Method for generating chlorine dioxide gas

Abstract

The present invention addresses the problem of providing a method for rapidly generating chlorine dioxide gas at a desired time while maintaining the temperature during a reaction at a low temperature. Provided is a method for producing chlorine dioxide gas, comprising a step of reacting a chlorite salt, an amino acid, and an aldehyde compound in a solvent in a container under acidic conditions.

Description

(19) State Intellectual Property Office (12) Invention Patent Application (10) Application Publication Number (43) Application Publication Date (21) Application Number 202480054568.3 (22) Application Date 2024.08.29 (30) Priority Data 2023-145894 2023.09.08 JP (85) PCT International Application Entering National Phase Date 2026.02.25 (86) PCT International Application Application Data PCT / JP2024 / 030867 2024.08.29 (87) PCT International Application Publication Data WO2025 / 053033 JA 2025.03.13 (71) Applicant Daiko Pharmaceutical Co., Ltd. Address 3-34, Naimoto-cho, Suita City, Osaka Prefecture, Japan Patent No. 14 (72) Inventor: Yuichi Hashizume (74) Patent Agency: Beijing Gecheng Intellectual Property Agency Co., Ltd. 11314 Patent Attorney: Wei Cheng (51) Int.Cl. C01B 11 / 02 (2006.01) A61L 9 / 01 (2006.01) A61L 9 / 02 (2006.01) (54) Invention Title: Method for Generating Chlorine Dioxide Gas (57) Abstract: The subject of this invention is to provide a method for rapidly generating chlorine dioxide gas at a predetermined time point while maintaining the temperature at a low temperature during the reaction. This invention provides a method for generating chlorine dioxide gas, comprising the following steps: reacting chlorite, amino acid, and aldehyde compound in a solvent in a container under acidic conditions. Claims 1 page, Description 14 pages, Drawings 3 pages, CN 121729380 A 2026.03.24 CN 1 21 72 93 80 A 1. A method for generating chlorine dioxide gas, comprising the following steps: reacting chlorite, amino acid, and aldehyde compound in a solvent within a container under acidic conditions. 2. The method for generating chlorine dioxide gas according to claim 1, wherein the temperature of the reaction system in the aforementioned reaction step does not rise above 100°C. 3. The method for generating chlorine dioxide gas according to claim 1, wherein the aforementioned chlorite is an alkali metal salt of chlorite or an alkaline earth metal salt of chlorite. 4. The method for generating chlorine dioxide gas according to claim 3, wherein the aforementioned alkali metal salt of chlorite is selected from the group consisting of sodium chlorite, potassium chlorite, and lithium chlorite; and the alkaline earth metal salt of chlorite is selected from the group consisting of calcium chlorite, magnesium chlorite, and barium chlorite. 5. The method for generating chlorine dioxide gas according to claim 1, wherein the concentration of chlorite in the aforementioned reaction system is 1.0 to 30.0 by weight.6. The method for generating chlorine dioxide gas according to claim 1, wherein the aforementioned aldehyde compound comprises one or more compounds selected from the group consisting of formaldehyde, trioxymethylene, acetaldehyde, propionaldehyde, butyraldehyde, hexanal, heptanal, octanal, nonanal, decanal, acrolein, benzaldehyde, cinnamaldehyde, perillaldehyde, vanillin, glyoxal, glyceraldehyde, D-erythrose, D-threose, D-ribose, D-arabinose, D-xylose, D-lythose, D-allose, D-azoleose, D-glucose, D-mannose, D-gulose, D-idolose, D-galactose, and D-tarose. 7. The method for generating chlorine dioxide gas according to claim 1, wherein the concentration of the aldehyde compound in the aforementioned reaction system is 0.5 to 32 by weight. 8. The method for generating chlorine dioxide gas according to claim 1, wherein the aforementioned amino acid is one or more amino acids selected from the group consisting of aspartic acid, glutamic acid, glycine, alanine, arginine, asparagine, glutamine, histidine, isoleucine, leucine, cysteine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine. 9. The method for generating chlorine dioxide gas according to claim 1, wherein the concentration of the amino acid in the aforementioned reaction system is 5.0 to 23% by weight. 10. The method for generating chlorine dioxide gas according to claim 1, wherein in the aforementioned reaction system, the concentration of chlorite is 1.0 to 30.0% by weight, the concentration of the aldehyde compound is 0.5 to 32% by weight, and the concentration of the amino acid is 5.0 to 23% by weight. 11. The method for generating chlorine dioxide gas according to claim 1, wherein the aforementioned acidic condition is below pH 6. 12. A method for fumigating a space, wherein the method for generating chlorine dioxide gas according to claim 1 is applied in a space where no humans are present. 13. A chlorine dioxide gas generating kit comprising a container body having a gas release section capable of releasing gas, a chlorite, an amino acid, and an aldehyde compound, wherein the chlorine dioxide gas generating kit is used to generate chlorine dioxide gas by mixing the aforementioned chlorite, the aforementioned amino acid, and the aforementioned aldehyde compound in a solvent within the aforementioned container body and reacting them under acidic conditions. 14. The chlorine dioxide gas generating kit according to claim 13, wherein, in the case that the aforementioned amino acid is not an acidic amino acid, a pH adjuster is further provided to make the reaction system acidic. 15. The chlorine dioxide gas generating kit according to claim 13, used for space fumigation. Claims 1 / 1 page 2 CN 121729380 A Method for generating chlorine dioxide gas Technical Field

