Method for generating chlorine dioxide gas

Abstract

[Problem] To provide a method for rapidly generating a chlorine dioxide gas at a desired timing while keeping the temperature at the time of reaction low.　[Solution] A method for generating a chlorine dioxide gas, comprising a step for reacting chlorite, an amino acid, and an aldehyde compound under acidic conditions in a solvent inside a container.

Description

How to generate chlorine dioxide gas

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

[0002] Chlorine dioxide gas is a gas that is safe for living animals at low concentrations (for example, 0.1 ppm or less), and even at such low concentrations, it is known to have deactivating effects on microorganisms such as bacteria, fungi, and viruses, as well as deodorizing effects.

[0003] Known methods for generating chlorine dioxide include, for example, a method of stably generating chlorine dioxide using a composition containing dissolved chlorine dioxide gas, a chlorite aqueous solution, and a pH adjuster (Patent Document 1), and a method of producing chlorine dioxide by electrolyzing an electrolyte solution containing chlorite (Patent Document 2).

[0004] Furthermore, as a method for rapidly generating chlorine dioxide gas at a desired timing, a method has been proposed in which chlorite is reacted with a specific dipolar molecule in a container (Patent Document 3).

[0005] WO2008 / 111357WO2009 / 154143WO2021 / 002262

[0006] The method described in Patent Document 3 is useful as a method for generating chlorine dioxide gas for purposes such as fumigating a space. However, in the method described in Patent Document 3, the reaction system generates high heat of 100°C or more when chlorine dioxide is rapidly generated. Therefore, when fumigating a space in which people have evacuated, there is a risk of accidents such as thermal degradation of equipment or fire. Furthermore, the reaction vessel used in the method described in Patent Document 3 is required to have high thermal durability, so the material for the reaction vessel is also limited.

[0007] The present inventors have investigated a method for rapidly generating chlorine dioxide gas at a desired timing while maintaining a low reaction temperature (for example, 100°C or lower), and have completed the present invention.

[0008] That is, the present invention relates to a method for generating chlorine dioxide gas, which comprises the step of reacting a chlorite, an amino acid, and an aldehyde compound in a solvent in a container under acidic conditions.

[0009] In one embodiment of the present invention, the temperature of the reaction system in the reaction step does not rise above 100°C.

[0010] In one embodiment of the present invention, the chlorite is an alkali metal chlorite or an alkaline earth metal chlorite.

[0011] In one embodiment of the present invention, the alkali metal chlorite is selected from the group consisting of sodium chlorite, potassium chlorite, and lithium chlorite, and the alkaline earth metal chlorite is selected from the group consisting of calcium chlorite, magnesium chlorite, and barium chlorite.

[0012] In one embodiment of the present invention, the concentration of chlorite in the reaction system is 1.0 to 30.0% by weight.

[0013] In one embodiment of the present invention, the aldehyde compound includes one or more compounds selected from the group consisting of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butanal, hexanal, heptanal, octanal, nonanal, decanal, acrolein, benzaldehyde, cinnamaldehyde, perillaldehyde, vanillin, glyoxal, glyceraldehyde, D-erythrose, D-threose, D-ribose, D-arabinose, D-xylose, D-lyxose, D-allose, D-altrose, D-glucose, D-mannose, D-gulose, D-idose, D-galactose, and D-talose.

[0014] In one embodiment of the present invention, the concentration of the aldehyde compound in the reaction system is 0.5 to 32% by weight.

[0015] In one embodiment of the present invention, the amino acids include 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.

[0016] In one embodiment of the present invention, the concentration of the amino acid in the reaction system is 5.0 to 23% by weight.

[0017] In one embodiment of the present invention, the reaction system is characterized in that the concentration of the chlorite is 1.0 to 30.0 wt %, the concentration of the aldehyde compound is 0.5 to 32 wt %, and the concentration of the amino acid is 5.0 to 23 wt %.

[0018] In one embodiment of the present invention, the acidic conditions are pH 6 or less.

[0019] Another embodiment of the present invention relates to a method of fumigating a space, comprising applying any of the methods described above in the space where no humans are present.

