WO2020090538A1 - Chlorine dioxide generator - Google Patents

Chlorine dioxide generator Download PDF

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Publication number
WO2020090538A1
WO2020090538A1 PCT/JP2019/041276 JP2019041276W WO2020090538A1 WO 2020090538 A1 WO2020090538 A1 WO 2020090538A1 JP 2019041276 W JP2019041276 W JP 2019041276W WO 2020090538 A1 WO2020090538 A1 WO 2020090538A1
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Prior art keywords
chlorine dioxide
catalyst
chlorite
aqueous solution
air
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PCT/JP2019/041276
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French (fr)
Japanese (ja)
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翔平 辻本
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大幸薬品株式会社
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Priority to CN201980059166.1A priority Critical patent/CN112672770A/en
Priority to KR1020217007121A priority patent/KR20210082433A/en
Priority to JP2020553796A priority patent/JP7401103B2/en
Publication of WO2020090538A1 publication Critical patent/WO2020090538A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/022—Chlorine dioxide (ClO2)
    • C01B11/023—Preparation from chlorites or chlorates
    • C01B11/024—Preparation from chlorites or chlorates from chlorites
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A61L9/04—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
    • A61L9/12—Apparatus, e.g. holders, therefor
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/14—Disinfection, sterilisation or deodorisation of air using sprayed or atomised substances including air-liquid contact processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2209/00—Aspects relating to disinfection, sterilisation or deodorisation of air
    • A61L2209/10—Apparatus features
    • A61L2209/13—Dispensing or storing means for active compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2209/00—Aspects relating to disinfection, sterilisation or deodorisation of air
    • A61L2209/20—Method-related aspects
    • A61L2209/21—Use of chemical compounds for treating air or the like

Definitions

  • the present invention relates to a novel chlorine dioxide generator.
  • Chlorine dioxide gas is a gas that is safe for living organisms of animals at low concentrations (for example, 0.1 ppm or less), but even at such low concentrations, it has an inactivating effect on microorganisms such as bacteria, fungi, and viruses. It is known to have a deodorizing effect and the like.
  • Patent Document 1 a method for stably generating chlorine dioxide with a composition containing a dissolved chlorine dioxide gas, an aqueous chlorite solution, and a pH adjusting agent
  • Patent Document 2 a method for producing chlorine dioxide by electrolyzing an electrolytic solution containing an acid salt
  • Patent Document 3 a device for generating chlorine dioxide by irradiating solid chlorite with visible light has been proposed.
  • the present invention has an object to provide a device which has a simpler structure and can stably generate chlorine dioxide for a long period of time as compared with a conventional chlorine dioxide generator.
  • the present invention is, in one embodiment, a chlorine dioxide generator including a bubbling mechanism
  • the apparatus includes a reaction vessel and an air introduction device,
  • the reaction vessel contains an aqueous chlorite solution and a catalyst,
  • the reaction container and the air introduction device are connected by a conduit,
  • air is bubbled through the aqueous chlorite solution in the reaction vessel, and the bubbling air is configured to come into contact with the catalyst.
  • the chlorine dioxide concentration contained in the air discharged from the device when the device is continuously operated for two weeks is included in the air discharged from the device when the device is continuously operated for one week. It is characterized by being maintained at least 50% or more as compared with the chlorine dioxide concentration.
  • the reaction vessel is at least partially opened, and the air containing chlorine dioxide produced in the reaction vessel is discharged to the outside of the apparatus. It is characterized by being done.
  • An embodiment of the present invention is characterized by not including an electrolysis mechanism.
  • the aqueous chlorite solution is an aqueous solution of alkali metal chlorite or an aqueous solution of alkaline earth metal chlorite.
  • the aqueous solution of alkali metal chlorite is an aqueous solution of sodium chlorite, an aqueous solution of potassium chlorite, or an aqueous solution of lithium chlorite, and an aqueous solution of alkaline earth metal chlorite.
  • the concentration of the aqueous chlorite solution is 0.01 to 45% by weight.
  • the catalyst is a solid catalyst.
  • One embodiment of the present invention is characterized in that the catalyst is a metal-based catalyst, a mineral-based catalyst, a carbon-based catalyst, or a combination thereof.
  • the metal catalyst is platinum (Pt), ruthenium (Rh), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), copper. (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo), or a compound containing these metals, wherein the mineral-based catalyst is silica (Si), or A compound containing silica, wherein the carbon-based catalyst is a catalyst containing activated carbon, Is characterized in that.
  • the catalyst is supported on a carrier.
  • the carrier is a carrier containing a material selected from the group consisting of titanium, valve metal, stainless steel, nickel, ceramics, carbon, and a porous substance.
  • the air introduction device is a device that introduces air into the flow path from the starting point of the flow path of the chlorine dioxide generation device, or from the end point of the flow path of the chlorine dioxide generation device.
  • the air introduction device is an electric air pump.
  • the present invention has at least one or more of the following advantages over the conventional chlorine dioxide generation method / generation device.
  • the present invention utilizes the generation of chlorine dioxide due to the reaction between a chlorite and a catalyst. With this technique, It has been confirmed that there is almost no risk that a large amount of chlorine dioxide will be generated due to a rapid reaction, and that no harmful gas other than chlorine dioxide gas will be generated.Therefore, an acidic substance is added to chlorite to add chlorine dioxide.
  • the safety is higher than that of the method of generating and the method of using electrolysis (for example, when chlorine dioxide is generated by electrolysis, chlorine gas or hydrogen gas may be generated when the electrolytic solution deteriorates). Further, since the power of the device of the present invention is only the air introduction device, the risk of device failure is low, and repairs when the device fails are easy.
  • the present invention stably generates chlorine dioxide for at least 2 weeks or more (preferably 3 weeks or more, more preferably 1 month or more) without maintenance, despite the simple structure. You can Further, when the chlorite aqueous solution reaches the end of its life, it is possible to continue the operation of the apparatus simply by exchanging the chlorite aqueous solution.
