A metal oxide sterilization material and its preparation method and application

Abstract

The present invention provides a metal oxide sterilization material and a preparation method and application thereof. The preparation method comprises the following steps: immersing a porous carrier in a metal salt solution, and then adding a precipitant, so that the metal ions loaded on the porous carrier are converted into hydroxides through a coprecipitation reaction, and then the hydroxides are converted into oxides through cleaning and drying, and then high-temperature sintering is performed to bond the oxides to the porous carrier to obtain the final metal oxide sterilization material, which has good sterilization effect, high safety, effective sterilization, full adhesion, and long service life.

Description

Technical Field

[0001] The present invention mainly relates to the technical field of sterilization materials, and in particular to a metal oxide sterilization material and a preparation method and application thereof. Background Art

[0002] Polluted places are everywhere. The indoor air at home often has odors in shoe cabinets and toilets. Some public places are even more seriously polluted. The bacterial content in hospitals and other environments is very high. Among the existing sterilization technologies, chemical disinfection is harmful to the human body itself. If it is used in industry, it is easy to cause secondary pollution. The physical disinfection in the existing technology, such as photocatalytic oxidation, requires external conditions such as ultraviolet irradiation to trigger. As the ultraviolet rays fluctuate, the disinfection effect is unstable. In addition, the coating process commonly used for the bactericidal active ingredients in the existing technology has weak adhesion, which affects the service life. The existing sterilization equipment is limited by the sterilization materials, is often large in size, and has limited space for use. Summary of the invention

[0003] The present invention provides a metal oxide sterilization material and a preparation method and application thereof, which solve the problems in the prior art that the sterilization material is easy to volatilize, diffuse or fall off, causing secondary pollution, has a short service life, poor safety, unsatisfactory sterilization effect and sterilization sustainability, complex manufacturing process, and high manufacturing cost.

[0004] The present invention provides the following technical solutions:

[0005] A method for preparing a metal oxide sterilization material, comprising

[0006] Step S1: providing a metal salt solution, including a single metal salt component or a double metal salt mixed component or a mixture of three or more metal salts dissolved in water,

[0007] Step S2: placing the porous carrier in the metal salt solution, taking out the porous carrier after soaking, and drying it to obtain a first-stage porous carrier loaded with metal ions.

[0008] Step S3: dissolving the precipitant in water to obtain a precipitant solution.

[0009] Step S4: soaking the first-stage porous carrier in the precipitant solution to produce a coprecipitation reaction, and after soaking, obtaining a second-stage porous carrier loaded with hydroxide,

[0010] Step S5: Soak the second-stage porous support in water, wash and dry to obtain a third-stage porous support loaded with oxides.

[0011] Step S6: sintering the third-stage porous carrier, and bonding reaction between the oxide and the porous carrier to obtain the metal oxide sterilization material.

[0012] Preferably, the monometallic salt component in step S1 is selected from: one of manganese salt, iron salt, zinc salt, nickel salt, magnesium salt, copper salt and cobalt salt, and the metal salt is a soluble acetate, sulfate, nitrate or chloride of manganese, iron, zinc, nickel, magnesium, copper or cobalt; the mixed component and molar mass ratio of the bimetallic salt are: Co 2+ Cu 2+ or Mg 2+ or Zn 2+ :Ni 2+ or Fe 3+ or Mn 2+ =3~7:2~5; the mixed components and molar mass ratio of three or more polymetallic salts are: Co 2+ Cu 2+ :Mg 2+ or Zn 2+ :Ni 2+ or Fe 3+ or Mn 2+ =2~6:1~5:0.5~3; the mass concentration of metal ions in the metal salt solution is 0.1~2% of the total solution.

[0013] Preferably, the porous carrier in step S2 is alumina ceramic, or clay adsorbent, or all-silicon honeycomb molecular sieve, or silicon-aluminum molecular sieve; the porous carrier is a spherical porous carrier or a honeycomb porous carrier, and the specific surface area of ​​the spherical porous carrier is 200-400 m 2 / g, the specific surface area of ​​the honeycomb porous carrier is 100-300 m 2 / g.

