CN114557364A - Chlorine dioxide slow-release air freshener - Google Patents

Chlorine dioxide slow-release air freshener Download PDF

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Publication number
CN114557364A
CN114557364A CN202210156300.3A CN202210156300A CN114557364A CN 114557364 A CN114557364 A CN 114557364A CN 202210156300 A CN202210156300 A CN 202210156300A CN 114557364 A CN114557364 A CN 114557364A
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chlorine dioxide
parts
air freshener
microporous ceramic
ceramic material
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CN114557364B (en
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杨崎峰
韦应南
林宏飞
王爱
谢春敏
周万挺
覃敏
磨薇薇
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Guangxi Environmental Protection Industry Development Research Institute Co ltd
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Guangxi Environmental Protection Industry Development Research Institute Co ltd
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Abstract

The invention discloses a chlorine dioxide slow-release air freshener which comprises a microporous ceramic material, a porous adsorption material, chlorine dioxide generation components and an adhesive, wherein the microporous ceramic material is two hemispherical shells, the chlorine dioxide generation components are adsorbed on the porous adsorption material, the porous adsorption material adsorbed with the chlorine dioxide generation components is coated in the microporous ceramic material, and the microporous ceramic materials are bonded and formed through the adhesive. The air freshener is adjusted along with the change of the environment through the regulation and control of the self-breathing material, so that the utilization rate of the chlorine dioxide generating agent is greatly improved, and the use experience of a user using the chlorine dioxide air freshener in a personal space is improved.

Description

Chlorine dioxide slow-release air freshener
Technical Field
The invention belongs to the field of daily air fresheners, and particularly relates to a chlorine dioxide slow-release air freshener.
Background
The chlorine dioxide has strong oxidation and bleaching performances, can decompose ammonia, sulfur-containing compounds, unsaturated hydrocarbons and partial VOC in the air, and can effectively remove trace peculiar smell diffused in the air. Meanwhile, the disinfectant also has a strong destroying effect on proteins of bacteria, fungi and algae, can quickly kill microorganisms in the air and attached to the surface of a general object, further eliminates odor which is difficult to eradicate in the air, such as musty odor, putrefactive odor and the like, and is a substance very suitable for air fresheners.
The chlorine dioxide has obvious pungent odor when the concentration is higher, and can cause discomfort to people, and researches show that the chlorine dioxide does not need to make people perceive the abnormal high concentration when used for air disinfection, and 0.01 ppm-0.1 ppm can have good killing effect on most pathogenic bacteria and mould. The lower limit of perception of human body to chlorine dioxide is 0.3ppm, the national standard 'workplace harmful factor occupational exposure limit' (GBZ 2-2007), and the allowable concentration of chlorine dioxide in workplaces is regulated to be 0.3mg/m3Amounting to 0.236 ppm. Therefore, the concentration of chlorine dioxide in the air is kept below 0.2ppm, so that very effective air disinfection can be performed, and the chlorine dioxide gas is controlled in the range, so that the average concentration of chlorine dioxide in the air is 0.01-0.2 ppm, and a good air refreshing effect is achieved.
Therefore, chlorine dioxide slow-release disinfectant and air freshener products are applied in many ways. Such as gels, particles and liquids, the buffer solution of chlorine dioxide is usually wrapped and thickened by macromolecules containing cavities, so that newly generated chlorine dioxide cannot rapidly migrate to the outer side of the gel/particle or other substances difficult to permeate after the generation, and the slow release of the chlorine dioxide is realized.