  • the present invention has an extremely simple structure as compared with, for example, a chlorine dioxide generation device by electrolysis, it is possible to reduce the size and cost of the device.
  • FIG. 1 shows a design example of the present invention.
  • FIG. 2 shows the result of Experiment 1 (amount of chlorine dioxide generated).
  • FIG. 3 shows the result of Experiment 2 (qualitative analysis of generated gas).
  • FIG. 4 shows the results of Experiment 3.
  • the chlorine dioxide generation device according to one embodiment of the present invention shown in FIG. 1 includes an air introduction device 1 and a reaction container 3, and the reaction container 3 includes an aqueous chlorite solution 4 and a catalyst 5.
  • the air introducing device 1 and the reaction container 3 are connected by a conduit 2.
  • chlorine dioxide is produced by the reaction between the aqueous chlorite solution 4 and the catalyst 5.
  • the air introducing device 1 operates, the air provided through the conduit 2 is bubbled into the reaction vessel 3 to stir the chlorite aqueous solution 4 and the catalyst 5.
  • the aqueous chlorite solution 4 and the catalyst 5 are stirred by bubbling, chlorine dioxide produced on the surface of the catalyst 5 is released from the catalyst surface, and chlorine dioxide is produced again on the surface of the catalyst 5.
  • Chlorine dioxide liberated by bubbling is discharged to the outside of the apparatus together with air from a conduit 2'provided in the upper part of the reaction vessel 3.
  • the chlorine dioxide generator of the present invention shown in FIG. 1 is produced by accelerating the reaction between the aqueous chlorite solution 4 and the catalyst 5 by providing a bubbling mechanism centered on the air introduction device 1. Chlorine dioxide can be released outside the device.
  • the present invention can be embodied in various aspects and should not be construed as being limited to the design examples described herein. ..
  • the size and shape of the device can be optimized by variously changing the arrangement of the containers and conduits that make up the device.
  • Examples of the chlorite used in the present invention include alkali metal chlorite and alkaline earth metal chlorite.
  • alkali metal chlorite examples include sodium chlorite, potassium chlorite, and lithium chlorite
  • examples of the alkaline earth metal chlorite include calcium chlorite, magnesium chlorite, and hypochlorite. Examples include barium chlorate.
  • sodium chlorite / potassium chlorite is preferable, and sodium chlorite is most preferable, from the viewpoint of easy availability.
  • These chlorite oxygen alkalis may be used alone or in combination of two or more.
  • the proportion of alkali chlorite in the aqueous chlorite solution is preferably 0.01% by weight to 45% by weight.
  • a preferable range is 0.1% by weight to 25% by weight, a more preferable range is 1% by weight to 20% by weight, and a further preferable range. Is 2 to 15%.
  • the catalyst used in the apparatus of the present invention is not limited as long as it is a catalyst that reacts with an aqueous solution of chlorite to generate chlorine dioxide, but is required to be separated from the aqueous solution of chlorite at the time of stopping the reaction, and thus solid. It is preferably a catalyst (or a heterogeneous catalyst).
  • solid catalysts that can be used in the device of the present invention include metal catalysts (for example, platinum (Pt), ruthenium (Rh), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron.
  • a mineral catalyst for example, silica (Si), or , A compound containing silica
  • a carbon-based catalyst for example, a catalyst containing activated carbon
  • the catalyst used in the apparatus of the present invention may be used alone, or may be supported on a carrier in order to improve the reaction efficiency between the aqueous chlorite solution and the catalyst.
  • the carrier on which the catalyst is carried is not limited as long as it contributes to the improvement of the reaction efficiency between the chlorite aqueous solution and the catalyst, but, for example, titanium, valve metal, stainless steel, nickel, ceramics, carbon, and a porous material, It is preferred that the carrier comprises a material selected from the group consisting of:
  • the air introduction device used in the device of the present invention is not limited as long as it can move the air or the chlorite aqueous solution in the flow path of the device in one direction, but is, for example, an electric air pump. Good. Electricity may be supplied to the electric air pump from a power supply device via a power cable, or a battery may be used.
  • the air introduction device used in the device of the present invention can be installed at various positions as long as the air or the chlorite aqueous solution in the flow path of the device can be moved in one direction.
  • an air introducing device may be installed at the starting point of the flow path to introduce air into the flow path, or an air introducing device may be installed in the middle of the flow path to move the air in the flow path in one direction.
  • the air introducing device may be installed at the end point of the flow path, and the air in the flow path of the device or the chlorite aqueous solution may be moved in one direction by sucking the air in the flow path. Good.
  • the gas introduced into the flow path in the apparatus by the air introduction apparatus is typically air, but an inert gas such as nitrogen or argon may be used.
  • the chlorine dioxide generator of the present invention may further include a blower fan for discharging the chlorine dioxide gas generated in the device to the outside of the device.
  • a blower fan for discharging the chlorine dioxide gas generated in the device to the outside of the device.
  • the chlorine dioxide gas outside the device is diffused further by strengthening the air volume of the blower fan, and when the amount of chlorine dioxide gas generated is relatively small, By preventing the chlorine dioxide gas outside the device from unnecessarily diffusing by weakening the air volume of the blower fan, it is possible to adjust the chlorine dioxide gas concentration outside the device to fall within a certain range.
  • Fig. 2 shows the comparison of chlorine dioxide generation under both conditions. As shown in FIG. 2, chlorine dioxide was generated under the condition of using the catalyst, but chlorine dioxide was not generated under the condition of not using the catalyst. That is, it was confirmed that a catalyst is required to generate chlorine dioxide in the device of the present invention.
  • the present invention can stably generate chlorine dioxide for a long period of time in spite of the extremely simple structure as compared with the conventional chlorine dioxide generator.