[0014] Preferably, in step S2, the soaking time is 4 to 24 hours, and the soaking temperature is 20 to 40°C; the drying time is 6 to 36 hours, and the drying temperature is 60 to 150°C; the mass ratio of the porous carrier to the metal salt solution is 1:2.

[0015] Preferably, the precipitant in step S3 is a single component or a two-component mixture of sodium hydroxide, potassium hydroxide, sodium carbonate and ammonia water, and the concentration of the precipitant solution is 0.5-3 mol / L.

[0016] Preferably, in step S4, the mass ratio of the first-stage porous carrier to the precipitant solution is 0.5~1:1~2, and the immersion time is 1~6 hours. If the pH drops below 8 during the immersion process, the precipitant solution is added to maintain the pH between 8 and 13. The second-stage porous carrier is loaded with hydroxides converted from metal ions through a coprecipitation reaction.

[0017] Preferably, in step S5, the volume ratio of water to the second-stage porous carrier is 2-3:0.5-1; the soaking time for one cleaning is 1-3 hours, the cleaning temperature is 10-40°C, the drying temperature is 60-150°C, and the drying time is 6-36 hours. The third-stage porous carrier is loaded with oxides converted from hydroxides after drying and dehydration.

[0018] Preferably, in step S6, the high-temperature sintering temperature is 300-800°C, the time is 2-8 hours, the oxide loaded on the porous carrier in the third stage is bonded to the porous carrier by bonding reaction, the thickness of the oxide on the surface of the porous carrier is 0.5-1 mm, and the metal oxide sterilization material is obtained, and the bulk density of the metal oxide sterilization material is 500 kg / m 3 ~750 kg / m 3 .

[0019] A metal oxide sterilization material is prepared by the above-mentioned method for preparing the metal oxide sterilization material. The metal oxide sterilization material comprises a porous carrier and an oxide loaded on the porous carrier through a bonding reaction.

[0020] The application of the metal oxide sterilization material in sterilization can be used to make air sterilization equipment and water sterilization equipment.

[0021] Beneficial effects of the present invention: The present invention provides a metal oxide sterilization material and a preparation method and application thereof. Compared with the coating process in the prior art, the sterilization active ingredients of the preparation method provided by the present invention are more firmly adhered and have a longer service life; the preparation method provided by the present invention optimizes the process steps, is simple to operate, and has a high yield; the sterilization material obtained by the preparation method of the present invention has high sterilization efficiency, fast sterilization time, does not require external triggering conditions for sterilization, has stable sterilization efficiency, and has strong plasticity in shape. It can be flexibly combined to meet the needs of different scenarios; the sterilization material obtained by the preparation method of the present invention has a wide range of application scenarios, has good sterilization effects on air and water, and can be applied to various sterilization equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Schematic diagram of the preparation method of Example 2 of the present invention;

[0023] Figure 2 Schematic diagram of the preparation method of Example 3 of the present invention;

[0024] Figure 3 Schematic diagram of the preparation method of Example 4 of the present invention;

[0025] Figure 4 Schematic diagram of the preparation method of Example 5 of the present invention;

[0026] Figure 5 Schematic diagram of the preparation method of Example 6 of the present invention;

[0027] Figure 6 It is a schematic diagram of the experimental detection device of the present invention;

[0028] Figure 7 This is a data schematic diagram of Experiment 1 of the present invention;

[0029] Figure 8 This is a data schematic diagram of Experiment 2 of the present invention;

[0030] Fig. 9 This is a data schematic diagram of Experiment 3 of the present invention; DETAILED DESCRIPTION

[0031] The present invention is described in detail below in conjunction with the accompanying drawings. The description in this part is only exemplary and explanatory and should not have any limiting effect on the scope of protection of the present invention.

[0032] The present invention provides a method for preparing a metal oxide sterilization material. The reaction container can be a jacketed stirring reaction tank, which can be heated or cooled, and comprises steps S1 to S6.

