Method for preparing micro-particle-size negative oxygen ion purifying agent from nano material

Abstract

The invention discloses a method for preparing a micro-particle-size negative oxygen ion purifying agent from a nano material, and relates to the technical field of air purifying agents, the method comprises the following preparation steps: step 1, pouring 5-6.5 g of modified tourmaline powder and 10 g of an amino acid-nano particle compound into 200 mL of deionized water, then adding 0.5-0.54 g of polyvinylpyrrolidone, carrying out ultrasonic treatment for 30-40 min, then adding 0.5-0.54 g of polyvinylpyrrolidone into the deionized water, carrying out ultrasonic treatment for 30-40 min, and carrying out ultrasonic treatment for 30-40 min; carrying out ball milling until the particle size is 1-5 microns; 2, adding 2-2.6 g of a chitosan solution with the concentration of 1% after ball milling, adjusting the pH value of the system to 6, and stirring at 50 DEG C for 1 h; according to the method for preparing the micro-particle-size negative oxygen ion purifying agent from the nano material, tourmaline powder is modified, so that the surface hydroxylation degree of the tourmaline powder is improved, lattice defects are increased, the negative oxygen ion release efficiency is remarkably improved, meanwhile, the tourmaline powder is compounded with white carbon black, interface charge conduction can be enhanced, and continuous release of negative oxygen ions is further promoted.

Description

Technical Field

[0001] The present invention relates to the technical field of air purifiers, in particular to a method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials. Background Art

[0002] Air purifiers utilize the inherent adsorption and decomposition properties of natural substances, processed through modern scientific technology, to eliminate harmful gases and odors from the air. Negative air ions are negatively charged oxygen ions in the air, known as the "cellulose of air." They not only purify the air and improve its structure, but also enhance lung and myocardial function, promote blood circulation, boost metabolism, enhance the body's resistance to disease, and alleviate respiratory ailments. They are also known as the "longevity factor."

[0003] The Chinese patent publication number CN111558295A discloses a method for preparing a negative oxygen ion air purifier, which relates to the field of air purification materials and manufacturing technology, and includes the following steps: (1) tourmaline screening and ash removal treatment (2) compressed air cleaning treatment (3) clean water cleaning treatment (4) grinding treatment (5) magnetic separation treatment (6) high temperature and high pressure treatment (7) preparation of composite additives (8) preparation of plant extracts (9) grinding and mixing treatment. The overall process of the method of the present invention is simple and easy to promote and apply. The air purifier prepared has good comprehensive performance, strong purification ability, and high concentration of negative oxygen ions released. However, the above-mentioned existing technical solutions have the following defects: natural tourmaline powder easily forms micron-sized agglomerates in water, resulting in the internal active sites being encapsulated, thereby affecting the purification effect; therefore, the present invention provides a method for preparing a micron-sized negative oxygen ion purifier from nanomaterials to solve the above-mentioned problems. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the present invention provides a method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials, which solves the problems mentioned in the above background technology.

[0005] To achieve the above objectives, the present invention is implemented by the following technical solution: a method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials, comprising the following preparation steps: Step 1: Pour 5-6.5 g of modified tourmaline powder and 10 g of amino acid-nanoparticle complex into 200 mL of deionized water, then add 0.5-0.54 g of polyvinyl pyrrolidone, ultrasonicate for 30-40 min, and then ball-mill to a particle size of 1-5 μm; Step 2: After ball milling, add 2-2.6 g of chitosan solution with a concentration of 1%, adjust the pH value of the system to 6, and stir at 50°C for 1 hour; Step 3: Use spray drying method, where the air inlet temperature is 180°C and the atomization pressure is 0.5MPa, dry the mixed liquid in step 2 into powder, and collect particles with a particle size of ≤5μm to obtain a microparticle-sized negative oxygen ion purifier.

