CN113662004A

CN113662004A - Slow-release chlorine dioxide disinfection card using zeolite as carrier

Info

Publication number: CN113662004A
Application number: CN202110900213.XA
Authority: CN
Inventors: 刘丹青; 孙鹏; 唐国明; 吕亚楠; 吴桐桐; 杨祎宁
Original assignee: Harbin University of Science and Technology
Current assignee: Harbin University of Science and Technology
Priority date: 2021-08-06
Filing date: 2021-08-06
Publication date: 2021-11-19

Abstract

A slow-release chlorine dioxide disinfection card using zeolite as a carrier mainly relates to the field of chlorine dioxide disinfection. The invention relates to a chlorine dioxide slow release agent and a preparation method thereof, aiming at solving the defects of unstable chlorine dioxide gas, short product preservation time and the like in the prior art. The invention takes natural zeolite material as a carrier, combines sodium chlorite and a combined catalyst, and utilizes the water and carbon dioxide in the air to participate in the reaction to generate the slow-release chlorine dioxide so as to realize the artificial control of the release rate of the chlorine dioxide gas and play a role in killing bacteria and viruses. The degerming card has the ultra-long slow-release capacity of more than 30 days, and has effective effects in protecting susceptible people from virus invasion, purifying harmful components in air and the like.

Description

Slow-release chlorine dioxide disinfection card using zeolite as carrier

Technical Field

The invention relates to the field of chlorine dioxide disinfection, in particular to a slow-release chlorine dioxide disinfection card taking zeolite as a carrier and a preparation method thereof.

Background

How to effectively sterilize the air and reduce the mutual infection caused by air transmission is always concerned by all the social circles. Air sterilization is one of the methods for cutting off the spread of respiratory infectious diseases, and currently accepted means for air purification include ultraviolet lamp irradiation sterilization, air purification equipment sterilization, and chemical sterilization. The chemical air disinfection method generally adopts 3 percent of hydrogen peroxide, 0.5 to 1 percent (5 to 10g/L) of peracetic acid aqueous solution or chlorine dioxide solution (0.01 to 0.02mg/L) for heating and evaporation for disinfection, and the method has safety risks and limits the application of the method in conventional families; sodium hypochlorite is generally used only to disinfect the surface of an object due to its strong toxicity and corrosiveness. In addition, in the actually developed chlorine dioxide dosage forms (stable chlorine dioxide solution and immobilized chlorine dioxide), the stable chlorine dioxide solution has large moisture content and low effective components of chlorine dioxide, and can be used only by adding an acid activating agent, and the activating agents of different types and dosage can cause negative effects of different degrees on the disinfection and sterilization effect, and limit the application range of the chlorine dioxide dosage forms in the aspects of transportation and storage; the chlorine dioxide solid preparation generally has the problems of poor release stability and unsatisfactory effect after long-time release, is not suitable for some occasions of quick sterilization, and limits the application of the chlorine dioxide solid preparation.

Research results show that the sterilization performance of the chlorine dioxide is that nascent oxygen released when the chlorine dioxide contacts with microorganisms has extremely strong adsorbability and penetrability on microbial cells, can effectively oxidize sulfur-based enzymes in the cells to destroy enzyme systems, and can oxidize and decompose amino acids in proteins, so that the microbial protein synthesis is rapidly controlled, and the effect of inhibiting bacteria or killing bacteria is achieved. Chlorine dioxide has good killing effect on spores, viruses, algae, fungi and the like, but has no influence on the cell structure of higher animals. When the concentration of the chlorine dioxide used is lower than 500ppm, the influence on the human body can be ignored, and when the concentration is lower than 100ppm, the influence on the human body can not be generated.

Chlorine dioxide is a safe, broad-spectrum and nontoxic disinfectant, has no 'three-cause' effect (carcinogenic, teratogenic and mutagenic), simultaneously does not generate chlorination reaction with organic matters in the disinfection process to generate organic chloride or other toxic substances which can generate 'three-cause' effect, is a 4 th generation A1 grade safe and environment-friendly disinfectant confirmed by the World Health Organization (WHO) of the United nations, has obvious effects on sterilization, food preservation, deodorization, air pollutant treatment and the like, and is recognized as an ideal material for air sterilization. However, since the chlorine dioxide is a gas, and is difficult to store, the chlorine dioxide is usually prepared and used at the present, and the price is relatively high, the research on the solid chlorine dioxide slow-release material is in progress.

Disclosure of Invention

The invention aims to provide a preparation method and an optimized process of a chlorine dioxide slow-release disinfection card with long slow-release time, controllable release amount and high safety, and the preparation method and the optimized process have the technical advantages of simple process, convenience in use, wide application and the like.