[0033] Step S1: Mix a single metal salt component or a double metal salt mixed component or a mixed component of three or more polymetallic salts in a certain proportion, stir and dissolve in water to obtain a metal salt solution, wherein the single metal salt component is selected from: one of manganese salt, iron salt, zinc salt, nickel salt, magnesium salt, copper salt and cobalt salt, and the metal salt is a soluble acetate, sulfate, nitrate or chloride of manganese, iron, zinc, nickel, magnesium, copper or cobalt;

[0034] The mixed components and molar mass ratio of the double metal salt are: Co 2+ Cu 2+ or Mg 2+ or Zn 2+ :Ni 2+ or Fe 3+ or Mn 2+ =3~7:2~5; the mixed components and molar mass ratio of three or more polymetallic salts are: Co 2+ Cu 2+ :Mg 2+ or Zn 2+ :Ni 2+ or Fe 3+ or Mn 2+=2~6:1~5:0.5~3; the mass concentration of metal ions in the metal salt solution is 0.1~2% of the total solution. Pour the well-proportioned metal salt into the reaction container and fully dissolve it by magnetic stirring or mechanical stirring at a temperature of 20~40°C for 1~3 hours. It should be noted that Co 2+ , Cu 2+ Mg 2+ 、Zn 2+ 、Ni 2+ , Fe 3+ , Mn 2+ They all refer to the metal salt corresponding to the ion, and the corresponding metal salt is, for example, water-soluble acetate, sulfate, nitrate or chloride.

[0035] Step S2: soaking the porous carrier in the metal salt solution for 4 to 24 hours at a temperature of 20 to 40° C., taking out the porous carrier after soaking and drying it, which can be dried by blast drying, for 6 to 36 hours at a temperature of 60 to 150° C., to obtain a first-stage porous carrier loaded with metal ions, wherein the porous carrier is alumina ceramic, or a clay adsorbent, or a full silicon honeycomb molecular sieve, or a silicon aluminum molecular sieve;

[0036] The porous carrier is a spherical porous carrier or a honeycomb porous carrier, and the specific surface area of ​​the spherical porous carrier is 200-400m 2 / g, the specific surface area of ​​the honeycomb porous carrier is 100-300 m 2 / g;

[0037] The spherical porous carrier is alumina ceramic (85-95% aluminum) or a clay adsorbent containing diatomaceous earth, attapulgite, and kaolin. The honeycomb porous carrier has a full silicon molecular sieve or a silicon-aluminum molecular sieve with a silicon-aluminum ratio of 1:1.

[0038] Step S3: Mix the precipitant in a certain proportion, wherein the precipitant is a single component or a two-component component of sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonia water, and stir and dissolve it in water to obtain a precipitant solution, wherein the concentration of the precipitant solution is 0.5-3 mol / L.

[0039] Step S4: soaking the first-stage porous carrier in the precipitant solution to produce a co-precipitation reaction, the mass ratio of the first-stage porous carrier to the precipitant solution is 0.5~1:1~2, the soaking time is 1~6 hours, if the pH drops below 8 during the soaking process, the precipitant solution is added to maintain the pH between 8 and 13, after soaking, the second-stage porous carrier loaded with hydroxide is obtained, and the second-stage porous carrier is loaded with hydroxide converted from metal ions through a co-precipitation reaction.

[0040] Step S5: Take out the second-stage porous carrier and soak it in water for cleaning, the volume ratio of water to the second-stage porous carrier is 2~3:0.5~1; the soaking time for one cleaning is 1~3 hours, the cleaning step is repeated at least 2 times, and after cleaning, it is dried and dehydrated, the drying temperature is 60~150℃, and the drying time is 6~36 hours, to obtain a third-stage porous carrier loaded with oxides, and the third-stage porous carrier is loaded with oxides converted from hydroxides by drying and dehydration.

[0041] Step S6: Place the third-stage porous carrier in a muffle furnace for high-temperature sintering, the high-temperature sintering temperature is 300-800°C, the time is 2-8 hours, the oxide loaded on the third-stage porous carrier is bonded to the porous carrier by bonding reaction, the thickness of the oxide on the surface of the porous carrier is 0.5-1 mm, and the metal oxide sterilization material is obtained, and the metal oxide sterilization material has a bulk density of 500 kg / m 3 ~750 kg / m 3 .

