fabric used in the invention is a non-woven fabric, which is a novel fiber product with soft, breathable and planar structure, and is formed by directly using polymer slices, short fibers or filaments to form a fiber net through air flow or machinery, then performing processes such as hydroentanglement, needling, spunbonding, melt blowing and the like, and finally performing after-treatment. The spun-bonded and melt-blown non-woven fabrics have complex fiber stacking structures and three-dimensional random distribution of fibers, so that the material contains a large number of tiny gaps, particles pass through various types of curved channels or paths around the fibers, the resistance of the air flow during passing can be greatly reduced, and meanwhile, the application of the spun-bonded and melt-blown non-woven fabrics in the mask filtering market is wider due to the fact that the spun-bonded and melt-blown non-woven fabrics have higher production speed and excellent structural performance.
Titanium dioxide is nontoxic, opaque, whiteness and brightness, has a good ultraviolet masking effect, can generate electronic transition to generate oxidative free radicals in the presence of ultraviolet light, has photocatalytic oxidation performance, and is widely applied to the field of photocatalysis as the most commonly used photocatalyst. However, titanium dioxide has a weak photocatalytic ability in an environment where visible light or light is weak. The invention adds metallic nickel in the common preparation method of titanium dioxide to improve the photocatalysis performance of titanium dioxide, and prepares the outer layer structure of the mask by the material.
Further preferably, the preparation step of the photocatalyst melt-blown nonwoven fabric outer layer comprises the following steps:
s1, uniformly stirring and mixing cetyl trimethyl ammonium bromide, absolute ethyl alcohol and tetrabutyl titanate to obtain a pale yellow solution I; subsequently, glacial acetic acid was added dropwise to the pale yellow solution I; stirring and aging at 50-70 ℃ to obtain milky gel; calcining the milky white gel at 450-550 ℃ for 3-5 h, naturally cooling, crushing and sieving to obtain titanium dioxide powder;
s2, adding nickel nitrate hexahydrate into water, and stirring to form a solution II; adding the titanium dioxide powder obtained in the step S1 into the solution II for ultrasonic dispersion, and then dipping for 10-15 h; drying insoluble matters after filtration, calcining for 3-5 hours at 450-550 ℃, naturally cooling, crushing and sieving to obtain titanium dioxide powder, and obtaining nickel-doped titanium dioxide powder;
s3, uniformly dispersing the nickel-doped titanium dioxide powder obtained in the step S2, sodium dodecyl benzene sulfonate and water, and then mixing with a composite nano antibacterial agent to obtain a coating liquid; coating the coating liquid on one surface of the melt-blown non-woven fabric, wherein the coating amount is 6-8 g/m based on the amount of nickel-doped titanium dioxide powder 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying; obtaining the photocatalyst melt-blown non-woven fabric outer layer.
Further preferably, the preparation method of the photocatalyst melt-blown nonwoven fabric outer layer comprises the following steps:
s1, adding 0.5 to 1 weight part of hexadecyl trimethyl ammonium bromide into 20 to 25 weight parts of absolute ethyl alcohol at a temperature of between 20 and 30 ℃, stirring to obtain a clear solution, adding 3 to 6 weight parts of tetrabutyl titanate, and continuously stirring to obtain a pale yellow solution I; then adding 1 to 1.5 weight parts of glacial acetic acid and 2 to 3 weight parts of water into the pale yellow solution I; stirring and aging at 50-70 ℃ to obtain milky gel; calcining the milky white gel at 450-550 ℃ for 3-5 h, naturally cooling to 20-30 ℃, and then crushing and sieving to obtain 300-500 meshes of titanium dioxide powder;
s2, adding 5-10 parts by weight of nickel nitrate hexahydrate into 100-150 parts by weight of water, and stirring to form a solution II; adding 5-10 parts by weight of the titanium dioxide powder obtained in the step S1 into the solution II, performing ultrasonic dispersion for 30-60 min, and then dipping for 10-15 h; after filtration, insoluble substances are dried for 2 to 5 hours at the temperature of 100 to 130 ℃, then calcined for 3 to 5 hours at the temperature of 450 to 550 ℃, naturally cooled to 20 to 30 ℃, crushed and sieved to obtain 300 to 500 meshes of titanium dioxide powder, and nickel-doped titanium dioxide powder is obtained;
s3, mixing 5 to 10 weight parts of nickel-doped titanium dioxide powder obtained in the step S2, 0.2 to 0.5 weight part of sodium dodecyl benzene sulfonate, 100 to 150 weight parts of water-dispersible nano antibacterial agent and 0.1 to 0.2 weight part of composite nano antibacterial agentMixing to obtain a coating liquid; coating the coating liquid on one surface of the melt-blown non-woven fabric, wherein the coating amount is 6-8 g/m based on the amount of nickel-doped titanium dioxide powder 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying; obtaining the photocatalyst melt-blown non-woven fabric outer layer.
Preferably, the preparation method of the composite nano antibacterial agent in the step S3 is as follows:
10-15g of graphene oxide and 0.5-0.8g of FeCl 3 ·6H 2 Dissolving O in 30-50mL of glycol to obtain a mixed solution 1, adding 1.5-2g of ammonium acetate and 0.5-1g of bacterial cellulose into the mixed solution 1, performing ultrasonic dispersion for 1-1.5h to obtain a mixed solution 2, transferring the mixed solution 2 into an autoclave lined with polytetrafluoroethylene to react for 10-12h at 150-200 ℃, filtering after the reaction is finished, collecting filter residues, respectively washing the filter residues with water and absolute ethyl alcohol for 3 times, and drying the filter residues in a drying oven at 50-70 ℃ for 10-12h to obtain the composite nano antibacterial agent.
