Slow-release type water body microorganism control material based on microsphere encapsulation technology and preparation method of slow-release type water body microorganism control material

Abstract

The invention provides a slow-release type water body microorganism control material based on a microsphere encapsulation technology and a preparation method of the slow-release type water body microorganism control material. The preparation raw materials comprise a disinfection mixture, a wax substance and vaseline, the disinfection mixture comprises sodium chlorite gel microspheres, an acid agent, sodium bicarbonate, sodium dichloroisocyanurate and sodium chloride, and the content of vaseline in the surface area of the disinfectant is smaller than the content of vaseline in the internal area of the disinfectant. The slow-release water microorganism control material based on the microsphere encapsulation technology is convenient to use and easy to carry, can continuously release chlorine dioxide within ten days for disinfection in water, has a good sterilization effect, and is suitable for being used in water pools, fish tanks, ponds and other water bodies needing slow-release disinfection.

Description

Technical Field

[0001] This invention belongs to the field of water disinfection technology, and particularly relates to a slow-release water microbial control material based on microsphere encapsulation technology and its preparation method. Background Technology

[0002] Chlorine dioxide is a yellowish-green gas commonly used as a water disinfectant. It boasts highly efficient and powerful disinfection effects, its strong oxidizing properties enabling it to quickly and effectively kill almost all microorganisms, including spores. Chlorine dioxide does not produce any teratogenic, carcinogenic, or other harmful substances during its action, making it an internationally recognized green disinfectant. The disinfection mechanism of chlorine dioxide primarily involves adsorption and osmosis, allowing it to enter cells and oxidize intracellular enzyme systems and biomolecules. It effectively kills bacteria and viruses without harming animals or plants, has a long-lasting bactericidal effect, and is not sensitive to pH changes. Furthermore, chlorine dioxide's superior performance in water treatment is also evident in its algae control. It has a certain binding capacity for benzene rings, altering them without producing an odor. The pyrrole rings in chlorophyll within algal cells are highly similar to benzene rings; chlorine dioxide can bind to these pyrrole rings, oxidizing chlorophyll and thus halting algal metabolism.

[0003] Water disinfection methods include chemical and physical methods, with chemical methods being the most common. These methods include adding heavy metal ions (such as silver and copper), adding alkalis or acids, adding surfactants, and adding oxidants (chlorine and its compounds, bromine, iodine, ozone), among which chlorine and its compounds are particularly widely used. However, regardless of whether chlorine or chlorine dioxide is added, existing methods can only disinfect water for a short time (generally within 30 minutes) and cannot maintain disinfection for a long period, resulting in a recurrence of excessive levels of bacteria, viruses, and other microorganisms in the water after a period of time.

[0004] Therefore, the preparation of disinfectants that can kill bacteria for a long time is of great significance to ensure the long-term cleanliness of water bodies. Summary of the Invention

[0005] This invention aims to at least partially address one of the technical problems in the prior art. Therefore, one objective of this invention is to provide a slow-release aquatic microbial control material based on microsphere encapsulation technology and its preparation method.

[0006] In a first aspect, the present invention proposes a slow-release aquatic microbial control material based on microsphere encapsulation technology, the raw materials for which include: a disinfectant mixture, waxy substances and petrolatum, wherein the disinfectant mixture includes sodium chlorite gel microspheres, an acid, sodium bicarbonate, sodium dichloroisocyanurate and sodium chloride, and the content of petrolatum on the surface of the disinfectant is less than the content of petrolatum in the internal region of the disinfectant.