[0042] like Figure 1 As shown, in Example 1 of the present invention, the metal salt solution is obtained by dissolving copper sulfate and water, and the mass concentration of copper ions in the metal salt solution is 0.5% of the total solution; the porous carrier adopts a honeycomb-shaped silicon-aluminum molecular sieve with a specific surface area of ​​185m 2 / g, soaking the porous carrier in the metal salt solution, the mass ratio of the porous carrier to the metal salt solution is 1:2, the soaking temperature is 20°C, the soaking time is 15 hours, and the first-stage porous carrier loaded with copper ions is obtained after soaking, the drying temperature is 60°C, and the drying time is 12 hours; the precipitant sodium hydroxide is dissolved in water to obtain a precipitant solution with a concentration of 0.5 mol / L; the first-stage porous carrier is immersed in the precipitant solution and a co-precipitation reaction is generated, the mass ratio of the first-stage porous carrier to the precipitant solution is 0.5:2, the soaking temperature is 2 0℃, soaking time 1 hour, maintaining pH value at 8 during soaking process, the obtained second-stage porous carrier is loaded with copper hydroxide; the second-stage porous carrier is soaked in 10℃ water for cleaning for 1 hour, the volume ratio of water to the second-stage porous carrier is 2:1, the cleaning is repeated twice, taken out and dried, the drying temperature is 150℃, the drying time is 12 hours, and the obtained third-stage porous carrier is loaded with copper oxide; the third-stage porous carrier is placed in a muffle furnace for sintering, the sintering temperature is 500℃, the sintering time is 2 hours, and the copper oxide is bonded to the porous carrier to obtain a metal oxide sterilization material.

[0043] like Figure 2As shown, in Example 2 of the present invention, the metal salt solution is obtained by dissolving cobalt nitrate and water, and the mass concentration of cobalt ions in the metal salt solution is 0.1% of the total solution; the porous carrier adopts a honeycomb-shaped all-silicon molecular sieve with a specific surface area of ​​100m 2 / g, soaking the porous carrier in the metal salt solution, the mass ratio of the porous carrier to the metal salt solution is 1:2, the soaking temperature is 20°C, the soaking time is 15 hours, and the first-stage porous carrier loaded with cobalt ions is obtained after soaking, the drying temperature is 60°C, and the drying time is 12 hours; the precipitant potassium hydroxide is dissolved in water to obtain a precipitant solution with a concentration of 0.8 mol / L; the first-stage porous carrier is immersed in the precipitant solution and a coprecipitation reaction is generated, the mass ratio of the first-stage porous carrier to the precipitant solution is 0.5:2, the soaking temperature is 2 0℃, soaking time 1 hour, maintaining pH value at 8 during soaking process, the obtained second-stage porous carrier is loaded with cobalt hydroxide; the second-stage porous carrier is soaked in 10℃ water for cleaning for 1 hour, the volume ratio of water to the second-stage porous carrier is 2:1, the cleaning is repeated twice, taken out and dried, the drying temperature is 150℃, the drying time is 12 hours, and the obtained third-stage porous carrier is loaded with cobalt oxide; the third-stage porous carrier is placed in a muffle furnace for sintering, the sintering temperature is 500℃, the sintering time is 2 hours, the cobalt oxide is bonded to the porous carrier to obtain a metal oxide sterilization material.