[0001] The present invention relates to a method for generating chlorine dioxide gas.Background Art

[0002] It is known that chlorine dioxide gas is safe for animal organisms when it is at a low concentration (e.g., below 0.1 ppm). On the other hand, even at such a low concentration, it still has an inactivating effect and a deodorizing effect on microorganisms such as bacteria, fungi, and viruses.

[0003] As methods for producing chlorine dioxide, for example, methods for stably producing chlorine dioxide by comprising a composition containing dissolved chlorine dioxide gas, an aqueous solution of chlorite, and a pH adjuster are known (Patent Document 1), and methods for producing chlorine dioxide by electrolyzing an electrolyte containing chlorite (Patent Document 2).

[0004] In addition, as a method for rapidly producing chlorine dioxide gas at a predetermined time point, a method of reacting chlorite with specific bipolar molecules in a container has been proposed (Patent Document 3).

[0005] [Prior Art Documents]

[0006] [Patent Documents]

[0007] [Patent Document 1] WO2008 / 111357

[0008] [Patent Document 2] WO2009 / 154143

[0009] [Patent Document 3] WO2021 / 002262. Summary of the Invention

[0010] [Problems to be Solved by the Invention]

[0011] The method described in Patent Document 3 can be used as a method for generating chlorine dioxide gas for purposes such as fumigating a space. However, in the method described in Patent Document 3, when chlorine dioxide is rapidly generated, the reaction system emits high heat of over 100°C. Therefore, when fumigating a space in which people have been evacuated, there is a risk of thermal deterioration of equipment and accidents such as fires. In addition, the reaction vessel used in the method described in Patent Document 3 requires high thermal durability, so the materials used for the reaction vessel are also limited.

[0012] [Means for Solving the Problem]

[0013] The inventors of this application have studied a method for maintaining the temperature during the reaction at a low temperature (e.g., below 100°C) and rapidly generating chlorine dioxide gas at a predetermined time point, and thus completed the present invention.

[0014] That is, the present invention relates to a method for generating chlorine dioxide gas, which includes the following steps: reacting chlorite, amino acid, and aldehyde compound in a solvent in a container under acidic conditions.

[0015] In one embodiment of the present invention, the characteristic is that the temperature of the reaction system in the aforementioned reaction step does not rise above 100°C.

[0016] In one embodiment of the present invention, the characteristic is that the aforementioned chlorite is an alkali metal salt of chlorite or an alkaline earth metal salt of chlorite.

[0017] In one embodiment of the present invention, the aforementioned alkali metal salt of chlorite is selected from the group consisting of sodium chlorite, potassium chlorite and lithium chlorite, and the alkaline earth metal salt of chlorite is selected from the group consisting of calcium chlorite, magnesium chlorite and barium chlorite.

[0018] In one embodiment of the present invention, the concentration of chlorite in the aforementioned reaction system is 1.0 to 30.0% by weight.

[0019] In one embodiment of the present invention, the aldehyde compound comprises one or more compounds selected from the group consisting of formaldehyde, trioxymethylene, acetaldehyde, propionaldehyde, butyraldehyde, hexanal, heptanal, octanal, nonanal, decanal, acrolein, benzaldehyde, cinnamaldehyde, perillaldehyde, vanillin, glyoxal, glyceraldehyde, D-erythrose, D-threose, D-ribose, D-arabinose, D-xylose, D-lythose, D-allose, D-azoleose, D-glucose, D-mannose, D-gulose, D-idolose, D-galactose, and D-tarose.

[0020] In one embodiment of the present invention, the concentration of aldehyde compound in the aforementioned reaction system is 0.5 to 32% by weight.

[0021] In one embodiment of the present invention, the aforementioned amino acid comprises one or more amino acids selected from the group consisting of aspartic acid, glutamic acid, glycine, alanine, arginine, asparagine, glutamine, histidine, isoleucine, leucine, cysteine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine.