Activated carbon is currently the most commonly used and inexpensive adsorbent, which is essentially a porous char, and is produced by heating an organic feedstock (carbon-hydrogen rich materials such as hulls, coal, wood, etc.) in the absence of air to reduce non-carbon content (this process is called charring), then reacting with gas, and the surface is eroded, resulting in a microporous structure (this process is called activation). The activation process is a microscopic process, namely, the surface erosion of a large number of molecular carbides is punctiform erosion, so that the surface of the activated carbon has numerous tiny pores with very rich pore structures, the micro-pore structure is developed, the specific surface area is larger, and the activated carbon can adsorb gas and liquid. The active carbon is added into the mask, so that particles with smaller diameters can be effectively prevented from invading the mouth and nose of a human body, and harmful gases such as benzene, formaldehyde, malodor and the like in the air can be effectively prevented, so that the effects of dust prevention, gas prevention and bacteria prevention are achieved. Some prior art researches on adsorption of benzene and toluene by activated carbon show that the activated carbon can effectively adsorb organic solvents and has certain selectivity.
The active carbon has rich sources of raw materials and simple preparation process, and can be added with low-melting-point salt and substances which are easy to react with carbon, and the carbon matrix is etched to prepare the active carbon material with high surface area. Some studies haveThe active carbon precursor is decomposed by water heat or cellulase is added to promote the reaction of the reactant and the carbon matrix at high temperature, and the multistage carbonization mode can prepare the catalyst with specific surface area more than 2500m 2 Activated carbon per gram. Although a high specific surface area is advantageous for adsorption of harmful substances by activated carbon. The inventors found that specific surface area is not the only factor affecting adsorption of PM2.5, increasing the reactive sites of activated carbon, introducing active substances to act with PM2.5 particles is a more efficient way. At the same time, a large amount of activating substances are used for etching the active carbon precursor, so that the preparation condition is complicated, the cost is increased, and the common activating agent KOH, naOH, znCl 2 The corrosion to the instrument is increased and more harmful gases are discharged.
The prior art activated carbon is generally prepared by blending a carbon precursor with an activator or soaking the carbon precursor in an activator solution, followed by calcination in an inert gas, and washing away inorganic impurities. The method does not depend on the high specific surface area of the activated carbon, and the active species are formed in situ during calcination, so that the pore diameter structure of the activated carbon can be blocked, and the overall activity is reduced; the morphology of the active species on the surface of the activated carbon is adjusted by adding a specific structure regulator.
Based on the method, the waste bamboo is used as a precursor of the active carbon, and the copper nitrate trihydrate and the structure regulator which are less corrosive to instruments are used for preparing the active carbon with stronger functionality, and the active carbon is used as an effective material of a filter layer in the mask.
The preparation method of the activated carbon melt-blown non-woven fabric comprises the following steps:
(1) Preparing bamboo powder;
(2) Soaking bamboo powder in copper nitrate solution; drying insoluble matters after filtration, and calcining under inert gas to obtain copper-doped activated carbon;
(3) And mixing the copper-doped activated carbon with the dispersion liquid to obtain a coating liquid, and coating the coating liquid on the melt-blown non-woven fabric to obtain the activated carbon melt-blown non-woven fabric.
Further preferably, the preparation method of the activated carbon melt-blown non-woven fabric comprises the following steps:
(1) Cleaning the waste bamboo stalks, and drying the waste bamboo stalks at 80-120 ℃ for 6-8 hours; then crushing to obtain bamboo powder;
(2) Adding 2-5 parts by weight of copper nitrate trihydrate and 0.02-0.05 part by weight of structure regulator into 100-150 parts by weight of water, and stirring to form solution A; adding 5-10 parts by weight of the bamboo powder obtained in the step (1) into the solution A, and soaking for 12-15 hours; filtering, and drying insoluble matters at 60-80 ℃ for 6-8 hours; calcining for 2-5 h in inert gas atmosphere at 650-850 ℃, naturally cooling to 20-30 ℃, washing the powder with water and acetone for three times, drying for 6-8 h at 60-80 ℃, crushing and sieving to obtain 300-500 mesh copper-doped activated carbon;
(3) 5 to 10 weight parts of copper-doped active carbon obtained in the step (2), 0.2 to 0.5 weight part of sodium dodecyl benzene sulfonate and 100 to 150 weight parts of water are dispersed to obtain coating liquid; coating the coating liquid on two sides of the melt-blown non-woven fabric, wherein the coating amount is 30-60 g/m based on the copper-doped activated carbon 2 The method comprises the steps of carrying out a first treatment on the surface of the And drying to obtain the active carbon melt-blown non-woven fabric.
Preferably, the number of the bamboo powder in the step (1) is 300-500 mesh.
Preferably, the structure regulator in the step (2) is at least one of 1-ethyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole bistrifluoro methanesulfonimide salt, 1-butyl-2, 3-dimethylimidazole hexafluorophosphate, hexamethylenetetramine and ethylenediamine.
Further preferably, the structure regulator in the step (2) is 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and hexamethylenetetramine according to the mass ratio of (2-4): 1, uniformly mixing to obtain the product.
Preferably, the temperature rising rate of the calcination in the step (2) is 2-10 ℃/min.
Preferably, the dispersion rate in the step (3) is 1200-1800 r/min.