However, such slow-release methods generally rely on solutions and hydrogels for activation, and chlorine dioxide in aqueous solutions is easily subjected to disproportionation reaction of auto-oxidation-reduction to decompose into substances incapable of generating chlorine dioxide again, such side reactions tend to occur when the pH value is maintained from weak acidity to weak alkalinity, and the reaction speed is easily accelerated due to temperature rise, so that a large amount of reactants are lost or slow release is out of control, and chlorine dioxide is released in a large amount in a short time. Chlorine dioxide and its former reactant are easily influenced by light, and under the catalysis of strong light irradiation, chlorine dioxide can be decomposed quickly to produce toxic chlorine gas, so that the effect of using chlorine dioxide to make safe air disinfection and killing can be lost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a chlorine dioxide slow-release air freshener, which uses a specially fired self-breathing microporous ceramic material as a shell material of a porous material, and a porous adsorption material adsorbs a chlorine dioxide generation component to regulate and control the temperature and humidity in the slow-release air freshener. The intelligent control of the start and stop of the sodium chlorite reaction is realized, the sodium chlorite disinfectant can be used for indoor odor removal, mildew prevention and sterilization, can disinfect the surfaces of objects which are easy to have residual peculiar smell and germs, and can effectively decompose harmful substances such as various amines, sulfur-containing compounds, formaldehyde and the like. The technical scheme used for realizing the purpose of the invention is as follows:
the chlorine dioxide slow-release air freshener consists of a microporous ceramic material, a porous adsorption material, chlorine dioxide generation components and an adhesive, wherein the microporous ceramic material is two hemispherical shells, the porous adsorption material adsorbs the chlorine dioxide generation components, the porous adsorption material adsorbing the chlorine dioxide generation components is coated in the microporous ceramic material, and the microporous ceramic materials are bonded and formed through the adhesive;
the microporous ceramic material is prepared from kaolin, diatomite, iron tourmaline, sodium fatty acid, potassium carbonate, rutile titanium dioxide and nano carbon black.
When the product is assembled, the porous adsorption material for adsorbing the chlorine dioxide generating component is filled into the hemispherical micropore ceramic material shell, the spherical shell is sealed by the adhesive, the temperature of the operation space is less than 30 ℃, and the humidity is less than 50%.
After the assembly is finished, the plastic bag or the aluminum-plastic bag is used for vacuum packaging, heat sealing and storage, the vacuum air exhaust is less than-0.1 Mpa, and the heat sealing and storage after the vacuum pumping are firm.
In the preferred technical scheme of the invention, the diameter of the microporous ceramic material is 5-8 mm, and the thickness of the microporous ceramic material is 1.5-2.5 mm.
In a preferred technical scheme of the invention, the chlorine dioxide generating component consists of sodium chlorite, polybasic weak acid or weak acid salt, weak base salt and a thickening dispersant, wherein the polybasic weak acid or weak acid salt is one of potassium hydrogen phthalate, EDTA, potassium hydrogen tartrate, potassium dihydrogen phosphate or aluminum sulfate; the weak base salt is one of disodium hydrogen phosphate, disodium EDTA, sodium citrate or sodium acetate; the thickening dispersant is one of polyethylene glycol 6000, sodium carboxymethylcellulose or gelatin.
In the preferred technical scheme of the invention, the components have the mass fractions: 55 to 70 percent of sodium chlorite, 10 to 15 percent of polybasic weak acid or weak acid salt, 10 to 15 percent of weak alkali salt and 5 to 15 percent of thickening dispersant; the pH value is controlled to be 6.5-7.0.
In the preferred technical scheme, the porous adsorption material is one of zeolite, a 3A molecular sieve, a 5A-grade molecular sieve, diatomite and calcium bentonite, and the pore diameter of the porous adsorption material is 3-10 nm.
In a preferred technical scheme of the invention, the adhesive is one or two of epoxy resin and aspartic acid polyurea.
In a preferred technical scheme of the invention, the preparation method of the microporous ceramic material comprises the following steps:
(1) weighing 30-50 parts of kaolin, 20-30 parts of diatomite, 5-15 parts of iron tourmaline, 5-10 parts of sodium aliphatate, 5-10 parts of potassium carbonate, 5-10 parts of rutile titanium dioxide and 1-5 parts of nano carbon black for later use;
(2) performing ball milling and crushing on the material obtained in the step (1) for 30-60 min to obtain powder with the particle size of 500-800 meshes, and dividing the powder into two parts;
(3) performing spray granulation on one part of the material in the step (2), forming a hemispherical shell on a grinding tool, isolating air at the temperature of 600-900 ℃, and firing for 30-60 min under the protection of nitrogen;
(4) forming the other material in the step (2) on the surface of the spherical shell by using a glaze spraying method and a glaze covering method, then sintering the glaze for 30-45 min at 1100-1150 ℃, and introducing air to sinter the glaze for forming; forming micropores of 200-300 nm on the surface of the enamel through micropore ablation;
(5) and (4) cooling the shell obtained in the steps (3) and (4) to room temperature, and polishing to obtain the shell.