[0022] In one embodiment of the present invention, the concentration of the amino acid in the aforementioned reaction system is 5.0 to 23% by weight.

[0023] In one embodiment of the present invention, the concentration of chlorite in the aforementioned reaction system is 1.0 to 30.0% by weight, the concentration of the aldehyde compound is 0.5 to 32% by weight, and the concentration of the amino acid is 5.0 to 23% by weight.

[0024] In one embodiment of the present invention, the aforementioned acidic condition is pH 6 or below.

[0025] Another embodiment of the present invention relates to a fumigation method for a space, which includes the steps of applying any of the above methods in a space where no human beings are present.

[0026] Another embodiment of the present invention relates to a chlorine dioxide gas generating kit, which includes a container body with a gas release section capable of releasing gas, a chlorite, an amino acid, and an aldehyde compound, wherein the aforementioned chlorite, the aforementioned amino acid, and the aforementioned aldehyde compound are mixed in a solvent within the aforementioned container body and reacted under acidic conditions to generate chlorine dioxide gas.

[0027] In one embodiment of the present invention, if the aforementioned amino acid in the aforementioned kit is not an acidic amino acid, a pH adjuster is more preferably used to make the reaction system acidic.

[0028] In one embodiment of the present invention, the aforementioned kit is characterized in that it is used for fumigating a space.

[0029] Inventions formed by any combination of one or more features of the present invention described above are also included within the scope of the present invention.

[0030] [Effects of the Invention]

[0031] The present invention has at least one of the following advantages over conventional chlorine dioxide generation methods.

[0032] (1) High safety

[0033] According to the method of the present invention, after mixing chlorite, amino acids, and aldehyde compounds, chlorine dioxide gas is rapidly generated after a certain period of time. The generation of chlorine dioxide gas by the method of the present invention is temporary and ends in a short time. Therefore, according to the method of the present invention, a state in which no chlorine dioxide gas is generated can be achieved from the time the operator mixes the chlorite, amino acids, and aldehyde compounds until the space is evacuated. That is, according to the method of the present invention, the safety of the operator can be ensured while the space is fumigated with chlorine dioxide gas. In addition, in the method of the present invention, the temperature of the reaction system can be controlled at a low temperature. Therefore, even if the method of the present invention is implemented in a space where humans have been evacuated, the risk of thermal deterioration of equipment and fire accidents is not likely to occur.

[0034] (2) High efficiency in chlorine dioxide production

[0035] According to the method of the present invention, chlorine dioxide can be produced stably and efficiently even with a relatively simple composition (see the embodiments in this application specification).

[0036] (3) Reduced cost

[0037] According to the method of the present invention, chlorine dioxide can be rapidly produced with good efficiency using widely available, low-cost materials. In addition, in the method of the present invention, the temperature of the reaction system can be controlled at a low temperature, so generally inexpensive materials can be used as the material for the reaction vessel (expensive heat-resistant materials are not required). Therefore, products using the method of the present invention can be manufactured at a lower cost. Brief Description of the Drawings

[0038] FIG1 shows a non-limiting embodiment of the method and / or kit of the present invention.

[0039] FIG2 shows a non-limiting embodiment of the method and / or kit of the present invention.

[0040] FIG3 shows a non-limiting embodiment of the method and / or kit of the present invention. Detailed Description

[0041] The present invention relates to a method for producing chlorine dioxide gas, which includes the step of reacting chlorite, amino acid and aldehyde compound in a solvent in a container under acidic conditions. Furthermore, the present invention also relates to a chlorine dioxide gas generating kit utilizing this method for generating chlorine dioxide gas.

[0042] FIG1 shows a non-limiting embodiment of the method and / or kit of the present invention. When a predetermined amount of amino acid and aldehyde compound (B) are added to a reaction vessel 1 containing an aqueous solution of chlorite (A) of a predetermined concentration and mixed to make it acidic, chlorine dioxide gas is rapidly generated after a certain period of time, and the chlorine dioxide gas is released into the space from the opening (gas release section 2) of the reaction vessel 1.

[0043] The gas release section 2 can also be an open system, but it can also be provided with a cover having a breathable structure and a breathable non-permeable component. As a non-permeable component, for example, a breathable waterproof sheet (or a breathable waterproof sheet) that allows gas, air, and moisture to pass through but not liquid can be used. The breathable waterproof sheet can be a microporous membrane (a membrane of a material with a large number of tiny pores) used alone, or it can be a material made by overlapping and bonding multiple sheets, a material that is non-porous but allows the movement of gas, air, and moisture (water vapor), or a coated material that has been subjected to a strong water-repellent treatment on high-density fabrics. Commercially available products include, for example, GORE TEX (registered trademark), EXEPOL (registered trademark: manufactured by Mitsubishi Resin Corporation: a material with excellent breathability, moisture permeability, and waterproofness made by combining microporous polyolefin membranes with various nonwoven fabrics), ENTRANTE (registered trademark: manufactured by Toray Industries, Inc.), etc. In addition, non-permeable components should have heat-sealing properties (heat-welding properties) for easy installation in containers.