The invention also provides a preparation method of the antibacterial active carbon mask, which comprises the following steps: according to the preparation method of the common mask, sequentially stacking the photocatalyst melt-blown non-woven fabric outer layer, the activated carbon melt-blown non-woven fabric inner layer and the pure cotton spun-laced non-woven fabric surface layer from top to bottom; the nose bridge strip is arranged in the middle of the upper end of the outer layer of the photocatalyst melt-blown non-woven fabric, and the nose bridge strip is covered by the non-woven fabric; respectively placing two ear belts at the left and right ends of the outer layer of the photocatalyst melt-blown non-woven fabric; and then hot-pressing to obtain the antibacterial active carbon mask.
The invention has the beneficial effects that:
(1) The antibacterial active carbon mask is prepared by combining the outer layer with photocatalytic degradation, the copper-doped active carbon filtering inner layer and the skin-friendly spunlaced non-woven fabric surface layer, and has the advantages of simple preparation process, good coordination of each functional layer, high filtering efficiency on particles and stable long-term use performance.
(2) The biomass waste is comprehensively utilized, the waste bamboo is used as a precursor of the activated carbon, the copper nitrate trihydrate is used as a mild modifier and a functional agent, and the structure regulator is added, so that the performance of the copper-doped activated carbon is remarkably improved, and the filtering efficiency of the antibacterial activated carbon mask is further improved.
(3) The composite nano antibacterial agent prepared from graphene oxide, ferric chloride and bacterial cellulose is added on the outer layer of the photocatalyst melt-blown non-woven fabric, so that the antibacterial performance of the non-woven fabric layer is effectively improved.
Drawings
Fig. 1 is a field emission scanning electron microscope image of activated carbon prepared in accordance with the present invention, a example 1, B example 2, C example 3, D example 4, E comparative example 1, F comparative example 2.
Fig. 2 shows the change of the filtering efficiency of the mask with time under the simulated human breathing environment of the masks prepared in example 4 and comparative example 3 of the present invention.
Detailed Description
The invention uses partial raw materials:
melt blown nonwoven fabric having a grammage of 40g/m 2 。
Pure cotton spunlaced non-woven fabric with gram weight of 100g/m 2 。
The waste bamboo stems were collected from martial arts.
KN95 melt-blown nonwoven fabric with gram weight of 50g/m 2 。
Example 1
A preparation method of an antibacterial active carbon mask comprises the following steps: cutting the outer layer of the photocatalyst melt-blown non-woven fabric, the inner layer of the activated carbon melt-blown non-woven fabric and the surface layer of the pure cotton spun-laced non-woven fabric into specifications with the upper and lower heights of 95mm and the left and right widths of 175mm according to a preparation method of a common mask, and sequentially stacking the outer layer of the photocatalyst melt-blown non-woven fabric, the inner layer of the activated carbon melt-blown non-woven fabric and the surface layer of the pure cotton spun-laced non-woven fabric from top to bottom; placing the nose bridge strip at a position 8mm away from the upper edge line and left and right centering on the outer layer of the photocatalyst melt-blown non-woven fabric, and covering the nose bridge strip by the non-woven fabric; two ear belts are respectively arranged at the left end and the right end of the outer layer of the photocatalyst melt-blown non-woven fabric, and the distance between the two ear belts and the upper edge line is 5mm; and hot-pressing to obtain the antibacterial active carbon mask.
The preparation method of the photocatalyst melt-blown non-woven fabric outer layer comprises the following steps:
s1, adding 0.5g of cetyltrimethylammonium bromide into 25g of absolute ethyl alcohol at the temperature of 25 ℃, stirring for 5min at the speed of 300r/min to obtain a clear solution, adding 5g of tetrabutyl titanate, and continuously stirring for 10min to obtain a pale yellow solution I; subsequently 1g of glacial acetic acid, 2g of water are added to the pale yellow solution I; stirring at 60deg.C for 6 hr, and aging for 24 hr to obtain milky gel; calcining the milky white gel at 550 ℃ for 3 hours, naturally cooling to 25 ℃, and then crushing and sieving to obtain 325-mesh titanium dioxide powder;
s2, adding 5g of nickel nitrate hexahydrate into 150g of water, and stirring to form a solution II; adding 10g of the titanium dioxide powder obtained in the step S1 into the solution II, dispersing for 30min at the ultrasonic power of 80W and the frequency of 50kHz, and then soaking for 12h; drying insoluble matters at 120 ℃ for 2 hours after filtration, calcining at 550 ℃ for 3 hours, naturally cooling to 25 ℃, crushing and sieving to obtain 325-mesh titanium dioxide powder, and obtaining nickel-doped titanium dioxide powder;
s3, dispersing 5g of the nickel-doped titanium dioxide powder obtained in the step S2, 0.2g of sodium dodecyl benzene sulfonate and 150g of water for 30min under the dispersion condition of a high-speed dispersing machine 1500r/min to obtain a coating liquid, and obtaining the coating liquid; spraying the coating liquid on one side of the melt-blown non-woven fabric in a airless spraying manner, wherein the coating amount is 8g/m based on the amount of nickel-doped titanium dioxide powder 2 Drying at 60deg.C for 3 hr; obtaining the photocatalyst melt-blown non-woven fabric outer layer.