[0006] Preferably, the preparation method of the amino acid-nanoparticle complex is: S1, 5-5.25g lysine and 2g sodium glycinate were dissolved in 92g deionized water, and 1-1.14g sodium dodecylbenzenesulfonate was added, and stirring was continued until the solution was completely colorless and transparent to obtain an amino acid mixed solution; S2. Add 0.5-0.64 g of nano-hydrated titanium dioxide and 0.5-0.6 g of nano-zinc oxide to the amino acid mixed solution, shear and emulsify for 5-8 minutes, stir for 30-40 minutes, and then add lactic acid to adjust the pH value of the system to 7.5 to obtain an amino acid-nanoparticle complex.

[0007] Preferably, in S2, the shear emulsification rate is 24000-25000 r / min, and the stirring rate is 250-300 r / min.

[0008] Preferably, in S2, the preparation method of the nano-hydrated titanium dioxide is: (1) Use high titanium slag as raw material, add sodium bicarbonate, heat to 1200-1250℃, calcine for 2h, cool naturally, crush and sieve; (2) Slowly add the treated high-titanium slag to 300 mL of 8-12 mol / L hydrochloric acid solution under stirring, react for 1-1.5 hours, let it stand overnight, and filter to obtain a titanium tetrachloride aqueous solution; (3) Heating: When the temperature reaches 80°C, add rutile nanocrystal seeds to the titanium tetrachloride aqueous solution, then continue to heat the solution to 106°C, rinse with 6.0 mol / L hydrochloric acid at 80°C for 2 hours, then vacuum filter, wash until neutral, and dry at 110°C for 4 hours to obtain nano-hydrated titanium dioxide.

[0009] Preferably, in (1), the mass of sodium bicarbonate is 10%-15% of the mass of the high titanium slag; In the above (3), the mass of the rutile nanocrystalline seeds is 0.5%-2% of the mass of the titanium tetrachloride aqueous solution.

[0010] Preferably, the preparation method of the modified tourmaline powder is: mixing the tourmaline powder with distilled water, and treating it with an ultrasonic cleaner for 20-30 minutes, then adding sodium hydroxide solution dropwise to adjust the pH value of the solution system to 11, then adding the modifier and the modification auxiliary agent in sequence, heating the water bath to 83-84°C, and stirring for 15-20 minutes to obtain the modified tourmaline powder.

[0011] Preferably, the mass ratio of tourmaline powder to distilled water is 1:10, and the masses of the modifier and the modification aid are 1.8%-2.1% and 4%-4.2% of the mass of the tourmaline powder, respectively.

[0012] Preferably, the modifier is a mixture of sodium polyacrylate and sodium polyphosphate, and the mass ratio thereof is 2:1; and the modification aid is white carbon black.

[0013] Beneficial effects The present invention provides a method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials. Compared with the prior art, it has the following advantages: (1) The method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials is to modify tourmaline powder to increase the degree of surface hydroxylation, increase the number of lattice defects, and significantly improve the negative oxygen ion release efficiency. At the same time, compounding with white carbon black can enhance interfacial charge conduction and further promote the continuous release of negative oxygen ions.

[0014] (2) The method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials, wherein nano-hydrated titanium dioxide and zinc oxide produce a photocatalytic effect under light to generate hydroxyl radicals (・OH) and superoxide anions (・O2 - ), can deeply decompose stubborn pollutants such as formaldehyde and toluene, and negative oxygen ions accelerate the degradation of pollutants through redox reactions, forming a "double-effect purification mechanism". At the same time, amino acids combine with nanoparticles through coordination to form a hydrophilic protective layer to prevent nanoparticles from agglomerating. At the same time, its polar groups can adsorb polar pollutants and improve the removal efficiency of water-soluble harmful substances; and the Zn released by nano zinc oxide 2+ The bacterial cell membrane is destroyed, and the free radicals generated by titanium dioxide photocatalysis oxidize bacterial DNA. The two work together to kill Escherichia coli and Staphylococcus aureus at a rate of more than 99%; the cationic properties of chitosan adsorb negatively charged bacteria, further enhancing the antibacterial effect.