[0044] Alternatively, permeable components with air permeability can be used instead of the aforementioned non-permeable components. Permeable components can be, for example, sheets that allow gas, air, and moisture to pass through but allow liquids to pass through almost completely. Permeable components can be, for example, known nonwoven fabrics. In particular, if hydrophobic nonwoven fabrics are used, they can be expected to have almost the same performance as non-permeable components because they have water-repellent properties.

[0045] "Acidic conditions" in this disclosure may refer, for example, to pH 6 or below (specifically, the range of pH 1 to 6, pH 2 to 6, pH 3 to 6, pH 1 to 5, pH 2 to 5, pH 3 to 5, pH 1 to 4, pH 2 to 4, pH 3 to 4)).

[0046] According to the method of the present invention, after mixing chlorite, amino acids, and aldehyde compounds, chlorine dioxide gas is rapidly generated after a certain period of time. The generation of chlorine dioxide gas by the method of the present invention is temporary and ends within a short period of time. Therefore, according to the method of the present invention, a state in which no chlorine dioxide gas is generated can be achieved from the time the operator mixes the chlorite, amino acid, and aldehyde compound until it is dispersed out of the space. That is, according to the method of the present invention, the safety of the operator can be ensured while the space is fumigated with chlorine dioxide gas.

[0047] In the method of the present invention, the temperature of the reaction system will not become extremely high.That is, in the method of the present invention, on the one hand, the reactivity for rapidly generating chlorine dioxide gas can be maintained, and on the other hand, the temperature of the reaction system can be controlled at a relatively low temperature (e.g., below 100°C, below 95°C, below 90°C, below 80°C, 35°C to 100°C, 35°C to 95°C, 35°C to 90°C, 35°C to 85°C, 35°C to 80°C, 40°C to 100°C, 40°C to 95°C, 40°C to 90°C, 40°C to 85°C, 40°C to 80°C). Therefore, even if the method of the present invention is carried out in a space where humans have been evacuated, the risk of accidents such as thermal deterioration of equipment and fire is not likely to occur. In addition, in the method of the present invention, the temperature of the reaction system will not become extremely high, so a certain type of material can be used as the material for the reaction container.

[0048] The material for the reaction container that can be used in the method of the present invention can be any material as long as it is resistant to chlorite, amino acids, aldehyde compounds, and chlorine dioxide, and does not necessarily have to have high heat resistance. Non-limiting examples include: glass, stainless steel and other metals, polypropylene resin, polyethylene (low-density, high-density) resin, fluoropolymers (e.g., TEFLON (trademark)), PET resin, ABS resin, acrylic resin, polystyrene resin, polyvinyl chloride resin, polyamide (nylon) resin, urea resin, melamine resin, silicone resin, cellulose resin, and other resins.

[0049] In this invention, the chlorite that serves as the direct raw material for chlorine dioxide can be an aqueous solution of chlorite or a solid chlorite. Examples of chlorites that can be used in the method of this invention include: alkali metal salts of chlorite and alkaline earth metal salts of chlorite. Examples of alkali metal salts of chlorite include: sodium chlorite, potassium chlorite, lithium chlorite; examples of alkaline earth metal salts of chlorite include: calcium chlorite, magnesium chlorite, barium chlorite. Among these, sodium chlorite and potassium chlorite are preferred from the viewpoint of ease of use, and sodium chlorite is most preferred. These chlorite bases can be used alone or in combination of two or more.

[0050] In this invention, the concentration of chlorite in the reaction system is preferably 1.0 to 30.0% by weight. If the concentration of chlorite is less than 1.0% by weight, chlorine dioxide gas may not be rapidly generated due to insufficient reaction. If the concentration of chlorite exceeds 30.0% by weight, the temperature of the reaction system may exceed 100°C due to excessive reaction.