The preparation method of the activated carbon melt-blown non-woven fabric inner layer comprises the following steps:
(1) Cleaning the waste bamboo stems, and drying at 90 ℃ for 6 hours; pulverizing, sieving to obtain 325 mesh bamboo powder;
(2) 2g of copper nitrate trihydrate is added into 150g of water and stirred for 5min at a speed of 300r/min to form solution A; adding 5g of the bamboo powder obtained in the step (1) into the solution A, and soaking for 12 hours; after filtration, the insoluble material was dried at 80 ℃ for 6h; then heating to 700 ℃ in nitrogen atmosphere at a heating rate of 5 ℃/min, preserving heat for 2 hours, naturally cooling to 25 ℃, washing the powder with water and acetone for three times respectively, drying at 60 ℃ for 6 hours, crushing and sieving to obtain 325-mesh copper-doped activated carbon;
(3) Dispersing 5g of the copper-doped active carbon obtained in the step (2), 0.2g of sodium dodecyl benzene sulfonate and 150g of water for 30min under the dispersion condition of a high-speed dispersing machine of 1500r/min to obtain a coating liquid; spraying the coating liquid on the two sides of the melt-blown non-woven fabric in a airless spraying manner, wherein the coating amount is 50g/m based on the copper-doped activated carbon 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying at 60 ℃ for 3 hours to obtain the activated carbon melt-blown non-woven fabric;
example 2
The preparation method of the antibacterial activated carbon mask is basically the same as that of the embodiment 1, and the only difference is that:
the preparation method of the activated carbon melt-blown non-woven fabric inner layer comprises the following steps:
(1) Cleaning the waste bamboo stems, and drying at 90 ℃ for 6 hours; pulverizing, sieving to obtain 325 mesh bamboo powder;
(2) 2g of copper nitrate trihydrate and 0.02g of hexamethylenetetramine are added into 150g of water and stirred for 5min at a speed of 300r/min to form a solution A; adding 5g of the bamboo powder obtained in the step (1) into the solution A, and soaking for 12 hours; after filtration, the insoluble material was dried at 80 ℃ for 6h; then heating to 700 ℃ in nitrogen atmosphere at a heating rate of 5 ℃/min, preserving heat for 2 hours, naturally cooling to 25 ℃, washing the powder with water and acetone for three times respectively, drying at 60 ℃ for 6 hours, crushing and sieving to obtain 325-mesh copper-doped activated carbon;
(3) Dispersing 5g of the copper-doped active carbon obtained in the step (2), 0.2g of sodium dodecyl benzene sulfonate and 150g of water under the dispersion condition of a high-speed dispersing machine of 1500r/min30min, obtaining coating liquid; spraying the coating liquid on the two sides of the melt-blown non-woven fabric in a airless spraying manner, wherein the coating amount is 50g/m based on the copper-doped activated carbon 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying at 60 ℃ for 3 hours to obtain the activated carbon melt-blown non-woven fabric;
example 3
The preparation method of the antibacterial activated carbon mask is basically the same as that of the embodiment 1, and the only difference is that:
the preparation method of the activated carbon melt-blown non-woven fabric inner layer comprises the following steps:
(1) Cleaning the waste bamboo stems, and drying at 90 ℃ for 6 hours; pulverizing, sieving to obtain 325 mesh bamboo powder;
(2) 2g of copper nitrate trihydrate and 0.02g of 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt are added into 150g of water and stirred for 5min at a speed of 300r/min to form a solution A; adding 5g of the bamboo powder obtained in the step (1) into the solution A, and soaking for 12 hours; after filtration, the insoluble material was dried at 80 ℃ for 6h; then heating to 700 ℃ in nitrogen atmosphere at a heating rate of 5 ℃/min, preserving heat for 2 hours, naturally cooling to 25 ℃, washing the powder with water and acetone for three times respectively, drying at 60 ℃ for 6 hours, crushing and sieving to obtain 325-mesh copper-doped activated carbon;
(3) Dispersing 5g of the copper-doped active carbon obtained in the step (2), 0.2g of sodium dodecyl benzene sulfonate and 150g of water for 30min under the dispersion condition of a high-speed dispersing machine of 1500r/min to obtain a coating liquid; spraying the coating liquid on the two sides of the melt-blown non-woven fabric in a airless spraying manner, wherein the coating amount is 50g/m based on the copper-doped activated carbon 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying at 60 ℃ for 3 hours to obtain the activated carbon melt-blown non-woven fabric.
Example 4
The preparation method of the antibacterial activated carbon mask is basically the same as that of the embodiment 1, and the only difference is that:
the preparation method of the activated carbon melt-blown non-woven fabric inner layer comprises the following steps:
(1) Cleaning the waste bamboo stems, and drying at 90 ℃ for 6 hours; pulverizing, sieving to obtain 325 mesh bamboo powder;
(2) 2g of copper nitrate trihydrate, 0.016g of 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt and 0.004g of hexamethylenetetramine are added into 150g of water and stirred at a speed of 300r/min for 5min to form a solution A; adding 5g of the bamboo powder obtained in the step (1) into the solution A, and soaking for 12 hours; after filtration, the insoluble material was dried at 80 ℃ for 6h; then heating to 700 ℃ in nitrogen atmosphere at a heating rate of 5 ℃/min, preserving heat for 2 hours, naturally cooling to 25 ℃, washing the powder with water and acetone for three times respectively, drying at 60 ℃ for 6 hours, crushing and sieving to obtain 325-mesh copper-doped activated carbon;
(3) Dispersing 5g of the copper-doped active carbon obtained in the step (2), 0.2g of sodium dodecyl benzene sulfonate and 150g of water for 30min under the dispersion condition of a high-speed dispersing machine of 1500r/min to obtain a coating liquid; spraying the coating liquid on the two sides of the melt-blown non-woven fabric in a airless spraying manner, wherein the coating amount is 50g/m based on the copper-doped activated carbon 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying at 60 ℃ for 3 hours to obtain the activated carbon melt-blown non-woven fabric.
