阅读说明：本技术 一种二氧化氯缓释液及其制备方法 (Chlorine dioxide slow-release liquid and preparation method thereof ) 是由 陈冬冬 王爱美 侯修家 王美成 赵战如 王娜 侯宇 侯君 于 2021-01-08 设计创作，主要内容包括：本发明公开了一种二氧化氯缓释液及其制备方法,首先将多孔材料和表面活性剂混合均匀,然后将其均匀分散在二氧化氯母液中混合均匀,再加入缓释激发剂,最后加入微纳银或微纳锌,混合均匀。二氧化氯不是单纯地溶解在水中,而是一部分溶于水,另一部分吸附在多孔材料孔隙中,所以二氧化氯缓释液中的二氧化氯是远大于二氧化氯在水中的溶解度(溶解度为0.8％),多孔材料不但能够增加缓释液中二氧化氯的含量,而且在释放的过程中先从多孔材料中释放到水中,当水溶液达到溶液度再向外释放,相比现有的固体负载的二氧化氯或液体二氧化氯,延长了释放的路径,进一步增强缓释的效果。(The invention discloses a chlorine dioxide slow-release liquid and a preparation method thereof. The chlorine dioxide is not simply dissolved in water, but one part is dissolved in water, and the other part is adsorbed in pores of the porous material, so that the chlorine dioxide in the chlorine dioxide slow-release liquid is far greater than the solubility (the solubility is 0.8%) of the chlorine dioxide in the water, the porous material not only can increase the content of the chlorine dioxide in the slow-release liquid, but also can be firstly released into the water from the porous material in the releasing process, and when the aqueous solution reaches the solution degree, the chlorine dioxide is released outwards.)

1. The chlorine dioxide slow-release liquid is characterized by being prepared from the following components in parts by weight: 70-90 parts of chlorine dioxide mother liquor, 6-25 parts of slow-release exciting agent, 2-15 parts of surfactant, 0-5 parts of micro-nano silver or micro-nano zinc and 1-10 parts of porous material.

2. A method for preparing a chlorine dioxide slow-release solution according to claim 1, which comprises the following steps,

(1) uniformly mixing the porous material and the surfactant;

(2) uniformly dispersing the porous material adsorbed with the surfactant in the chlorine dioxide mother liquor, wherein the surfactant is adsorbed on the surface of the porous material;

(3) adding the slow-release exciting agent into the chlorine dioxide mother liquor dispersed with the porous material for reaction to generate chlorine dioxide molecules, wherein the chlorine dioxide molecules are dispersed in the aqueous solution and the pores of the porous material;

(4) adding a small amount of micro-nano silver or micro-nano zinc into the solution obtained in the step (3);

(5) subpackaging the mixed liquid obtained in the step (4) into bottles according to the required amount; the chlorine dioxide mother liquor is one or a mixture of aqueous solution of sodium chlorite, potassium chlorite and barium chlorite; the slow release excitant is a weakly acidic substance.

3. The method for preparing a chlorine dioxide slow-release solution according to claim 2, wherein the porous material is a stable substance with a pore structure.

4. The preparation method of the chlorine dioxide slow-release solution according to claim 2, wherein the porous material is one of activated carbon, molecular sieve, graphene and modified substances thereof.

5. The preparation method of the chlorine dioxide slow-release solution according to claim 2, characterized in that the surfactant is one or more of cationic surfactant, anionic surfactant or nonionic surfactant.

Technical Field

The invention belongs to the technical field of microcapsule preparation, and particularly relates to a chlorine dioxide slow-release solution and a preparation method thereof.

Background

Chlorine dioxide is a high-efficient, safe, broad-spectrum disinfecting and sterilizing agent, apply to various water treatment, air purification and sterilization and food antisepsis, especially the chlorine dioxide product of slow release can release the chlorine dioxide gas of low concentration slowly and continuously in a longer time automatically, kill germ and bacterium in the air effectively, remove the peculiar smell in the air, prevent the indoor article from going milden and rot in the humid air, sterilize the air, sterilize the dual efficiency, improve the soil of farming, the atomic oxygen that it decomposes out can also fresh the air at the same time, will not bring harm and minus effect to the human body, can apply to the aspects such as air freshening and purifying, soil improvement, sterilization and disinfection, mildew-proof, deodorization, fresh-keeping of food and agricultural by-product extensively, etc.