[0020] Another embodiment of the present invention relates to a kit for generating chlorine dioxide gas, which includes a container body having a gas release portion capable of releasing gas, a chlorite, an amino acid, and an aldehyde compound, in which the chlorite, the amino acid, and the aldehyde compound are mixed in a solvent within the container body and reacted under acidic conditions to generate chlorine dioxide gas.

[0021] In one embodiment of the present invention, when the amino acid in the kit is not an acidic amino acid, the kit further comprises a pH adjuster for making the reaction system acidic.

[0022] In one embodiment of the present invention, the kit is for fumigating a space.

[0023] Any combination of one or more of the features of the present invention described above is also included within the scope of the present invention.

[0024] The present invention has at least one or more of the following advantages over conventional chlorine dioxide generation methods.

[0025] (1) High Safety According to the method of the present invention, rapid generation of chlorine dioxide gas begins after a certain time has elapsed after mixing chlorite, an amino acid, and an aldehyde compound. The generation of chlorine dioxide gas by the method of the present invention is transient and ceases in a short time. Therefore, according to the method of the present invention, no chlorine dioxide gas is generated from the time when the worker mixes chlorite, an amino acid, and an aldehyde compound until the worker evacuates the space. That is, according to the method of the present invention, fumigation of a space with chlorine dioxide gas can be performed while ensuring the safety of the worker. Furthermore, according to the method of the present invention, the temperature of the reaction system can be controlled to a relatively low temperature. Therefore, even if the method of the present invention is carried out in a space where people have evacuated, there is little risk of accidents such as thermal denaturation of equipment or fire.

[0026] (2) High Efficiency of Chlorine Dioxide Generation According to the method of the present invention, chlorine dioxide can be generated stably and highly efficiently, despite the relatively simple configuration (see the Examples in the present specification).

[0027] (3) Cost Reduction According to the method of the present invention, chlorine dioxide can be generated efficiently and rapidly using widely available, relatively inexpensive materials. Furthermore, since the temperature of the reaction system can be controlled to a relatively low temperature in the method of the present invention, common, inexpensive materials can be used as the material for the reaction vessel (expensive heat-resistant materials are not required). Therefore, products produced using the method of the present invention can be produced relatively inexpensively.

[0028] Figure 1 illustrates a non-limiting embodiment of a method and / or kit of the present invention. Figure 2 illustrates a non-limiting embodiment of a method and / or kit of the present invention. Figure 3 illustrates a non-limiting embodiment of a method and / or kit of the present invention.

[0029] The present invention relates to a method for generating chlorine dioxide gas, which comprises a step of reacting a chlorite, an amino acid, and an aldehyde compound under acidic conditions in a solvent in a container. The present invention also relates to a kit for generating chlorine dioxide gas that utilizes the method for generating chlorine dioxide gas.

[0030] 1 shows a non-limiting embodiment of the method and kit of the present invention. When a predetermined amount of an amino acid and an aldehyde compound (B) are added to and mixed with a reaction vessel 1 containing a chlorite aqueous solution (A) of a predetermined concentration and the mixture is made acidic, chlorine dioxide gas is rapidly generated after a certain period of time and is released into space from an opening (gas release part 2) of the reaction vessel 1.

[0031] The gas release section 2 may be an open system, but it may also be provided with a lid having a breathable structure or a breathable, water-impermeable material. Examples of water-impermeable materials include a moisture-permeable waterproof sheet (or a breathable waterproof sheet) that allows gas, air, and moisture to pass through but not liquid. The moisture-permeable waterproof sheet may be a microporous film (a film made of a material with many very small pores) used alone, or a laminate of multiple sheets, a non-porous material that allows the movement of gas, air, and moisture (water vapor), or a high-density woven fabric coated with a strong water-repellent treatment. Examples of commercially available materials include Gore-Tex (registered trademark), Excelpol (registered trademark: manufactured by Mitsubishi Plastics, Inc.; a material that combines a microporous polyolefin film with various nonwoven fabrics, etc., and has excellent breathability, moisture permeability, and waterproof properties), and Entrant E (registered trademark, manufactured by Toray Industries, Inc.). It is desirable for the water-impermeable material to have heat-sealing properties (thermal welding) to facilitate attachment to the container.