Example 5
The preparation method of the antibacterial activated carbon mask is basically the same as that of example 4, and the only difference is that:
the preparation method of the photocatalyst melt-blown non-woven fabric outer layer comprises the following steps:
s1, adding 0.5g of cetyltrimethylammonium bromide into 25g of absolute ethyl alcohol at the temperature of 25 ℃, stirring for 5min at the speed of 300r/min to obtain a clear solution, adding 5g of tetrabutyl titanate, and continuously stirring for 10min to obtain a pale yellow solution I; subsequently 1g of glacial acetic acid, 2g of water are added to the pale yellow solution I; stirring at 60deg.C for 6 hr, and aging for 24 hr to obtain milky gel; calcining the milky white gel at 550 ℃ for 3 hours, naturally cooling to 25 ℃, and then crushing and sieving to obtain 325-mesh titanium dioxide powder;
s2, adding 5g of nickel nitrate hexahydrate into 150g of water, and stirring to form a solution II; adding 10g of the titanium dioxide powder obtained in the step S1 into the solution II, dispersing for 30min at the ultrasonic power of 80W and the frequency of 50kHz, and then soaking for 12h; drying insoluble matters at 120 ℃ for 2 hours after filtration, calcining at 550 ℃ for 3 hours, naturally cooling to 25 ℃, crushing and sieving to obtain 325-mesh titanium dioxide powder, and obtaining nickel-doped titanium dioxide powder;
s3 dispersing 5g of the nickel-doped titanium dioxide powder obtained in the step S2, 0.2g of sodium dodecyl benzene sulfonate and 150g of water under the dispersion condition of 1500r/min of a high-speed dispersing machineMixing with 0.2g of composite nano antibacterial agent after 30min to obtain a coating liquid, and obtaining the coating liquid; spraying the coating liquid on one side of the melt-blown non-woven fabric in a airless spraying manner, wherein the coating amount is 8g/m based on the amount of nickel-doped titanium dioxide powder 2 Drying at 60deg.C for 3 hr; obtaining the photocatalyst melt-blown non-woven fabric outer layer.
The preparation method of the composite nano-microbial agent comprises the following steps:
10g of graphene oxide and 0.6g of FeCl 3 ·6H 2 O is dissolved in 40mL of glycol to obtain a mixed solution 1, then 1.5g of ammonium acetate and 0.8g of bacterial cellulose are added into the mixed solution 1, ultrasonic dispersion is carried out for 1h to obtain a mixed solution 2, the mixed solution 2 is transferred into an autoclave with a polytetrafluoroethylene lining to react for 10h at 180 ℃, after the reaction is finished, filtration is carried out, filter residues are collected, the filter residues are respectively washed 3 times by water and absolute ethyl alcohol, and then the filter residues are placed into a 60-position drying oven to be dried for 12h to obtain the composite nano antibacterial agent.
Comparative example 1
The preparation method of the antibacterial activated carbon mask is basically the same as that of the embodiment 1, and the only difference is that:
the preparation method of the activated carbon melt-blown non-woven fabric inner layer comprises the following steps:
(1) Cleaning the waste bamboo stems, and drying at 90 ℃ for 6 hours; pulverizing, sieving to obtain 325 mesh bamboo powder;
(2) Heating bamboo powder to 700 ℃ in nitrogen atmosphere at a heating rate of 5 ℃/min, preserving heat for 2 hours, naturally cooling to 25 ℃, washing the powder with water and acetone for three times respectively, drying at 60 ℃ for 6 hours, crushing and sieving to obtain 325-mesh activated carbon;
(3) Dispersing 5g of the activated carbon obtained in the step (2), 0.2g of sodium dodecyl benzene sulfonate and 150g of water for 30min under the dispersion condition of a high-speed dispersing machine of 1500r/min to obtain a coating liquid; spraying the coating liquid on the two sides of the melt-blown non-woven fabric in a airless spraying manner, wherein the coating amount is 50g/m based on the copper-doped activated carbon 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying at 60 ℃ for 3 hours to obtain the activated carbon melt-blown non-woven fabric.
Comparative example 2
The preparation method of the antibacterial activated carbon mask is basically the same as that of the embodiment 1, and the only difference is that: in the preparation of the inner layer of the activated carbon melt-blown non-woven fabric, KOH activated carbon is used for replacing copper-doped activated carbon in the inner layer of the activated carbon melt-blown non-woven fabric.
The preparation method of the KOH activated carbon comprises the following steps: cleaning the waste bamboo stems, and drying at 90 ℃ for 6 hours; pulverizing, sieving to obtain 325 mesh bamboo powder; mixing bamboo powder of 325 meshes with KOH of 5 times of mass at 25 ℃, heating to 750 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and naturally cooling to 25 ℃; the solid was immersed in 2mol/L hydrochloric acid, washed with water to give supernatant ph=7.0, the insoluble matter was filtered, and dried in an oven at 100 ℃ for 6 hours, followed by pulverization and sieving to give 325 mesh KOH activated carbon.
Comparative example 3
The preparation method of the antibacterial activated carbon mask is basically the same as that of the embodiment 1, and the only difference is that: and replacing the active carbon melt-blown non-woven fabric inner layer with the KN95 melt-blown non-woven fabric.