[0007] The slow-release aquatic microbial control material based on microsphere encapsulation technology provided by the present invention is prepared from raw materials including a disinfectant mixture, waxy substances, and petrolatum. When the disinfectant is added to water, the sodium chlorite gel microspheres and citric acid on the surface of the disinfectant react immediately in the aquatic environment to generate chlorine dioxide. Simultaneously, the sodium bicarbonate on the surface of the disinfectant decomposes and releases chlorine dioxide in the acidic microenvironment created by the acidifier. This opens channels to the internal waxy substances, allowing water to enter and react with the internal sodium chlorite gel microspheres and citric acid to continue forming chlorine dioxide. Due to the effect of the waxy substances and a small amount of petrolatum on the surface of the disinfectant, the disinfectant can maintain an appropriate chlorine dioxide release level during the initial release process, achieving short-term effective killing of aquatic microorganisms. Compared to the traditional one-time release of chlorine dioxide, this avoids the strong irritation caused by the initial high concentration of chlorine dioxide release. In addition, the amount of petroleum jelly on the surface of the disinfectant provided by this invention is less than that in the internal area of ​​the disinfectant, meaning that the disinfectant contains more petroleum jelly inside. Since petroleum jelly is denser than waxes at room temperature, it can slow down water penetration. Therefore, the penetration rate of water into the disinfectant is slowed down, which slows down the release rate of chlorine dioxide. This allows the disinfectant to slowly release chlorine dioxide, maintaining a low concentration of chlorine dioxide in the water and ensuring the long-term sterility of the water.

[0008] Compared to directly using sodium chlorite, this invention utilizes sodium chlorite gel microspheres, which offer the following advantages: It reduces the initial chlorine dioxide release rate, resulting in a more stable release curve; it also improves component stability and shelf life. The sodium chlorite inside the microspheres forms "point-to-point" reaction sites with the external acidifier (such as citric acid), preventing excessively high local concentrations during powder mixing. Precise controlled release: Through physical barriers and chemical isolation, chlorine dioxide is released "on demand." Long-lasting safety: It inhibits burst releases and byproducts, ensuring the biological safety of aquatic bodies. Process compatibility: It is compatible with advanced formulation designs such as gradient encapsulation and temperature / humidity response. Specifically, tests show that the disinfectant of this invention can continuously release chlorine dioxide for more than 20 days, continuously inhibiting the growth of microorganisms and algae during the chlorine dioxide release period.

[0009] Electron microscopy images of the sodium chlorite gel microspheres used in this invention are shown below. Figure 1 As shown, the diameter of the sodium chlorite gel microspheres is approximately 38 μm. A physical image of the slow-release aquatic microbial control material based on microsphere encapsulation technology prepared in this invention is shown below. Figure 2 As shown, the diameter of the slow-release aquatic microbial control material based on microsphere encapsulation technology is about 5.3 cm.

[0010] In some embodiments of the present invention, the mass ratio of the disinfectant mixture to the petroleum jelly is 2:(1-2). Controlling the mass ratio of the disinfectant mixture to petroleum jelly within the above range can improve the slow release of the disinfectant and ensure a certain amount of chlorine dioxide is released, thus achieving both effective sterilization of the water and long-lasting disinfection.

[0011] In some embodiments of the present invention, the mass ratio of the total mass of the disinfectant mixture and the petroleum jelly to the mass of the waxy substance is (3-1):1. Controlling the mass ratio of the total mass of the disinfectant mixture and the petroleum jelly to the mass of the waxy substance within the above range can ensure that the chlorine dioxide of the disinfectant is released at a suitable rate to sterilize the water in the early stage, while ensuring a continuous and slow release of chlorine dioxide in the later stage, thereby increasing the release time of chlorine dioxide.

[0012] In some embodiments of the present invention, the sodium chlorite gel microspheres are formed by directly mixing sodium chlorite and sodium alginate and then crosslinking them in a crosslinking agent.

[0013] Preferably, the sodium chlorite gel microspheres have a particle size of 35-40 μm; Preferably, the crosslinking agent is selected from calcium chloride-span80; Preferably, the mass ratio of sodium chlorite to sodium alginate is 1:(1-5).

