A water-improving povidone iodine disinfectant and a preparation method thereof

Abstract

The present application relates to iodine disinfectant technical field, disclose a kind of water body improved povidone-iodine disinfectant and its preparation method, raw material each component is by weight fraction, including porous activated carbon@TiO 2 20~80 parts, povidone-iodine 5~10 parts, surfactant 0.1~2 parts, ferrous activated persulfate 0.1~5 parts, 2-phosphonic acid butane-1,2,4-tricarboxylic acid 0.1-5 parts, stabilizer 0.1~2 parts, adjuvant 0.01~100 parts, water 0~500 parts.The water body improved povidone-iodine disinfectant provided by the present application can increase the solubility of povidone-iodine, improve the bactericidal performance of povidone-iodine, and achieve the purpose of purifying water quality.

Description

Technical Field

[0001] This invention relates to the field of iodine disinfectant technology, and more specifically, to a water-modified povidone-iodine disinfectant and its preparation method. Background Technology

[0002] Because aquaculture water contains a large amount of organic matter, some of the dissolved organic matter dissolves in the water, causing changes in the pH of the water, which in turn affects the solubility and bactericidal properties of povidone-iodine.

[0003] Povidone-iodine has good bactericidal properties and low environmental pollution, making it suitable for water disinfection. However, the presence of a large amount of soluble organic matter in water affects the solubility of povidone-iodine, thus reducing its disinfection and bactericidal performance. Existing technologies use conventional anionic and nonionic surfactants to improve solubility and emulsification, increasing the solubility of povidone-iodine in water, but the bactericidal effect is still somewhat reduced. Furthermore, a large amount of surfactant in water can easily decompose into soluble organic acids, further polluting the water. Summary of the Invention

[0004] The technical problem solved by this invention:

[0005] This is intended to address the problem of poor sterilization performance in existing products.

[0006] The technical solution adopted in this invention is as follows:

[0007] To address the aforementioned technical problems, the present invention aims to provide a water-modified povidone-iodine disinfectant and its preparation method, which can increase the solubility of povidone-iodine, improve its bactericidal performance, and simultaneously achieve the purpose of purifying water quality. The specific details are as follows:

[0008] A water-modified povidone-iodine disinfectant comprises, by weight, 20-80 parts porous activated carbon@TiO2, 5-10 parts povidone-iodine, 0.1-2 parts surfactant, 0.1-5 parts ferrous activated persulfate, 0.1-5 parts 2-phosphonobutane-1,2,4-tricarboxylic acid, 0.1-2 parts stabilizer, 0.01-100 parts excipients, and 0-500 parts water.

[0009] According to some preferred embodiments, the raw materials, by weight, include porous activated carbon@TiO2, 5-10 parts of povidone-iodine, 0.5-2 parts of surfactant, 0.5-2 parts of ferrous activated persulfate, 0.1-5 parts of 2-phosphonobutane-1,2,4-tricarboxylic acid, 0.1-2 parts of stabilizer, 0.01-100 parts of excipients, and 0.1-50 parts of water.

[0010] According to some preferred embodiments, the formulation of the water-modified povidone-iodine disinfectant is selected from powder, paste, suspension, and solution. Different formulations are achieved by adding different amounts of water according to actual conditions.

[0011] According to some preferred embodiments, the surfactant contains at least a carboxylic acid group. Specifically, it may be at least one of sodium fatty alcohol polyoxyethylene ether carboxylate and long-chain alkyl carboxylate betaine. In the sodium fatty alcohol polyoxyethylene ether carboxylate, the fatty alcohol is a C8-C16 alkanol, and the EO number of the sodium fatty alcohol polyoxyethylene ether carboxylate is 5-30. More preferably, in the sodium fatty alcohol polyoxyethylene ether carboxylate, the fatty alcohol is a C8-C12 alkanol, and the EO number is 10-30. In the long-chain alkyl carboxylate betaine, the long-chain alkyl group is a C12-C22 alkyl group. More preferably, the long-chain alkyl carboxylate betaine is a C12-C16 alkyl carboxylate betaine.

[0012] According to some preferred embodiments, the stabilizer is a C10-C16 long alcohol. More preferably, it is a C10-C14 long alcohol, and most preferably, it is a C10 long alcohol.

