A slow-release bactericidal chlorine dioxide air freshener and its preparation and application

Abstract

The present invention belongs to the fields of sanitation, epidemic prevention, and disinfection, and relates to a slow-release bactericidal chlorine dioxide air freshener, its preparation, and use. The slow-release bactericidal chlorine dioxide air freshener comprises the following components, by weight: 10-15 parts slow-release chlorine dioxide, 0.1-0.3 parts light stabilizer, 2-3 parts gelling agent, 3-9 parts modified negative oxygen ion powder, 0.1-1.5 parts auxiliary agent, 0.5-1.0 parts plant essential oil, and 10-82 parts deionized water. The invention primarily utilizes slowly released chlorine dioxide gas to achieve high-efficiency, broad-spectrum bactericidal and antibacterial properties. Chlorine dioxide comes into contact with airborne microorganisms and viruses, destroying their proteins, DNA, and RNA. This disinfectant has a sterilizing and disinfecting effect in confined spaces such as rooms, cars, and trains, and maintains a sustained sterilizing effect for 210 days. The addition of modified negative oxygen ion powder, which has negative oxygen ion induction properties, can synergistically kill and inhibit bacteria, improving air quality.

Description

Technical Field

[0001] The invention belongs to the field of sanitation, epidemic prevention and disinfection, and relates to a slow-release bactericidal chlorine dioxide air freshener and its preparation and application. Background Art

[0002] Tourmaline is a complex silicate mineral with a characteristic boron-containing ring structure. It belongs to the trigonal crystal system and exhibits significant thermoelectric and piezoelectric properties, as well as the ability to induce negative oxygen ions. Smaller tourmaline particles increase their specific surface area and surface energy, which in turn induces more negative oxygen ions. However, tourmaline easily aggregates during preparation and processing, resulting in uneven dispersion in composite materials and affecting the overall performance of the composite. Therefore, chemical modification of tourmaline is necessary to inhibit aggregation without altering its intrinsic negative oxygen ion-inducing properties.

[0003] Aerosol transmission is a key mode of airborne viral spread. Aerosols are dispersed systems of solid or liquid particles stably suspended in a gaseous medium. Healthy, uninfected individuals can become infected by inhaling airborne aerosols containing viruses without direct contact with an infected individual. In confined indoor spaces, where air is stagnant, viruses can survive longer. Therefore, ensuring good indoor ventilation, regular indoor disinfection, and ensuring that suspected or mildly ill patients wear masks to protect their families while in home isolation can help prevent airborne transmission of the virus.

[0004] Traditional air fresheners are primarily known for their lingering fragrance and refreshing air. With the rapid spread of viruses, the development of a novel antibacterial solid air freshener that not only improves the surrounding air environment, relieves fatigue, and provides a refreshing feeling, but also offers long-lasting bactericidal and antimicrobial properties is becoming increasingly important. Therefore, developing an antibacterial air freshener with a prolonged duration of sterilization is crucial for suppressing the spread of viruses in confined indoor spaces and improving air quality. Summary of the Invention

[0005] The main purpose of the present invention is to provide a slow-release bactericidal chlorine dioxide air freshener and its preparation and application.

[0006] To achieve the above purpose, the present invention adopts the following technical solutions:

[0007] A slow-release bactericidal chlorine dioxide air freshener, characterized in that the components, calculated by weight, are as follows: 10 to 15 parts of slow-release chlorine dioxide, 0.1 to 0.3 parts of a light stabilizer, 2 to 3 parts of a gelling agent, 3 to 9 parts of negative oxygen ion powder, 0.1 to 1.5 parts of an auxiliary agent, 0.5 to 1.0 parts of a plant essential oil, and 10 to 82 parts of deionized water.

[0008] The slow-release chlorine dioxide is achieved by loading a saturated chlorine dioxide solution into a caged nickel cobaltate using a vacuum impregnation method, thereby slowly releasing chlorine dioxide gas through adsorption-desorption equilibrium.