[0014] In some embodiments of the present invention, the mass ratio of the sodium chlorite gel microspheres, the acid agent, the sodium bicarbonate, the sodium dichloroisocyanurate, and the sodium chloride in the disinfectant mixture is (5-20):(10-20):(5-10):(1-3);(40-60). By controlling the components in the disinfectant mixture within the above range, stable chlorine dioxide release, good structural stability, and optimized slow-release performance can be achieved, thereby meeting the slow-release disinfection requirements of water bodies such as pools, fish tanks, and ponds.

[0015] In some embodiments of the present invention, the waxy substance is selected from one or more of paraffin wax, beeswax, palm wax, plant wax, glyceryl stearate, polyethylene wax, and polypropylene wax.

[0016] In some embodiments of the present invention, the acid is selected from at least one of citric acid, malic acid, tartaric acid, L-lactic acid, fumaric acid, formic acid, acetic acid, propionic acid, butyric acid, sorbic acid, and benzoic acid, with citric acid being preferred.

[0017] In some embodiments of the present invention, the slow-release aquatic microbial control material based on microsphere encapsulation technology is granular, and the particle size of the slow-release aquatic microbial control material based on microsphere encapsulation technology is 1cm-10cm, preferably 3cm-7cm. Controlling the particle size of the slow-release aquatic microbial control material based on microsphere encapsulation technology within the above range ensures that the disinfectant releases chlorine dioxide at a certain rate, ensuring a sufficient concentration of chlorine dioxide in the water, achieving effective sterilization of the water, and simultaneously enabling the disinfectant to release chlorine dioxide slowly and for a long period.

[0018] Those skilled in the art will understand that, for regularly shaped particles (such as spherical particles), the particle size of the slow-release aquatic microbial control material based on microsphere encapsulation technology refers to the diameter of the particle. For irregularly shaped particles (such as rectangular, elliptical, etc.), the particle size is described by the equivalent diameter, that is, the diameter assuming the particle is spherical. Furthermore, the disinfectant of the present invention is in granular form, and the granular form includes, but is not limited to, circular, rectangular, elliptical, cylindrical, etc.

[0019] In a second aspect, the present invention provides a method for preparing the above-mentioned slow-release aquatic microbial control material based on microsphere encapsulation technology, the method comprising: (1) Sodium chlorite gel microspheres, acid, sodium bicarbonate, sodium dichloroisocyanurate and sodium chloride are crushed and sieved separately and then mixed evenly to obtain disinfection mixture; (2) Mix the disinfectant mixture and petroleum jelly evenly at room temperature to obtain the first mixture; (3) The first mixture and the heated and melted waxy substance are mixed evenly and then prepared in a low temperature environment to obtain a slow-release water microbial control material based on microsphere encapsulation technology.

[0020] According to the method for preparing a slow-release aquatic microbial control material based on microsphere encapsulation technology provided by the present invention, by first mixing a disinfectant mixture and petroleum jelly, and then uniformly mixing the resulting first mixture with melted wax, and then preparing it at a low temperature, the method ensures that the petroleum jelly content inside the disinfectant is greater than the petroleum jelly content on the surface of the disinfectant, and that the wax content on the surface of the disinfectant is greater than the wax content in the interior of the disinfectant. Specifically, firstly, the disinfectant mixture is mixed with petroleum jelly. The semi-solid nature of petroleum jelly allows it to be uniformly dispersed in the disinfectant mixture. Next, melted wax is uniformly mixed with the first mixture (disinfectant mixture + petroleum jelly). Since the wax is liquid after heating, it can be fully mixed with petroleum jelly and the disinfectant mixture. At a low temperature, the mixture begins to cool and gradually solidify. The wax crystallizes first during the cooling process, forming a solid structure. Because the wax crystallizes relatively quickly, it is easier for it to accumulate on the surface, forming a thicker wax layer. Vaseline remains relatively soft at lower temperatures and does not crystallize rapidly. Therefore, it is more concentrated in the interior of the mixture. Consequently, the surface area has a higher wax content and lower Vaseline content due to the rapid crystallization of waxes, while the interior area has a higher Vaseline content and lower wax content due to its slower crystallization and higher compatibility. The higher wax content in the surface area results in a slower drug release rate, prolonging the release time. The high Vaseline content in the interior area provides a good drug carrier, ensuring continuous drug release within the required area. Therefore, this not only achieves an appropriate chlorine dioxide release during the initial release of the disinfectant, enabling short-term effective killing of aquatic microorganisms, but also slows down the penetration rate of water into the disinfectant, further reducing the chlorine dioxide release rate. This allows the disinfectant to slowly release chlorine dioxide, maintaining a low concentration in the water and ensuring long-term sterility.

