Chlorine dioxide generating agent and method for producing a chlorine dioxide generating agent

Abstract

To provide a chlorine dioxide generating agent and a method for producing a chlorine dioxide generating agent, which can efficiently generate chlorine dioxide gas.SOLUTION: A chlorine dioxide generating agent generates chlorine dioxide gas upon contact with air. The chlorine dioxide generating agent is in the form of powder. The powder comprises a porous carrier having a transition metal supported on its surface, and powders of a chlorite and a coating agent are attached to the surface of the carrier with an adhesive. When the chlorine dioxide generating agent comes into contact with air, chlorine dioxide gas can be stably generated.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a chlorine dioxide generating agent and a method for producing the same.

Background Art

[0002] In the atmosphere, there are various germs such as viruses. When such viruses are inhaled, there is a possibility of being infected with the virus and getting sick. In recent years, attention has been paid to the bactericidal power of chlorine dioxide, and technologies for generating chlorine dioxide gas (for example, Patent Documents 1 to 4, etc.) and technologies for supplying chlorine dioxide gas into the atmosphere to inactivate viruses, etc. have been developed (for example, Patent Documents 5, 6, etc.). Products using such technologies are also sold in the market.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

[0004] As described above, although a large number of chlorine dioxide generating agents are currently sold, in order to popularize the sterilization of the atmosphere using chlorine dioxide, a chlorine dioxide generating agent that can generate chlorine dioxide gas more efficiently is required.

[0005] In view of the above circumstances, the present invention aims to provide a chlorine dioxide generating agent that efficiently generates chlorine dioxide gas and a method for producing a chlorine dioxide generating agent. [Means for solving the problem]

[0006] <Chlorine dioxide generating agent> The present invention relates to a chlorine dioxide generating agent that generates chlorine dioxide gas upon contact with air, characterized in that the chlorine dioxide generating agent is in powder form and comprises a porous carrier on which a transition metal is supported, with chlorite powder and coating powder attached to the surface with an adhesive. <Method for producing chlorine dioxide generator> The present invention provides a method for producing a chlorine dioxide generating agent, characterized by sequentially performing the following steps: obtaining carrier particles on which a transition metal is supported on the surface of a carrier; forming a coating layer on which a coating layer containing chlorite particles is formed on the surface of the carrier particles; and drying the carrier particles on which the coating layer has been formed. [Effects of the Invention]

[0007] <Chlorine dioxide generating agent> The chlorine dioxide generating agent of the present invention can stably generate chlorine dioxide gas when it comes into contact with air. <Method for producing chlorine dioxide generator> According to the method for producing a chlorine dioxide generating agent of the present invention, it is possible to produce a chlorine dioxide generating agent that stably generates chlorine dioxide gas when it comes into contact with air. [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic diagram illustrating the manufacturing process of the chlorine dioxide generating agent according to this embodiment. [Figure 2] This is a graph showing the experimental results. [Modes for carrying out the invention]

[0009] The chlorine dioxide generating agent of this embodiment is a chlorine dioxide generating agent that can efficiently generate chlorine dioxide gas.

[0010] The method and location of use of the chlorine dioxide generating agent of this embodiment are not particularly limited. For example, it can be used to disinfect the air in partitioned spaces such as rooms or livestock barns. Furthermore, the apparatus used to use the chlorine dioxide generating agent of this embodiment is not particularly limited. For example, it can be used as a chlorine dioxide generating agent in commercially available chlorine dioxide generators or gel formulations.

[0011] The chlorine dioxide generating agent of this embodiment is a granular substance containing the components described later, in which a chlorite (for example, sodium chlorite (NaClO2)) is supported on the surface of a carrier that forms the main body of the substance (for example, zeolite).

[0012] <Shape of chlorine dioxide generating agent> The chlorine dioxide generating agent in this embodiment is generally a powder in the form of spherical or granular particles, and is formed such that its average particle size is 0.6 to 5 mm, preferably 0.9 to 3 mm, and preferably 0.9 to 1 mm.

[0013] <Ingredients of chlorine dioxide generating agent> The chlorine dioxide generating agent of this embodiment is formed from the following substances.