[0051] Considering safety, stability, and chlorine dioxide generation efficiency, the preferred range of chlorite concentration is 2.0% to 25.0% by weight, a more preferred range is 3.0% to 24.0% by weight, and a further preferred range is 4.0% to 22.0% by weight. Furthermore, the lower limit of the chlorite concentration range can be selected, for example, from 1.0% by weight, 1.5% by weight, 2.0% by weight, 2.5% by weight, 3.0% by weight, 3.5% by weight, 4.0% by weight, 4.5% by weight, and 5.0% by weight.The upper limit of the chlorite concentration range can be selected, for example, from 30.0 wt%, 29.5 wt%, 29.0 wt%, 28.5 wt%, 28.0 wt%, 27.5 wt%, 27.0 wt%, 26.5 wt%, 26.0 wt%, 25.5 wt%, 25.0 wt%, 24.5 wt%, 24.0 wt%, 23.5 wt%, 23.0 wt%, 22.5 wt%, 22.0 wt%, 21.5 wt%, 21.0 wt%, 20.5 wt%, 20.0 wt%, 19.5 wt%, 19.0 wt%, 18.5 wt%, 18.0 wt%, 17.5 wt%, 17.0 wt%, 16.5 wt%, 16.0 wt%. 15.5 wt%, 15.0 wt%, 14.5 wt%, 14.0 wt%, 13.5 wt%, 13.0 wt%, 12.5 wt%, 12.0 wt%, 11.5 wt%, 11.0 wt%, 10.5 wt%, 10.0 wt%.

[0052] In the method of the present invention, when solid chlorite is used, the solid chlorite can also be supported on a porous material. By supporting the solid chlorite on a porous material, the surface area of ​​the solid chlorite can be increased, thereby improving its contact with the solvent. Non-limiting examples of porous materials include: sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, pearlite, and calcium silicate. Specification 4 / 14 Page 6 CN 121729380 A

[0053] The term "aldehyde compound" in this disclosure may refer to a compound having an -CHO (aldehyde group or formyl group) in its molecule (general formula: R-CHO). Various commercially available aldehyde compounds can be used in the method of this invention. Examples of aldehyde compounds that can be used in the method of this invention include: sugars (aldehyde sugars) having an aldehyde group, aliphatic aldehydes, and aromatic aldehydes. Non-limiting examples of aldehyde sugars include: D-glyceraldehyde, D-erythrose, D-threose, D-ribose, D-arabinose, D-xylose, D-lythose, D-aloose, D-azoleose, D-glucose, D-mannose, D-gulose, D-idolose, D-galactose, and D-tarose. Non-limiting examples of aliphatic aldehydes include: formaldehyde, trioxymethylene, acetaldehyde, propionaldehyde, butyraldehyde, hexanal, heptanal, octanal, nonanal, decanal, acrolein, and glyoxal. Non-limiting examples of aromatic aldehydes include: benzaldehyde, cinnamaldehyde, perillaldehyde, and vanillin.

[0054] In this invention, the concentration of the aldehyde compound in the reaction system is preferably 0.5% to 32.0% by weight. If the concentration of the aldehyde compound is less than 0.5% by weight, chlorine dioxide gas may not be generated rapidly due to insufficient reaction. If the concentration of the aldehyde compound exceeds 32.0% by weight, an appropriate reaction may not occur due to the presence of an excess of aldehyde compound.

[0055] Considering safety, stability, and the efficiency of chlorine dioxide production, the preferred concentration range of the aldehyde compound is 0.5 wt% to 30.0 wt%, a more preferred range is 1.0 wt% to 25.0 wt%, and a still preferred range is 1.5 wt% to 22.0 wt%. Furthermore, the lower limit of the concentration range of the aldehyde compound can be selected, for example, from 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, and 5.0 wt%. The upper limit of the concentration range of the aldehyde compound can be selected, for example, from 32.0 wt%, 31.5 wt%, 31.0 wt%, 30.5 wt%, 30.0 wt%, 29.5 wt%, 29.0 wt%, 28.5 wt%, 28.0 wt%, 27.5 wt%, 27.0 wt%, 26.5 wt%, 26.0 wt%, 25.5 wt%, 25.0 wt%, 24.5 wt%, 24.0 wt%, 23.5 wt%, 23.0 wt%, 22.5 wt%, 22.0 wt%, 21.5 wt%, 21.0 wt%, 20.5 wt%, 20.0 wt%.

[0056] In the method of the present invention, various commercially available amino acids, such as amino acids that exist in nature (natural amino acids) or amino acids that do not exist in nature (non-natural amino acids) produced by chemical synthesis, can be used. In the method of the present invention, especially from the viewpoint of ease of acquisition, natural amino acids constituting organisms (e.g., aspartic acid, glutamic acid, glycine, alanine, arginine, asparagine, glutamine, histidine, isoleucine, leucine, cysteine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine) can be used.

[0057] In the present invention, the concentration of amino acids in the reaction system is preferably 5.0 to 23.0% by weight. If the concentration of amino acids is less than 5.0% by weight, chlorine dioxide gas may not be generated rapidly due to insufficient reaction. If the concentration of amino acids exceeds 23.0% by weight, an appropriate reaction may not occur due to the presence of excess amino acids.