[0021] In some embodiments of the present invention, in step (1), the mesh size of the sieve is 60-100 mesh. Controlling the mesh size of the sieve within the above range can ensure that the raw material particles are of appropriate size and mixed evenly. The prepared slow-release aquatic microbial control material based on microsphere encapsulation technology has good slow-release performance and structural stability, meeting the slow-release disinfection needs of water bodies such as pools, fish tanks, and ponds.

[0022] In some embodiments of the present invention, the temperature of the heated and melted paraffin is 55-70°C.

[0023] In some embodiments of the present invention, in step (3), the temperature of the low-temperature environment is 2-6°C.

[0024] In some embodiments of the present invention, the preparation process of the sodium chlorite gel microspheres includes: dispersing sodium chlorite in deionized water to obtain a mixed solution; adding the mixed solution to a sodium alginate solution and stirring until homogeneous to obtain a sodium alginate gel solution; and adding the sodium alginate gel solution dropwise into a calcium chloride solution. Specifically, the sodium alginate gel solution formed by uniformly mixing sodium chlorite and sodium alginate solutions is dropwise into a calcium chloride solution. The sodium alginate undergoes cross-linking under the action of calcium chloride, thereby dispersing sodium chlorite in the cross-linked network. By adding the sodium alginate to the calcium chloride solution dropwise, microspheres of a certain volume can be formed.

[0025] It should be noted that the sodium chlorite gel microspheres can be prepared using existing conventional methods. Those skilled in the art can select specific preparation process parameters according to actual conditions, as long as the sodium chlorite gel microspheres of the present invention are ultimately obtained.

[0026] For example, sodium chlorite gel microspheres can be prepared by adding sodium alginate gel solution dropwise into calcium chloride solution using a syringe.

[0027] For example, microspheres can be prepared using a dedicated microsphere preparation device. A dispersed phase (sodium alginate gel solution) is injected into the outer channel, and a continuous phase (calcium chloride-Span 80) is injected into the inner channel. A protective gas is introduced into the outer channel to push the dispersed phase through the microporous filter membrane, forming droplets in the inner channel, which then mix with the continuous phase to form an emulsion. After emulsification, the emulsion in the inner channel is discharged into an emulsion storage device for storage. The emulsion is then stirred, the solvent evaporated, and freeze-dried to obtain microspheres.

[0028] The present invention has at least the following technical effects: (1) The present invention uses petrolatum and waxy substances to encapsulate sodium chlorite gel microspheres, acid, sodium bicarbonate and other substances to prepare granular disinfectant. Sodium chlorite gel microspheres, acid, sodium bicarbonate and other substances are uniformly dispersed on the surface and inside of the granular disinfectant, while waxy substances are more abundant on the surface of the pellets and petrolatum is more abundant inside the pellets. Through the difference in the internal and external components of the disinfectant, different water permeability is formed inside and outside, so that chlorine dioxide can be slowly released and sterilized for a long time.

[0029] (2) After sodium bicarbonate volatilizes, it forms a hollow channel in the disinfectant, which introduces water into the disinfectant. Inside the disinfectant, due to the large amount of petroleum jelly, the water penetration and contact with the sodium chlorite gel microspheres and acid are slowed down, thus achieving the effect of slow release of chlorine dioxide. The disinfectant can continuously release chlorine dioxide for more than 20 days.