[0009] The slow-release chlorine dioxide is obtained by subjecting a nickel-containing substance, a cobalt-containing substance and sodium acetate to a high-temperature hydrothermal method to obtain caged nickel cobaltate; and then mixing the caged nickel cobaltate with a saturated aqueous solution of chlorine dioxide.

[0010] The caged nickel cobaltate is prepared by dissolving nickel nitrate, cobalt nitrate and sodium acetate in polyethylene glycol, stirring the mixture evenly, placing the mixture in an autoclave, keeping it at 200-300°C for 12-18 hours, air cooling, washing it with deionized water 3-5 times, and drying it; then calcining it in a muffle furnace at 300-450°C for 2-5 hours, cooling it with the furnace, and finally obtaining the caged nickel cobaltate; wherein the mass ratio of nickel nitrate, cobalt nitrate and sodium acetate is 25-35:55-65:45-50.

[0011] The caged nickel cobaltate is mixed with a saturated aqueous solution of chlorine dioxide, stirred continuously for 15 to 24 hours in a vacuum, then returned to normal pressure, and the cycle is repeated 3 to 5 times, followed by centrifugation to obtain slow-release chlorine dioxide, wherein the mass ratio of the caged nickel cobaltate to the saturated aqueous solution of chlorine dioxide is 18-25:40-60.

[0012] The modified negative oxygen ion powder is prepared by solid-phase reaction of mica powder and tourmaline powder at a high temperature of 550°C to 900°C in a B2O3 atmosphere for 5 to 10 hours, and is mainly compounded at high temperature through Si-O-Si bonds in the mica powder and tourmaline powder. The mass ratio of mica powder to tourmaline powder is 1:5 to 1:10, the mica powder has a flaky structure with a diameter of 0.1 to 0.5 μm, and the tourmaline powder has a particle size of 1 to 20 μm.

[0013] The light stabilizer is composed of an antioxidant and a light absorber in a mass ratio of 1:1 to 1:5, wherein the antioxidant is 2,6-tert-butyl-4-methylphenol and / or bis(3,5-tert-butyl-4-hydroxyphenyl) sulfide, and the light absorber is dihydroartemisinin, erythromycin or kanamycin.

[0014] The gelling agent is one or a combination of carbomer, sodium carboxymethyl cellulose and xanthan gum;

[0015] The auxiliary agent is one or more of sodium hydroxide and disodium edetate, glycerol or polyethylene glycol; that is, a combination of one or more of sodium hydroxide and disodium edetate, glycerol or polyethylene glycol is used as an auxiliary agent.

[0016] The plant essential oil is one or a combination of rose essential oil, peppermint essential oil and lavender essential oil.

[0017] 1) Add the gelling agent to deionized water and soak for 12 to 24 hours, add the auxiliary agent (other components of the auxiliary agent except sodium hydroxide), and ultrasonically disperse to obtain a mixture A;

[0018] 2) adding a light stabilizer to mixture A and stirring uniformly, then adding slow-release chlorine dioxide and stirring uniformly to obtain mixture B;

[0019] 3) Mixing the mixture B with the plant essential oil and the negative oxygen ion powder is stirred, and then sodium hydroxide in the auxiliary agent is added to adjust the pH value of the gel to neutral to obtain a mixture C, that is, a slow-release bactericidal chlorine dioxide air freshener.

[0020] An application of the slow-release bactericidal chlorine dioxide air freshener, wherein the slow-release bactericidal chlorine dioxide can be used as a slowly volatile freshener to sterilize, inhibit bacteria and refresh the air.

[0021] The product has a sterilization and disinfection function in confined spaces such as rooms, cars and trains, and has a continuous sterilization effect for 180 days.

[0022] Compared with the prior art, the present invention has the following technical advances:

[0023] 1. The present invention loads chlorine dioxide gas into caged nickel cobaltate, so that the chlorine dioxide gas achieves a sustained release effect in the caged nickel cobaltate through adsorption-desorption equilibrium, thereby achieving a long-lasting, safe, non-toxic and efficient sterilization and air purification effect. At the same time, chlorine dioxide has a certain oxidative decomposition function of formaldehyde.