[0058] Considering safety, stability, and the efficiency of chlorine dioxide generation, the preferred concentration range of amino acids is 6.0% by weight to 22.0% by weight, a more preferred range is 7.0% by weight to 21.0% by weight, and a further preferred range is 8.0% by weight to 20.0% by weight. In addition, the lower limit of the concentration range of amino acids can be selected, for example, from 5.0 wt%, 5.5 wt%, 6.0 wt%, 6.5 wt%, 7.0 wt%, 7.5 wt%, and 8.0 wt%.The upper limit of the concentration range of amino acids can be selected, for example, from 23.0 wt%, 22.5 wt%, 22.0 wt%, 21.5 wt%, 21.0 wt%, 20.5 wt%, 20.0 wt%, 19.5 wt%, 19.0 wt%, 18.5 wt%, 18.0 wt%, 17.5 wt%, 17.0 wt%, 16.5 wt%, 16.0 wt%, 15.5 wt%, 15.0 wt%.

[0059] The method of the present invention includes the step of reacting each compound under acidic conditions. In the case of using acidic amino acids (e.g., aspartic acid, glutamic acid) in the method of the present invention, the mixture becomes acidic due to the acidic amino acids, so it is not necessary to use a pH adjuster. In the case of using amino acids other than acidic amino acids in the method of the present invention, a pH adjuster may be used to make the mixture acidic. As a pH adjuster, there is no limitation as long as it can make the mixture of chlorite, amino acid and aldehyde compound into an acidic pH adjuster. Examples include: hydrochloric acid, sulfuric acid, sulfurous acid, thiosulfate, nitric acid, nitrous acid, iodic acid, phosphoric acid, alkali metal salts of dihydrogen phosphate (sodium salt, potassium salt, etc.), phosphorous acid, sodium bisulfate, potassium bisulfate, chromic acid and other inorganic acids, as well as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, pyruvic acid, citric acid, malic acid, tartaric acid, gluconic acid, glycolic acid, fumaric acid, malonic acid, maleic acid, oxalic acid, succinic acid, acrylic acid, crotonic acid, oxalic acid, glutaric acid and other organic acids.

[0060] In the method of the present invention, a superabsorbent polymer (SAP) may also be added to the mixture of aldehyde compound, amino acid and chlorite. By adding the superabsorbent polymer, the solution can be solidified and easily discarded after use. Examples of superabsorbent resins include: polycarboxylate resins, polyacrylate resins, carboxymethyl cellulose resins, polysulfonate resins, polyacrylamide resins, polyvinyl alcohol resins, polyoxyethylene resins, etc., but are not limited to these. Commercially available superabsorbent resins include, for example, SUNWET (trademark), SUNFRESH (trademark) (manufactured by Sanyo Chemical Co., Ltd.), AQUALIC CA (trademark), AQUALIC CS (trademark), ACRYHOPE (trademark) (manufactured by Nippon Catalyst Co., Ltd.), AQUKEEP (trademark) (manufactured by Sumitomo Seika Co., Ltd.), SUNROSE (trademark) (manufactured by Nippon Paper Co., Ltd.), AQUA COKE (trademark) (manufactured by Sumitomo Seika Co., Ltd.), etc., but are not limited to these.

[0061] FIG2 shows a non-limiting embodiment of the method and / or kit of the present invention. In the example shown in FIG2, the aqueous solution of chlorite (A), amino acid and aldehyde compound (B) are respectively contained in the reaction container 1 in a non-contact state.When using an amino acid other than an acidic amino acid as the amino acid, a pH adjuster may also be included to make the mixture acidic.

[0062] The aqueous chlorite solution (A) is further contained in a fragile container 3 within the reaction vessel 1. If an external force is applied to the reaction vessel 1 at a predetermined time, the fragile container 3 is destroyed, causing the aqueous chlorite solution (A), the amino acid and the aldehyde compound (B) to mix with a pH adjuster as appropriate. Then, after a certain time, chlorine dioxide gas is rapidly generated and released into the space from the opening (gas release section 2) of the reaction vessel 1.

[0063] FIG3 shows a non-limiting embodiment of the method and / or kit of the present invention. In the example shown in FIG3, the solid chlorite (A'), the amino acid and the aldehyde compound (B) are contained in the reaction vessel 1 in a contact state or a non-contact state. When using an amino acid other than an acidic amino acid as the amino acid, a pH adjuster may also be included to make the mixture acidic.

[0064] If solvent 4 (e.g., water) is added to reaction vessel 1 at the expected time point and stirred, chlorite (A'), amino acid and aldehyde compound (B), and a pH adjuster as appropriate are mixed. Then, after a certain time, chlorine dioxide gas is rapidly generated and released into the space from the opening (gas release section 2) of reaction vessel 1.