[0030] (3) The slow-release water microbial control material based on microsphere encapsulation technology provided by the present invention is easy to use and carry. It can continuously release chlorine dioxide in water for disinfection within ten days and has a good bactericidal effect. It is suitable for use in water bodies such as pools, fish tanks, and ponds that require slow-release disinfection.

[0031] (4) The method for preparing slow-release water microbial control materials based on microsphere encapsulation technology provided by the present invention is simple to operate, has low equipment cost, has significant practicality, and is suitable for large-scale promotion. Attached Figure Description

[0032] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0033] Figure 1 These are electron microscope images of sodium chlorite gel microspheres according to an embodiment of the present invention; Figure 2 This is a physical image of the slow-release aquatic microbial control material based on microsphere encapsulation technology provided by the present invention; Figure 3 This is a graph showing the disinfection effect of the disinfectant pills prepared in Example 1 of this invention on Staphylococcus aureus; Figure 4 This is a graph showing the disinfection effect of the disinfectant pills prepared in Example 1 of the present invention on Escherichia coli; Figure 5 This is a graph showing the disinfection effect of the disinfectant pills prepared in Comparative Example 1 of this invention on Staphylococcus aureus; Figure 6 This is a graph showing the disinfection effect of the disinfectant pills prepared in Comparative Example 1 of this invention on Escherichia coli. Figure 7 This is a graph showing the disinfection effect of the disinfectant pills prepared in Comparative Example 2 of this invention on Staphylococcus aureus; Figure 8 This is a graph showing the disinfection effect of the disinfectant pills prepared in Comparative Example 2 of this invention on Escherichia coli. Detailed Implementation

[0034] Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention. The invention will now be described with reference to specific embodiments. It should be noted that these embodiments are merely descriptive and do not limit the invention in any way.

[0035] Example 1 This embodiment provides a slow-release aquatic microbial control material based on microsphere encapsulation technology, the raw materials for which are prepared: 2g of disinfectant mixture, including 12wt% sodium chlorite gel microspheres, 20wt% citric acid, 6wt% sodium bicarbonate, 2wt% sodium dichloroisocyanurate, and 60wt% sodium chloride. 1g of Vaseline; 1g of paraffin.

[0036] The preparation process of the slow-release aquatic microbial control material based on microsphere encapsulation technology in this embodiment is as follows: (1) The above sodium chlorite gel microspheres (microsphere diameter is 38±1.4μm), citric acid, sodium bicarbonate, sodium dichloroisocyanurate and sodium chloride are crushed in a pulverizer, passed through a 60-mesh sieve and mixed evenly to obtain disinfection mixture; The preparation process of sodium chlorite gel microspheres is as follows: 1g of sodium chlorite is dispersed in 50mL of deionized water and stirred to obtain a mixed solution; the mixed solution is added to 100mL of 4wt% sodium alginate solution and stirred until homogeneous to obtain a sodium alginate gel solution; the sodium alginate gel solution is used as the dispersed phase (outer channel) and 5% w / v calcium chloride-span-80 solution is used as the continuous phase (inner channel). A protective gas is introduced into the outer channel to push the dispersed phase through the microporous filter membrane, forming droplets in the inner channel, which are then mixed with the continuous phase to form an emulsion. The emulsion is stirred, the solvent is evaporated, and the emulsion is freeze-dried to obtain microspheres.

[0037] (2) Mix the disinfectant mixture with petroleum jelly at room temperature to obtain mixture A; (3) Add mixture A to paraffin at 60°C (at which point the paraffin is in a liquid state), and quickly stir mixture A and paraffin at 200 rpm / min for 2 min to mix evenly. Then immediately place it in an environment at 4°C and roll it into pellets to obtain the final slow-release water disinfection pellets. The particle size of the disinfection pellets is 5.34 ± 0.21 cm.

[0038] The performance of the slow-release aquatic microbial control material based on microsphere encapsulation technology in Example 1 was measured, as follows: (a) Disinfectant tablets were placed in a 250ml beaker containing 200ml of water. The beaker was left open and allowed to stand under normal ventilation conditions. The concentration of chlorine dioxide in the water was measured and recorded every 48 hours. The specific results are shown in Table 1.