Abstract

[Problem] The present invention addresses the problem of providing an apparatus capable of stably generating chlorine dioxide for a long period of time, with a simpler configuration, as compared with a conventional chlorine dioxide generator. [Solution] Provided is a novel chlorine dioxide generator utilizing the reaction between a chlorite aqueous solution and a catalyst.

Description

二酸化塩素発生装置Chlorine dioxide generator
　本発明は、新規な二酸化塩素発生装置に関する。 The present invention relates to a novel chlorine dioxide generator.
　二酸化塩素ガスは、低濃度（例えば、０．１ｐｐｍ以下）では動物の生体に対して安全なガスである一方、そのような低濃度でも、細菌・真菌・ウイルス等の微生物に対する失活作用や、消臭作用等を有していることが知られている。 Chlorine dioxide gas is a gas that is safe for living organisms of animals at low concentrations (for example, 0.1 ppm or less), but even at such low concentrations, it has an inactivating effect on microorganisms such as bacteria, fungi, and viruses. It is known to have a deodorizing effect and the like.
　二酸化塩素の発生方法としては、例えば、溶存二酸化塩素ガス、亜塩素酸塩水溶液、および、ｐＨ調整剤を含む組成物により、安定的に二酸化塩素を発生させる方法（特許文献１）や、亜塩素酸塩を含有する電解液を電気分解して二酸化塩素を製造する方法が知られている（特許文献２）。 As a method for generating chlorine dioxide, for example, a method for stably generating chlorine dioxide with a composition containing a dissolved chlorine dioxide gas, an aqueous chlorite solution, and a pH adjusting agent (Patent Document 1), and chlorine dioxide A method for producing chlorine dioxide by electrolyzing an electrolytic solution containing an acid salt is known (Patent Document 2).
　また、近年、固形の亜塩素酸塩に可視光を照射することによって二酸化塩素を発生させる装置も提案されている（特許文献３） Also, in recent years, a device for generating chlorine dioxide by irradiating solid chlorite with visible light has been proposed (Patent Document 3).
ＷＯ／２００８／１１１３５７WO / 2008/111357 ＷＯ／２００９／１５４１４３WO / 2009/154143 ＷＯ／２０１５／０９８７３２WO / 2015/098732.
　本発明は、従来の二酸化塩素発生装置と比較して、より簡易な構成で、長期間安定して二酸化塩素を発生させることができる装置を提供することを課題とした。 The present invention has an object to provide a device which has a simpler structure and can stably generate chlorine dioxide for a long period of time as compared with a conventional chlorine dioxide generator.
　本発明者らは、鋭意研究を重ねた結果、亜塩素酸塩水溶液と触媒との反応による二酸化塩素発生メカニズムを利用した、新規な二酸化塩素発生装置の開発に成功し、本発明を完成させるに到った。 As a result of intensive studies, the present inventors have succeeded in developing a new chlorine dioxide generator utilizing the chlorine dioxide generation mechanism by the reaction between an aqueous chlorite solution and a catalyst, and to complete the present invention. Arrived
　すなわち本発明は、一実施形態は、バブリング機構を備えた二酸化塩素発生装置であって、
　前記装置は、反応用容器と空気導入装置とを含み、
　前記反応用容器は、亜塩素酸塩水溶液と触媒とを含み、
　前記反応用容器と前記空気導入装置とは導管によって接続されており、
　前記空気導入装置の作動時に、前記反応用容器中の亜塩素酸塩水溶液に空気がバブリングされ、バブリングされる空気が前記触媒に接触するように構成されており、
　前記装置を２週間継続して作動させた時点において前記装置から放出される空気に含まれる二酸化塩素濃度が、前記装置を１週間継続して作動させた時点において前記装置から放出される空気に含まれる二酸化塩素濃度と比較して、少なくとも５０％以上維持されることを特徴とする。 That is, the present invention is, in one embodiment, a chlorine dioxide generator including a bubbling mechanism,
The apparatus includes a reaction vessel and an air introduction device,
The reaction vessel contains an aqueous chlorite solution and a catalyst,
The reaction container and the air introduction device are connected by a conduit,
At the time of operation of the air introducing device, air is bubbled through the aqueous chlorite solution in the reaction vessel, and the bubbling air is configured to come into contact with the catalyst.
The chlorine dioxide concentration contained in the air discharged from the device when the device is continuously operated for two weeks is included in the air discharged from the device when the device is continuously operated for one week. It is characterized by being maintained at least 50% or more as compared with the chlorine dioxide concentration.
　本発明の一実施形態においては、前記反応用容器は、少なくとも部分的に開放されており、前記反応用容器内で生成された二酸化塩素を含む空気が前記装置の外部へ放出されるように構成されることを特徴とする。 In an embodiment of the present invention, the reaction vessel is at least partially opened, and the air containing chlorine dioxide produced in the reaction vessel is discharged to the outside of the apparatus. It is characterized by being done.
　本発明の一実施形態においては、電気分解機構を含まないことを特徴とする。 An embodiment of the present invention is characterized by not including an electrolysis mechanism.
　本発明の一実施形態においては、前記亜塩素酸塩水溶液が、亜塩素酸アルカリ金属塩水溶液または亜塩素酸アルカリ土類金属塩水溶液であることを特徴とする。 In one embodiment of the present invention, the aqueous chlorite solution is an aqueous solution of alkali metal chlorite or an aqueous solution of alkaline earth metal chlorite.