[0065] The terms used in this specification are used to describe specific embodiments and are not intended to limit the invention.

[0066] In addition, the term "comprising" as used in this specification means, except where it is obvious from the context that a different interpretation is warranted, the presence of the described items (components, steps, elements, or numbers, etc.) and does not exclude the presence of other items (components, steps, elements, or numbers, etc.).

[0067] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as widely understood by those skilled in the art to which this invention pertains. The terms used herein, unless otherwise explicitly defined, shall be interpreted as having an integrated meaning with the meaning in this specification and related technical fields, and shall not be interpreted in an idealized or excessive manner.

[0068] Embodiments of the present invention are illustrated with reference to schematic diagrams, but sometimes the diagrams are exaggerated for clarity.

[0069] In this specification, for example, when it is stated as "1 to 10 w / w%, those skilled in the art will understand that the statement on page 6 / 14 of the specification CN 121729380 A specifically refers to 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 w / w%.

[0070] In this specification, all values ​​used to indicate the content and range of ingredients, unless otherwise explicitly stated, shall be interpreted as including the meaning of the term "about".For example, the so-called "10 times" is understood to mean "approximately 10 times" unless otherwise explicitly stated.

[0071] The references cited in this specification should be considered as all disclosures thereof being incorporated into this specification. Those skilled in the art, based on the context of this specification, shall incorporate the relevant disclosures in these prior art documents as part of this specification without departing from the spirit and scope of the invention.

[0072] [Examples]

[0073] 1. Materials

[0074] An aqueous solution of sodium chlorite is prepared as an example of chlorite. L-aspartic acid (acidic amino acid), L-glutamic acid (acidic amino acid), L-asparagine monohydrate and L-glutamine are prepared as examples of amino acids. Vanillin, trioxymethylene, benzaldehyde, glucose, galactose and xylose are prepared as examples of aldehyde compounds. Citric acid is prepared as a pH adjuster.

[0075] 2. Experimental Methods

[0076] As shown in Tables 1 and 2 below, amino acids and aldehyde compounds were added to an aqueous solution of chlorite in a container to verify the rapid generation time of chlorine dioxide gas (the time from the addition of amino acids and aldehyde compounds to the start of rapid generation of chlorine dioxide gas) and the reaction temperature (Examples 1-14). In addition, when the amino acid used was not an acidic amino acid (aspartic acid, glutamic acid), citric acid was further added as a pH adjuster to make the pH of the mixture acidic.

[0077] Table 1 Specification 7 / 14 pages 9 CN 121729380 A

[0078]

[0079] Table 2 Specification 8 / 14 pages 10 CN 121729380 A

[0080]

[0081] In addition, comparative examples 1-5, which lack the components of the present invention, were also verified.

[0082] • Comparative Example 1: An example formed by mixing only acidic amino acids and chlorite (aldehyde-free compound)

[0083] • Comparative Example 2: An example formed by mixing only aldehyde compound (vanillin) and chlorite (amino acid-free)

[0084] • Comparative Example 3: An example formed by mixing only aldehyde compound (vanillin), citric acid, and chlorite (amino acid-free)

[0085] • Comparative Example 4: An example formed by mixing only aldehyde compound (glucose), citric acid, and chlorite (amino acid-free)

[0086] • Comparative Example 5: An example in which the concentration of the aqueous chlorite solution in Comparative Example 4 was increased to 10%

[0087] Table 3 Specification 9 / 14 pages 11 CN 121729380 A

[0088]

[0089] 3. Results

[0090] In any of Examples 1-14, the reaction temperature was kept at a low temperature while chlorine dioxide gas was rapidly generated. On the other hand, chlorine dioxide gas was not rapidly generated in Comparative Examples 1-5.

[0091] From the above results, it can be seen that in order to maintain the reaction temperature at a low temperature on the one hand and to rapidly generate chlorine dioxide gas on the other, aldehyde compounds, amino acids, and chlorites are all necessary. In addition, under the condition of the absence of amino acids, even if the concentration of chlorites increases, chlorine dioxide gas will not be rapidly generated.

[0092] 4. Additional Experiment I (Various Amino Acids)

[0093] As shown in Table 4, the present invention can be carried out using various amino acids.

[0094] Table 4 Specification 10 / 14 pages 12 CN 121729380 A

[0095]

[0096] 5. Additional Experiment II (Various Aldehyde Compounds)

[0097] As shown in Table 5, the present invention can be carried out using various aldehyde compounds.