[0013] According to some preferred embodiments, the excipients include at least one of pH adjusters, preservatives, nutrients, and water quality improvers. The pH adjuster is generally a commonly used pH adjuster such as hydrochloric acid, phosphoric acid, citric acid, sodium carbonate, or sodium bicarbonate, mainly used to adjust the pH value of the product, aiming to achieve a pH of 3-4 during formulation. The preservative is generally potassium sorbate. The nutrient is selected from trace elements and vitamins, primarily supplementing the water body with nutrients to promote better growth of farmed fish, shrimp, crabs, and other aquatic organisms. The water quality improver is mainly an adsorbent substance, such as vermiculite, bentonite, or silicates.

[0014] According to some preferred embodiments, the preparation method of porous activated carbon @TiO2 is as follows: Biomass raw materials (such as rice husks, straw, sugarcane bagasse, etc.) are pretreated and then placed together with a titanium precursor (tetrabutyl titanate), ethanol, and glacial acetic acid in a high-pressure reactor for hydrothermal reaction (180℃, 12h). The mixture is then washed alternately with deionized water and ethanol to obtain the treated material. The mass ratio of biomass, titanium precursor, ethanol, and glacial acetic acid is 10:2~5:15~25:15~25. The treated material is frozen at -25℃ for 30h, and then freeze-dried for 30h to obtain a frozen material. The frozen material is then heat-treated to obtain porous activated carbon @TiO2. The heat treatment is carried out at 800~1000℃ for 1~3h under a N2 atmosphere.

[0015] Second, the present invention provides a method for preparing the aforementioned water-modified povidone-iodine disinfectant, comprising the following steps:

[0016] S1 porous activated carbon@TiO2 was placed in a plasma reactor (power 800W, pressure 0.3MPa) and treated for 5-10 minutes to obtain modified porous activated carbon@TiO2.

[0017] S2 is prepared by uniformly mixing povidone-iodine, surfactant, 2-phosphonobutane-1,2,4-tricarboxylic acid, stabilizer, excipients and water to form a suspension. Modified porous activated carbon@TiO2 is then added for full adsorption, followed by the addition of ferrous activated persulfate for blending, thus obtaining povidone-iodine disinfectant.

[0018] The technical mechanism and beneficial effects of this invention are as follows:

[0019] (1) The activated carbon provided by the present invention has a porous structure, which can effectively maintain the stability of iodine after adsorbing povidone-iodine and surfactants.

[0020] (2) The porous activated carbon provided by the present invention is modified to obtain porous activated carbon@TiO2. The photothermal and photocatalytic effects brought by activated carbon and TiO2 are utilized to achieve a further purification effect. By loading TiO2 on activated carbon in situ, the problem of TiO2 agglomeration can be avoided.

[0021] (3) The modified activated carbon @TiO2 provided by the present invention is subjected to plasma treatment to introduce polar groups, which can not only improve the pore structure and active sites of porous carbon, but also enhance the adsorption effect of povidone-iodine.

[0022] (4) The stabilizer added in this invention is a long carbon alcohol. Hydrogen bonds can be formed between the hydroxyl group of the long carbon alcohol and the end group (hydrophilic group) of the surfactant, so that the long carbon alcohol is embedded between the surfactant molecules, making the hydrophobic chain more compact, reducing the surface tension of the solution, thereby improving the stability of povidone-iodine in water.

[0023] (5) The porous activated carbon, long carbon alcohol and povidone-iodine provided by the present invention are compounded to improve water quality. The improved water quality has a positive promoting effect on the disinfection of povidone-iodine.

[0024] (6) The ferrous activated persulfate provided by the present invention can promote the oxidation of iodide ions to active iodine, thereby enhancing the bactericidal effect of povidone-iodine and prolonging the bactericidal effect.

[0025] (7) The carboxylic acid group (2-phosphonobutane-1,2,4-tricarboxylic acid) provided by this invention introduces a large number of hydrogen ions, thereby inhibiting the hydrolysis of iodine and thus improving the stability of iodine. At the same time, it can also chelate metal ions (such as iron ions) in water. The iron ions react with the iodide ions, and the iodide ions are oxidized to elemental iodine, thereby improving the stability of iodine.

[0026] (8) By combining the surfactant and 2-phosphonobutane-1,2,4-tricarboxylic acid, the present invention can not only facilitate the formation of a complex of povidone-iodine, thereby further improving its stability and dispersibility, but also enable the surfactant to promote the penetration of povidone-iodine into the cell wall of microorganisms, thereby improving the bactericidal effect. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0028] Example 1

[0029] A water-modified povidone-iodine disinfectant comprises, by weight, 20 parts porous activated carbon@TiO2, 5 parts povidone-iodine, 0.1 parts ferrous activated persulfate, 4 parts 2-phosphonobutane-1,2,4-tricarboxylic acid, 0.1 parts surfactant lauryl polyoxyethylene ether-5-carboxylate sodium, 0.5 parts stabilizer decanol, 50 parts silicate, and 10 parts water.