[0044] like Figure 3 As shown, in Example 3 of the present invention, the metal salt solution is obtained by dissolving nickel acetate and water, and the mass concentration of nickel ions in the metal salt solution is 1.2% of the total solution; the porous carrier is a spherical alumina ceramic with a specific surface area of ​​200 m 2 / g, soaking the porous carrier in the metal salt solution, the mass ratio of the porous carrier to the metal salt solution is 1:2, the soaking temperature is 30°C, the soaking time is 6 hours, and the first-stage porous carrier loaded with nickel ions is obtained after soaking, the drying temperature is 120°C, and the drying time is 6 hours; the precipitant sodium carbonate is dissolved in water to obtain a precipitant solution with a concentration of 3 mol / L; the first-stage porous carrier is immersed in the precipitant solution and a co-precipitation reaction is generated, the mass ratio of the first-stage porous carrier to the precipitant solution is 1:2, the soaking temperature is 30°C, and the soaking The soaking time is 3 hours, and the pH value is maintained at 12 during the soaking process. The second-stage porous carrier is loaded with nickel hydroxide; the second-stage porous carrier is soaked in 25°C water for cleaning for 3 hours, and the volume ratio of water to the second-stage porous carrier is 2:0.5. The cleaning is repeated twice, and the carrier is taken out and dried at a drying temperature of 120°C and a drying time of 36 hours. The third-stage porous carrier is loaded with nickel oxide; the third-stage porous carrier is placed in a muffle furnace for sintering at a sintering temperature of 300°C and a sintering time of 4 hours. The nickel oxide is bonded to the porous carrier to obtain a metal oxide sterilization material.

[0045] like Figure 4 As shown, in Example 4 of the present invention, the metal salt solution is obtained by dissolving zinc chloride and water, and the mass concentration of zinc ions in the metal salt solution is 1.8% of the total solution; the porous carrier adopts a spherical clay adsorbent with a specific surface area of ​​250 m 2 / g, soaking the porous carrier in the metal salt solution, the mass ratio of the porous carrier to the metal salt solution is 1:2, the soaking temperature is 30°C, the soaking time is 6 hours, and the first-stage porous carrier loaded with zinc ions is obtained after soaking, the drying temperature is 120°C, and the drying time is 6 hours; the precipitant ammonia water is dissolved in water to obtain a precipitant solution with a concentration of 1 mol / L; the first-stage porous carrier is soaked in the precipitant solution and a co-precipitation reaction is generated, the mass ratio of the first-stage porous carrier to the precipitant solution is 1:2, the soaking temperature is 30°C, and the soaking The soaking time is 3 hours, and the pH value is maintained at 12 during the soaking process. The second-stage porous carrier is loaded with zinc hydroxide; the second-stage porous carrier is soaked in 25°C water for cleaning for 3 hours, and the volume ratio of water to the second-stage porous carrier is 2:0.5. The cleaning is repeated twice, and the carrier is taken out and dried at a drying temperature of 120°C and a drying time of 36 hours. The third-stage porous carrier is loaded with zinc oxide; the third-stage porous carrier is placed in a muffle furnace for sintering at a sintering temperature of 300°C and a sintering time of 4 hours. The zinc oxide is bonded to the porous carrier to obtain a metal oxide sterilization material.

[0046] like Figure 5 As shown, in Example 5 of the present invention, the metal salt solution is obtained by dissolving copper sulfate, nickel sulfate, magnesium sulfate and water, and the molar mass ratio is Cu2+ :Ni 2+ :Mg 2+ =4:2:1, Cu in metal salt solution 2+ 、Ni 2+ Mg 2+ The total mass concentration of ions in the total solution is 2%; the porous carrier adopts honeycomb-shaped silica-alumina molecular sieve with a specific surface area of ​​300 m 2 / g, soaking the porous carrier in the metal salt solution, the mass ratio of the porous carrier to the metal salt solution is 1:2, the soaking temperature is 40°C, the soaking time is 24 hours, and after soaking, the porous carrier is taken out and dried at a drying temperature of 150°C for 24 hours to obtain a Cu-loaded 2+ 、Ni 2+ Mg 2+ The first-stage porous carrier of ions; dissolving the precipitant sodium hydroxide in water to obtain a precipitant solution with a concentration of 1.5 mol / L; immersing the first-stage porous carrier in the precipitant solution and generating a coprecipitation reaction, the mass ratio of the first-stage porous carrier to the precipitant solution is 0.7:1.5, the immersion temperature is 40°C, the immersion time is 5 hours, and the pH value is maintained at 13 during the immersion process, and the obtained second-stage porous carrier is loaded with copper, nickel, and magnesium mixed hydroxides; immersing the second-stage porous carrier in 30°C water for cleaning for 2 hours, the volume ratio of water to the second-stage porous carrier is 3:1, and the cleaning is repeated twice, and the carrier is taken out and dried, the drying temperature is 60°C, and the drying time is 24 hours, and the obtained third-stage porous carrier is loaded with copper, nickel, and magnesium mixed oxides; the third-stage porous carrier is placed in a muffle furnace for sintering, the sintering temperature is 800°C, and the sintering time is 8 hours, and the copper, nickel, and magnesium mixed oxides are bonded to the porous carrier to obtain a metal oxide sterilization material.