The glaze layer microporous ceramic obtained by calcination is further subjected to short-time heat treatment to sublimate nano metal particles reserved for sublimation out of pores, thus obtaining the glaze layer microporous ceramic.
In a preferred technical scheme of the invention, the steps of adsorbing chlorine dioxide generation components by the porous adsorbing material are as follows: the chlorine dioxide generating components are mixed according to the mass ratio of 1: 20, stirring and completely dissolving in a nitrogen protected environment after mixing with deionized water, and mixing the following solutions in percentage by weight in the nitrogen protected environment: the mass ratio of the porous adsorption material is 2: 1, stirring for 15-30 min, and then performing reduced pressure air drying at 45 ℃ for 2-5 h under the pressure of 0.085-0.090 mPa.
In a preferred technical scheme of the invention, the freshener is in a spherical shape or a tablet shape.
In the preferable technical scheme of the invention, the freshener is vacuum-packaged by using a PE bag or an aluminum plastic packaging bag.
Because the microporous ceramic self-breathing material has a dynamic regulation and control effect on humidity, the microporous ceramic material has certain water vapor adsorption capacity, and can keep a relatively stable state when the external environment changes less violently by the water absorption capacity of the microporous ceramic in a closed space, under the condition, chlorine dioxide generating components in the material can be released at a relatively stable rate, and the stable chlorine dioxide slow release is realized due to the effects that the crystal form changes and the permeability changes after the tourmaline mineral absorbs water easily and absorbs water.
The air conditioning mode of the freshener disclosed by the application is as follows:
due to the self-respiration effect of the microporous ceramic, the internal part of the material is dynamically controlled in humidity, so that the constant humidity and temperature stability of the internal part of the material relative to the external environment are realized, and a chlorine dioxide generating system adsorbed and coated in the material can be activated to release chlorine dioxide in a stable influence state under the condition of humidity (50% -80%) and proper and only slightly changed external temperature and humidity, thereby playing the role of an air freshener.
When the external humidity is larger than the threshold value (more than 80%) which can be buffered by the microporous ceramic, the ceramic stops regulating and controlling the humidity to form a loose passage of water vapor, and the internal chlorine dioxide is excited to perform component rapid reaction. The effects of space sterilization and disinfection are achieved aiming at the mould breeding caused by the high-humidity and high-temperature conditions in the air.
Chlorine dioxide can freely enter and exit from the pore channel of the microporous ceramic, and the stability of the chlorine dioxide is not influenced because the ceramic body is high in chemical stability of silicon-calcium inorganic matters.
When the external humidity is extremely low (< 50%), the material can be used as a barrier for drying the internal air, so that only a small amount of water vapor can enter the interior to activate the reaction, and the material is released in a suspension manner in an environment with low drying temperature and less peculiar smell. The air freshener reaction rate is then substantially slowed, and if necessary, activated by splashing water onto the material. The self-breathing material can block moisture in the air, greatly delay the release of chlorine dioxide and enter dormancy, and greatly prolong the effective time of the product.
In summary, because the invention adopts the above technical scheme, the invention has the following technical effects:
the freshener is prepared from microporous ceramics, the microporous ceramics have a self-respiration effect, and chlorine dioxide generation components adsorbed by a porous material wrapped by a microporous ceramic shell can be regulated and controlled according to the environment in the material for intelligently regulating the temperature and the humidity, so that the chlorine dioxide generation components can be regulated along with the change of the environment through the regulation and control of the self-respiration material, and the utilization rate of a chlorine dioxide generator is greatly improved: aiming at the changes of different seasons and environmental conditions, such as warm and cold alternate seasons easily breeding mildew, the material can improve the release amount of chlorine dioxide, the intelligent regulation and control effect of chlorine dioxide release can be reduced and even stopped in drier materials in autumn and winter, and the use experience of users using chlorine dioxide air fresheners in personal spaces is greatly improved.
In conclusion, the chlorine dioxide slow-release solid air freshener disclosed by the invention has a self-breathing effect, can intelligently identify the temperature and humidity change and the environmental quality change of a personal space, and automatically adjusts the release amount of chlorine dioxide according to the environment in the space.