[0032] Furthermore, instead of the non-permeable material described above, a breathable, water-impermeable material may be used. The water-impermeable material may be, for example, a sheet that allows gas, air, and moisture to pass through but is almost impermeable to liquids. For example, a known nonwoven fabric can be used as the water-impermeable material. In particular, if a hydrophobic nonwoven fabric is used, it has a water-repellent effect, and therefore performance almost equivalent to that of the non-permeable material can be expected.

[0033] In the present disclosure, "acidic conditions" may mean, for example, a pH of 6 or lower (specifically, a 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, or pH 3 to 4).

[0034] According to the method of the present invention, after mixing chlorite, amino acid, and aldehyde compound, rapid generation of chlorine dioxide gas begins after a certain time has elapsed. The generation of chlorine dioxide gas by the method of the present invention is transient and ends in a short time. Therefore, according to the method of the present invention, no chlorine dioxide gas is generated from the time when the worker mixes chlorite, amino acid, and aldehyde compound until he evacuates to the outside of the space. In other words, according to the method of the present invention, the space can be fumigated with chlorine dioxide gas while ensuring the safety of the worker.

[0035] In the method of the present invention, the temperature of the reaction system does not reach extremely high temperatures. That is, in the method of the present invention, the temperature of the reaction system can be controlled to a relatively low temperature (e.g., 100°C or less, 95°C or less, 90°C or less, 80°C or less, 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) while maintaining the reactivity required for rapid generation of chlorine dioxide gas. Therefore, even if the method of the present invention is carried out in a space where people have evacuated, there is little risk of accidents such as thermal denaturation of equipment or fire. Furthermore, because the temperature of the reaction system does not reach extremely high temperatures in the method of the present invention, commonly used materials can be used for the reaction vessel.

[0036] The material of the reaction vessel that can be used in the method of the present invention may be various materials as long as they are resistant to chlorite, amino acids, aldehyde compounds, and chlorine dioxide, and do not necessarily have to be highly heat-resistant. Non-limiting examples include glass, metals such as stainless steel, polypropylene resin, polyethylene (low-density / high-density) resin, fluororesin (e.g., Teflon™), PET resin, ABS resin, acrylic resin, polystyrene resin, polyvinyl chloride resin, polyamide (nylon) resin, urea resin, melamine resin, silicone resin, and cellulose-based resin.

[0037] In the present invention, the chlorite that is the direct raw material for chlorine dioxide may be a chlorite aqueous solution or a solid chlorite.The chlorite that can be used in the method of the present invention includes, for example, alkali metal chlorite and alkaline earth metal chlorite.The alkali metal chlorite includes, for example, sodium chlorite, potassium chlorite, and lithium chlorite, and the alkaline earth metal chlorite includes, for example, calcium chlorite, magnesium chlorite, and barium chlorite.Among them, sodium chlorite and potassium chlorite are preferred from the viewpoint of easy availability, and sodium chlorite is most preferred.These alkali chlorites may be used alone or in combination of two or more.

[0038] In the present 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, the rapid generation of chlorine dioxide gas may not occur due to insufficient reaction, while if the concentration of chlorite exceeds 30.0% by weight, the temperature of the reaction system may exceed 100°C due to excessive reaction.

[0039] Considering safety, stability, chlorine dioxide generation efficiency, etc., the preferred range of chlorite is 2.0 wt% to 25.0 wt%, more preferably 3.0 wt% to 24.0 wt%, and even more preferably 4.0 wt% to 22.0 wt%. The lower limit of the chlorite concentration range may be selected from, for example, 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 chlorite concentration range is, for example, 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%.

[0040] When using solid chlorite in the method of the present invention, the solid chlorite can 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, and the contactability when mixed with a solvent can be improved.Non-limiting examples of the porous material can include sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, perlite, and calcium silicate.

[0041] In the present disclosure, "aldehyde compound" may refer to a compound having -CHO (aldehyde group or formyl group) in the molecule (general formula: R-CHO). Various commercially available aldehyde compounds can be used in the method of the present invention. Examples of aldehyde compounds that can be used in the method of the present invention include sugars having an aldehyde group (aldoses), aliphatic aldehydes, and aromatic aldehydes. Non-limiting examples of aldoses include D-glyceraldehyde, D-erythrose, D-threose, D-ribose, D-arabinose, D-xylose, D-lyxose, D-allose, D-altrose, D-glucose, D-mannose, D-gulose, D-idose, D-galactose, and D-talose. Non-limiting examples of aliphatic aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butanal, hexanal, heptanal, octanal, nonanal, decanal, acrolein, and glyoxal. Non-limiting examples of aromatic aldehydes include benzaldehyde, cinnamaldehyde, perillaldehyde, and vanillin.