[0015] In summary, tourmaline provides an electrostatic field to continuously electrolyze water molecules to generate negative oxygen ions; nano-hydrated TiO2 / ZnO generates active oxygen species through photocatalysis, decomposes pollutants and assists in the release of negative oxygen ions; amino acid complexes stabilize nanomaterials and enhance water molecule adsorption; chitosan adsorbs pollutants and regulates the slow release of negative oxygen ions; and the hydroxyl groups on the surface of nano-hydrated TiO2 can adsorb more water molecules, which are electrolyzed into H by the electrostatic field of tourmaline. + and OH - , and then generate negative oxygen ions. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The SEM images of the tourmaline powder provided by the present invention before and after modification; Figure 2 TEM image of nano-hydrated titanium dioxide provided by the present invention; Figure 3 This is a comparison chart of the antibacterial performance test provided by the present invention. DETAILED DESCRIPTION

[0017] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0018] Example 1 A method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials comprises the following preparation steps: Step 1: Pour 5 g of modified tourmaline powder and 10 g of amino acid-nanoparticle complex into 200 mL of deionized water, add 0.5 g of polyvinyl pyrrolidone, ultrasonicate for 30 min, and then ball-mill to a particle size of 1 μm; The modified tourmaline powder is prepared by mixing 10 g of tourmaline powder with 100 g of distilled water, treating the mixture with an ultrasonic cleaner for 20 min, adding a sodium hydroxide solution dropwise to adjust the pH value of the solution to 11, and then adding 0.18 g of a mixture of sodium polyacrylate and sodium polyphosphate in a mass ratio of 2:1 and 0.4 g of white carbon black in sequence, heating the mixture in a water bath to 83° C., and stirring the mixture for 15 min to obtain the modified tourmaline powder. The preparation method of amino acid-nanoparticle complex is as follows: (1) 100g of high titanium slag was used as raw material, 10g of sodium bicarbonate was added, the temperature was raised to 1200℃, calcined for 2h, cooled naturally, crushed and sieved; under stirring, the treated high titanium slag was slowly added to 300mL of 8mol / L hydrochloric acid solution, reacted for 1h, allowed to stand overnight and filtered to obtain a titanium tetrachloride aqueous solution; the temperature was raised, and when heated to 80℃, 0.5% of the mass of rutile nanocrystal seeds were added to the titanium tetrachloride aqueous solution, and then the temperature was continued to be raised to 106℃, and then rinsed with 6.0mol / L hydrochloric acid at 80℃ for 2h, and then vacuum filtered, washed until neutral, and dried at 110℃ for 4h to obtain nano-hydrated titanium dioxide; (2) Dissolve 55 g of lysine and 2 g of sodium glycinate in 92 g of deionized water, then add 1 g of sodium dodecylbenzenesulfonate, and continue stirring until the solution becomes completely colorless and transparent to obtain an amino acid mixed solution; add 0.5 g of nano-hydrated titanium dioxide and 0.5 g of nano-zinc oxide to the amino acid mixed solution, first shear emulsify at a rate of 24,000 r / min for 5 min, then stir at a rate of 250 r / min for 30 min, and then add lactic acid to adjust the pH value of the system to 7.5 to obtain an amino acid-nanoparticle complex; Step 2: After ball milling, add 2 g of chitosan solution with a concentration of 1%, adjust the pH value of the system to 6, and stir at 50°C for 1 hour; Step 3: Use spray drying method, where the air inlet temperature is 180°C and the atomization pressure is 0.5MPa, dry the mixed liquid in step 2 into powder, and collect particles with a particle size of ≤5μm to obtain a microparticle-sized negative oxygen ion purifier.