[0024] 2. The modified negative oxygen ion powder added in the present invention is formed by a high-temperature solid-phase reaction of mica and tourmaline powder. High-temperature compounding occurs through the Si-O-Si bonds in the mica and tourmaline powders. The flaky mica reduces tourmaline powder agglomeration and improves the dispersion of the modified negative oxygen ion powder in the gel. The negative oxygen ions induced by the modified negative oxygen ion powder can form a negative ion protective layer in the air, reducing high-voltage static electricity, having certain bactericidal and anti-toxic effects, and improving air quality.

[0025] 3. The slow-release bactericidal chlorine dioxide air freshener of the present invention has the function of refreshing the air and improving the surrounding air environment by adding plant essential oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a schematic diagram of the operating steps for preparing slow-release chlorine dioxide in Example 1 of the present invention.

[0027] Figure 2 This is a scanning electron microscope (SEM) photograph of a rectangular cage-shaped nickel cobalt oxide prepared in Example 1 of the present invention.

[0028] Figure 3 This is a simulated structural diagram of nickel cobaltate-coated chlorine dioxide prepared in Example 1 of the present invention.

[0029] Figure 4 The present invention provides an X-ray diffraction pattern (XRD) of nickel cobalt oxide prepared in Example 1.

[0030] Figure 5 This is the infrared absorption spectrum (FT-IR) of nickel cobalt oxide prepared in Example 1 of the present invention.

[0031] Figure 6 This is an X-ray photoelectron spectroscopy (XPS) spectrum of rectangular caged nickel cobalt oxide prepared in Example 1 provided in the embodiments of the present invention.

[0032] Figure 7 Schematic diagram of the preparation of modified negative oxygen ion powder in Example 1 of the present invention.

[0033] Table 1 Antibacterial rates of the air freshener prepared in Example 1 after different time periods.

[0034] Table 2 Antibacterial rates of the air fresheners prepared in different embodiments and comparative examples after 180 days and 210 days DETAILED DESCRIPTION

[0035] The present invention is further described in detail below through specific examples. It should be understood that the described examples are only used to illustrate the present invention and are not intended to limit the present invention.

[0036] The sustained-release bactericidal chlorine dioxide air freshener of the present invention mainly realizes its sustained-release function by loading a saturated chlorine dioxide solution onto caged nickel cobaltate. The saturated chlorine dioxide solution is loaded into the self-made caged nickel cobaltate by a vacuum impregnation method, and then a sustained-release effect is achieved through adsorption-desorption equilibrium. The air freshener of the present invention has a bactericidal and disinfecting function for confined spaces such as rooms, cars and trains, and has a sustained bactericidal effect for 210 days. It also achieves high-efficiency and broad-spectrum bactericidal effects. At the same time, the modified negative oxygen ion powder added to the ingredients has negative oxygen ion inducing properties, which can synergistically kill bacteria and improve air quality.

[0037] Example 1 Preparation method and application of a slow-release bactericidal chlorine dioxide air freshener

[0038] 1) Preparation of slow-release chlorine dioxide

[0039] Schematic diagram of the operation steps of slow-release chlorine dioxide Figure 1Specifically, 30.2g nickel nitrate, 61.3g cobalt nitrate and 49.5g sodium acetate were dissolved in 100mL polyethylene glycol (PEG-400), stirred evenly, and then placed in a polytetrafluoroethylene-lined stainless steel autoclave, kept at 280℃ for 15h, cooled in air, washed with deionized water 5 times, and dried. The mixture was calcined at 380℃ for 3h in a muffle furnace and cooled with the furnace to finally obtain nickel cobalt oxide powder, the micromorphology of which is shown in the photo. Figure 2 The nickel cobalt oxide powder has a hollow structure inside, with an undulating surface and an interlaced texture. The overall structure resembles a rectangular cage, which provides ample inlet and outlet channels and internal space for the loading and adsorption-desorption equilibrium of chlorine dioxide.