In order to realize the purpose, the invention adopts the following technical scheme:

the invention provides a slow-release solid chlorine dioxide disinfection card and a preparation method thereof, which are characterized in that the filler of the product is made of an adsorptive and environment-friendly material as a carrier, can effectively control the release rate of chlorine dioxide gas, and optimizes the preparation process.

According to the design, the porous carrier, the chlorite, the load amount, the combined catalyst and the like in the preparation of the chlorine dioxide sustained-release tablet are selected as follows:

1. selection of porous support

Common solid carriers include silica gel, calcium silicate, diatomite, talcum powder, molecular sieves, activated carbon, zeolite, super absorbent polyacrylic resin, agar, super absorbent resin, carboxymethyl cellulose and the like. In order to control the generation speed of chlorine dioxide, the porous substance can slow down the contact reaction of chlorite and water and carbon dioxide in the air through steric hindrance and a porous structure, so as to play the roles of delaying the reaction and slowly releasing the chlorine dioxide, and simultaneously, natural zeolite with the particle size of 1-2mm is preferably used as a carrier from the economic point of view.

2. Selection of chlorite and loading

The chlorite selected by the invention can be selected from sodium chlorite, potassium chlorite, magnesium chlorite, zinc chlorite and the like, and the sodium chlorite is preferred from the aspects of cost and production convenience. According to the interval set by the invention and the efficiency of the chlorite reaction, the loading amount of the chlorite is determined as follows: 16 to 20 percent.

3. Selection of the Integrated catalysts

According to the invention, nitrate is selected as a catalyst, a combined catalyst of ferric nitrate and cupric nitrate is preferably selected from the view point of slow release capacity, and the optimum condition is determined when the content of the catalyst is 0.02 mol/L-0.05 mol/L% according to a set interval and the release amount of chlorine dioxide.

4. Determination of water content and sealing material of chlorine dioxide sustained-release tablet

Since chlorite is decomposed in water, the water content is high to accelerate the decomposition of the chlorine dioxide sustained release tablet and is lost when not used, so the water content of the chlorine dioxide sustained release tablet is preferably less than 0.5 percent, and the chlorine dioxide sustained release tablet does not contain water optimally. The chlorine dioxide slow release tablet can react with carbon dioxide in the air, in order to reduce the contact with the air, the chlorine dioxide slow release tablet needs to be packaged before use, the packaging materials can be PP, PE, PET, PBT plastic films and aluminum foil bags, but from the air permeation angle, the optimal packaging material is selected from the aluminum foil bags for packaging, and the influence of air and water on the product is isolated.

The preparation method of the slow-release solid chlorine dioxide disinfection card comprises the following steps:

sieving natural zeolite, washing with clear water, removing fine powder and dust, oven drying for 12 hr, soaking natural zeolite in mixed chlorite solution containing 16-20% in combination with catalyst for 12 hr, vacuum drying, bagging in non-woven fabric bag, and packaging with packaging material.

The invention has the beneficial effects that:

1. the slow-release chlorine dioxide disinfection card takes natural pollution-free zeolite material as a carrier, has low price, is simply and harmlessly treated after the product is invalid, and is extremely friendly to the environment; the zeolite is used as a solid carrier, and the sodium chlorite and the combined catalyst are compounded, so that the release rate of chlorine dioxide gas can be artificially controlled, the effect of continuous sterilization can be achieved, and the composite material is superior to the existing product.

2. The slow-release chlorine dioxide disinfection card has good lasting and slow-release capacity, the disinfection card has an ultra-long slow-release time of more than 30 days, the disinfection effect is lasting, and the use cost of the disinfectant is greatly reduced.

3. The slow-release chlorine dioxide disinfection clamp has an obvious sterilization effect, can ensure that the generation amount of chlorine dioxide gas is fixed in an effective concentration range, and does not cause harm to human bodies.

4. The filler coated by the non-woven fabric of the slow-release chlorine dioxide disinfectant card is made of the aluminum foil material, can isolate air and water, and has the characteristics of good sealing effect, convenience in use and transportation, high safety and the like

5. The slow-release chlorine dioxide disinfection card is directly opened when being used and placed in a space needing sterilization and disinfection, is convenient and quick, has simple components and preparation method, and is suitable for industrial production.

6. The slow-release chlorine dioxide disinfection card can be used in various indoor and outdoor scenes, such as closed environments of home environments, schools, office places and the like, and various outdoor personnel intensive occasions such as physical activities, traveling, parties and the like, according to the product specification which is designed from 4g to 20 g. And aiming at a fixed scene and sterilization and deodorization in a large space, a large package design of 100-300 g can be designed, and the device has the advantages of safety, long acting, low labor and management cost in the use process and the like.