[0098] Table 5 Specification 11 / 14 pages 13 CN 121729380 A

[0099]

[0100] 6. Additional Experiment III (Addition of Superabsorbent Polymer (SAP))

[0101] The addition of superabsorbent polymer (SAP) to the basic composition of the present invention (aldehyde compound, amino acid, chlorite) was further verified. AQUALIC CA (trademark) (Japanese catalyst, trade name: A361 and H2) as a polyacrylic acid-polyacrylic acid Na-based superabsorbent polymer was used as SAP. As shown in Tables 6 and 7, the present invention can be carried out even with the addition of superabsorbent polymer.

[0102] Table 6 Specification 12 / 14 pages 14 CN 121729380 A

[0103]

[0104] Table 7

[0105]

[0106] Explanation of reference numerals

[0107] A chlorite aqueous solution

[0108] A' solid chlorite

[0109] B Amino acid and aldehyde compound specification 13 / 14 pages 15 CN 121729380 A

[0110] 1 Reaction container

[0111] 2 Gas release section

[0112] 3 Easily destructible container

[0113] 4 Solvent. Instruction manual 14 / 14 pages 16 CN 121729380 A Figure 1 Instruction manual drawing 1 / 3 pages 17 CN 121729380 A Figure 2 Instruction manual drawing 2 / 3 pages 18 CN 121729380 A Figure 3 Instruction manual drawing 3 / 3 pages 19 CN 121729380 A.

Claims

1. A method for generating chlorine dioxide gas, comprising the following steps: reacting chlorite, amino acid, and aldehyde compound under acidic conditions in a solvent within a container.

2. The method for generating chlorine dioxide gas according to claim 1, wherein, The temperature of the reaction system in the aforementioned reaction steps does not rise above 100°C.

3. The method for generating chlorine dioxide gas according to claim 1, wherein, The aforementioned chlorites are alkali metal salts or alkaline earth metal salts of chlorites.

4. The method for generating chlorine dioxide gas according to claim 3, wherein, The aforementioned alkali metal chlorites are selected from the group consisting of sodium chlorite, potassium chlorite, and lithium chlorite; Alkaline earth metal salts of chlorite are selected from the group consisting of calcium chlorite, magnesium chlorite, and barium chlorite.

5. The method for generating chlorine dioxide gas according to claim 1, wherein, The concentration of chlorite in the aforementioned reaction system is 1.0 to 30.0 by weight.

6. The method for generating chlorine dioxide gas according to claim 1, wherein, The aforementioned aldehyde compounds include one or more compounds selected from the group consisting of formaldehyde, trioxymethylene, acetaldehyde, propionaldehyde, butyraldehyde, hexanal, heptanal, octanal, nonanal, decanal, acrolein, benzaldehyde, cinnamaldehyde, perillaldehyde, vanillin, glyoxal, glyceraldehyde, D-erythrose, D-threose, D-ribose, D-arabinose, D-xylose, D-lythose, D-aloose, D-aloose, D-glucose, D-mannose, D-gulose, D-iduroose, D-galactose, and D-tarose.

7. The method for generating chlorine dioxide gas according to claim 1, wherein, The concentration of the aldehyde compound in the aforementioned reaction system is 0.5 to 32 by weight.

8. The method for generating chlorine dioxide gas according to claim 1, wherein, The aforementioned amino acids are selected from one or more amino acids in the group consisting of aspartic acid, glutamic acid, glycine, alanine, arginine, asparagine, glutamine, histidine, isoleucine, leucine, cysteine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine.

9. The method for generating chlorine dioxide gas according to claim 1, wherein, The concentration of amino acids in the aforementioned reaction system is 5.0 to 23 by weight.

10. The method for generating chlorine dioxide gas according to claim 1, wherein, In the aforementioned reaction system, the concentration of chlorite is 1.0 to 30.0 wt%, the concentration of aldehyde compound is 0.5 to 32 wt%, and the concentration of amino acid is 5.0 to 23 wt%.

11. The method for generating chlorine dioxide gas according to claim 1, wherein, The aforementioned acidic conditions refer to a pH level below 6.

12. A method for fumigating a space in which the method for generating chlorine dioxide gas according to claim 1 is applied in a space where no human beings are present.

13. A chlorine dioxide gas generating assembly comprising a container body having a gas release section capable of releasing gas, chlorite, amino acids, and an aldehyde compound. The chlorine dioxide gas generating assembly is formed by mixing the aforementioned chlorite, amino acid, and aldehyde compound in a solvent within the aforementioned container body and reacting them under acidic conditions to generate chlorine dioxide gas.

14. The chlorine dioxide gas generating assembly according to claim 13, wherein, In the case of the aforementioned non-acidic amino acids, a pH adjuster is more readily available to make the reaction system acidic.

15. The chlorine dioxide gas generating kit according to claim 13, used for space fumigation.

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