[0042] In the present 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, the rapid generation of chlorine dioxide gas may not occur due to insufficient reaction, while if the concentration of the aldehyde compound exceeds 32.0% by weight, the presence of an excessive amount of the aldehyde compound may prevent the appropriate reaction.

[0043] Considering safety, stability, chlorine dioxide generation efficiency, etc., the concentration of the aldehyde compound is preferably in the range of 0.5 wt % to 30.0 wt %, more preferably 1.0 wt % to 25.0 wt %, and even more preferably 1.5 wt % to 22.0 wt %. The lower limit of the concentration range of the aldehyde compound may be selected from, for example, 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 may be selected from, for example, 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 %, and 20.0 wt %.

[0044] In the method of the present invention, various commercially available amino acids can be used, such as amino acids that exist in nature (natural amino acids) and amino acids that do not exist in nature (unnatural amino acids) that are produced by chemical synthesis, etc. In particular, from the viewpoint of ease of availability, natural amino acids that constitute living organisms (e.g., aspartic acid, glutamic acid, glycine, alanine, arginine, asparagine, glutamine, histidine, isoleucine, leucine, cysteine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine) may be used in the method of the present invention.

[0045] In the present invention, the concentration of the amino acid in the reaction system is preferably 5.0 to 23.0% by weight. If the concentration of the amino acid is less than 5.0% by weight, the rapid generation of chlorine dioxide gas may not occur due to insufficient reaction, while if the concentration of the amino acid is more than 23.0% by weight, the presence of an excess amount of amino acid may prevent the appropriate reaction.

[0046] Considering safety, stability, chlorine dioxide generation efficiency, etc., the amino acid concentration range is preferably 6.0 wt % to 22.0 wt %, more preferably 7.0 wt % to 21.0 wt %, and even more preferably 8.0 wt % to 20.0 wt %. The lower limit of the amino acid concentration range may be selected from, for example, 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 amino acid concentration range may be selected from, for example, 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%, and 15.0 wt%.

[0047] The method of the present invention includes a step of reacting each compound under acidic conditions. When an acidic amino acid (e.g., aspartic acid, glutamic acid) is used in the method of the present invention, the mixture is acidic due to the acidic amino acid, so the use of a pH adjuster is not necessarily required. When an amino acid other than an acidic amino acid is used in the method of the present invention, a pH adjuster may be used to acidify the mixture. The pH adjuster is not limited as long as it can acidify the mixture of chlorite, amino acid, and aldehyde compound. Examples of pH adjusters include inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, thiosulfuric acid, nitric acid, nitrous acid, iodic acid, phosphoric acid, alkali dihydrogen phosphate salts (e.g., sodium salt, potassium salt), phosphorous acid, sodium hydrogen sulfate, potassium hydrogen sulfate, and chromic acid, and organic acids such 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, and glutaric acid.

[0048] In the method of the present invention, a superabsorbent polymer (SAP) may be further added to the mixture of the aldehyde compound, amino acid, and chlorite. Adding the superabsorbent polymer solidifies the solution, facilitating disposal after use. Examples of superabsorbent polymers include, but are not limited to, polycarboxylate-based resins, polyacrylate-based resins, carboxymethyl cellulose-based resins, polysulfonate-based resins, polyacrylamide-based resins, polyvinyl alcohol-based resins, and polyoxyethylene-based resins. Commercially available superabsorbent polymers include, but are not limited to, Sanwet™ and Sunfresh™ (all manufactured by Sanyo Chemical Industries, Ltd.), Aqualic CA™, Aqualic CS™, and Acrihope™ (all manufactured by Nippon Shokubai Co., Ltd.), Aquakeep™ (manufactured by Sumitomo Seika Chemicals Co., Ltd.), Sunrose™ (manufactured by Nippon Paper Industries Co., Ltd.), and Aquacork™ (manufactured by Sumitomo Seika Chemicals Co., Ltd.).