The application of chlorine dioxide is mainly made into solid form, when in use, the chlorine dioxide product is added into water by medium, such as water, to react to generate chlorine dioxide (for example, patent CN 108464302A). This has limitations when used. And there will be a significant amount of solid material as a contaminant. Due to the instability of chlorine dioxide, few products are currently made as aqueous solutions. Our current invention is a stable aqueous solution of free chlorine dioxide. In order to maintain high stability of chlorine dioxide, a stabilizing material such as graphene needs to be added during the preparation process.

Disclosure of Invention

The invention aims to provide a preparation method of a chlorine dioxide slow-release solution.

In order to achieve the aim, the invention relates to a chlorine dioxide slow-release solution which is prepared from the following components in parts by weight: 70-90 parts of chlorine dioxide mother liquor, 6-25 parts of slow-release exciting agent, 2-15 parts of surfactant, 0-5 parts of micro-nano silver or micro-nano zinc and 1-10 parts of porous material.

The preparation method of the chlorine dioxide slow-release liquid specifically comprises the following steps:

(1) uniformly mixing the porous material and the surfactant to ensure that the surface of the porous material adsorbs the surfactant and has wettability;

(2) the porous material adsorbed with the surfactant is uniformly dispersed in the chlorine dioxide mother liquor, and the surface of the porous material is adsorbed with the surfactant, so that the porous material is more easily dispersed in the chlorine dioxide mother liquor, and the chlorine dioxide mother liquor enters the pores in the porous material;

(3) adding the slow-release exciting agent into the chlorine dioxide mother liquor dispersed with the porous material for reaction to generate chlorine dioxide molecules, wherein the chlorine dioxide molecules are dispersed in the aqueous solution and the pores of the porous material;

(4) adding a small amount of micro-nano silver or micro-nano zinc into the solution obtained in the step (3), so as to further enhance the broad spectrum of sterilization and disinfection of the chlorine dioxide solution;

(5) subpackaging the mixed liquid obtained in the step (4) into bottles according to the required amount; the chlorine dioxide mother liquor is one or a mixture of aqueous solution of sodium chlorite, potassium chlorite and barium chlorite; the slow release activator is weakly acidic material, such as one or mixture of boric acid, sodium bisulfate, citric acid, tartaric acid, oxalic acid, dihydrogen phosphate, and acetic acid.

The porous material is a stable substance with a pore structure, and includes but is not limited to one of activated carbon, molecular sieve, graphene and modified substances thereof.

The surfactant is one or more of cationic surfactant, anionic surfactant or nonionic surfactant, such as tetrabutylammonium bromide, triethylbenzylammonium chloride, ammonium dodecyl benzene sulfonate, alkylphenol polyoxyethylene, etc.

The chlorine dioxide stabilization mechanism: in the high-porosity porous material, chlorine dioxide gas (5 ClO) is generated after the activation reaction of chlorine dioxide parent and slow-release activator₂ ^-+4H⁺＝＝4ClO₂+Cl^-+2H₂O), the pore size range is 1-100 nanometers, and because the pore size is equivalent to that of chlorine dioxide molecules, the chlorine dioxide molecules can be stored in the pores for a long time and can freely enter and exit the pores, so that the stabilizing effect is achieved and the using effect of the chlorine dioxide is not influenced.

Compared with the prior art, the invention has the following beneficial effects: (1) the chlorine dioxide is not simply dissolved in water, but one part is dissolved in water, the other part is adsorbed in pores of the porous material, the mass of the adsorbed gas of the porous material is 0.1-1 times or even more than that of the porous material, so the chlorine dioxide in the chlorine dioxide slow-release solution is far greater than the solubility (the solubility is 0.8%) of the chlorine dioxide in water; (2) the porous material can increase the content of chlorine dioxide in the slow-release liquid, and the chlorine dioxide is firstly released into water from the porous material in the release process, and then released outwards when the aqueous solution reaches the solution degree, so that compared with the existing solid-loaded chlorine dioxide or liquid chlorine dioxide, the slow-release porous material prolongs the release path and further enhances the slow-release effect; (3) when the graphene or the derivative thereof is used as the porous material, the graphene or the derivative thereof can form a special bond with chlorine dioxide molecules, so that the adsorption stability is improved.

Detailed Description

The present invention is further illustrated by the following examples.

Example 1

Stirring and mixing 5 parts of graphene and 10 parts of alkylphenol polyoxyethylene ether uniformly for later use; then, the solution was added to 75 parts of an aqueous solution containing 25% sodium chlorite, and stirred at a high speed to allow sodium chlorite to enter pores of graphene. And then adding 20 parts of aqueous solution containing 20% of sodium bisulfate into the solution, and stirring for 2 hours at room temperature to ensure that the chlorine dioxide mother liquor fully reacts and is excited to generate chlorine dioxide molecules which are fully adsorbed into pores of the graphene. Then, one thousandth of micro-nano silver is added, fully stirred and dispersed to obtain the chlorine dioxide slow-release solution.

Example 2

Stirring and mixing 6 parts of molecular sieve and 15 parts of aqueous solution containing 40% tetrabutylammonium bromide uniformly for later use; and then adding the uniformly mixed molecular sieve into 80 parts of aqueous solution containing 30% of potassium chlorite, and stirring at high speed to ensure that the potassium chlorite enters pores of the molecular sieve. And then adding 25 parts of aqueous solution containing 20% of citric acid into the solution, stirring for 2 hours at room temperature, fully reacting and exciting the chlorine dioxide mother liquor to generate chlorine dioxide molecules, and fully adsorbing the chlorine dioxide molecules into pores of the molecular sieve. Then, one thousandth of micro-nano zinc is added to be fully stirred and dispersed to obtain the chlorine dioxide slow-release solution.

Example 3

Stirring and mixing 7 parts of activated carbon and 15 parts of sodium dodecyl benzene sulfonate aqueous solution containing 20% uniformly for later use; and then adding the uniformly mixed activated carbon into 80 parts of water solution containing 25% of barium chlorite, and stirring at high speed to ensure that the barium chlorite enters pores of the activated carbon. And then adding 20 parts of aqueous solution containing 15% of sodium dihydrogen phosphate into the solution, stirring for 2 hours at room temperature, fully reacting and activating the chlorine dioxide mother liquor to generate chlorine dioxide molecules, and fully adsorbing the chlorine dioxide molecules into pores of the activated carbon. Then adding micro-nano silver of 0.5 per thousand parts, fully stirring and dispersing to obtain the chlorine dioxide slow-release solution.

Example 4

Stirring and uniformly mixing 10 parts of graphene oxide and 15 parts of 20% triethyl benzyl ammonium chloride aqueous solution for later use; and then adding the uniformly mixed graphene oxide into 90 parts of aqueous solution containing 20% of barium chlorite, and stirring at high speed to enable the barium chlorite to enter pores of the graphene oxide. And then adding 20 parts of aqueous solution of tartaric acid 15%, stirring at room temperature for 2 hours to enable the chlorine dioxide mother liquor to fully react and activate to generate chlorine dioxide molecules, and fully adsorbing the chlorine dioxide molecules into pores of the graphene oxide.

Example 5

Stirring and mixing 5 parts of graphene oxide and 2 parts of 20% alkylphenol polyoxyethylene ether aqueous solution uniformly for later use; and then adding the uniformly mixed graphene oxide into 70 parts of aqueous solution containing 10% of barium chlorite, and stirring at a high speed to enable the barium chlorite to enter pores of the graphene oxide. And then adding 6 parts of 15% aqueous solution of dihydric phosphate into the solution, stirring for 2 hours at room temperature, fully reacting and exciting the chlorine dioxide mother liquor to generate chlorine dioxide molecules, and fully adsorbing the chlorine dioxide molecules into pores of the graphene oxide. Then adding micro-nano silver of 0.5 per thousand parts, fully stirring and dispersing to obtain the chlorine dioxide slow-release solution.