[0014] <carrier> First, the carrier that forms the main body of the chlorine dioxide generator in this embodiment, that is, the substance that supports the chlorite, is zeolite having the structure (shape, particle size) as described above (hereinafter sometimes referred to as carrier zeolite). The carrier zeolite has a large number of voids communicating with the outer surface inside, and the surface area (the area combining both the outer surface area and the inner surface area of the carrier) compared to its particle size is large. Therefore, the carrier zeolite can support more chlorite compared to its particle size. Moreover, the chlorite supported on the inner surface through the voids can be effectively contacted with air, and the chlorine dioxide gas generated inside can also be effectively released to the outside. The amount of this carrier zeolite relative to the total weight of the chlorine dioxide generator in this embodiment is 40 to 80% by weight, preferably 50 to 75% by weight, more preferably 60 to 70% by weight.

[0015] In addition, transition metals are supported on the surface of this carrier zeolite (including both the outer surface and the inner surface of the carrier zeolite). The supported transition metals are, for example, iron, manganese, copper, cerium, chromium, cadmium, etc. This transition metal is provided to improve the adhesion between the surface of the carrier zeolite and sodium chlorite. That is, by supporting the transition metal on the surface of the carrier zeolite, the chlorite can be supported on the surface of the carrier zeolite in a stable state. The amount of this transition metal supported, that is, the amount of the transition metal relative to the total weight of the chlorine dioxide generator in this embodiment is 0.5 to 10% by weight, preferably 0.5 to 8% by weight, more preferably 3 to 7% by weight.

[0016] In addition to the above-mentioned carrier zeolite, it is also possible to employ known porous materials as the carrier that forms the main body. For example, substances that can be used as the carrier include sepiolite, diatomaceous earth, and the like.

[0017] <Chlorite> The chlorine dioxide generator of this embodiment contains sodium chlorite (NaClO2), which is a chlorite, attached to the carrier zeolite as a component that reacts with moisture and carbon dioxide in the air to generate chlorine dioxide gas. The amount of sodium chlorite attached, that is, the amount of sodium chlorite relative to the total weight of the chlorine dioxide generator of this embodiment, is 1 to 40% by weight, preferably 8 to 30% by weight, more preferably 8 to 25% by weight. The larger the amount of sodium chlorite, the easier it is to generate chlorine dioxide gas, and the larger the amount of chlorine dioxide gas that can be generated. On the other hand, if the amount of sodium chlorite exceeds 25% by weight relative to the total weight of the chlorine dioxide generator, it will be designated as a poisonous substance. Therefore, in order to facilitate the use of the chlorine dioxide generator of this embodiment while maintaining the stable generation of chlorine dioxide gas, the amount of sodium chlorite relative to the total weight of the chlorine dioxide generator of this embodiment is 8 to 30% by weight, more preferably 8 to 25% by weight. In particular, when the carrier is carrier zeolite, the amount of sodium chlorite relative to the total weight of the chlorine dioxide generator of this embodiment is preferably 8 to 25% by weight.

[0018] In addition to sodium chlorite described above, known chlorites can also be used as the chlorite to be attached to carriers such as carrier zeolite. For example, alkali metal salts such as potassium chlorite and lithium chlorite, and alkaline earth metal salts such as magnesium chlorite and calcium chlorite can be mentioned as chlorites.

[0019] <Coating agent> In this embodiment of the chlorine dioxide generating agent, chlorine dioxide gas is generated by reacting moisture and carbon dioxide in the air with sodium chlorite, which is a chlorite salt. In order to generate chlorine dioxide gas stably for a long period of time (for example, about 90 days), a coating layer is formed on the outer surface of the carrier zeolite by a coating agent. This coating agent can form a coating layer on the outer surface of the carrier zeolite so as to suppress contact with moisture and carbon dioxide in the air; in other words, it can form a coating layer on the outer surface of the carrier zeolite that is permeable to some extent to moisture and carbon dioxide in the air. For example, silicone powder or diatomaceous earth can be used as the coating agent. The amount of this coating agent, that is, the amount of the coating agent relative to the total weight of the chlorine dioxide generating agent in this embodiment, is 15 to 25% by weight, preferably 18 to 22% by weight.

[0020] Furthermore, the coating layer may be formed not only on the outer surface of the carrier zeolite but also on the inner surface of the carrier zeolite. Furthermore, the coating layer may be designed to cover the surface of a carrier such as a carrier zeolite to which the aforementioned chlorite salts are attached, or the coating layer itself may contain chlorite salts.