[0040] Take 20g of nickel cobaltate powder and mix it with 50mL of chlorine dioxide saturated aqueous solution, stir it continuously in vacuum for 20h, then return to normal pressure, and repeat the cycle 4 times to improve the loading effect of chlorine dioxide. Finally, centrifuge to obtain a slow-release chlorine dioxide product. The simulated structure of nickel cobaltate coated chlorine dioxide is shown in Figure 3 The outer rectangular cage structure is a nickel cobalt oxide skeleton prepared by hydrothermal method, while the inner red sphere is chlorine dioxide loaded into the skeleton by vacuum impregnation method (see Figure 4-Figure 6 ).

[0041] Depend on Figure 4 There are obvious diffraction peaks at 31.3°, 36.7°, 44.4°, 55.7°, 59.1°, and 64.9°, corresponding to the five crystal planes (220), (311), (400), (422), (511), and (440). This is completely consistent with the corresponding situation of the nickel cobalt oxide standard card (JCPDS No. 02-1074), and there are no impurity peaks between the diffraction peaks, which indicates that the prepared nickel cobalt oxide has a high purity. The infrared spectrum of the prepared nickel cobalt oxide is shown in Figure 5 , 555cm -1 and 652cm -1 The stretching vibration of Ni-O and Co-O bonds proves that the chemical bonds of the self-made nickel cobalt oxide do exist. Figure 6 ) Further characterize and prepare more detailed element composition information and element oxidation state information of nickel cobalt oxide. For the Ni element, its 2p orbital has two Ni 2+ and Ni 3+ Characteristic spin-orbit double peaks, two oscillation satellite peaks, such as Figure 6 b. For the Co element, as shown in its 2p emission spectrum, two Co 2+ and Co 3+ Characteristic spin-orbit doublet, a recombination satellite peak, such as Figure 6c. For the O element, its emission spectrum can be well fitted with three sub-peaks, among which the peak at 529.2eV is a typical metal-oxygen bond, the peak at 532.6eV and the peak at 530.8 correspond to low oxygen defects on or near the surface and adsorbed water defects, respectively. Figure 6 d.

[0042] 2) Preparation of modified negative oxygen ion powder

[0043] The preparation process of modified negative oxygen ion powder is shown in Figure 7 , which is characterized by a high-temperature solid-phase reaction of 100g mica powder and 500g tourmaline powder in a B2O3 atmosphere at 700℃ tube furnace, and high-temperature compounding through the Si-O-Si bond in the mica powder and tourmaline powder. The mica powder has a flaky structure with a diameter of 0.1-0.5μm, and the tourmaline powder has a particle size of 1-20μm. After the high-temperature solid-phase reaction for 8h, the powder is cooled in the furnace to finally obtain the modified negative oxygen ion powder. Its microscopic morphology is shown in the photo. Figure 7 , Figure 7 It can be observed that mica powder can inhibit the agglomeration of tourmaline powder through high-temperature solid-phase reaction, and subsequently improve the dispersion performance of modified negative oxygen ion powder in gel.

[0044] 3) Slow-release bactericidal chlorine dioxide air freshener and its preparation method

[0045] 1. Soak 2g of xanthan gum and 1g of carbomer in 73g of deionized water, add 0.2g of disodium edetate, and ultrasonically disperse for 5h to obtain mixture A;

[0046] 2. Add 0.3 g of light stabilizer (composed of 0.1 g of 2,6-tert-butyl-4-methylphenol and 0.2 g of erythromycin) to mixture A and stir evenly. Then add 15 g of homemade slow-release chlorine dioxide and stir evenly to obtain mixture B.

[0047] 3. Mixture B is mixed with 0.5 g of rose essential oil and 8 g of modified negative oxygen ion powder, and then the pH value is adjusted to pH 7.5 with 0.1 mol / L sodium hydroxide solution to obtain mixture C, that is, a slow-release bactericidal chlorine dioxide air freshener.