[0039] Table 1 Days 2 4 6 8 10 12 14 16 18 20 22 Concentration in water (ppm) 13.27 15.43 19.48 23.74 22.41 18.52 15.65 13.41 9.4 4.32 1.41 (b) Verify the disinfection effect of the disinfectant pills prepared in Example 1 on Staphylococcus aureus.

[0040] (1) Staphylococcus aureus positive control group: The Staphylococcus aureus bacterial suspension was centrifuged at 6000 rpm for 5 min and diluted to 10. 6 CFU was taken, 100 μL of LB culture medium was resuspended, spread on LB solid medium and cultured overnight, and then photographed and counted for analysis.

[0041] Staphylococcus aureus sterilization sample group Sample group 1: Centrifuge a suspension of Staphylococcus aureus at 6000 rpm for 5 min, then dilute to 10⁻⁶. 6 CFU was used to treat Staphylococcus aureus bacterial dilution with one disinfectant tablet for 30 minutes. Then, 100 μL of LB culture medium was taken, the mixture was resuspended, spread on LB solid medium, and cultured overnight. The samples were photographed and counted for analysis. Sample group 2: Centrifuge the Staphylococcus aureus bacterial suspension at 6000 rpm for 5 min, and dilute to 10⁻⁶. 6 CFU was used to mix 200 ml of Staphylococcus aureus bacterial dilution with a sterile pellet (which had been placed in water for 7 / 14 / 21 days and then placed in the above Staphylococcus aureus bacterial dilution) for 30 min. Then, 100 μl of LB culture medium was taken to resuspend the pellet and spread it on LB solid medium for overnight culture. The pellet was photographed and counted for analysis.

[0042] For details, please see [link / details]. Figure 3 The culture medium of the control group was covered with Staphylococcus aureus, while no Staphylococcus aureus grew on the culture dishes of sample group 1 and sample group 2. This indicates that the disinfectant pills of the present invention can be continuously released in water for more than 21 days, achieving a long-lasting bactericidal effect.

[0043] (c) Verify the disinfection effect of the disinfectant pills prepared in Example 1 on Escherichia coli.

[0044] E. coli positive control group: The E. coli bacterial suspension was centrifuged at 6000 rpm for 5 min and diluted to 10. 6 CFU was taken, 100 μL of LB culture medium was resuspended, spread on LB solid medium and cultured overnight, and then photographed and counted for analysis.

[0045] E. coli sterilization sample group Sample group 3: Centrifuge the E. coli bacterial suspension at 6000 rpm for 5 min, and dilute to 10⁻⁶. 6 CFU was used to treat 200 ml of Escherichia coli bacterial dilution with one disinfectant tablet from Example 1 for 30 min. Then, 100 μl of LB culture medium was taken to resuspend the bacteria and spread on LB solid medium for overnight culture. The bacteria were photographed and counted for analysis. Sample group 4: Centrifuge the E. coli bacterial suspension at 6000 rpm for 5 min, and dilute to 10⁻⁶. 6CFU was used to mix 200 ml of Escherichia coli bacterial dilution with one disinfectant tablet (which had been placed in water for 7 / 14 / 21 days and then placed in the above Staphylococcus aureus bacterial dilution) for 30 min. Then, 100 μl of LB culture medium was taken to resuspend the mixture and spread it on LB solid medium for overnight culture. The mixture was then photographed and counted for analysis.

[0046] For details, please see [link / details]. Figure 4 The culture medium of the control group was covered with Escherichia coli, while no Escherichia coli grew on the culture dishes of sample group 3 and sample group 4. This indicates that the disinfectant pills of the present invention can be continuously released in water for more than 21 days, achieving a long-lasting bactericidal effect.

[0047] Comparative Example 1 This comparative example provides a slow-release aquatic microbial control material based on microsphere encapsulation technology. The difference between the raw materials used in this material and those used in Example 1 is that sodium chlorite is used instead of sodium chlorite gel microspheres in Example 1 in Comparative Example 1.