Test example 1 structural test of activated carbon
The activated carbon materials prepared in examples 1 to 4 and comparative examples 1 to 2 of the present invention were subjected to morphology test by using a field emission scanning electron microscope, and the results are shown in fig. 1. In fig. 1, a example 1, B example 2, C example 3, D example 4, E comparative example 1, F comparative example 2. As can be seen from the direct calcination of the activated carbon (fig. 1E) with the bamboo powder of comparative example 1 and the KOH-activated carbon (fig. 1F) of comparative example 2, the etching of the bamboo structure with KOH activation is remarkable, and the KOH-activated bamboo powder has a large number of irregular pore structures, remarkably increasing the specific surface area of the activated carbon. Example 1A copper-doped activated carbon (fig. 1A) prepared by adding copper nitrate trihydrate has an overall structure similar to that of comparative example 1, and has randomly distributed and obvious spherical particles (copper or cuprous oxide is analyzed by XRD) on the surface, which indicates that copper species reduced to a low valence state in situ at a high temperature are inlaid on the surface of the activated carbon after copper nitrate trihydrate is added. Examples 2-4 are similar overall to example 1 except that the morphology and size of the surface particles (copper or cuprous oxide as analyzed by XRD) are different. Example 2 (figure 1B) copper-doped activated carbon prepared by adding copper nitrate trihydrate and hexamethylenetetramine, wherein the copper species on the surface of the activated carbon is obviously refined and widely dispersed; example 3 (fig. 1C) copper-doped activated carbon prepared by adding copper nitrate trihydrate, 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt, copper species became coarse and agglomerated and distributed on the surface of the activated carbon; example 4 (fig. 1D) copper-doped activated carbon prepared by adding copper nitrate trihydrate, 1-butyl-3-methylimidazole bistrifluoromethylsulfonylimine salt, hexamethylenetetramine, the copper species dispersed most uniformly without significant agglomeration and the presence of large particles. These results indicate that hexamethylenetetramine, 1-butyl-3-methylimidazole bistrifluoromethylsulfonylimine salt, have a great effect on the morphology of copper species in the copper-doped activated carbon. This is probably because hexamethylenetetramine, 1-butyl-3-methylimidazole bistrifluoromethylsulfonylimine salt enhances the action of bamboo powder in liquid phase environment and copper ions, and the addition of hexamethylenetetramine can refine copper species generated in situ, and 1-butyl-3-methylimidazole bistrifluoromethylsulfonylimine salt can enable the copper species to be properly dispersed on the surface and promote decomposition to form a coarse structure; the combined action of the hexamethylenetetramine and the 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt ensures that the copper species on the surface of the activated carbon has uniform structure and appearance and a rougher surface.
Specific surface area test by nitrogen adsorption test the specific surface areas of the activated carbon materials prepared in examples 1 to 4 and comparative examples 1 to 2 of the present invention were measured, and the results are shown in table 1.
TABLE 1 results of specific surface area of activated carbon materials
From the results of comparative example 1 and example 1, it was found that the addition of copper nitrate trihydrate increased the surface area of the activated carbon, increased the pore size structure, and further increased the specific surface areas of comparative examples 2 to 4, which indicated that the addition of hexamethylenetetramine, 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt enhanced the decomposition-induced pore structure of the bamboo powder, and that the complexation of hexamethylenetetramine and 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt was stronger in the etching action on the bamboo powder. Although the activated carbon prepared by KOH activation in the comparative example has the highest specific surface area, the pore diameter thereof is concentrated in micropores, and tiny impurities are easily adsorbed and lose activity, and may not be suitable for preparing PM2.5 prevention masks.
Test example 2 mask Performance test
The PM2.5 in contact with the living environment is mainly non-oily particles such as dust with different sizes, and smaller particles possibly enter alveoli to influence the health of a human body. Therefore, the filtration efficiency of non-oily particulate matter is an important index for PM2.5 prevention masks. According to the invention, an automatic filter material tester is used for simulating PM2.5 with NaCl aerogel under the condition of 85 L+/-1L/min air flow, so that the filtering efficiency and the respiratory resistance of the mask are tested; the size distribution of the NaCl aerogel particles used accords with the median diameter of particle number of 0.075 mu m plus or minus 0.020 mu m, the geometric standard deviation is in the range of 1.86, and the concentration is lower than 200mg/m 3 . The results of the filtration efficiency of the mask are shown in table 2.
Table 2 filtration efficiency of mask
As can be seen from the results of table 2, comparative example 1 was prepared by directly carbonizing bamboo powder and comparative example 2 was prepared by activating with KOH, and when used as a filter inner layer material of a mask, the filtration efficiency was limited and did not meet the standards. Comparative example 3 uses KN95 melt blown nonwoven as the inner filter layer, and the filtration efficiency reaches 96.7%. Comparative example 4 copper-doped activated carbon prepared from copper nitrate trihydrate, 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt, and hexamethylenetetramine was used as a material for the inner layer of filtration, and the filtration efficiency was 97.3%. This is probably because the addition of 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and hexamethylenetetramine promotes the decomposition of the carbon matrix to increase the specific surface area of the activated carbon, and simultaneously makes the structure morphology of the copper species on the surface of the activated carbon uniform and the surface rougher, so that the copper-doped activated carbon has larger pore diameter and more binding sites, and can effectively adsorb particles.