　本発明の一実施形態においては、前記亜塩素酸アルカリ金属塩水溶液が、亜塩素酸ナトリウム水溶液、亜塩素酸カリウム水溶液、または、亜塩素酸リチウム水溶液であり、亜塩素酸アルカリ土類金属塩水溶液が、亜塩素酸カルシウム水溶液、亜塩素酸マグネシウム水溶液、または、亜塩素酸バリウム水溶液であることを特徴とする。 In an embodiment of the present invention, the aqueous solution of alkali metal chlorite is an aqueous solution of sodium chlorite, an aqueous solution of potassium chlorite, or an aqueous solution of lithium chlorite, and an aqueous solution of alkaline earth metal chlorite. Is a calcium chlorite aqueous solution, a magnesium chlorite aqueous solution, or a barium chlorite aqueous solution.
　本発明の一実施形態においては、前記亜塩素酸塩水溶液の濃度が０．０１～４５重量％であることを特徴とする。 In one embodiment of the present invention, the concentration of the aqueous chlorite solution is 0.01 to 45% by weight.
　本発明の一実施形態においては、前記触媒が、固体触媒であることを特徴とする。 In one embodiment of the present invention, the catalyst is a solid catalyst.
　本発明の一実施形態においては、前記触媒が、金属系触媒、鉱物系触媒、炭素系触媒、または、これらの組み合わせであることを特徴とする。 One embodiment of the present invention is characterized in that the catalyst is a metal-based catalyst, a mineral-based catalyst, a carbon-based catalyst, or a combination thereof.
　本発明の一実施形態においては、前記金属触媒が、白金（Ｐｔ）、ルテニウム（Ｒｈ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、イリジウム（Ｉｒ）、オスミウム（Ｏｓ）、鉄（Ｆｅ）、銅（Ｃｕ）、マンガン（Ｍｎ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、モリブデン（Ｍｏ）、または、これらの金属の化合物、を含む触媒であり、前記鉱物系触媒が、シリカ（Ｓｉ）、または、シリカを含む化合物、を含む触媒であり、前記炭素系触媒が、活性炭を含む触媒、
であることを特徴とする。 In one embodiment of the present invention, the metal catalyst is platinum (Pt), ruthenium (Rh), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), copper. (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo), or a compound containing these metals, wherein the mineral-based catalyst is silica (Si), or A compound containing silica, wherein the carbon-based catalyst is a catalyst containing activated carbon,
Is characterized in that.
　本発明の一実施形態においては、前記触媒が、担体に担持されていることを特徴とする。 In one embodiment of the present invention, the catalyst is supported on a carrier.
　本発明の一実施形態においては、前記担体が、チタン、バルブ金属、ステンレス、ニッケル、セラミックス、炭素、および、多孔質物質からなる群から選択される材料を含む担体であることを特徴とする。 In one embodiment of the present invention, the carrier is a carrier containing a material selected from the group consisting of titanium, valve metal, stainless steel, nickel, ceramics, carbon, and a porous substance.
　本発明の一実施形態においては、前記空気導入装置が、前記二酸化塩素発生装置の流路の始点から前記流路内へ空気を導入する装置、または、前記二酸化塩素発生装置の流路の終点から前記流路内の空気を吸引する装置、であることを特徴とする。 In one embodiment of the present invention, the air introduction device is a device that introduces air into the flow path from the starting point of the flow path of the chlorine dioxide generation device, or from the end point of the flow path of the chlorine dioxide generation device. A device for sucking air in the flow path.
　本発明の一実施形態においては、前記空気導入装置が、電動式のエアポンプであることを特徴とする。 In one embodiment of the present invention, the air introduction device is an electric air pump.
　上記に挙げた本発明の一又は複数の特徴を任意に組みわせた発明も、本発明の範囲に含まれる。 An invention in which one or more features of the present invention described above are arbitrarily combined is also included in the scope of the present invention.
　本発明は、従来の二酸化塩素発生方法／発生装置に対して、少なくとも以下の１つ以上の利点を有する。 The present invention has at least one or more of the following advantages over the conventional chlorine dioxide generation method / generation device.
（１）安全性、耐久性の向上
　本発明は、亜塩素酸塩と触媒との反応による二酸化塩素の発生を利用する。この手法では、
急激な反応により大量の二酸化塩素が発生するリスクがほとんどなく、また、二酸化塩素ガス以外の有害ガスが発生しないことが確認されているため、亜塩素酸塩に酸性物質を添加して二酸化塩素を発生させる手法や、電気分解を用いる手法と比較して安全性が高い（例えば、電気分解による二酸化塩素発生においては、電解液が劣化すると塩素ガスや水素ガス等が発生し得る）。また、本発明の装置の動力は空気導入装置のみであるため、装置の故障のリスクが低く、また、装置が故障した場合の修繕も容易である。 (1) Improvement of safety and durability The present invention utilizes the generation of chlorine dioxide due to the reaction between a chlorite and a catalyst. With this technique,
It has been confirmed that there is almost no risk that a large amount of chlorine dioxide will be generated due to a rapid reaction, and that no harmful gas other than chlorine dioxide gas will be generated.Therefore, an acidic substance is added to chlorite to add chlorine dioxide. The safety is higher than that of the method of generating and the method of using electrolysis (for example, when chlorine dioxide is generated by electrolysis, chlorine gas or hydrogen gas may be generated when the electrolytic solution deteriorates). Further, since the power of the device of the present invention is only the air introduction device, the risk of device failure is low, and repairs when the device fails are easy.
（２）メンテナンスフリー
　本発明は、簡素な構造にも関わらず、少なくとも２週間以上（好ましくは３週間以上、より好ましくは１カ月以上）に渡ってメンテナンスなしで安定的に二酸化塩素を発生させることができる。また、亜塩素酸塩水溶液が寿命に達したときは、亜塩素酸塩水溶液を交換するだけで装置の稼働を継続することができる。 (2) Maintenance-free The present invention stably generates chlorine dioxide for at least 2 weeks or more (preferably 3 weeks or more, more preferably 1 month or more) without maintenance, despite the simple structure. You can Further, when the chlorite aqueous solution reaches the end of its life, it is possible to continue the operation of the apparatus simply by exchanging the chlorite aqueous solution.