[0047] In Example 6 of the present invention, the metal salt solution is obtained by dissolving copper acetate, manganese acetate and water, and the molar mass ratio is Cu 2+ : Mn 2+ =3:2, Cu in metal salt solution 2+ , Mn 2+ The total mass concentration of ions in the total solution is 1.5%; the porous carrier is spherical alumina ceramic with a specific surface area of ​​350 m 2 / g, soaking the porous carrier in the metal salt solution, the mass ratio of the porous carrier to the metal salt solution is 1:2, the soaking temperature is 25°C, the soaking time is 4 hours, and after soaking, the porous carrier is taken out and dried, the drying temperature is 120°C, and the drying time is 36 hours to obtain a porous carrier loaded with Cu 2+ , Mn 2+The first-stage porous carrier of ions; dissolving the precipitant sodium carbonate in water to obtain a precipitant solution with a concentration of 2 mol / L; immersing the first-stage porous carrier in the precipitant solution and generating a coprecipitation reaction, the mass ratio of the first-stage porous carrier to the precipitant solution is 0.5:1.5, the immersion temperature is 25°C, the immersion time is 6 hours, and the pH value is maintained at 11 during the immersion process, and the obtained second-stage porous carrier is loaded with copper and manganese mixed hydroxides; the second-stage porous carrier is immersed in 40°C water for cleaning for 1 hour, the volume ratio of water to the second-stage porous carrier is 2.5:1, the cleaning is repeated twice, and the carrier is taken out and dried, the drying temperature is 120°C, and the drying time is 6 hours, and the obtained third-stage porous carrier is loaded with copper and manganese mixed oxides; the third-stage porous carrier is placed in a muffle furnace for sintering, the sintering temperature is 600°C, and the sintering time is 6 hours, and the copper and manganese mixed oxides are bonded to the porous carrier to obtain a metal oxide sterilization material.

[0048] In the prior art, bactericidal active ingredients are often made into powders and then adhered to the surface of a carrier by a binder. The adhesion between the metal oxide and the carrier is poor and the metal oxide is easy to fall off. The preparation method of the metal oxide bactericidal material provided by the present invention is to immerse the carrier in a metal solution, adsorb metal ions, and obtain the bactericidal active ingredients after co-precipitation. The adhesion effect between the active ingredients and the carrier is good, and the metal oxide of the active ingredient reacts chemically with the carrier, bonding together and not easy to fall off.

[0049] The metal oxide sterilizing material provided by the present invention has good sterilization effect, high sterilization rate, fast sterilization speed, and the bacteria removal rate is tested by a self-built dynamic cycle sterilization device, such as Figure 6 As shown, the test device includes a circulation tank with a volume of 1m 3 The circulation tank contains a bacteria generator and a humidity controller. The bacteria generator produces a bacterial aerosol that enters a volume of 1m 3 The circulation tank is connected to the circulation tank through a humidity controller to adjust the air humidity in the circulation tank. The circulation tank is connected through a pipeline to realize circulation. A fan is provided on the pipeline to provide circulation power. A flow meter detects the circulation flow rate, as well as metal oxide sterilization materials. The laser particle detector measures the bacterial concentration in the tank. When the bacterial concentration in the circulation tank reaches the preset value, the fan is turned on, and the bacterial aerosol passes through the metal sterilizer, circulates in the circulation tank and the pipeline, and continues to pass through the metal sterilizer. The change of bacterial concentration with the extension of the circulation time is detected, and the initial concentration and circulation time concentration are obtained. The bacterial removal rate can be calculated. The experimental test bacteria are: Escherichia coli, Staphylococcus aureus, and Candida albicans.