[0030] A method for preparing a water-modified povidone-iodine disinfectant is as follows:

[0031] (1) The straw was crushed and washed for later use. Then, tetrabutyl titanate, ethanol, and glacial acetic acid were added and mixed. The mixture was then placed in a high-pressure reactor and treated at 180°C for 12 hours. After that, it was washed alternately with deionized water and ethanol to obtain the treated material. The mass ratio of biomass, tetrabutyl titanate, ethanol, and glacial acetic acid was 10:3:20:20. The freeze-dried material was then frozen at -25°C for 30 hours and then treated in a freeze dryer for 30 hours to obtain the frozen material. The frozen material was then heat-treated at 800°C for 2 hours under a N2 atmosphere to obtain porous activated carbon@TiO2.

[0032] (2) The porous activated carbon @TiO2 was placed in a plasma reactor (power 800W, pressure 0.3MPa) and treated for 8 minutes to obtain modified porous activated carbon @TiO2.

[0033] (3) After uniformly mixing povidone-iodine, surfactant, 2-phosphonobutane-1,2,4-tricarboxylic acid, stabilizer, excipients and water to form a suspension, the modified porous activated carbon@TiO2 is fully adsorbed, and then ferrous activated persulfate is added for blending to obtain povidone-iodine disinfectant.

[0034] Example 2

[0035] The difference between this embodiment and Embodiment 1 is that the components of the povidone-iodine disinfectant are different.

[0036] 30 parts porous activated carbon@TiO2, 5 parts povidone-iodine, 0.1 parts ferrous activated persulfate, 0.5 parts 2-phosphonobutane-1,2,4-tricarboxylic acid, 0.1 parts surfactant lauryl polyoxyethylene ether-25 carboxylate, 0.5 parts stabilizer decanol, 50 parts silicate, and 10 parts water.

[0037] Example 3

[0038] The difference between this embodiment and Embodiment 1 is that the components of the povidone-iodine disinfectant are different.

[0039] 50 parts of porous activated carbon@TiO2, 10 parts of povidone-iodine, 0.5 parts of ferrous activated persulfate, 3 parts of 2-phosphonobutane-1,2,4-tricarboxylic acid, 0.1 parts of surfactant lauryl polyoxyethylene ether-25 carboxylate, 1 part of stabilizer decanol, 50 parts of silicate, and 12 parts of water.

[0040] Example 4

[0041] The difference between this embodiment and Embodiment 1 is that the components of the povidone-iodine disinfectant are different.

[0042] 50 parts of porous activated carbon@TiO2, 10 parts of povidone-iodine, 0.5 parts of ferrous activated persulfate, 0.5 parts of 2-phosphonobutane-1,2,4-tricarboxylic acid, 0.1 parts of surfactant lauryl polyoxyethylene ether-25 carboxylate, 2 parts of stabilizer dodecanol, 100 parts of silicate, and 12 parts of water.

[0043] Example 5

[0044] The difference between this embodiment and Embodiment 1 is that the components of the povidone-iodine disinfectant are different.

[0045] 50 parts of porous activated carbon@TiO2, 10 parts of povidone-iodine, 0.5 parts of ferrous activated persulfate, 4.5 parts of 2-phosphonobutane-1,2,4-tricarboxylic acid, 0.1 parts of surfactant lauryl polyoxyethylene ether-5-carboxylate, 2 parts of stabilizer tetradecanol, 100 parts of bentonite, and 12 parts of water.

[0046] Example 6

[0047] The difference between this embodiment and Embodiment 1 is that the components of the povidone-iodine disinfectant are different.

[0048] 50 parts of porous activated carbon@TiO2, 10 parts of povidone-iodine, 0.5 parts of ferrous activated persulfate, 0.8 parts of 2-phosphonobutane-1,2,4-tricarboxylic acid, 0.1 parts of surfactant lauryl polyoxyethylene ether-9-carboxylate, 2 parts of stabilizer decanol, 50 parts of silicate, and 12 parts of water.

[0049] Example 7

[0050] The difference between this embodiment and Embodiment 1 is that the components of the povidone-iodine disinfectant are different.

[0051] Porous activated carbon@TiO2 80 parts, povidone-iodine 10 parts, ferrous activated persulfate 0.5 parts, 2-phosphonobutane-1,2,4-tricarboxylic acid 3 parts, surfactant lauryl polyoxyethylene ether-5-carboxylate sodium 0.1 parts, stabilizer decanol 0.5 parts, silicate 100 parts, water 20 parts.

[0052] Example 8

[0053] The difference between this embodiment and Embodiment 1 is that the components of the povidone-iodine disinfectant are different.

[0054] Porous activated carbon@TiO2 80 parts, povidone-iodine 10 parts, ferrous activated persulfate 0.5 parts, 2-phosphonobutane-1,2,4-tricarboxylic acid 4 parts, surfactant lauryl polyoxyethylene ether-5-carboxylic acid sodium salt 0.1 parts, stabilizer decanol 0.5 parts, silicate 100 parts, water 20 parts.

[0055] Example 9

[0056] The difference between this embodiment and Embodiment 1 is that the components of the povidone-iodine disinfectant are different.

[0057] Porous activated carbon@TiO2 80 parts, povidone-iodine 10 parts, ferrous activated persulfate 0.5 parts, 2-phosphonobutane-1,2,4-tricarboxylic acid 5 parts, surfactant dodecyl carboxylate betaine 0.5 parts, stabilizer decanol 0.5 parts, silicate 100 parts, water 20 parts.

[0058] Example 10

[0059] The difference between this embodiment and Embodiment 1 is that the components of the povidone-iodine disinfectant are different.

[0060] Porous activated carbon@TiO2 80 parts, povidone-iodine 10 parts, ferrous activated persulfate 0.5 parts, 2-phosphonobutane-1,2,4-tricarboxylic acid 4 parts, surfactant tetradecyl carboxylate betaine 0.5 parts, stabilizer decanol 0.5 parts, silicate 100 parts, water 20 parts.

[0061] Example 11

[0062] The difference between this embodiment and Embodiment 1 is that the components of the povidone-iodine disinfectant are different.

[0063] Porous activated carbon@TiO2 80 parts, povidone-iodine 10 parts, ferrous activated persulfate 0.2 parts, 2-phosphonobutane-1,2,4-tricarboxylic acid 2.5 parts, surfactant dodecyl carboxylate betaine 0.5 parts, tetradecyl carboxylate betaine 0.5 parts, stabilizer decanol 0.5 parts, silicate 100 parts, water 20 parts.

[0064] Example 12

[0065] The difference between this embodiment and Embodiment 1 is that the components of the povidone-iodine disinfectant are different.

[0066] Porous activated carbon@TiO2 80 parts, povidone-iodine 10 parts, ferrous activated persulfate 0.2 parts, 2-phosphonobutane-1,2,4-tricarboxylic acid 3 parts, surfactant dodecyl carboxylate betaine 0.3 parts, tetradecyl carboxylate betaine 0.2 parts, fatty alcohol polyoxyethylene ether-25 carboxylate sodium 0.5 parts, stabilizer decanol 0.5 parts, silicate 100 parts, water 20 parts.

[0067] Comparative Example 1

[0068] Activated carbon is selected.

[0069] Comparative Example 2

[0070] Silicate cement should be selected.

[0071] Comparative Example 3

[0072] Ferrous persulfate was activated.

[0073] Comparative Example 4

[0074] The difference between this comparative example and Example 1 is that porous activated carbon@TiO2 is replaced with porous activated carbon.

[0075] Comparative Example 5

[0076] The difference between this comparative example and Example 1 is that the porous activated carbon@TiO2 was not treated with plasma.

[0077] Comparative Example 6

[0078] The difference between this comparative example and Example 1 is that no stabilizer and surfactant were added.

[0079] Comparative Example 7

[0080] The difference between this comparative example and Example 1 is that 2-phosphonobutane-1,2,4-tricarboxylic acid was not added.

[0081] Experimental Example 1

[0082] Water quality improvement and sterilization performance testing.

[0083] Water samples were taken from a fish fry pond in Sichuan Province. The water samples were divided into multiple groups, each containing 500 mL. The original water quality and the presence of several bacteria in the pond were tested. Disinfectants (water conditioners) obtained in Examples 1-12 and Comparative Examples 1-7 were added, with the amount of disinfectant being 0.5% of the water sample volume. A blank control group 1 was also established.

[0084] The water quality was observed after 7 days of use, and the results are shown in Table 1.