[0021] <Adhesive> The coating agent described above is fixed to the outer surface of the carrier zeolite (or the outer and inner surfaces of the carrier zeolite) by an adhesive. For example, if silicone powder or diatomaceous earth is used, its particles are adhered to the outer surface of the carrier zeolite by the adhesive, forming a coating layer. The adhesive prevents the silicone powder or diatomaceous earth particles from falling off the outer surface of the carrier zeolite even when chlorine dioxide gas is generated. This adhesive can be any substance that can adhere the material forming the coating layer to the outer surface of the carrier zeolite, and any substance that functions as an adhesive can be used. For example, if silicone powder or diatomaceous earth is used as the coating agent, sodium alginate, polyvinyl alcohol, or carboxymethylcellulose can be used as the adhesive. The amount of this adhesive, that is, the amount of adhesive relative to the total weight of the chlorine dioxide generating agent in this embodiment, is 1 to 5% by weight, preferably 1 to 3% by weight, and more preferably 2 to 3% by weight.

[0022] Furthermore, once the coating agent adheres to the carrier zeolite and a coating layer is formed, the adhesive itself functions as a coating layer that blocks contact between chlorites such as sodium chlorite and water vapor.

[0023] <Example of component ratio of chlorine dioxide generating agent> The proportions of each component contained in the chlorine dioxide generating agent of this embodiment are as described above, but for example, if a carrier zeolite is used as the carrier and sodium chlorite is used as the chlorite salt, the components and their proportions can be as follows. With this blending ratio, the amount of chlorine dioxide gas generated can be increased by approximately 30-50% compared to conventional granular chlorine dioxide generating agents of the same weight (carrier: 92% or more by weight, chlorite: 5% or less by weight), and the duration of chlorine dioxide gas generation can be extended by approximately 20%. Note that the weight percentages of each component represent the weight ratio to the total weight of the chlorine dioxide generating agent in this embodiment. 1) Carrier zeolite: 70% by weight 2) Sodium chlorite powder (sodium chlorite content 82%): 8.0% by weight (sodium chlorite) 3) Transition metals (one or more of the following: iron, manganese, copper, cerium, chromium, cadmium): 7.0% by weight 4) Coating agent (silicone powder, diatomaceous earth, or a mixture thereof): 18-20% by weight 5) Adhesive (one or more of the following: sodium alginate, polyvinyl alcohol, or carboxymethylcellulose): 2.0% by weight 6) Other: 13% by weight

[0024] <Method for producing chlorine dioxide generator> The chlorine dioxide generating agent of this embodiment, that is, the granular chlorine dioxide generating agent, can be manufactured by a method of supporting chemicals or the like on various granular carriers. For example, it can be manufactured by the following method (see Figure 1).

[0025] <Process for manufacturing acid-modified zeolite particles> First, acid-modified zeolite particles, which are the raw material for the zeolite particles that will serve as the carrier, are manufactured. Acid-modified zeolite particles are produced by modifying the surface of natural zeolite particles to an acidic state by immersing them in an acid solution. Specifically, an inorganic acid solution is prepared by mixing one or a mixture of several inorganic acids, such as hydrochloric acid, sulfuric acid, or nitric acid, with water. At this time, the inorganic acid solution is prepared so that the concentration of the inorganic acid solution, that is, the amount of mixture mixed with water, is 0.5 to 5 ml / L. To this inorganic acid solution, a surfactant such as sodium dodecylbenzenesulfonate (DBS), sodium 1,2-alkylsulfonate, sodium 1,2-alkyl sulfate, coconut oil amide, or beet alkali is added to prepare a mixed solution. The surfactant is added in an amount of 500 to 1000 mg per liter of inorganic acid solution. Once the mixed solution is prepared, natural zeolite with a particle size of 0.5 to 3 mm is immersed in the mixed solution in a weight ratio of 1:10 to 1:20 (natural zeolite: mixed solution). Then, after immersion for 1-2 hours, the natural zeolite can be removed from the mixed solution to obtain acid-modified zeolite particles whose surface has been modified to an acidic state.

[0026] <Transition metal loading process> Once acid-modified zeolite particles are obtained, a transition metal is supported on the surface of these particles. Specifically, a nitrate solution is prepared by mixing one or a mixture of iron nitrate, manganese nitrate, copper nitrate, cerium nitrate, chromium nitrate, and cadmium nitrate with water. The concentration of the nitrate solution, i.e., the amount of the mixture mixed with water, is adjusted to 0.1 to 1 ml / L. Once the nitrate solution is prepared, the acid-modified zeolite particles are immersed in the solution in a weight ratio of 1:10 to 1:20 (natural zeolite: mixed solution). After immersion for 12 to 24 hours, the acid-modified zeolite particles are removed from the mixed solution and then calcined at 200 to 800°C for 2 to 5 hours to obtain a carrier zeolite with the transition metal supported on its surface.

[0027] <Coating preparation process> Next, a coating agent to be attached to the surface of the carrier zeolite is prepared. Specifically, a nitrite powder such as sodium chlorite powder, silicone powder, and diatomaceous earth are mixed in a weight ratio of 2:1:1 using a known mixer such as a V-type mixer to prepare the coating agent. The nitrite powder such as sodium chlorite powder has a sodium chlorite content of 82% or more and a particle size of 50 to 100. The silicone powder is type B silica gel powder with a particle size of 100 to 200. The diatomaceous earth is diatomaceous earth concentrate with an SiO2 content of 90%.

[0028] <Adhesive preparation process> Furthermore, an adhesive is prepared for use in attaching the coating to the surface of the carrier zeolite. Specifically, a mixture of one or more of sodium alginate, polyvinyl alcohol, and carboxymethylcellulose is dissolved in water to prepare an aqueous solution, i.e., the adhesive, in which the concentration of the adhesive mixture is 0.5 to 5% by weight per liter of water.

[0029] <Coating layer formation process> Once the coating agent and adhesive are prepared, a coating layer is formed on the surface of the carrier zeolite. Specifically, the carrier zeolite and coating agent are mixed in a 1:1 weight ratio while being sprayed into the adhesive. For example, the carrier zeolite and coating agent are placed in a 1:1 weight ratio into a disc-type particle forming machine, and the mixture is coated and granulated while the adhesive is sprayed. This produces a carrier zeolite having a coating layer formed by the coating agent adhering to the surface by the adhesive. If the amount of adhesive sprayed is 3-8% of the total solid weight, a carrier zeolite with a coating layer having a particle size of 1-5 mm can be obtained. By drying this carrier zeolite with a coating layer at 80-105°C for 2-4 hours, particles of the chlorine dioxide generating agent of this embodiment can be obtained.

[0030] <Storage method> The chlorine dioxide generating agent of this embodiment generates chlorine dioxide gas when it comes into contact with carbon dioxide and moisture in the air. Therefore, when storing, the chlorine dioxide generating agent of this embodiment is stored in a way that prevents it from coming into contact with air, specifically gases containing carbon dioxide and moisture, or gases containing carbon dioxide and water. For example, it may be stored in a breathable inner bag made of a material such as nonwoven fabric or a plastic dialysis membrane, and then airtightly sealed in an outer bag having an aluminum layer, or it may be stored airtightly in an outer bag that does not contain an inner bag. In this case, by enclosing a desiccant or degasser inside the outer bag, the chlorine dioxide generating agent of this embodiment can be stored in a stable state.

[0031] <How to use> The chlorine dioxide generating agent of this embodiment can generate chlorine dioxide gas if it is brought into contact with air or the like from its storage state. For example, if it is airtightly sealed in an outer bag as described above, opening the outer bag will bring the chlorine dioxide generating agent of this embodiment into contact with air (i.e., carbon dioxide and moisture in the air), either directly or through the inner bag, to generate chlorine dioxide gas.

[0032] In this embodiment, the chlorine dioxide generating agent is designed so that the generation of chlorine dioxide gas can be suppressed to some extent by the coating agent. However, if the generation of chlorine dioxide gas needs to be accelerated, water can be sprayed directly onto the chlorine dioxide generating agent of this embodiment or onto the surface of the inner bag containing the chlorine dioxide generating agent of this embodiment. [Examples]

[0033] We have confirmed that the chlorine dioxide generating agent of the present invention can generate a large amount of chlorine dioxide gas and maintain that state for a long period of time.

[0034] The examples show products manufactured using the above-described manufacturing method, adjusted to have the following component ratios. A commercially available chlorine dioxide generator was used for comparison. <Examples> 1) Carrier zeolite: 70% by weight 2) Sodium chlorite powder (82% sodium chlorite content, particle size 50-100): 8% by weight (sodium chlorite) 3) glue (Sodium alginate): 2% by weight 4) Coating agent Silicone powder (Type B silica gel powder, particle size 100-200): 7% by weight Diatomaceous earth (diatomaceous earth concentrate with 90% SiO2 content): 7% by weight 5) Adhesive: 6% by weight

[0035] In the experiment, 10g of chlorine dioxide generating agent, sealed in an airtight bag (aluminum-coated bag), was opened, and the amount of chlorine dioxide gas generated was measured to confirm the change in the amount of chlorine dioxide gas generated over time.

[0036] Figure 2 shows the experimental results. As shown in Figure 2, the example product generates significantly more chlorine dioxide gas than the commercially available product immediately after opening, producing more than three times the amount. Furthermore, while the commercially available product virtually stops generating chlorine dioxide gas after about 30 days of opening, the example product still generates more than twice the amount of chlorine dioxide gas generated by the commercially available product immediately after opening, even after 84 days.

[0037] Based on the above results, it was confirmed that the chlorine dioxide generating agent of the present invention can generate a larger amount of chlorine dioxide gas compared to conventional chlorine dioxide generating agents, and can maintain that state for a long period of time. [Industrial applicability]

[0038] The chlorine dioxide generating agent of this embodiment is suitable as a chemical agent for generating chlorine dioxide in partitioned spaces where disinfection is necessary, such as indoors or in livestock barns.

Claims

1. A chlorine dioxide generating agent that generates chlorine dioxide gas upon contact with air, The chlorine dioxide generating agent is in powder form, This device consists of a porous carrier on which a transition metal is supported, with chlorite powder and coating powder attached to its surface using an adhesive. The powder of the coating agent is It is a mixture containing silica gel and diatomaceous earth. A chlorine dioxide generating agent characterized by the following features.

2. The chlorite powder is sodium chlorite powder. A chlorine dioxide generating agent according to claim 1, characterized in that it is a feature of the present invention.

3. The transition metal is one or more of the following: iron, manganese, copper, cerium, chromium, and cadmium. A chlorine dioxide generating agent according to claim 1 or 2, characterized by the features described above.

4. The aforementioned adhesive, An aqueous solution of one or more of the following: sodium alginate, polyvinyl alcohol, or carboxymethylcellulose. A chlorine dioxide generating agent according to claim 1, 2, or 3, characterized by the features described herein.

5. The porous carrier is a zeolite, The weight ratio of zeolite, transition metal, chlorite powder, and coating agent powder to the total weight of the chlorine dioxide generating agent is: The carrier zeolite makes up 40-80% by weight. Transition metals are present in 0.5 to 10% by weight. Chlorite powder in an amount of 1 to 40% by weight, The coating is 15-25% by weight. A chlorine dioxide generating agent according to claim 1, 2, 3, or 4, characterized by its features.

6. A method for producing a chlorine dioxide generating agent according to claims 1 to 5, A process to obtain carrier particles on which a transition metal is supported on the surface of a carrier, A coating layer formation step in which a coating layer containing chlorite particles is formed on the surface of the carrier particles, The process involves a drying step to dry the carrier particles on which the coating layer has been formed, and then proceeding as follows: In the process of obtaining carrier particles, A process for producing acid-modified carrier particles in which the surface of the carrier is modified to an acidic state, A transition metal loading step to obtain carrier particles on which a transition metal is supported on the surface of the acid-modifiable carrier particles, The process involves sequentially performing a coating layer formation step, which involves forming a coating layer on the surface of the carrier particles, and A method for producing a chlorine dioxide generating agent, characterized by the above.

7. In the aforementioned acid-modified carrier particle manufacturing process, The carrier is immersed in a mixed solution containing an inorganic acid solution and a surfactant. A method for producing a chlorine dioxide generating agent according to claim 6, characterized in that it is as described above.

8. In the aforementioned transition metal loading process, Acid-modifying carrier particles are immersed in a nitrate solution, and the immersed acid-modifying carrier particles are calcined. A method for producing a chlorine dioxide generating agent according to claim 6 or 7, characterized in that it is a method for producing a chlorine dioxide generating agent according to claim 6 or 7.

9. In the aforementioned coating layer formation step, While supplying the adhesive, the carrier particles, chlorite powder, and coating agent powder are mixed and stirred. A method for producing a chlorine dioxide generating agent according to claim 6, 7, or 8, characterized by the above.

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