[0049] Figure 2 shows a non-limiting embodiment of the method and kit of the present invention. In the example shown in Figure 2, an aqueous chlorite solution (A), an amino acid, and an aldehyde compound (B) are contained in a reaction vessel 1 without contact with each other. When an amino acid other than an acidic amino acid is used as the amino acid, a pH adjuster for making the mixture acidic may be further contained.

[0050] The chlorite aqueous solution (A) is further contained in a breakable container 3 within the reaction vessel 1. When an external force is applied to the reaction vessel 1 at a desired timing, the breakable container 3 is broken, and the chlorite aqueous solution (A), the amino acid, the aldehyde compound (B), and optionally a pH adjuster are mixed together. Then, after a certain time, chlorine dioxide gas is rapidly generated and released into the space from an opening (gas release part 2) of the reaction vessel 1.

[0051] Figure 3 shows a non-limiting embodiment of the method and kit of the present invention. In the example shown in Figure 3, a solid chlorite (A'), an amino acid, and an aldehyde compound (B) are contained in a reaction vessel 1 in a contact or non-contact state. When an amino acid other than an acidic amino acid is used as the amino acid, a pH adjuster for making the mixture acidic may be further contained.

[0052] When a solvent 4 (e.g., water) is added to the reaction vessel 1 at a desired timing and stirred, the chlorite (A'), the amino acid, the aldehyde compound (B), and optionally a pH adjuster are mixed together. After a certain time, chlorine dioxide gas is rapidly generated and released into the space from the opening (gas release part 2) of the reaction vessel 1.

[0053] The terms used in this specification are used to describe particular embodiments and are not intended to limit the invention.

[0054] Furthermore, the term "comprise" used in this specification intends that the stated items (components, steps, elements, or numbers, etc.) are present, unless the context clearly dictates otherwise, and does not exclude the presence of other items (components, steps, elements, or numbers, etc.).

[0055] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by a person skilled in the art to which this invention belongs. Terms used herein should be interpreted as having a meaning consistent with the meaning in this specification and the related technical field, and should not be interpreted in an idealized or overly formal sense, unless otherwise defined.

[0056] Embodiments of the present invention may be described with reference to schematic diagrams, in which the elements may be exaggerated for clarity of illustration.

[0057] In the present specification, for example, when it is expressed as "1 to 10 w / w %", a person skilled in the art will understand that the expression individually and specifically refers to 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 w / w %.

[0058] In this specification, all numerical values ​​used to indicate component contents or numerical ranges are interpreted as including the meaning of the term "about" unless otherwise specified. For example, "10 times" is understood to mean "about 10 times" unless otherwise specified.

[0059] The entire disclosures of the documents cited in this specification should be considered to be incorporated herein by reference, and a person skilled in the art would understand that, in accordance with the context of this specification, the relevant disclosure contents of those prior art documents are incorporated as part of this specification without departing from the spirit and scope of the present invention.

[0060] 1. Materials: A sodium chlorite solution was prepared as an example of a chlorite salt. L-aspartic acid (an acidic amino acid), L-glutamic acid (an acidic amino acid), L-asparagine monohydrate, and L-glutamine were prepared as examples of amino acids. Vanillin, paraformaldehyde, benzaldehyde, glucose, galactose, and xylose were prepared as examples of aldehyde compounds. Citric acid was prepared as a pH adjuster.

[0061] 2. Experimental Method As shown in Tables 1 and 2 below, an amino acid and an aldehyde compound were added to a chlorite aqueous solution in a container, and the rapid generation time of chlorine dioxide gas (the time from adding the amino acid and the aldehyde compound to the chlorite aqueous solution to the start of the rapid generation of chlorine dioxide gas) and the reaction temperature were investigated (Examples 1-14). Note that when the amino acid used was other than 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.