The mask melt-blown filter inner layer used in the market utilizes the electrostatic force effect of electric charges to trap air dust particles, and when the mask melt-blown filter inner layer is used, moisture consumes electric charges inevitably to cause the trapping effect failure of the functional layer, so that the mask needs to be replaced frequently. Monitoring the long-term service performance test of the mask is extremely important. The test utilizes the breathing environment of human mouth simulated by a constant temperature and humidity box, the mask is put into the environment with the set temperature of 37 ℃ and the relative humidity of 80%, the filter performance of the mask is tested every 2 hours, the test is continuously carried out for 8 hours, and the filter efficiency at intervals of time is recorded. The results are shown in FIG. 2.
The results of fig. 2 show that the filtration efficiency of the mask prepared in example 4 of the present invention is not significantly reduced in 8 hours of simulated use, and the continuous filtration effect of the inner filter material is significantly better than that of KN95 meltblown. These results indicate that the mask prepared in example 4 of the present invention has good filtration efficiency and long-term use.
Test example 3 antibacterial Effect test
The photocatalyst melt-blown nonwoven fabric prepared in example 4 and example 5 was subjected to a sterilization rate test for 5 minutes by referring to GB15979-2002 "hygienic Standard for disposable hygienic products" appendix C "method for testing product sterilization Performance, antibacterial Property and stability", the specific test data are shown in Table 3, wherein Escherichia coli is purchased from the China center for Industrial microorganism culture Collection, and the strain number is CICC10899; staphylococcus aureus is purchased from the China center for type culture Collection of microorganisms, and the strain number is CICC21600.
TABLE 3 test results of the sterilization rate of the outer layer of the photo-catalyst meltblown nonwoven fabric
As can be seen from the data in Table 3, graphene oxide and FeCl were added 3 ·6H 2 The sterilization rate of the photocatalyst melt-blown non-woven fabric outer layer of the composite nano antibacterial agent prepared by O and bacterial cellulose is obviously higher than that of the non-woven fabric outer layer without adding graphene oxide and FeCl 3 ·6H 2 The photocatalyst melt-blown non-woven fabric of the composite nano antibacterial agent prepared by O and bacterial cellulose is provided with an outer layer,the possible reason is that the composite nano antibacterial agent is adsorbed on the surface of bacteria and changes the permeability of the cell wall of the bacteria, and damages the cell structure of the bacteria to enable substances in the cells to flow out, so that the bacteria lose the metabolism capacity to achieve the sterilization effect.
Claims (6)
1. A preparation method of an antibacterial active carbon mask comprises sequentially stacking a photocatalyst melt-blown non-woven fabric outer layer, an active carbon melt-blown non-woven fabric inner layer and a pure cotton spun-laced non-woven fabric surface layer from top to bottom; the nose bridge strip is arranged in the middle of the upper end of the outer layer of the photocatalyst melt-blown non-woven fabric, and the nose bridge strip is covered by the non-woven fabric; respectively placing two ear belts at the left and right ends of the outer layer of the photocatalyst melt-blown non-woven fabric; and then hot-pressing to obtain the product; the method is characterized in that:
the preparation method of the photocatalyst melt-blown non-woven fabric outer layer comprises the following steps:
s1, uniformly stirring and mixing cetyl trimethyl ammonium bromide, absolute ethyl alcohol and tetrabutyl titanate to obtain a pale yellow solution I; subsequently, glacial acetic acid was added dropwise to the pale yellow solution I; stirring and aging at 50-70 ℃ to obtain milky gel; calcining the milky white gel at 450-550 ℃ for 3-5 hours, naturally cooling, crushing and sieving to obtain titanium dioxide powder;
s2, adding nickel nitrate hexahydrate into water, and stirring to form a solution II; adding the titanium dioxide powder obtained in the step S1 into a solution II, performing ultrasonic dispersion, and then dipping for 10-15 h; drying insoluble matters after filtration, calcining for 3-5 hours at 450-550 ℃, naturally cooling, crushing and sieving to obtain nickel-doped titanium dioxide powder;
s3, uniformly dispersing the nickel-doped titanium dioxide powder obtained in the step S2, sodium dodecyl benzene sulfonate and water, and then mixing with a composite nano antibacterial agent to obtain a coating liquid; coating the coating liquid on one surface of the melt-blown non-woven fabric, wherein the coating amount is 6-8 g/m based on the nickel-doped titanium dioxide powder 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying; obtaining the outer layer of the photo-catalyst melt-blown non-woven fabric;
the preparation method of the activated carbon melt-blown non-woven fabric inner layer comprises the following steps:
(1) Cleaning the waste bamboo stems, and drying at 80-120 ℃ for 6-8 hours; then crushing to obtain bamboo powder;
(2) Adding 2-5 parts by weight of copper nitrate trihydrate and 0.02-0.05 part by weight of a structure regulator into 100-150 parts by weight of water, and stirring to form a solution II; adding 5-10 parts by weight of the bamboo powder obtained in the step (1) into the solution II, and soaking for 12-15 hours; after filtration, drying insoluble matters at 60-80 ℃ for 6-8 hours; calcining for 2-5 hours at 650-850 ℃ in an inert gas atmosphere, naturally cooling to 20-30 ℃, washing the powder with water and acetone three times respectively, drying for 6-8 hours at 60-80 ℃, crushing and sieving to obtain 300-500 mesh copper-doped activated carbon;
(3) Dispersing 5-10 parts by weight of the copper-doped active carbon obtained in the step (2), 0.2-0.5 part by weight of sodium dodecyl benzene sulfonate and 100-150 parts by weight of water to obtain a coating liquid; coating the coating liquid on two sides of the melt-blown non-woven fabric, wherein the coating amount is 30-60 g/m based on the copper-doped activated carbon 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying to obtain the active carbon melt-blown non-woven fabric;
the preparation method of the composite nano antibacterial agent comprises the following steps: 10-15g of graphene oxide and 0.5-0.8g of FeCl 3 ∙6H 2 Dissolving O in 30-50mL of glycol to obtain a mixed solution 1, adding 1.5-2g of ammonium acetate and 0.5-1g of bacterial cellulose into the mixed solution 1, performing ultrasonic dispersion for 1-1.5h to obtain a mixed solution 2, transferring the mixed solution 2 into an autoclave lined with polytetrafluoroethylene to react for 10-12h at 150-200 ℃, filtering after the reaction is finished, collecting filter residues, respectively washing the filter residues with water and absolute ethyl alcohol for 3 times, and drying the filter residues in a drying oven at 50-70 ℃ for 10-12h to obtain the composite nano antibacterial agent.