[0050] Experiment 1, constant temperature and humidity conditions, determination of the bacterial removal rate within the cycle time, testing the metal oxide sterilization material prepared by the method of Example 5, the specification is: 100mm*100mm*50mm honeycomb-silicon aluminum molecular sieve porous carrier, weight 250g, the experimental test bacteria is Escherichia coli. It can be seen from the experimental data that under the conditions of temperature 35°C and humidity 60%, with the increase of cycle time, the bacterial removal rate continues to increase, and the bacterial removal rate within 2 hours is more than 90%. For experimental data, see Figure 7 .

[0051] Experiment 2, constant humidity conditions, determination of bacteria removal rate within 60 minutes at different temperatures, testing the metal oxide bactericidal material prepared by the method of Example 6, specifications: 5mm diameter spherical-alumina ceramic porous carrier, weight 200g, the experimental test bacteria is Staphylococcus aureus. From the experimental data, it can be seen that under the condition of 60% humidity and temperature between 20-35℃, the bacteria removal rate within 60 minutes increases first and then decreases with the change of temperature. For experimental data, see Figure 8 .

[0052] Experiment 3, constant temperature conditions, determination of bacteria removal rate within 60 minutes under different humidity, test the metal oxide bactericidal material prepared by the method of Example 4, the specification is: diameter 3mm spherical - clay adsorbent porous carrier, weight 200g, the experimental test bacteria is Candida albicans. It can be seen from the experimental data that under the condition of temperature 35℃, humidity between 30-90%, the bacteria removal rate within 60 minutes increases with the change of humidity. The experimental data can be seen in Fig. 9 .

[0053] Experiments show that the metal oxide sterilization material of the present invention can achieve a higher and faster sterilization rate at room temperature, and compared with the prior art, such as photocatalytic oxidation which requires external conditions such as ultraviolet irradiation to trigger, the metal oxide sterilization material of the present invention is less restricted and is simpler and more convenient to use.

[0054] The metal oxide sterilization material of the present invention has a wide range of application scenarios, and can be applied to air sterilization equipment, such as a household air purifier, which includes a fan, a pipeline, and a metal oxide sterilization material. The indoor air is continuously circulated through the metal oxide sterilization material for sterilization, so as to achieve the effect of sterilizing and purifying the indoor air.

[0055] It can also be used to disinfect shoe cabinets. Home shoe cabinets often have odors, and there are many bacteria inside the shoes. The air in the shoe cabinet can be continuously circulated through the metal oxide sterilization material by the fan, which can kill the bacteria in the shoe cabinet. With fewer bacteria, the shoe cabinet will naturally have no odor.

[0056] It can also be used to sterilize wardrobes, bathrooms, and even water. The sterilization principle is the same. It is easier to sterilize in water because metal ions are more easily dissolved and will produce active oxygen groups. It can also be used in hospitals and other places with a lot of environmental bacteria, etc. The examples here are not to be construed as limitations on the application of the present invention.