（３）小型化、コストダウン
　本発明は、例えば電気分解による二酸化塩素発生装置等と比較して極めて簡素な構造であるため、装置の小型化やコストダウンが可能である。 (3) Miniaturization and cost reduction Since the present invention has an extremely simple structure as compared with, for example, a chlorine dioxide generation device by electrolysis, it is possible to reduce the size and cost of the device.
図１は、本発明の設計例を示す。FIG. 1 shows a design example of the present invention. 図２は、実験１の結果（二酸化塩素の発生量）を示す。FIG. 2 shows the result of Experiment 1 (amount of chlorine dioxide generated). 図３は、実験２の結果（発生ガスの定性分析）を示す。FIG. 3 shows the result of Experiment 2 (qualitative analysis of generated gas). 図４は、実験３の結果を示す。FIG. 4 shows the results of Experiment 3.
　本発明を実施するための形態を、図１に示す設計例を用いて説明する。 A mode for carrying out the present invention will be described using a design example shown in FIG.
設計例
　図１に示す本発明の一実施形態に係る二酸化塩素発生装置は、空気導入装置１と反応用容器３とを備え、反応用容器３は亜塩素酸塩水溶液４および触媒５を含む。空気導入装置１と反応用容器３とは、導管２によって接続されている。 Design Example The chlorine dioxide generation device according to one embodiment of the present invention shown in FIG. 1 includes an air introduction device 1 and a reaction container 3, and the reaction container 3 includes an aqueous chlorite solution 4 and a catalyst 5. The air introducing device 1 and the reaction container 3 are connected by a conduit 2.
　反応用容器３においては、亜塩素酸塩水溶液４と触媒５との反応により、二酸化塩素が生成される。空気導入装置１が作動すると、導管２を介して提供される空気が反応用容器３中にバブリングされ、亜塩素酸塩水溶液４および触媒５を撹拌する。バブリングによって亜塩素酸塩水溶液４と触媒５とが撹拌されると、触媒５の表面で生成された二酸化塩素が触媒表面から遊離し、再び触媒５の表面で二酸化塩素が生成される。バブリングによって遊離した二酸化塩素は、反応用容器３の上部に設けられた導管２’から、空気とともに装置外へ放出される。 In the reaction container 3, chlorine dioxide is produced by the reaction between the aqueous chlorite solution 4 and the catalyst 5. When the air introducing device 1 operates, the air provided through the conduit 2 is bubbled into the reaction vessel 3 to stir the chlorite aqueous solution 4 and the catalyst 5. When the aqueous chlorite solution 4 and the catalyst 5 are stirred by bubbling, chlorine dioxide produced on the surface of the catalyst 5 is released from the catalyst surface, and chlorine dioxide is produced again on the surface of the catalyst 5. Chlorine dioxide liberated by bubbling is discharged to the outside of the apparatus together with air from a conduit 2'provided in the upper part of the reaction vessel 3.
　すなわち、図１に示す本発明の二酸化塩素発生装置は、空気導入装置１を中心とするバブリング機構を備えることにより、亜塩素酸塩水溶液４と触媒５との反応を促進させつつ、生成された二酸化塩素を装置外へ放出することができる。 That is, the chlorine dioxide generator of the present invention shown in FIG. 1 is produced by accelerating the reaction between the aqueous chlorite solution 4 and the catalyst 5 by providing a bubbling mechanism centered on the air introduction device 1. Chlorine dioxide can be released outside the device.
　以上において、設計例を参照して本発明の内容を説明したが、本発明はいろいろな態様により具現化することができ、ここに記載される設計例に限定されるものとして解釈されてはならない。例えば、本発明の一実施形態においては、装置を構成する容器や導管の配置を様々に変更することによって、装置の大きさや形状を最適化することができる。 Although the contents of the present invention have been described above with reference to the design examples, the present invention can be embodied in various aspects and should not be construed as being limited to the design examples described herein. .. For example, in one embodiment of the present invention, the size and shape of the device can be optimized by variously changing the arrangement of the containers and conduits that make up the device.
　本発明で使用される亜塩素酸塩としては、例えば亜塩素酸アルカリ金属塩や亜塩素酸アルカリ土類金属塩が挙げられる。亜塩素酸アルカリ金属塩としては、例えば亜塩素酸ナトリウム・亜塩素酸カリウム・亜塩素酸リチウムが挙げられ、亜塩素酸アルカリ土類金属塩としては、亜塩素酸カルシウム・亜塩素酸マグネシウム・亜塩素酸バリウムが挙げられる。なかでも、入手が容易という点から、亜塩素酸ナトリウム・亜塩素酸カリウムが好ましく、亜塩素酸ナトリウムが最も好ましい。これら亜塩素酸素アルカリは１種を単独で用いてもよいし、２種以上を併用しても構わない。亜塩素酸塩水溶液における亜塩素酸アルカリの割合は、０．０１重量％～４５重量％であることが好ましい。０．０１重量％未満の場合は、二酸化塩素の発生に必要な亜塩素酸塩が短期間で枯渇する可能性があり、４５重量％を超える場合は、亜塩素酸塩が飽和して結晶が析出しやすいという問題が生じる可能性がある。安全性や安定性、二酸化塩素の発生効率などを鑑みた場合、好ましい範囲は、０．１重量％～２５重量％であり、より好ましい範囲は１重量％～２０重量％であり、さらに好ましい範囲は２～１５％である。 Examples of the chlorite used in the present invention include alkali metal chlorite and alkaline earth metal chlorite. Examples of the alkali metal chlorite include sodium chlorite, potassium chlorite, and lithium chlorite, and examples of the alkaline earth metal chlorite include calcium chlorite, magnesium chlorite, and hypochlorite. Examples include barium chlorate. Among them, sodium chlorite / potassium chlorite is preferable, and sodium chlorite is most preferable, from the viewpoint of easy availability. These chlorite oxygen alkalis may be used alone or in combination of two or more. The proportion of alkali chlorite in the aqueous chlorite solution is preferably 0.01% by weight to 45% by weight. If it is less than 0.01% by weight, the chlorite necessary for generating chlorine dioxide may be depleted in a short period of time, and if it exceeds 45% by weight, the chlorite is saturated and crystals are formed. The problem of easy precipitation may occur. In view of safety, stability, generation efficiency of chlorine dioxide, etc., a preferable range is 0.1% by weight to 25% by weight, a more preferable range is 1% by weight to 20% by weight, and a further preferable range. Is 2 to 15%.