2. The method for producing an antibacterial activated carbon mask according to claim 1, wherein the number of the bamboo powder in the step (1) is 300 to 500 mesh.
3. The method for producing an antibacterial active carbon mask according to claim 1, wherein the structure-adjusting agent in the step (2) is at least one of 1-ethyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-butyl-2, 3-dimethylimidazole hexafluorophosphate, hexamethylenetetramine and ethylenediamine.
4. The method for preparing an antibacterial active carbon mask according to claim 1, wherein the structure regulator in the step (2) is 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and hexamethylenetetramine in a mass ratio of (2-4): 1, and mixing.
5. The method for producing an antibacterial activated carbon mask according to claim 1, wherein the temperature rising rate of calcination in the step (2) is 2-10 ℃/min.
6. An antibacterial activated carbon mask is characterized in that: the method according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210118065.0A CN114343273B (en) | 2022-02-08 | 2022-02-08 | Antibacterial active carbon mask and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210118065.0A CN114343273B (en) | 2022-02-08 | 2022-02-08 | Antibacterial active carbon mask and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114343273A CN114343273A (en) | 2022-04-15 |
| CN114343273B true CN114343273B (en) | 2023-05-12 |
Family
ID=81093442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210118065.0A Active CN114343273B (en) | 2022-02-08 | 2022-02-08 | Antibacterial active carbon mask and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114343273B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN206586434U (en) * | 2017-03-17 | 2017-10-27 | 王妍 | Catalyst mouth mask |
| CN108618235A (en) * | 2017-03-17 | 2018-10-09 | 王妍 | catalyst mask |
| CN111374152B (en) * | 2020-03-24 | 2021-09-21 | 高登科学(深圳)有限公司 | Bactericide and preparation method thereof, and air filter, mask, modified emulsion paint and modified concrete |
| CN111481850A (en) * | 2020-05-22 | 2020-08-04 | 深圳三爱美容科技有限公司 | Mask with traditional Chinese medicine tablet for supplying fresh air |
-
2022
- 2022-02-08 CN CN202210118065.0A patent/CN114343273B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114343273A (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Multifunctional TiO2/polyacrylonitrile nanofibers for high efficiency PM2. 5 capture, UV filter, and anti-bacteria activity | |
| CN110936676B (en) | Filter layer body for efficient dust mask | |
| CN201248380Y (en) | Mask for proofing dust haze and ozone | |
| CN107569967B (en) | It is a kind of for formaldehyde adsorption and the vehicle-mounted air purification piece of TVOC and preparation method thereof | |
| CN105688660B (en) | Using photocatalyst of titanium dioxide as material for air purification of base material and preparation method thereof | |
| CN111359582A (en) | Graphene composite aerogel formaldehyde-removing material and preparation method thereof | |
| CN111535033B (en) | Preparation method and application of iodine antimicrobial microporous fiber material | |
| CN112127049B (en) | Preparation method of polypropylene melt-blown non-woven fabric material for mask | |
| CN112516685A (en) | Visible light photocatalysis air purification glass fiber filter element and preparation method thereof | |
| CN102872473A (en) | Environment-friendly air purifying preparation and method for manufacturing same | |
| CN203586427U (en) | Portable air purifier | |
| CN114343273B (en) | Antibacterial active carbon mask and preparation method thereof | |
| KR102262276B1 (en) | A filter and non-woven fabric comprising ceramic carrier and active ingredient | |
| CN106108175B (en) | A kind of efficient haze and organic pollution mouth mask and preparation method thereof | |
| CN114263037B (en) | PM 2.5-preventing active carbon mask and preparation method thereof | |
| CN209978229U (en) | Anion fresh air ecological box for simulating raining and sunny water filtering purification | |
| CN202774252U (en) | Initiative protective type antibacterial mask | |
| CN112371084A (en) | Preparation method and application of sterilized activated carbon | |
| CN114797888B (en) | Indoor formaldehyde-removing air purifying agent and preparation method thereof | |
| CN106938164A (en) | A kind of anti-haze immunologic function film and preparation method and application | |
| CN109758831A (en) | The preparation method of high-efficiency air filtering material | |
| CN109797442A (en) | A kind of Multifunctional gauze mask and preparation method thereof | |
| CN205757364U (en) | A kind of gauze mask | |
| CN212661579U (en) | Photocatalyst antibacterial curtain with air purification performance | |
| CN109011920B (en) | Antibacterial air filtering membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |