Water body improved povidone iodine disinfectant and preparation method thereof

Abstract

The present invention relates to the technical field of iodine disinfectants, and discloses a water body improved povidone iodine disinfectant and a preparation method thereof, the water body improved povidone iodine disinfectant comprises the following raw material components by weight: 20-80 parts of porous activated carbon coated TiO2, 5-10 parts of povidone iodine, 0.1-2 parts of a 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 a stabilizer, 0.01-100 parts of an auxiliary material, and 0-500 parts of water. According to the water body improved povidone iodine disinfectant provided by the invention, the solubility of povidone iodine can be increased, the sterilization performance of povidone iodine is improved, and meanwhile, the purpose of purifying water is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of iodine disinfectants, in particular to a water-modified povidone-iodine disinfectant and a preparation method thereof. Background Art

[0002] Since aquaculture water contains a large amount of organic matter, some soluble organic matter dissolves in the water, causing changes in the pH of the water, thereby affecting the solubility and bactericidal properties of povidone iodine.

[0003] Povidone iodine has good bactericidal properties and little environmental pollution, and is suitable for water sterilization. However, the presence of a large amount of soluble organic matter in water causes the solubility of povidone iodine in water to be affected, so the disinfection and sterilization performance of povidone iodine decreases. Conventional anionic surfactants, nonionic surfactants, etc. are added in the prior art to improve solubility and emulsification, increase the solubility of povidone iodine in water, but the bactericidal property of povidone iodine is still reduced. At the same time, due to a large amount of surfactants in water, it is also easy to decompose into soluble organic acids, thereby further polluting the water quality. Summary of the invention

[0004] Technical problems solved by the present invention:

[0005] It is used to solve the problem of poor existing bactericidal performance.

[0006] The technical solution adopted by the present invention is:

[0007] In view of the above technical problems, the purpose of the present invention is to provide a water-modified povidone-iodine disinfectant and a preparation method thereof, which can increase the solubility of povidone-iodine, improve the bactericidal performance of povidone-iodine, and achieve the purpose of purifying water quality. The specific contents are as follows:

[0008] A water-modified povidone-iodine disinfectant, wherein the raw material components are calculated by weight and include 20-80 parts of 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 auxiliary materials and 0-500 parts of water.

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

[0010] According to some preferred embodiments, the dosage form of the water-modified povidone-iodine disinfectant is selected from powder, paste, suspension and solution. Different dosage forms 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 can be at least one of sodium fatty alcohol polyoxyethylene ether carboxylate and long-chain alkyl carboxylate betaine. Among them, in sodium fatty alcohol polyoxyethylene ether carboxylate, the fatty alcohol is an alkanol of C8-C16, and the EO number of sodium fatty alcohol polyoxyethylene ether carboxylate is 5-30. As more preferred, in sodium fatty alcohol polyoxyethylene ether carboxylate, the fatty alcohol is an alkanol of C8-C12, and the EO number is 10-30. Among them, the long-chain alkyl in the long-chain alkyl carboxylate betaine is a C12-C22 alkyl. As more preferred, the long-chain alkyl in 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 carbon alcohol, more preferably a C10-C14 long carbon alcohol, and most preferably a C10 long carbon alcohol.

[0013] According to some preferred embodiments, the auxiliary materials include at least one of a pH regulator, a preservative, a nutrient, and a water quality improver. Among them, the pH regulator is generally a commonly used pH regulator such as hydrochloric acid, phosphoric acid, citric acid, sodium carbonate, sodium bicarbonate, etc., which is mainly used to adjust the pH value of the product. During the preparation process, the pH value of the product can be kept between 3 and 4. The preservative is generally potassium sorbate, and the nutrient is selected from trace elements and vitamins. The nutrient is mainly used to supplement the nutrients in the water body so that the farmed fish, shrimp, crabs and other artificially cultivated organisms in the water grow better. The water quality improver is mainly an adsorbent substance, such as vermiculite, bentonite, silicate, etc.

[0014] According to some preferred embodiments, the preparation method of porous activated carbon @TiO2 is to pre-treat the biomass raw materials (such as rice husks, straws, bagasse, etc.), place them together with titanium precursor (tetrabutyl titanate), ethanol, and glacial acetic acid in a high-pressure reactor for hydrothermal reaction (180°C, 12h), and then wash them alternately with deionized water and ethanol to obtain a treated product. The mass ratio of biomass, titanium precursor, ethanol, and glacial acetic acid is 10:2~5:15~25:15~25. After freezing the treated product at -25°C for 30h, it is treated in a freeze dryer for 30h to obtain a frozen product. The frozen product is then heat-treated to obtain porous activated carbon @TiO2, heat treatment: 800~1000°C, 1~3h under N2 atmosphere.

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

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

[0017] S2 uniformly mixes povidone iodine, surfactant, 2-phosphonobutane-1,2,4-tricarboxylic acid, stabilizer, auxiliary materials and water to form a suspension, then adds modified porous activated carbon @TiO2 for full adsorption, and then adds ferrous activated persulfate for blending to obtain povidone iodine disinfectant.

[0018] The technical mechanism and beneficial effects adopted by the present invention are as follows:

[0019] (1) The activated carbon provided by the present invention has a porous structure and can adsorb povidone iodine and surfactants, thereby effectively maintaining the stability of iodine.

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

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

[0022] (4) The stabilizer added in the present invention is a long carbon alcohol, and hydrogen bonds can be formed between the hydroxyl groups of the long carbon alcohol and the end groups (hydrophilic groups) of the surfactant, so that the long carbon alcohol is embedded between the surfactant molecules, so that the hydrophobic chains are arranged more closely, the surface tension of the solution is reduced, and the stability of povidone iodine in water is improved.

[0023] (5) The porous activated carbon, long carbon alcohol and povidone iodine provided by the present invention are compounded to improve water quality, and 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 into 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 the present invention introduces a large amount of hydrogen ions, thereby being able to inhibit the hydrolysis of iodine, thereby achieving the effect of improving the stability of iodine. At the same time, it can also chelate metal ions (such as iron ions) in the water body, and 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) The present invention combines a surfactant with 2-phosphonobutane-1,2,4-tricarboxylic acid, which not only facilitates the formation of a complex with povidone iodine, thereby further improving its stability and dispersibility, but the surfactant can also promote the penetration of povidone iodine into the cell wall of microorganisms, thereby improving the bactericidal effect. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0028] Example 1

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

[0030] A method for preparing a water-modified povidone-iodine disinfectant comprises:

[0031] (1) The straw was crushed and cleaned for use; then, tetrabutyl titanate, ethanol, and glacial acetic acid were added and mixed, and then placed in a high-pressure reactor for treatment at 180°C for 12 hours, and then washed alternately with deionized water and ethanol to obtain a treated product. The mass ratio of biomass, tetrabutyl titanate, ethanol, and glacial acetic acid was 10:3:20:20. The freeze-dried product was then frozen at -25°C for 30 hours, and then treated in a freeze dryer for 30 hours to obtain a frozen product. The frozen product 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 of 800 W, gas pressure of 0.3 MPa) and treated for 8 minutes to obtain modified porous activated carbon @TiO2.

[0033] (3) Povidone iodine, a surfactant, 2-phosphonobutane-1,2,4-tricarboxylic acid, a stabilizer, an auxiliary material and water are uniformly mixed to form a suspension, and then the suspension is fully adsorbed by the modified porous activated carbon @TiO2, and then ferrous activated persulfate is added for blending to obtain a 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 of porous activated carbon @TiO2, 5 parts of povidone iodine, 0.1 parts of ferrous activated persulfate, 0.5 parts of 2-phosphonobutane-1,2,4-tricarboxylic acid, 0.1 parts of surfactant sodium lauryl polyoxyethylene ether-25 carboxylate, 0.5 parts of stabilizer decanol, 50 parts of silicate, and 10 parts of 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 sodium 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 sodium 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 sodium 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 sodium 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] 80 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 sodium lauryl polyoxyethylene ether-5 carboxylate, 0.5 parts of stabilizer decanol, 100 parts of silicate, and 20 parts of water.

[0052] Example 8

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

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

[0055] Example 9

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

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

[0058] Example 10

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

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

[0061] Embodiment 11

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

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

[0064] Example 12

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

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

[0067] Comparative Example 1

[0068] Choose activated carbon.

[0069] Comparative Example 2

[0070] Use silicate cement.

[0071] Comparative Example 3

[0072] Ferrous iron was used to activate persulfate.

[0073] Comparative Example 4

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

[0075] Comparative Example 5

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

[0077] Comparative Example 6

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

[0079] Comparative Example 7

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

[0081] Test Example 1

[0082] Water quality improvement and bactericidal performance testing.

[0083] The water from a fish fry pond in Sichuan was used as a water sample, and the water samples were divided into multiple groups, each with 500 mL, and the original water quality and several bacteria in the fish pond were tested. The disinfectant (water body improver) obtained in Examples 1-12 and Comparative Examples 1-7 was added, and the amount of the disinfectant was 0.5% of the amount of the water sample. At the same time, a blank group 1 was set up.

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

[0085] The main primitive bacteria in the water and their contents (0d) were detected, and they were marked as Vibrio alginolyticus, Vibrio harzianus, Vibrio parahaemolyticus, Streptococcus, and Aeromonas hydrophila; Comparative Examples 8-9 were set: Comparative Example 8: 0.5% glutaraldehyde was used in the water sample;

[0086] Comparative Example 9: 0.5% of decylmethylammonium bromide in water sample dosage;

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

[0088] The colony was detected again 3 days after use. The results are shown in Table 2.

[0089] Table 1 Water quality improvement of disinfectants

[0090]

[0091] The pH range of general aquaculture water is between 6.5-8.5. It can be seen from the experimental results of Table 1 that the samples of Example 1-12 are used in aquaculture water, and the pH is not greatly affected. After use, the pH is stabilized in the normal range. The pH of the water body of Comparative Example 1-3 fluctuates slightly, indicating that the water body improver of Comparative Example 1-3 has a small effect on water body improvement. It can be seen from the blank group that the pH rises beyond the normal range, indicating that there is pollution in the water body. The pH of the water body of Comparative Example 4-7 changes less, indicating that the water body improver of Comparative Example 4-7 has a certain improvement effect on water body improvement, but the improvement effect is inferior to the water body improver of Example 1. It can also be seen from the COD value that the use of the povidone iodine water body improver of Example 1-12 reduces the amount of COD and reduces the degree of pollution. On the contrary, the pollution of the blank group increases. The effect of the water body improver of Comparative Example 1-3 is not as good as that of Example 1-12, and the effect of the water body improver of Comparative Example 4-7 is not as good as that of Example 1.

[0092]

[0093]

[0094] From the data in Table 2, it can be seen that after using the improved disinfectant, the number of Vibrio, Aeromonas hydrophila, and Streptococcus in the water of Examples 1-12 decreased by about 70%-80%, and the bactericidal effect was good. However, the bactericidal effect of Comparative Examples 8-9 was not obvious, and the number of colonies in the water of Blank Group 2 increased significantly.

[0095] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A water-modified povidone-iodine disinfectant, characterized in that: The raw material components are calculated by weight and include 20-80 parts of 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 auxiliary materials, and 0-500 parts of water.

2. The water-modifying povidone-iodine disinfectant according to claim 1, characterized in that: The raw material components are calculated by weight and include porous activated carbon @TiO2, 5 to 10 parts of povidone iodine, 0.5 to 2 parts of surfactant, 0.5 to 2 parts of ferrous activated persulfate, 0.5 to 5 parts of 2-phosphonobutane-1,2,4-tricarboxylic acid, 0.1 to 2 parts of stabilizer, 0.01 to 100 parts of auxiliary materials, and 0.1 to 50 parts of water.

3. The water-modifying povidone-iodine disinfectant according to claim 1, characterized in that: The surfactant includes at least one of sodium fatty alcohol polyoxyethylene ether carboxylate and long-chain alkyl carboxylic acid betaine.

4. The water-modifying povidone-iodine disinfectant according to claim 1, characterized in that: The stabilizer is a C10-C16 long carbon alcohol.

5. The water-modifying povidone-iodine disinfectant according to claim 1, characterized in that: The auxiliary materials include at least one of a pH regulator, a preservative, a nutrient, and a water quality improver.

6. The water-modifying povidone-iodine disinfectant according to any one of claims 1 to 5, characterized in that: After pretreatment, the biomass raw material is placed in a high-pressure reactor together with a titanium precursor, ethanol, and glacial acetic acid for hydrothermal reaction, and then washed to obtain a treated product; the treated product is frozen and then treated in a freeze dryer to obtain a frozen product; and then the frozen product is heat-treated to obtain porous activated carbon@TiO2.

7. The water-modifying povidone-iodine disinfectant according to claim 6, 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: under N2 atmosphere, 800-1000°C, 1-3h.

8. A method for preparing the water-modifying povidone-iodine disinfectant according to any one of claims 1 to 7, characterized in that: The steps include: S1 porous activated carbon @TiO2 is treated with plasma to obtain modified porous activated carbon @TiO2; S2 uniformly mixes povidone iodine, surfactant, 2-phosphonobutane-1,2,4-tricarboxylic acid, stabilizer, auxiliary materials and water to form a suspension, then adds modified porous activated carbon @TiO2 for full adsorption, and then adds ferrous activated persulfate for blending to obtain povidone iodine disinfectant.

9. The method for preparing the water-modifying povidone-iodine disinfectant according to claim 8, characterized in that: Plasma treatment: power is 800W, gas pressure is 0.3MPa, and treatment time is 5 to 10 minutes.

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