Drawings
FIG. 1 is a schematic structural view of an air freshener of example 1;
FIG. 2 is a graph of the release profile and humidity of the freshener prepared in example 1 over 72 hours;
FIG. 3 is a schematic structural view of an air freshener of example 2;
fig. 4 is a release profile and humidity profile of the freshener prepared in example 2 over 72 hours.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings by way of examples of preferred embodiments. It should be noted, however, that the numerous details set forth in the description are merely for the purpose of providing the reader with a thorough understanding of one or more aspects of the present invention, which may be practiced without these specific details.
Example 1
According to the method, 37 parts of kaolin, 23 parts of diatomite, 10 parts of iron tourmaline, 8 parts of sodium fatty acid, 7 parts of potassium carbonate, 10 parts of rutile titanium dioxide and 5 parts of nano carbon black are subjected to ball milling and crushing for 30-60 min, the obtained particle size is 500-800 meshes, the obtained ceramic powder is divided into two parts, one part is sprayed to prepare a hemisphere with the diameter of 8mm and the thickness of 1.5mm, and the hemisphere is fired and formed at the temperature of 650 +/-10 ℃ for 30 min. During the firing process, the furnace is continuously filled with nitrogen under normal pressure for protection.
And spraying glaze on the other part of the ceramic ball to form glaze with the thickness of 0.1-0.2 mm on the surface of the ceramic ball. Introducing air to normal pressure, and sintering at 1130 +/-10 deg.C for 30 min. At this time, the nano carbon powder reacts, leaving micropores. The surface of the enamel is ablated by micropores to form micropores of 200-300 nm.
And cooling the microporous ceramic material to room temperature to obtain the microporous ceramic shell with the thickness of 1.5-2.5 mm and the diameter of 8mm for later use.
Preparing chlorine dioxide generating solution, dissolving 1.5 parts of monopotassium phosphate, 1 part of monopotassium phosphate, 6.5 parts of sodium chlorite, 60001 parts of polyethylene glycol and 200 parts of water in a three-neck flask, wherein the volume of the solution is 1/3-1/4, continuously introducing normal-pressure nitrogen into the flask, adding 100 parts of zeolite with the diameter of 5.0-5.5 mm into the solution after reactants are completely dissolved, stirring for 30min, placing the flask in a rotary evaporator, and completely evaporating water in the solution in the process of reduced pressure evaporation.
And assembling the obtained porous adsorption material for adsorbing chlorine dioxide generation components in a microporous ceramic material, and then bonding the material by using epoxy sealant to obtain the chlorine dioxide adsorbing material. The product effect is shown in figure 1.
The prepared freshener is placed in a lightproof container with the volume of 10L, the outside air flows at the speed of 1L/h, the air is exchanged with the outside circulating gas, the concentration of chlorine dioxide gas in the container is measured by an electrochemical detector with the precision of 0.01ppm, and the detection is carried out once every 30 min. The release profile and humidity profile of the tested materials over 72h are shown in fig. 2. The result shows that the release of the chlorine dioxide can be regulated and controlled according to the environmental humidity.
Example 2
40 parts of kaolin, 20 parts of diatomite, 10 parts of iron tourmaline, 8 parts of sodium fatty acid, 7 parts of potassium carbonate, 10 parts of rutile titanium dioxide and 5 parts of nano carbon black are subjected to ball milling and sieving. The obtained ceramic powder is divided into two parts, the spraying blank is a hemisphere with the diameter of 8mm and the thickness of 1.5mm, and the ceramic powder is firstly fired and formed at the temperature of 650 +/-10 ℃ for 30 min.
During the firing process, the furnace is continuously filled with nitrogen under normal pressure for protection.
And spraying glaze on the other part of the ceramic ball to form glaze with the thickness of 0.1-0.2 mm on the surface of the ceramic ball.
Introducing air to normal pressure, and sintering the glaze for 30min at the temperature of 1140 +/-10 ℃ for forming.
The obtained microporous ceramic material is ready for use.