[0062] Table 1

[0063] Table 2

[0064] The following Comparative Examples 1 to 5, in which some of the configurations of the present invention were omitted, were also examined. Comparative Example 1: An example in which only an acidic amino acid and chlorite were mixed (no aldehyde compound) Comparative Example 2: An example in which only an aldehyde compound (vanillin) and chlorite were mixed (no amino acid) Comparative Example 3: An example in which only an aldehyde compound (vanillin), citric acid, and chlorite were mixed (no amino acid) Comparative Example 4: An example in which only an aldehyde compound (glucose), citric acid, and chlorite were mixed (no amino acid) Comparative Example 5: An example in which the concentration of the chlorite aqueous solution in Comparative Example 4 was increased to 10%

[0065] Table 3

[0066] 3. Results In all of Examples 1 to 14, rapid generation of chlorine dioxide gas occurred while the reaction temperature was kept low. On the other hand, in Comparative Example 1 to 5, rapid generation of chlorine dioxide gas did not occur.

[0067] From the above results, it was confirmed that in order to rapidly generate chlorine dioxide gas while maintaining a low reaction temperature, all of the aldehyde compound, amino acid, and chlorite are necessary. Furthermore, it was confirmed that in the absence of amino acid, the rapid generation of chlorine dioxide gas does not occur even if the concentration of chlorite is increased.

[0068] 4. Additional Experiment I (Various Types of Amino Acids) As shown in Table 4, the present invention could be carried out using various types of amino acids.

[0069] Table 4

[0070] 5. Additional Experiment II (Various Types of Aldehyde Compounds) As shown in Table 5, the present invention could be carried out using various aldehyde compounds.

[0071] Table 5

[0072] 6. Additional Experiment III (Addition of Super Absorbent Polymer (SAP)) The addition of a super absorbent polymer (SAP) to the basic components of the present invention (aldehyde compound, amino acid, chlorite) was investigated. Aqualic CA (trademark) (Nippon Shokubai, product names: A361 and H2), a polyacrylic acid-sodium polyacrylate-based super absorbent polymer, was used as the SAP. As shown in Tables 6 and 7, the present invention could be carried out even when a super absorbent polymer was added.

[0073] Table 6

[0074] Table 7

[0075] Explanation of symbols A: chlorite aqueous solution A': solid chlorite B: amino acid and aldehyde compound 1: reaction vessel 2: gas release part 3: easily breakable vessel 4: solvent

Claims

1. A method for generating chlorine dioxide gas, comprising the step of reacting a chlorite salt, an amino acid, and an aldehyde compound under acidic conditions in a solvent in a container.

2. The method according to claim 1, wherein the temperature of the reaction system in the reaction step does not rise above 100°C.

3. The method of claim 1, wherein the chlorite is an alkali metal chlorite or an alkaline earth metal chlorite.

4. The method of claim 3, wherein the alkali metal chlorite is selected from the group consisting of sodium chlorite, potassium chlorite, and lithium chlorite, and the alkaline earth metal chlorite is selected from the group consisting of calcium chlorite, magnesium chlorite, and barium chlorite.

5. The method according to claim 1, wherein the concentration of chlorite in the reaction system is 1.0 to 30.0% by weight.

6. The method of claim 1, wherein the aldehyde compound comprises one or more compounds selected from the group consisting of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butanal, hexanal, heptanal, octanal, nonanal, decanal, acrolein, benzaldehyde, cinnamaldehyde, perillaldehyde, vanillin, glyoxal, glyceraldehyde, D-erythrose, D-threose, D-ribose, D-arabinose, D-xylose, D-lyxose, D-allose, D-altrose, D-glucose, D-mannose, D-gulose, D-idose, D-galactose, and D-talose.

7. The method according to claim 1, wherein the concentration of the aldehyde compound in the reaction system is 0.5 to 32% by weight.

8. The method of claim 1, wherein the amino acids comprise 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 according to claim 1, wherein the concentration of the amino acid in the reaction system is 5.0 to 23% by weight.

10. The method according to claim 1, wherein in the reaction system, the concentration of the 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 of claim 1, wherein the acidic conditions are pH 6 or less.

12. A method of fumigating a space, comprising applying the method of claim 1 in the space free of human presence.

13. A kit for generating chlorine dioxide gas comprising a container body having a gas release portion capable of releasing gas, a chlorite, an amino acid, and an aldehyde compound, wherein the chlorite, the amino acid, and the aldehyde compound are mixed in a solvent within the container body and reacted under acidic conditions to generate chlorine dioxide gas.

14. The kit according to claim 13, further comprising a pH adjuster for making the reaction system acidic when the amino acid is not an acidic amino acid.

15. The kit according to claim 13, for fumigating an air space.

Images