[0019] Example 2 A method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials comprises the following preparation steps: Step 1: Pour 5.5 g of modified tourmaline powder and 10 g of amino acid-nanoparticle complex into 200 mL of deionized water, then add 0.52 g of polyvinyl pyrrolidone, ultrasonicate for 35 min, and then ball-mill to a particle size of 1-5 μm; The modified tourmaline powder is prepared by mixing 10 g of tourmaline powder with 100 g of distilled water, treating the mixture with an ultrasonic cleaner for 25 minutes, adding a sodium hydroxide solution dropwise to adjust the pH value of the solution to 11, and then adding 0.192 g of a mixture of sodium polyacrylate and sodium polyphosphate in a mass ratio of 2:1 and 0.41 g of white carbon black in sequence, heating the mixture in a water bath to 83° C., and stirring the mixture for 18 minutes to obtain the modified tourmaline powder. The preparation method of amino acid-nanoparticle complex is as follows: (1) 100g of high titanium slag was used as the raw material, 12g of sodium bicarbonate was added, the temperature was raised to 1230℃, calcined for 2h, cooled naturally, crushed and sieved; under stirring, the treated high titanium slag was slowly added to 300mL of 10mol / L hydrochloric acid solution, reacted for 1.2h, allowed to stand overnight and filtered to obtain a titanium tetrachloride aqueous solution; the temperature was raised, and when heated to 80℃, 1.5% of the mass of rutile nanocrystal seeds were added to the titanium tetrachloride aqueous solution, and then the temperature was continued to be raised to 106℃, and then rinsed with 6.0mol / L hydrochloric acid at 80℃ for 2h, and then vacuum filtered, washed until neutral, and dried at 110℃ for 4h to obtain nano-hydrated titanium dioxide; (2) A mixture of 5.15 g of lysine and 2 g of sodium glycinate was dissolved in 92 g of deionized water, and then 1.07 g of sodium dodecylbenzenesulfonate was added and stirred until the solution was completely colorless and transparent to obtain an amino acid mixed solution; 0.57 g of nano-hydrated titanium dioxide and 0.55 g of nano-zinc oxide were added to the amino acid mixed solution, and the mixture was first sheared and emulsified at a rate of 24500 r / min for 6 min, and then stirred at a rate of 280 r / min for 35 min, and then lactic acid was added to adjust the pH value of the system to 7.5 to obtain an amino acid-nanoparticle complex; Step 2: After ball milling, add 2.3 g of chitosan solution with a concentration of 1%, adjust the pH value of the system to 6, and stir at 50°C for 1 hour; Step 3: Use spray drying method, where the air inlet temperature is 180°C and the atomization pressure is 0.5MPa, dry the mixed liquid in step 2 into powder, and collect particles with a particle size of ≤5μm to obtain a microparticle-sized negative oxygen ion purifier.