Preparing chlorine dioxide generating solution, dissolving 1.5 parts of monopotassium phosphate, 1 part of monopotassium phosphate, 6.5 parts of sodium chlorite, 60001 parts of polyethylene glycol and 200 parts of water in a three-neck flask, wherein the volume of the solution is 1/3-1/4, continuously introducing normal-pressure nitrogen into the flask, adding 100 parts of zeolite with the diameter of 0.5-1.0 mm into the solution after reactants are completely dissolved, stirring for 30min, placing the flask in a rotary evaporator, and completely evaporating water in the solution in the process of reduced pressure evaporation.
The obtained porous adsorbing material adsorbing chlorine dioxide generating components was assembled in a microporous ceramic material, and then bonded with an epoxy resin sealant, and the effect thereof is shown in fig. 3.
The prepared freshener is placed in a lightproof container with the volume of 10L, the outside air flows at the speed of 1L/h, the air is exchanged with the outside circulating gas, the concentration of chlorine dioxide gas in the container is measured by an electrochemical detector with the precision of 0.01ppm, and the detection is carried out once every 30 min. The release profile and humidity profile of the tested materials over 72h are shown in fig. 4. The results showed that the amount of chlorine dioxide released increased with increasing humidity and was below 0.2 ppm.
Example 3
30 parts of kaolin, 25 parts of diatomite, 5 parts of iron tourmaline, 10 parts of sodium fatty acid, 5 parts of potassium carbonate, 8 parts of rutile titanium dioxide and 3 parts of nano carbon black are subjected to ball milling and crushing for 60min, the obtained particle size is 500-800 meshes, the obtained ceramic powder is divided into two parts, one part is sprayed to prepare a hemisphere with the diameter of 8mm and the thickness of 1.5mm, and the hemisphere is fired and formed at the temperature of 750 +/-10 ℃ for 30 min. During the firing process, the furnace is continuously filled with nitrogen under normal pressure for protection.
And spraying and glazing the other part of the ceramic ball to form glaze with the thickness of 0.1-0.2 mm on the surface of the ceramic ball. Introducing air to normal pressure, and sintering the glaze for 30min at the temperature of 1110 +/-10 ℃ to form. At this time, the nano carbon powder reacts, leaving micropores. The surface of the enamel is ablated by micropores to form micropores of 200-300 nm.
And cooling the microporous ceramic material to room temperature to obtain the microporous ceramic shell with the thickness of 1.5-2.5 mm and the diameter of 8mm for later use.
Preparing chlorine dioxide generating solution, 1.5 parts of potassium hydrogen tartrate, 1 part of sodium citrate, 6.5 parts of sodium chlorite, 1 part of sodium carboxymethylcellulose and 200 parts of water, dissolving the chlorine dioxide generating solution in a three-neck flask, wherein the volume of the solution is 1/3-1/4, continuously introducing normal-pressure nitrogen into the flask, adding 100 parts of a 3A molecular sieve with the diameter of 5.0-5.5 mm into the solution after reactants are completely dissolved, stirring for 30min, placing the flask in a rotary evaporator, and completely evaporating water in the solution in the process of reduced pressure evaporation. And (3) assembling the obtained porous adsorbing material for adsorbing chlorine dioxide generating components in a microporous ceramic material, then bonding the porous adsorbing material with epoxy resin and aspartic acid polyurea sealing adhesive, compressing and forming the ceramic microporous material and the adhesive through a compression procedure, and curing the forming agent to form a spherical shape of 8-10 mm to obtain the chlorine dioxide generating component adsorbing material.
Example 4
50 parts of kaolin, 30 parts of diatomite, 15 parts of iron tourmaline, 10 parts of sodium fatty acid, 10 parts of potassium carbonate, 10 parts of rutile titanium dioxide and 5 parts of nano carbon black are subjected to ball milling and crushing for 60min, the obtained particle size is 500-800 meshes, the obtained ceramic powder is divided into two parts, one part is sprayed to prepare a hemisphere with the diameter of 8mm and the thickness of 1.5mm, and the hemisphere is fired and formed at the temperature of 850 +/-10 ℃ for 30 min. During the firing process, the furnace is continuously filled with nitrogen under normal pressure for protection.