　本発明の装置において用いる触媒は、亜塩素酸塩水溶液と反応して二酸化塩素を発生させる触媒であれば限定されないが、反応停止時において亜塩素酸塩水溶液と分離される必要があるため、固体触媒（または、不均一系触媒）であることが好ましい。本発明の装置に用い得る固体触媒の例としては、金属触媒（例えば、白金（Ｐｔ）、ルテニウム（Ｒｈ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、イリジウム（Ｉｒ）、オスミウム（Ｏｓ）、鉄（Ｆｅ）、銅（Ｃｕ）、マンガン（Ｍｎ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、モリブデン（Ｍｏ）、または、これらの金属の化合物）、鉱物系触媒（例えば、シリカ（Ｓｉ）、または、シリカを含む化合物）、炭素系触媒（例えば、活性炭を含む触媒）が挙げられる。 The catalyst used in the apparatus of the present invention is not limited as long as it is a catalyst that reacts with an aqueous solution of chlorite to generate chlorine dioxide, but is required to be separated from the aqueous solution of chlorite at the time of stopping the reaction, and thus solid. It is preferably a catalyst (or a heterogeneous catalyst). Examples of solid catalysts that can be used in the device of the present invention include metal catalysts (for example, platinum (Pt), ruthenium (Rh), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron. (Fe), copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo), or a compound of these metals), a mineral catalyst (for example, silica (Si), or , A compound containing silica), and a carbon-based catalyst (for example, a catalyst containing activated carbon).
　本発明の装置において用いる触媒は、単独で用いられてもよいが、亜塩素酸塩水溶液と触媒との反応効率を向上させるために、担体に担持されたものを用いてもよい。触媒が担持される担体は、亜塩素酸塩水溶液と触媒との反応効率の向上に寄与する限り限定されないが、例えば、チタン、バルブ金属、ステンレス、ニッケル、セラミックス、炭素、および、多孔質物質、からなる群から選択される材料を含む担体であることが好ましい。 The catalyst used in the apparatus of the present invention may be used alone, or may be supported on a carrier in order to improve the reaction efficiency between the aqueous chlorite solution and the catalyst. The carrier on which the catalyst is carried is not limited as long as it contributes to the improvement of the reaction efficiency between the chlorite aqueous solution and the catalyst, but, for example, titanium, valve metal, stainless steel, nickel, ceramics, carbon, and a porous material, It is preferred that the carrier comprises a material selected from the group consisting of:
　本発明の装置において用いられる空気導入装置は、装置の流路中の空気または亜塩素酸塩水溶液を一方向に移動させることができるものであれば限定されないが、例えば電動式のエアポンプであってよい。電動式のエアポンプへの電気の供給は、電力ケーブルを介して電力供給装置から行ってもよいし、電池を利用してもよい。 The air introduction device used in the device of the present invention is not limited as long as it can move the air or the chlorite aqueous solution in the flow path of the device in one direction, but is, for example, an electric air pump. Good. Electricity may be supplied to the electric air pump from a power supply device via a power cable, or a battery may be used.
　本発明の装置において用いられる空気導入装置は、装置の流路中の空気または亜塩素酸塩水溶液を一方向に移動させることができる限り、様々な位置に設置することができる。例えば、空気導入装置を流路の始点に設置して、流路内へ空気を導入してもよく、空気導入装置を流路の途中に設置して、流路内の空気を一方向に移動させてもよく、空気導入装置を流路の終点に設置して、流路内の空気を吸引することにより、装置の流路中の空気または亜塩素酸塩水溶液を一方向に移動させてもよい。 The air introduction device used in the device of the present invention can be installed at various positions as long as the air or the chlorite aqueous solution in the flow path of the device can be moved in one direction. For example, an air introducing device may be installed at the starting point of the flow path to introduce air into the flow path, or an air introducing device may be installed in the middle of the flow path to move the air in the flow path in one direction. The air introducing device may be installed at the end point of the flow path, and the air in the flow path of the device or the chlorite aqueous solution may be moved in one direction by sucking the air in the flow path. Good.
　本発明の装置において、空気導入装置によって装置内の流路に導入されるガスは、典型的には空気であるが、例えば、窒素やアルゴン等の不活性化ガスを用いてもよい。 In the apparatus of the present invention, the gas introduced into the flow path in the apparatus by the air introduction apparatus is typically air, but an inert gas such as nitrogen or argon may be used.