[0057] The above-described embodiments of the present invention do not constitute a limitation on the protection scope of the present invention. Any modification, equivalent substitution and improvement made within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A method for preparing a metal oxide sterilization material, characterized in that: Include Step S1: providing a metal salt solution, including a single metal salt component or a double metal salt mixed component or a mixture of three or more metal salts dissolved in water, Step S2: placing the porous carrier in the metal salt solution, taking out the porous carrier after soaking, and drying it to obtain a first-stage porous carrier loaded with metal ions. Step S3: dissolving the precipitant in water to obtain a precipitant solution. Step S4: soaking the first-stage porous carrier in the precipitant solution to produce a coprecipitation reaction, and after soaking, obtaining a second-stage porous carrier loaded with hydroxide, Step S5: Soak the second-stage porous support in water, wash and dry to obtain a third-stage porous support loaded with oxides. Step S6: sintering the third-stage porous carrier, and bonding the oxide with the porous carrier to obtain the metal oxide sterilization material; Specifically, when the metal salt solution is obtained by dissolving copper sulfate, nickel sulfate, magnesium sulfate and water, the molar mass ratio is Cu 2+ :Ni 2+ :Mg 2+ =4:2:1, Cu in metal salt solution 2+ 、Ni 2+ Mg 2+ The total mass concentration of ions in the total solution is 2%; the porous carrier adopts honeycomb-shaped silica-alumina molecular sieve with a specific surface area of ​​300 m 2 / g, soaking the porous carrier in the metal salt solution, the mass ratio of the porous carrier to the metal salt solution is 1:2, the soaking temperature is 40°C, the soaking time is 24 hours, and after soaking, the porous carrier is taken out and dried at a drying temperature of 150°C for 24 hours to obtain a Cu-loaded 2+ 、Ni 2+ Mg 2+ The first-stage porous carrier of ions; dissolving the precipitant sodium hydroxide in water to obtain a precipitant solution with a concentration of 1.5 mol / L; immersing the first-stage porous carrier in the precipitant solution and generating a coprecipitation reaction, the mass ratio of the first-stage porous carrier to the precipitant solution is 0.7:1.5, the immersion temperature is 40°C, the immersion time is 5 hours, and the pH value is maintained at 13 during the immersion process, and the obtained second-stage porous carrier is loaded with copper, nickel, and magnesium mixed hydroxides; immersing the second-stage porous carrier in 30°C water for washing for 2 hours, the volume ratio of water to the second-stage porous carrier is 3:1, and the washing is repeated twice, and the carrier is taken out and dried, the drying temperature is 60°C, and the drying time is 24 hours, and the obtained third-stage porous carrier is loaded with copper, nickel, and magnesium mixed oxides; the third-stage porous carrier is placed in a muffle furnace for sintering, the sintering temperature is 800°C, and the sintering time is 8 hours, and the copper, nickel, and magnesium mixed oxides are bonded to the porous carrier to obtain a metal oxide sterilization material; When the metal salt solution is obtained by dissolving copper acetate, manganese acetate and water, the molar mass ratio is Cu 2+ :Mn 2+ =3:2, Cu in metal salt solution 2+ , Mn 2+ The total mass concentration of ions in the total solution is 1.5%; the porous carrier is spherical alumina ceramic with a specific surface area of ​​350 m 2 / g, soaking the porous carrier in the metal salt solution, the mass ratio of the porous carrier to the metal salt solution is 1:2, the soaking temperature is 25°C, the soaking time is 4 hours, and after soaking, the porous carrier is taken out and dried, the drying temperature is 120°C, and the drying time is 36 hours to obtain a porous carrier loaded with Cu 2+ , Mn 2+ The first-stage porous carrier of ions; dissolving the precipitant sodium carbonate in water to obtain a precipitant solution with a concentration of 2 mol / L; immersing the first-stage porous carrier in the precipitant solution and generating a coprecipitation reaction, the mass ratio of the first-stage porous carrier to the precipitant solution is 0.5:1.5, the immersion temperature is 25°C, the immersion time is 6 hours, and the pH value is maintained at 11 during the immersion process, and the obtained second-stage porous carrier is loaded with copper and manganese mixed hydroxides; the second-stage porous carrier is immersed in 40°C water for cleaning for 1 hour, the volume ratio of water to the second-stage porous carrier is 2.5:1, the cleaning is repeated twice, and the carrier is taken out and dried, the drying temperature is 120°C, and the drying time is 6 hours, and the obtained third-stage porous carrier is loaded with copper and manganese mixed oxides; the third-stage porous carrier is placed in a muffle furnace for sintering, the sintering temperature is 600°C, and the sintering time is 6 hours, and the copper and manganese mixed oxides are bonded to the porous carrier to obtain a metal oxide sterilization material.

2. A metal oxide sterilization material, characterized in that: The metal oxide sterilization material is prepared by the preparation method of the metal oxide sterilization material according to claim 1, wherein the metal oxide sterilization material comprises a porous carrier and an oxide loaded on the porous carrier through a bonding reaction.

3. The use of the metal oxide sterilizing material in sterilization according to claim 2, characterized in that: Used to make air sterilization equipment and water sterilization equipment.

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