And spraying glaze on the other part of the ceramic ball to form glaze with the thickness of 0.1-0.2 mm on the surface of the ceramic ball. Introducing air to normal pressure, and sintering the glaze for 30min at the temperature of 1110 +/-10 ℃ to form. At this time, the nano carbon powder reacts, leaving micropores. The surface of the enamel is ablated by micropores to form micropores of 200-300 nm.
And cooling the microporous ceramic material to room temperature to obtain the microporous ceramic shell with the thickness of 1.5-2.5 mm and the diameter of 8mm for later use.
Preparing chlorine dioxide generating solution, dissolving 1.5 parts of potassium hydrogen phthalate, 1 part of EDTA disodium, 6.5 parts of sodium chlorite, 1 part of gelatin and 200 parts of water in a three-neck flask, wherein the volume of the solution is 1/3-1/4, continuously introducing normal-pressure nitrogen into the flask, adding 100 parts of calcium bentonite with the diameter of 5.0-5.5 mm into the solution after reactants are completely dissolved, stirring for 30min, placing the flask into a rotary evaporator, and completely evaporating water in the solution in the process of reduced pressure evaporation. And (3) assembling the obtained porous adsorbing material for adsorbing chlorine dioxide generating components in a microporous ceramic material, then bonding the porous adsorbing material with aspartic acid polyurea sealing adhesive, compressing and forming the ceramic microporous material and the bonding agent through a compression procedure, and curing the forming agent to form a medicine tablet with the thickness of 8-10 mm, thus obtaining the chlorine dioxide generating component.
Examples of the applications
Application example 1
3g of each of the air fresheners of examples 1 to 4 was taken and placed in a space of 1m3The content of bacteria is 250-290cfu/m3And a closed test container with the humidity of 60% is used for a sterilization test, the temperature in the container is controlled to be 26-28 ℃, the sterilization time is 2 hours, staphylococcus albus is taken as a test object, and the test results are shown in table 1.
Serial number Initial bacterial content cfu/m3 The content of the terminated bacteria cfu/m3 The sterilization rate%
Example 1 259 17 93.4
Example 2 280 21 92.5
Example 3 265 18 93.2
Example 4 275 12 95.6
The results in table 1 show that the utilization rate of the air purifier has a good sterilization effect, the sterilization rate is more than 92%, and the air purifier has a good air purification effect.
Application example 2
3g of each of the air fresheners of examples 1 to 4 was taken and placed in a space of 1m3And testing the release amount of chlorine dioxide in a transparent glass container with humidity of 45%, setting the illumination intensity of the container to be 5000-8000 Lux, controlling the temperature in the container to be 33-35 ℃, measuring the concentration of chlorine dioxide gas by adopting an electrochemical detector with the precision of 0.001ppm, detecting once every 30min and collecting for 3 times, and testing the result such as
Shown in table 2.
Serial number Concentration (ppm) for 30min Concentration (ppm) at 60min Concentration (ppm) at 90min
Example 1 0.0012 0.0024 0.0038
Examples2 0.0011 0.0022 0.0042
Example 3 0.0013 0.0020 0.0032
Example 4 0.0016 0.0023 0.0035
The results in Table 2 show that examples 1-4 release very little chlorine dioxide and release essentially no chlorine dioxide in a high light, low humidity environment.
In conclusion, the air freshener disclosed by the invention is contacted with the air humidity (50-80%), and the air freshener immediately takes effect, can effectively decompose harmful substances in the air by virtue of slow-release chlorine dioxide, kill pathogenic microorganisms and mould, reduce peculiar smell, and can intelligently adjust the release amount by virtue of humidity and temperature so as to meet the air purification requirements of different seasons and scenes. Therefore, the self-breathing material chlorine dioxide slow-release solid air freshener has good application prospect.