　本発明の二酸化塩素発生装置は、装置において発生した二酸化塩素ガスを装置の外へと放出するための送風ファンをさらに備えてもよい。送風ファンを備えることによって、装置内で発生した二酸化塩素ガスを効率よく装置外へと送り出すことができ、また、ファンの風量を調節することによって、装置外へと送り出す二酸化塩素ガスの量を調節することもできる。例えば、二酸化塩素ガスの発生量が比較的多い場合は、送風ファンの風量を強めることによって装置外の二酸化塩素ガスをより遠くへ拡散させ、二酸化塩素ガスの発生量が比較的少ない場合には、送風ファンの風量を弱めることによって装置外の二酸化塩素ガスが必要以上に拡散されることを防ぐことにより、装置外の二酸化塩素ガス濃度が一定の範囲内に収まるように調節することができる。 The chlorine dioxide generator of the present invention may further include a blower fan for discharging the chlorine dioxide gas generated in the device to the outside of the device. By installing a blower fan, chlorine dioxide gas generated inside the device can be efficiently sent out of the device, and by adjusting the fan air volume, the amount of chlorine dioxide gas sent out of the device can be adjusted. You can also do it. For example, when the amount of chlorine dioxide gas generated is relatively large, the chlorine dioxide gas outside the device is diffused further by strengthening the air volume of the blower fan, and when the amount of chlorine dioxide gas generated is relatively small, By preventing the chlorine dioxide gas outside the device from unnecessarily diffusing by weakening the air volume of the blower fan, it is possible to adjust the chlorine dioxide gas concentration outside the device to fall within a certain range.
　本明細書において用いられる用語は、特定の実施態様を説明するために用いられるのであり、発明を限定する意図ではない。 The terms used in the present specification are used to describe specific embodiments, and are not intended to limit the invention.
　また、本明細書において用いられる「含む」との用語は、文脈上明らかに異なる理解をすべき場合を除き、記載された事項（部材、ステップ、要素または数字等）が存在することを意図するものであり、それ以外の事項（部材、ステップ、要素または数字等）が存在することを排除しない。 Further, the term “comprising” as used in the present specification is intended to mean that the described items (members, steps, elements, numbers, etc.) exist unless there is a clear difference in context. It does not exclude the existence of other matters (members, steps, elements, numbers, etc.).
　異なる定義が無い限り、ここに用いられるすべての用語（技術用語および科学用語を含む。）は、本発明が属する技術の当業者によって広く理解されるのと同じ意味を有する。ここに用いられる用語は、異なる定義が明示されていない限り、本明細書および関連技術分野における意味と整合的な意味を有するものとして解釈されるべきであり、理想化され、または、過度に形式的な意味において解釈されるべきではない。 Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used herein should be construed as having meanings consistent with the meanings in the present specification and the related technical fields, and idealized or excessively formal unless stated otherwise. It should not be construed in a conventional sense.
　本発明の実施態様は模式図を参照しつつ説明される場合があるが、模式図である場合、説明を明確にするために、誇張されて表現されている場合がある。 The embodiments of the present invention may be described with reference to schematic diagrams, but in the case of schematic diagrams, they may be exaggerated for clarity of explanation.
　本明細書において、例えば、「１～１０ｗ／ｗ％」と表現されている場合、当業者は、当該表現が、１、２、３、４、５、６、７、８、９、または１０ｗ／ｗ％を個別具体的に指すことを理解する。 In the present specification, for example, when the expression “1 to 10 w / w%” is used, those skilled in the art will understand that the expression is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 w. Understand that / w% specifically refers to each.
　本明細書において、成分含有量や数値範囲を示すのに用いられるあらゆる数値は、特に明示がない限り、用語「約」の意味を包含するものとして解釈される。例えば、「１０倍」とは、特に明示がない限り、「約１０倍」を意味するものと理解される。 In the present specification, all numerical values used to indicate the content of components and numerical ranges are to be construed 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.
　本明細書中に引用される文献は、それらのすべての開示が、本明細書中に援用されているとみなされるべきであって、当業者は、本明細書の文脈に従って、本発明の精神および範囲を逸脱することなく、それらの先行技術文献における関連する開示内容を、本明細書の一部として援用して理解する。 References cited herein should be considered to be incorporated herein by reference in their entireties, and a person of ordinary skill in the art, in accordance with the context of the present specification, should understand the spirit of the invention. And without departing from the scope, the relevant disclosures in those prior art documents are understood to be incorporated as part of this specification.
　本発明の効果を確認するため、以下の実験を行った。 The following experiment was conducted to confirm the effect of the present invention.
[実験１．触媒と亜塩素酸塩水溶液との反応]
　図１に示す装置を用いて、二酸化塩素発生実験を行った。触媒としてはチタン（担体）に白金ベースの触媒を担持させたものを用い、亜塩素酸塩水溶液は１％亜塩素酸塩ナトリウム水溶液１Ｌを用いた。空気導入装置１を用いて、亜塩素酸塩水溶液４および触媒５を含む反応用容器３へ、約１Ｌ／ｍｉｎの流量で空気をバブリングさせた。一方、コントロールとして、触媒を使用しないこと以外は上記と同様の条件で、装置を作動させた。 [Experiment 1. Reaction of catalyst with aqueous chlorite solution]
A chlorine dioxide generation experiment was conducted using the apparatus shown in FIG. The catalyst used was a titanium (support) carrying a platinum-based catalyst, and the aqueous chlorite solution was 1 L of a 1% aqueous sodium chlorite solution. Using the air introduction device 1, air was bubbled into the reaction container 3 containing the aqueous chlorite solution 4 and the catalyst 5 at a flow rate of about 1 L / min. On the other hand, as a control, the device was operated under the same conditions as above except that no catalyst was used.
　両条件における二酸化塩素発生量の比較を図２に示す。図２に示すとおり、触媒を用いる条件においては二酸化塩素が発生したが、触媒を用いない条件においては二酸化塩素が発生しなかった。すなわち、本発明の装置において二酸化塩素を発生させるためには、触媒が必要であることが確認された。 Fig. 2 shows the comparison of chlorine dioxide generation under both conditions. As shown in FIG. 2, chlorine dioxide was generated under the condition of using the catalyst, but chlorine dioxide was not generated under the condition of not using the catalyst. That is, it was confirmed that a catalyst is required to generate chlorine dioxide in the device of the present invention.