Drawings

FIG. 1 is a flow chart of a process for preparing a chlorine dioxide bacteria-removing card;

FIG. 2 is an SEM photograph of a high temperature treatment and a virgin zeolite;

FIG. 3 is a graph of the corresponding chlorine dioxide release for zeolites treated at different calcination temperatures;

FIG. 4 is a graph of sample weight loss rate versus time;

FIG. 5 is a graph showing the long-term release of the aseptic card chlorine dioxide.

Detailed Description

Embodiment 1. the chlorine dioxide slow-release bacteria removal card is prepared.

Step S1: sieving zeolite to obtain 1-2mm zeolite; washing with clear water to remove fine powder and dust; then drying for 12h at 100 ℃; then roasting at the temperature of 400 ℃ and 600 ℃.

Step S2: in terms of mass percent, 18% sodium chlorite was dissolved in deionized water, and 0.3 mol/L% ferric nitrate and cupric nitrate were added as activators to prepare a mixed solution.

Step S3: 4.6g of natural zeolite and artificial zeolite are respectively weighed and put into the solution to be soaked for 12 hours.

Step S4: and (3) drying the soaked natural zeolite and artificial zeolite at 100 ℃ for 3 h.

Step S5: the natural zeolite and the artificial zeolite obtained above were tabletted and molded to obtain

samples

1 and 2, and the tabletted samples were sealed in a non-woven fabric bag, wherein the non-woven fabric was a non-woven fabric of a double-layer mask.

Example 2: the invention relates to a performance experiment of a chlorine dioxide slow-release bacteria removal card.

Placing a group of

samples

1 and 2 and similar Japanese degerming card Air vector products for children and adults in the same indoor environment, and measuring ClO released by the

samples

1 and 2 and Japanese products during Air blowing₂The gas concentration. Thereafter, the introduction of CO was continued₂ClO was measured every 30min₂The gas concentration. Another set of

samples

1 and 2 prepared under the same conditions and Japanese product were additionally left sealed for 12 hours, and ClO was measured₂The gas concentration.

Example 3: the effective action time experiment of the chlorine dioxide slow-release bacteria removal card is carried out.

Samples

1 and 2 and Japanese similar product Air factor were placed in the same indoor environment, and ClO released at 0d, 1d, 2d, 7d, and 10d times was recorded₂And (4) concentration.

According to the test results, the chlorine dioxide bacteria removal card loaded by natural zeolite releases ClO initially₂Concentration and Japanese Air DThe octor children are approximately 5ppm in money; ClO is initially released by chlorine dioxide bacteria removal card loaded by artificial zeolite₂The concentration was about 10ppm, similar to the adult version of Air vector in Japan.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims

1. The slow-release chlorine dioxide disinfection card using zeolite as a carrier is characterized by comprising the following components: the natural zeolite has strong adsorption capacity, is environment-friendly and pollution-free, takes sodium chlorite as a chlorine dioxide precursor of a main material, and takes nitrate as an activating agent mainly.

2. The slow-release chlorine dioxide disinfectant card using zeolite as carrier according to claim 1, wherein said non-woven fabric is a non-woven fabric of a double-layer mask.

3. A slow release chlorine dioxide disinfectant card as claimed in claim 1, wherein said zeolite is a wide distribution silicate-based porous mineral material; it comprises clinoptilolite, mordenite, analcime and chabazite; the zeolite raw material is produced from zeolite in the original region, and the average particle size of the zeolite raw material is 1-2 mm.

4. The slow-release chlorine dioxide disinfectant card as claimed in claim 3, wherein said zeolite is calcined at a high temperature of 300-600 ℃ for 4-7 hours.

5. A slow release chlorine dioxide disinfectant card according to any of claims 1 to 4, wherein said substance capable of releasing chlorine dioxide is a treated zeolite.

6. A slow release chlorine dioxide disinfectant card as claimed in claim 5, which is composed of treated zeolite body and activating agent, wherein the zeolite body comprises chlorine dioxide precursor substance and zeolite particles; the activating agent is a catalyst for catalyzing the high-purity chlorine dioxide, and comprises ferric nitrate and cupric nitrate.

7. A chlorine dioxide disinfectant card according to claim 6, wherein said chlorine dioxide disinfectant card is adapted to be placed in use such that said chlorine dioxide precursor substance contacts air and reacts with carbon dioxide and water in the air to form chlorine dioxide at a concentration.