[0048] The slow-release bactericidal chlorine dioxide air freshener is filled into a perforated plastic box and packaged to obtain a commercially available air freshener. The resulting slow-release bactericidal chlorine dioxide air freshener has a bactericidal and disinfecting function in confined spaces such as rooms, cars, and trains, and maintains a sustained bactericidal effect for 180 days.

[0049] 4) Application and evaluation of slow-release bactericidal chlorine dioxide air freshener

[0050] In 30m 3Indoor room, the windows are closed, and the doors are closed after each sampling. The ambient temperature is 15-20 ° C, the humidity is 55-75%, and there is no forced exhaust (deactivate air conditioning, electric fans, etc.). Place two fragrance bottles containing 100 mL of the air freshener prepared in Example 1 above on a shelf 1 meter above the ground at equal distances on the AC diagonal, and open the bottle caps. During the antibacterial experiment, three 9 cm diameter plates are placed on the BD diagonal at equal distances on a shelf 1 meter above the ground, and the test is carried out according to the disinfection and antibacterial test specification (2002 edition standard). After cultivation, the number of colonies on the three plates is determined, and the antibacterial rate is calculated after the average counting. The specific results are shown in Table 1. After 210 days, the antibacterial rate is still as high as 89.1%.

[0051] Table 1

[0052] Time / day 1 14 28 49 100 150 180 210 Antibacterial rate% 99.9 99.9 99.9 99.9 95.6 94.5 93.8 89.1

[0053] Example 2

[0054] The preparation method and application of the slow-release bactericidal chlorine dioxide air freshener in Example 2 are basically the same as those in Example 1, except that the calcination temperature of nickel cobalt oxide in the muffle furnace is 420°C and the calcination time is 3 hours. To confirm the successful preparation of nickel cobalt oxide (NiCo2O4), the calcined product is tested for components using an X-ray diffraction spectrometer (XRD), and the results are consistent with those described in Example 1. Their application process is the same as that in Example 1, and their bactericidal effects after 180 days and 210 days are detailed in Table 2.

[0055] Example 3

[0056] Example 3: A sustained-release bactericidal chlorine dioxide air freshener is essentially the same as Example 1, except that, during the preparation of the air freshener, 3 g of xanthan gum was used for the gel, and no carbomer was added. The application process was the same as in Example 1, and the bactericidal effects after 180 and 210 days are detailed in Table 2.

[0057] Comparative Example 1

[0058] Comparative Example 1 The sustained-release bactericidal chlorine dioxide air freshener is basically the same as Example 1, except that during the preparation of the air freshener, 8 g of modified negative oxygen ion powder is added instead of 8 g of deionized water. Their application process is the same as that of Example 1, except that the sterilization results are different. The sterilization effects after 180 days and 210 days are shown in Table 2.

[0059] Comparative Example 2

[0060] Comparative Example 2 The slow-release bactericidal chlorine dioxide air freshener is basically the same as Example 1, except that during the preparation of the air freshener, 15 g of slow-release chlorine dioxide is added instead of 15 g of deionized water. Their application process is the same as Example 1, except that the bactericidal results are different. The bactericidal effects after 180 days and 210 days are shown in Table 2.

[0061] Comparative Example 3

[0062] The comparative example 2 slow-release bactericidal chlorine dioxide air freshener is basically the same as that in Example 1, except that in the preparation process of the air freshener, 15 g of slow-release chlorine dioxide is added instead of 15 g of saturated chlorine dioxide solution. Their application process is the same as that in Example 1, except that the bactericidal results are different. The bactericidal effects after 180 days and 210 days are shown in Table 2.

[0063] Table 2

[0064] Antibacterial rate after 180 days Antibacterial rate after 210 days Example 1 93.8 89.1 Example 2 92.5 88.1 Example 3 92.9 88.9 Comparative Example 1 82.1 73.1 Comparative Example 2 No sterilization No sterilization Comparative Example 3 32.1 28.2

[0065] A comprehensive comparison of the bactericidal effects of the air fresheners prepared in different embodiments and comparative examples after 180 and 210 days reveals that the modified negative oxygen ion powder has a synergistic effect on the bactericidal efficiency of the sustained-release chlorine dioxide. If the negative oxygen ion powder is added alone to the air freshener, the product has no bactericidal effect after 180 days. If the caged nickel cobaltate loaded saturated chlorine dioxide solution prepared in the embodiment of the present invention is not used, the chlorine dioxide evaporates rapidly in the air freshener, and the antibacterial effect deteriorates after long-term storage.