[0020] Example 3 A method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials comprises the following preparation steps: Step 1: Pour 6.5 g of modified tourmaline powder and 10 g of amino acid-nanoparticle complex into 200 mL of deionized water, add 0.54 g of polyvinyl pyrrolidone, ultrasonicate for 40 min, and then ball-mill to a particle size of 5 μm; The modified tourmaline powder is prepared by mixing 10 g of tourmaline powder with 100 g of distilled water, treating the mixture with an ultrasonic cleaner for 30 min, adding a sodium hydroxide solution dropwise to adjust the pH value of the solution to 11, and then adding 0.21 g of a mixture of sodium polyacrylate and sodium polyphosphate in a mass ratio of 2:1 and 0.42 g of white carbon black in sequence, heating the mixture to 84° C. in a water bath, and stirring the mixture for 20 min to obtain the modified tourmaline powder. The preparation method of amino acid-nanoparticle complex is as follows: (1) 100g of high titanium slag was used as raw material, 15g of sodium bicarbonate was added, the temperature was raised to 1250℃, calcined for 2h, cooled naturally, crushed and sieved; under stirring, the treated high titanium slag was slowly added to 300mL of hydrochloric acid solution with a concentration of 12mol / L, reacted for 1.5h, allowed to stand overnight and filtered to obtain a titanium tetrachloride aqueous solution; the temperature was raised, and when heated to 80℃, 0.5%-2% of the mass of rutile nanocrystal seeds were added to the titanium tetrachloride aqueous solution, and then the temperature was continued to be raised to 106℃, and then rinsed with 6.0mol / L hydrochloric acid at 80℃ for 2h, and then vacuum filtered, washed until neutral, and dried at 110℃ for 4h to obtain nano-hydrated titanium dioxide; (2) A mixture of 5.25 g of lysine and 2 g of sodium glycinate was dissolved in 92 g of deionized water, and then 1.14 g of sodium dodecylbenzenesulfonate was added and stirred until the solution was completely colorless and transparent to obtain an amino acid mixed solution; 0.64 g of nano-hydrated titanium dioxide and 0.6 g of nano-zinc oxide were added to the amino acid mixed solution, first sheared and emulsified at a rate of 25,000 r / min for 8 min, then stirred at a rate of 300 r / min for 40 min, and then lactic acid was added to adjust the pH value of the system to 7.5 to obtain an amino acid-nanoparticle complex; Step 2: After ball milling, add 2.6 g of chitosan solution with a concentration of 1%, adjust the pH value of the system to 6, and stir at 50°C for 1 hour; Step 3: Use spray drying method, where the air inlet temperature is 180°C and the atomization pressure is 0.5MPa, dry the mixed liquid in step 2 into powder, and collect particles with a particle size of ≤5μm to obtain a microparticle-sized negative oxygen ion purifier.

[0021] Comparative Example 1 Compared with Example 1, the difference is that the modified tourmaline powder is replaced by tourmaline powder; the rest remains unchanged.

[0022] Comparative Example 2 Compared with Example 1, the difference is that the nano-hydrated titanium dioxide is replaced by nano-titanium dioxide; the rest remains unchanged.

[0023] Formaldehyde removal rate test: A UV-visible spectrophotometer was used to test the formaldehyde removal rate in accordance with GB / T 18883-2022. The results are shown in Table 1.

[0024] Benzene removal rate test: The test was conducted using a gas chromatograph in accordance with GB / T 18883-2022; the results are shown in Table 1.

[0025] Negative oxygen ion release monitoring: using XDB-6400 negative oxygen ion detector, with a resolution of 1 / cm 3 , monitoring was carried out in accordance with the national standard GB / T 28628-2012, and the average value of the sample within 120 minutes was calculated; the results are shown in Table 1.

[0026] Table 1 Formaldehyde removal rate / % Benzene removal rate / % Negative oxygen ion release (pcs / cm3) Example 1 93.4 91.2 417 Example 2 92.8 90.4 396 Example 3 92.1 88.7 384 Comparative Example 1 83.6 82.1 313 Comparative Example 2 87.5 83.9 348 like Figure 1 As shown in the figure, the particle size of the modified tourmaline powder is significantly smaller than that before modification, thereby reducing the agglomeration phenomenon between particles and improving the uniformity of its dispersion.

[0027] like Figure 2As shown in the figure, the shape of nano-hydrated titanium dioxide particles is relatively regular spherical. This is because the electrostatic repulsion generated by the overlap of the double electric layers between the elementary particles increases with the increase of the surface positive charge density, thus preventing the tendency of elementary particles to agglomerate.

[0028] Antibacterial performance test: Escherichia coli, Staphylococcus aureus, and Bacillus subtilis were used as the strains to test the changes in their antibacterial performance after 24 hours; the results are shown in Table 1: the bactericidal rates of the samples of Examples 1-3 were significantly improved compared to those of Comparative Examples 1-2.

[0029] At the same time, the contents not described in detail in this specification belong to the existing technology well known to those skilled in the art.