[0048] The preparation process of the slow-release aquatic microbial control material based on microsphere encapsulation technology in this comparative example is the same as that in Example 1.

[0049] The performance of the slow-release aquatic microbial control material based on microsphere encapsulation technology in Comparative Example 1 was determined as follows: (a) Disinfectant tablets were placed in a 250ml beaker containing 200ml of water. The beaker was left open and allowed to stand under normal ventilation conditions. The concentration of chlorine dioxide in the water was measured and recorded every 48 hours. The specific results are shown in Table 2.

[0050] Table 2 Days 2 4 6 8 10 12 14 16 18 Concentration in water (ppm) 15.85 16.35 21.6 13.32 6.86 5.83 0.73 0 0 (b) Verify the disinfection effect of the disinfectant pills prepared in Comparative Example 1 on Staphylococcus aureus. The specific process is the same as in Example 1.

[0051] For details, please see [link / details]. Figure 5 ,from Figure 5 It is known that the release cycle of the disinfectant pill is within 14 days, and it has a good bactericidal effect on Staphylococcus aureus. However, by day 21, because there is no release of chlorine dioxide, the culture dish is full of Staphylococcus aureus.

[0052] (c) Verify the disinfection effect of the disinfectant pills prepared in Comparative Example 1 on Escherichia coli. The specific process is the same as in Example 1.

[0053] For details, please see [link / details]. Figure 6 ,from Figure 6 It is known that the release cycle of the disinfectant pill is within 14 days, and it has a good bactericidal effect on E. coli. However, by day 21, because there is no release of chlorine dioxide, the culture dish is full of E. coli.

[0054] Comparative Example 2 This comparative example provides a slow-release aquatic microbial control material based on microsphere encapsulation technology. The difference between the raw materials used in its preparation and those in Comparative Example 1 is that Comparative Example 2 does not contain petrolatum.

[0055] The preparation process of the slow-release aquatic microbial control material based on microsphere encapsulation technology in this comparative example is as follows: (1) Sodium chlorite, citric acid, sodium bicarbonate, sodium dichloroisocyanurate and sodium chloride are pulverized in a pulverizer, passed through a 60-mesh sieve and mixed evenly to obtain a disinfection mixture; (2) Put the disinfectant mixture into the paraffin at 60°C (at which time the paraffin is in a liquid state), quickly mix the disinfectant mixture and paraffin evenly, and roll it into pellets. Then immediately place it in an environment at 4°C and roll it into pellets to obtain the final slow-release water disinfectant pellets. The particle size of the disinfectant pellets is about 5.3 cm.

[0056] The performance of the slow-release aquatic microbial control material based on microsphere encapsulation technology in Comparative Example 2 was determined as follows: (a) Disinfectant tablets were placed in a 250ml beaker containing 200ml of water. The beaker was left open and allowed to stand under normal ventilation conditions. The concentration of chlorine dioxide in the water was measured and recorded every 48 hours. The specific results are shown in Table 3.

[0057] Table 3 Days 2 4 6 8 10 Concentration in water (ppm) 10.53 7.72 0.58 0 0 (b) Verify the disinfection effect of the disinfectant pills prepared in Comparative Example 2 on Staphylococcus aureus. The specific process is the same as in Example 1.

[0058] For details, please see [link / details]. Figure 7 ,from Figure 7 It can be seen that after the disinfectant tablets were placed in water for 7 days, they no longer had a bactericidal effect on Staphylococcus aureus, indicating that the release period of the disinfectant tablets in Comparative Example 2 was particularly short.

[0059] (c) Verify the disinfection effect of the disinfectant pills prepared in Comparative Example 2 on Escherichia coli. The specific process is the same as in Example 1.

[0060] For details, please see [link / details]. Figure 8 ,from Figure 8 It can be seen that after the disinfectant tablets were placed in water for 7 days, they no longer had a bactericidal effect on E. coli, indicating that the release period of the disinfectant tablets in Comparative Example 2 was particularly short.