[0085] The main primitive bacteria in the water and their content (0d) were detected and labeled as Vibrio alginolyticus, Vibrio harzianum, Vibrio parahaemolyticus, Streptococcus, and Aeromonas hydrophila; Comparative examples 8-9 were set up: Comparative example 8: 0.5% of the water sample volume of glutaraldehyde was used;

[0086] Comparative Example 9: 0.5% of the water sample volume of decanoic acid bromide;

[0087] At the same time, a blank group 2 was set up.

[0088] The bacterial colony count was tested again after 3 days of use, and the results are shown in Table 2.

[0089] Table 1. Water quality improvement effect of disinfectant

[0090]

[0091] The pH range of general aquaculture water is between 6.5 and 8.5. As shown in Table 1, the samples in Examples 1-12 had little impact on the pH of the aquaculture water, stabilizing within the normal range after use. Comparative Examples 1-3 showed small pH fluctuations, indicating that the water conditioner in these examples had a limited effect on water quality improvement. The blank group showed a pH increase exceeding the normal range, indicating water pollution. Comparative Examples 4-7 showed relatively small pH changes, suggesting that the water conditioner in these examples had some improvement effect, but this effect was less pronounced than that of the water conditioner in Example 1. The COD values ​​also show that the use of the povidone-iodine water conditioner in Examples 1-12 reduced COD and decreased pollution levels, while pollution worsened in the blank group. The water conditioner in Comparative Examples 1-3 was less effective than that in Examples 1-12, and the water conditioner in Comparative Examples 4-7 was less effective than that in Example 1.

[0092]

[0093]

[0094] As shown in Table 2, after using the modified disinfectant, the number of Vibrio, Aeromonas hydrophila, and Streptococcus in the water bodies of Examples 1-12 decreased by approximately 70%-80%, indicating a good bactericidal effect. However, the bactericidal effect was not obvious in Comparative Examples 8-9, and the number of bacterial colonies in the water body of the blank group 2 increased significantly.

[0095] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A water-modified povidone-iodine disinfectant, characterized in that, The raw materials, by weight, include 20-80 parts of modified porous activated carbon@TiO2, 5-10 parts of povidone-iodine, 0.1-2 parts of surfactant, 0.1-5 parts of ferrous activated persulfate, 0.1-5 parts of 2-phosphonobutane-1,2,4-tricarboxylic acid, 0.1-2 parts of stabilizer, 0.01-100 parts of excipients, and 0.1-50 parts of water; the modified porous activated carbon@TiO2 is obtained by plasma treatment of porous activated carbon@TiO2.

2. The water-modified povidone-iodine disinfectant according to claim 1, characterized in that, Surfactants include at least one of sodium fatty alcohol polyoxyethylene ether carboxylate and long-chain alkyl carboxylate betaine.

3. The water-modified povidone-iodine disinfectant according to claim 1, characterized in that, The stabilizer is a long carbon alcohol of C10-C16.

4. The water-modified povidone-iodine disinfectant according to claim 1, characterized in that, The auxiliary materials include at least one of pH adjuster, preservative, nutrient, and water quality improver.

5. The water-modified povidone-iodine disinfectant according to any one of claims 1 to 4, characterized in that, After pretreatment, the biomass raw material, along with titanium precursor, ethanol, and glacial acetic acid, is placed in a high-pressure reactor for hydrothermal reaction, followed by washing to obtain the treated material. The treated material is then frozen and freeze-dried to obtain the frozen material. Finally, the frozen material is heat-treated to obtain porous activated carbon@TiO2.

6. The water-modified povidone-iodine disinfectant according to claim 5, characterized in that, The mass ratio of biomass, titanium precursor, ethanol, and glacial acetic acid is 10:2~5:15~25:15~25; and / or, heat treatment: 800~1000℃ for 1~3h under N2 atmosphere.

7. A method for preparing a water-modified povidone-iodine disinfectant as described in any one of claims 1 to 6, characterized in that, Includes the following steps: S1 porous activated carbon@TiO2 was subjected to plasma treatment to obtain modified porous activated carbon@TiO2; S2 involves uniformly mixing povidone-iodine, surfactant, 2-phosphonobutane-1,2,4-tricarboxylic acid, stabilizer, excipients, and water to form a suspension. Modified porous activated carbon@TiO2 is then added for full adsorption, followed by the addition of ferrous activated persulfate for blending, thus obtaining povidone-iodine disinfectant.

8. The method for preparing the water-modified povidone-iodine disinfectant according to claim 7, characterized in that, Plasma treatment: power 800W, gas pressure 0.3MPa, treatment time 5~10min.

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