[0030] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0031] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials, characterized in that: The method comprises the following preparation steps: Step 1: Pour 5-6.5 g of modified tourmaline powder and 10 g of amino acid-nanoparticle complex into 200 mL of deionized water, then add 0.5-0.54 g of polyvinyl pyrrolidone, ultrasonicate for 30-40 min, and then ball-mill to a particle size of 1-5 μm; Step 2: After ball milling, add 2-2.6 g of chitosan solution with a concentration of 1%, adjust the pH value of the system to 6, and stir at 50°C for 1 hour; Step 3: Use spray drying method, where the air inlet temperature is 180°C and the atomization pressure is 0.5MPa, dry the mixed liquid in step 2 into powder, and collect particles with a particle size of ≤5μm to obtain a microparticle-sized negative oxygen ion purifier.

2. The method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials according to claim 1, characterized in that: The preparation method of the amino acid-nanoparticle complex is: S1, 5-5.25g lysine and 2g sodium glycinate were dissolved in 92g deionized water, and 1-1.14g sodium dodecylbenzenesulfonate was added, and stirring was continued until the solution was completely colorless and transparent to obtain an amino acid mixed solution; S2. Add 0.5-0.64 g of nano-hydrated titanium dioxide and 0.5-0.6 g of nano-zinc oxide to the amino acid mixed solution, shear and emulsify for 5-8 minutes, stir for 30-40 minutes, and then add lactic acid to adjust the pH value of the system to 7.5 to obtain an amino acid-nanoparticle complex.

3. The method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials according to claim 2, characterized in that: In the S2, the shear emulsification rate is 24000-25000 r / min, and the stirring rate is 250-300 r / min.

4. The method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials according to claim 2, characterized in that: In S2, the preparation method of the nano-hydrated titanium dioxide is: (1) Use high titanium slag as raw material, add sodium bicarbonate, heat to 1200-1250℃, calcine for 2h, cool naturally, crush and sieve; (2) Slowly add the treated high-titanium slag to 300 mL of 8-12 mol / L hydrochloric acid solution under stirring, react for 1-1.5 hours, let it stand overnight, and filter to obtain a titanium tetrachloride aqueous solution; (3) Heating: When the temperature reaches 80°C, add rutile nanocrystal seeds to the titanium tetrachloride aqueous solution, then continue to heat the solution to 106°C, rinse with 6.0 mol / L hydrochloric acid at 80°C for 2 hours, then vacuum filter, wash until neutral, and dry at 110°C for 4 hours to obtain nano-hydrated titanium dioxide.

5. The method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials according to claim 4, characterized in that: In (1), the mass of sodium bicarbonate is 10%-15% of the mass of the high titanium slag; In the above (3), the mass of the rutile nanocrystalline seeds is 0.5%-2% of the mass of the titanium tetrachloride aqueous solution.

6. The method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials according to claim 1, characterized in that: The preparation method of the modified tourmaline powder comprises the following steps: mixing the tourmaline powder with distilled water, treating the mixture with an ultrasonic cleaning machine for 20-30 minutes, adding a sodium hydroxide solution dropwise to adjust the pH value of the solution system to 11, then sequentially adding a modifier and a modification auxiliary agent, heating the mixture in a water bath to 83-84° C., and stirring the mixture for 15-20 minutes to obtain the modified tourmaline powder.

7. The method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials according to claim 6, characterized in that: in, The mass ratio of tourmaline powder to distilled water is 1:10, and the masses of the modifier and the modification auxiliary are 1.8%-2.1% and 4%-4.2% of the mass of the tourmaline powder, respectively.

8. The method for preparing a microparticle-sized negative oxygen ion purifier from nanomaterials according to claim 6, characterized in that: The modifier is a mixture of sodium polyacrylate and sodium polyphosphate, and the mass ratio thereof is 2:1; the modification auxiliary agent is white carbon black.

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