[0066] It should be noted that the above embodiments are only for illustrating the technical concepts and features of the present invention. Their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it accordingly. Any technician familiar with this profession may use the above technical content as inspiration to change or modify it into an equivalent embodiment with equivalent changes. However, as long as it does not deviate from the technical essence of the claims of the present invention, simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of protection of the claims of the present invention.

Claims

1. A slow-release bactericidal chlorine dioxide air freshener, characterized in that: The components are as follows by weight: 10-15 parts of slow-release chlorine dioxide, 0.1-0.3 parts of light stabilizer, 2-3 parts of gelling agent, 3-9 parts of modified negative oxygen ion powder, 0.1-1.5 parts of auxiliary agent, 0.5-1.0 parts of plant essential oil, and 10-82 parts of deionized water; The slow-release chlorine dioxide is achieved by loading a saturated chlorine dioxide solution into the caged nickel cobaltate using a vacuum impregnation method; The slow-release chlorine dioxide is obtained by subjecting a nickel-containing substance, a cobalt-containing substance and sodium acetate to a high-temperature hydrothermal method to obtain caged nickel cobaltate; and then mixing the caged nickel cobaltate with a saturated aqueous solution of chlorine dioxide. The caged nickel cobaltate is prepared by dissolving nickel nitrate, cobalt nitrate and sodium acetate in polyethylene glycol, stirring the mixture evenly, placing the mixture in an autoclave, keeping it at 200-300°C for 12-18 hours, cooling it in air, washing it with deionized water 3-5 times, and drying it; then calcining it in a muffle furnace at 300-450°C for 2-5 hours, cooling it with the furnace, and finally obtaining the caged nickel cobaltate; wherein the mass ratio of nickel nitrate, cobalt nitrate and sodium acetate is 25-35:55-65:45-50; The modified negative oxygen ion powder is prepared by solid-phase reaction of mica powder and tourmaline powder in a B2O3 atmosphere at 550°C to 900°C for 5 to 10 hours, wherein the mass ratio of mica powder to tourmaline powder is 1:5 to 1:10; The auxiliary agent is one or more of the following substances: sodium hydroxide, disodium edetate, glycerol or polyethylene glycol.

2. The sustained-release bactericidal chlorine dioxide air freshener according to claim 1, characterized in that: The caged nickel cobaltate is mixed with a saturated aqueous solution of chlorine dioxide, stirred continuously for 15 to 24 hours in a vacuum, then returned to normal pressure, and the cycle is repeated 3 to 5 times, followed by centrifugation to obtain slow-release chlorine dioxide, wherein the mass ratio of the caged nickel cobaltate to the saturated aqueous solution of chlorine dioxide is 18-25:40-60.

3. The sustained-release bactericidal chlorine dioxide air freshener according to claim 1, characterized in that: The light stabilizer is composed of an antioxidant and a light absorber in a mass ratio of 1:1 to 1:5, wherein the antioxidant is 2,6-tert-butyl-4-methylphenol and / or bis(3,5-tert-butyl-4-hydroxyphenyl) sulfide, and the light absorber is dihydroartemisinin, erythromycin or kanamycin; and the gelling agent is one or a combination of carbomer, sodium carboxymethyl cellulose and xanthan gum.

4. The sustained-release bactericidal chlorine dioxide air freshener according to claim 1, characterized in that: The plant essential oil is one or a combination of rose essential oil, peppermint essential oil and lavender essential oil.

5. An application of the slow-release bactericidal chlorine dioxide air freshener according to claim 1, characterized in that: The slow-release bactericidal chlorine dioxide air freshener is used as a slowly volatile freshener.

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