[0061] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A slow-release aquatic microbial control material based on microsphere encapsulation technology, characterized in that, The raw materials for preparation include: disinfectant mixture, waxy substances and petrolatum. The disinfectant mixture includes sodium chlorite gel microspheres, acid, sodium bicarbonate, sodium dichloroisocyanurate and sodium chloride. The petrolatum content on the surface of the disinfectant is less than the petrolatum content in the interior of the disinfectant.

2. The slow-release aquatic microbial control material based on microsphere encapsulation technology according to claim 1, characterized in that, The mass ratio of the disinfectant mixture to the petroleum jelly is 2:(1-2). And / or, the total mass ratio of the disinfectant mixture and the petroleum jelly to the mass ratio of the waxy substance is (3-1):

1.

3. The slow-release aquatic microbial control material based on microsphere encapsulation technology according to claim 1, characterized in that, The sodium chlorite gel microspheres are formed by directly mixing sodium chlorite and sodium alginate and then crosslinking them in a crosslinking agent. Preferably, the sodium chlorite gel microspheres have a particle size of 35-40 μm; Preferably, the crosslinking agent is selected from calcium chloride-span80; Preferably, the mass ratio of sodium chlorite to sodium alginate is 1:(1-5).

4. The slow-release aquatic microbial control material based on microsphere encapsulation technology according to any one of claims 1-3, characterized in that, In the disinfection mixture, the mass ratio of the sodium chlorite gel microspheres, the acid agent, the sodium bicarbonate, the sodium dichloroisocyanurate and the sodium chloride is (5-20):(10-20):(5-10):(1-3);(40-60).

5. The slow-release aquatic microbial control material based on microsphere encapsulation technology according to any one of claims 1-3, characterized in that, The waxy substance is selected from one or more of paraffin wax, beeswax, palm wax, plant wax, glyceryl stearate, polyethylene wax, and polypropylene wax; And / or, the acid is selected from at least one of citric acid, malic acid, tartaric acid, L-lactic acid, fumaric acid, formic acid, acetic acid, propionic acid, butyric acid, sorbic acid, and benzoic acid, preferably citric acid.

6. The slow-release aquatic microbial control material based on microsphere encapsulation technology according to any one of claims 1-3, characterized in that, The slow-release aquatic microbial control material based on microsphere encapsulation technology is granular, and the particle size of the slow-release aquatic microbial control material based on microsphere encapsulation technology is 1cm-10cm, preferably 3cm-7cm.

7. The slow-release aquatic microbial control material based on microsphere encapsulation technology according to any one of claims 1-3, characterized in that, The slow-release aquatic microbial control material based on microsphere encapsulation technology can continuously release chlorine dioxide in water for more than 20 days.

8. A method for preparing a slow-release aquatic microbial control material based on microsphere encapsulation technology as described in any one of claims 1-7, characterized in that, include: (1) Sodium chlorite gel microspheres, acid, sodium bicarbonate, sodium dichloroisocyanurate and sodium chloride are crushed and sieved separately and then mixed evenly to obtain disinfection mixture; (2) Mix the disinfectant mixture and petroleum jelly evenly at room temperature to obtain the first mixture; (3) The first mixture and the heated and melted waxy substance are mixed evenly and then prepared in a low temperature environment to obtain a slow-release water microbial control material based on microsphere encapsulation technology.

9. The method according to claim 8, characterized in that, In step (1), the mesh size of the sieve is 60-100 mesh; And / or, the temperature of the low-temperature environment is 2-6°C.

10. The method according to claim 8 or 9, characterized in that, The preparation process of the sodium chlorite gel microspheres includes: dispersing sodium chlorite in deionized water to obtain a mixed solution; adding the mixed solution to a sodium alginate solution and stirring evenly to obtain a sodium alginate gel solution; and adding the sodium alginate gel solution dropwise into a calcium chloride solution.

Images