The invention greatly solves the problem that the release amount of the existing chlorine dioxide slow-release agent product is very easy to be unstable due to the influence of factors such as illumination, temperature, humidity, air flow and the like. The deodorant has the effects of deodorizing and refreshing air, and is extremely suitable for deodorizing and sterilizing the environment such as personal space, inside a vehicle, a wardrobe, a toilet and the like, and also can be used for mildew prevention and sterilization in cold and hot alternate seasons when seasons are changed in winter and spring. The composition has the advantages of convenient use, long validity period, stable and appropriate release amount, no corrosion to metal, fabric and pets, no harmful influence to human bodies, and good commercial application prospect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (9)

1. The chlorine dioxide slow-release air freshener is characterized by comprising a microporous ceramic material, a porous adsorption material, chlorine dioxide generating components and an adhesive, wherein the microporous ceramic material is composed of two hemispherical shells, the chlorine dioxide generating components are adsorbed on the porous adsorption material, the porous adsorption material adsorbing the chlorine dioxide generating components is coated in the microporous ceramic material, and the microporous ceramic material is bonded and formed through the adhesive;
the microporous ceramic material is prepared from kaolin, diatomite, iron tourmaline, sodium fatty acid, potassium carbonate, rutile titanium dioxide and nano carbon black.
2. The chlorine dioxide slow-release air freshener according to claim 1, wherein the diameter of the microporous ceramic material is 5-8 mm, and the thickness of the microporous ceramic material is 1.5-2.5 mm.
3. The chlorine dioxide slow-release air freshener according to claim 1, wherein the chlorine dioxide generating component consists of sodium chlorite, polybasic weak acid or weak acid salt, weak base salt and thickening dispersant, wherein the polybasic weak acid or weak acid salt is one of potassium hydrogen phthalate, EDTA, potassium hydrogen tartrate, potassium dihydrogen phosphate or aluminum sulfate; the weak base salt is one of disodium hydrogen phosphate, disodium EDTA, sodium citrate or sodium acetate; the thickening dispersant is one of polyethylene glycol 6000, sodium carboxymethylcellulose or gelatin.
4. The chlorine dioxide slow-release air freshener according to claim 3, wherein the components are as follows in parts by mass: 55 to 70 percent of sodium chlorite, 10 to 15 percent of polybasic weak acid or weak acid salt, 10 to 15 percent of weak alkali salt and 5 to 15 percent of thickening dispersant.
5. The chlorine dioxide slow-release air freshener according to claim 1, wherein the porous adsorption material is one of zeolite, a 3A molecular sieve, a 5A-grade molecular sieve, diatomite and calcium bentonite, and the pore diameter of the porous adsorption material is 3-10 nm.
6. The chlorine dioxide slow-release air freshener according to claim 1, wherein the adhesive is one or two of epoxy resin and aspartic acid polyurea.
7. The chlorine dioxide slow-release air freshener according to claim 1, wherein the preparation method of the microporous ceramic material comprises the following steps:
(1) weighing 30-50 parts of kaolin, 20-30 parts of diatomite, 5-15 parts of iron tourmaline, 5-10 parts of sodium aliphatate, 5-10 parts of potassium carbonate, 5-10 parts of rutile titanium dioxide and 1-5 parts of nano carbon black for later use;
(2) performing ball milling and crushing on the material obtained in the step (1) for 30-60 min to obtain powder with the particle size of 500-800 meshes, and dividing the powder into two parts;
(3) performing spray granulation on one part of the material in the step (2), forming a hemispherical shell on a grinding tool, isolating air at the temperature of 600-900 ℃, and firing for 30-60 min under the protection of nitrogen;
(4) forming the other material in the step (2) on the surface of the spherical shell by using a glaze spraying method and a glaze covering method, then sintering the glaze for 30-45 min at 1100-1150 ℃, and introducing air to sinter the glaze for forming;
(5) and (4) cooling the shell obtained in the steps (3) and (4) to room temperature, and polishing to obtain the shell.
8. The chlorine dioxide slow-release air freshener according to claim 1, wherein the step of adsorbing the chlorine dioxide generating component by the porous adsorbing material is as follows: the chlorine dioxide generating components are mixed according to the mass ratio of 1: 20, stirring and completely dissolving in a nitrogen protected environment after mixing with deionized water, and mixing the following solutions in percentage by weight in the nitrogen protected environment: the mass ratio of the porous adsorption material is 2: 1, stirring for 15-30 min, and then performing reduced pressure air drying at 45 ℃ for 2-5 h under the pressure of 0.085-0.090 mPa.
9. The chlorine dioxide slow-release air freshener according to claim 1, wherein the freshener is in a shape of a sphere or a tablet.
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