[実験２．発生ガスの定性分析]
　実験１の方法で発生したガスを収集し、その成分をイオンクロマトグラフィによって定性分析を行った。その結果を図３に示す。図３に示すとおり、亜塩素酸塩と触媒との反応によって発生したガス成分は、実質的に二酸化塩素のみであった。 [Experiment 2. Qualitative analysis of generated gas]
The gas generated by the method of Experiment 1 was collected, and its components were qualitatively analyzed by ion chromatography. The result is shown in FIG. As shown in FIG. 3, the gas component generated by the reaction between the chlorite and the catalyst was substantially only chlorine dioxide.
[実験３．長時間の稼働性の検証]
　実験１で使用した装置（図１に示す装置）用いて、長時間の装置稼働テストを行った。その結果を図４に示す。図４に示すとおり、本発明の装置は、約１カ月の間、安定的に二酸化塩素を発生させることができた。 [Experiment 3. Verification of long-term operation]
Using the apparatus used in Experiment 1 (the apparatus shown in FIG. 1), a long-term apparatus operation test was conducted. The result is shown in FIG. As shown in FIG. 4, the device of the present invention could stably generate chlorine dioxide for about one month.
　以上のとおり、本発明は、従来の二酸化塩素発生装置と比較して極めて簡素な構造にもかかわらず、長期間安定して二酸化塩素を発生させることができる。

  As described above, the present invention can stably generate chlorine dioxide for a long period of time in spite of the extremely simple structure as compared with the conventional chlorine dioxide generator.

Claims (13)

  1. 　バブリング機構を備えた二酸化塩素発生装置であって、
    　前記装置は、反応用容器と空気導入装置とを含み、
    　前記反応用容器は、亜塩素酸塩水溶液と触媒とを含み、
    　前記反応用容器と前記空気導入装置とは導管によって接続されており、
    　前記空気導入装置の作動時に、前記反応用容器中の亜塩素酸塩水溶液に空気がバブリングされ、バブリングされる空気が前記触媒に接触するように構成されており、
    　前記装置を２週間継続して作動させた時点において前記装置から放出される空気に含まれる二酸化塩素濃度が、前記装置を１週間継続して作動させた時点において前記装置から放出される空気に含まれる二酸化塩素濃度と比較して、少なくとも５０％以上維持されることを特徴とする、
    装置。     A chlorine dioxide generator equipped with a bubbling mechanism,
    The apparatus includes a reaction vessel and an air introduction device,
    The reaction vessel contains an aqueous chlorite solution and a catalyst,
    The reaction container and the air introduction device are connected by a conduit,
    At the time of operation of the air introducing device, air is bubbled through the aqueous chlorite solution in the reaction vessel, and the bubbling air is configured to come into contact with the catalyst.
    The chlorine dioxide concentration contained in the air discharged from the device when the device is continuously operated for two weeks is included in the air discharged from the device when the device is continuously operated for one week. The chlorine dioxide concentration is maintained at least 50% or more,
    apparatus.
  2. 　請求項１に記載の二酸化塩素発生装置であって、
    　前記反応用容器は、少なくとも部分的に開放されており、前記反応用容器内で生成された二酸化塩素を含む空気が前記装置の外部へ放出されるように構成されることを特徴とする、
    装置。     The chlorine dioxide generator according to claim 1, wherein
    The reaction vessel is at least partially opened, and the air containing chlorine dioxide produced in the reaction vessel is configured to be discharged to the outside of the apparatus.
    apparatus.
  3. 　請求項１に記載の二酸化塩素発生装置であって、
    　電気分解機構を含まないことを特徴とする、
    装置。     The chlorine dioxide generator according to claim 1, wherein
    Characterized by not including an electrolysis mechanism,
    apparatus.
  4. 　請求項１に記載の二酸化塩素発生装置であって、
    　前記亜塩素酸塩水溶液が、亜塩素酸アルカリ金属塩水溶液または亜塩素酸アルカリ土類金属塩水溶液であることを特徴とする、
    装置。     The chlorine dioxide generator according to claim 1, wherein
    The chlorite aqueous solution is characterized in that it is an aqueous solution of an alkali metal chlorite or an aqueous solution of an alkaline earth metal chlorite.
    apparatus.
  5. 　請求項４に記載の二酸化塩素発生装置であって、
    　前記亜塩素酸アルカリ金属塩水溶液が、亜塩素酸ナトリウム水溶液、亜塩素酸カリウム水溶液、または、亜塩素酸リチウム水溶液であり、
    　亜塩素酸アルカリ土類金属塩水溶液が、亜塩素酸カルシウム水溶液、亜塩素酸マグネシウム水溶液、または、亜塩素酸バリウム水溶液である、
    ことを特徴とする、
    装置。     The chlorine dioxide generator according to claim 4, wherein
    The alkali metal chlorite aqueous solution is a sodium chlorite aqueous solution, a potassium chlorite aqueous solution, or a lithium chlorite aqueous solution,
    The alkaline earth metal chlorite aqueous solution is a calcium chlorite aqueous solution, a magnesium chlorite aqueous solution, or a barium chlorite aqueous solution,
    Characterized by that
    apparatus.
  6. 　請求項１に記載の二酸化塩素発生装置であって、
    　前記亜塩素酸塩水溶液の濃度が０．０１～４５重量％であることを特徴とする、
    装置。     The chlorine dioxide generator according to claim 1, wherein
    The concentration of the aqueous chlorite solution is 0.01 to 45% by weight,
    apparatus.
  7. 　請求項１に記載の二酸化塩素発生装置であって、
    　前記触媒が、固体触媒であることを特徴とする、
    装置。     The chlorine dioxide generator according to claim 1, wherein
    Wherein the catalyst is a solid catalyst,
    apparatus.
  8. 　請求項７に記載の二酸化塩素発生装置であって、
    　前記触媒が、金属系触媒、鉱物系触媒、炭素系触媒、または、これらの組み合わせであることを特徴とする、
    装置。     The chlorine dioxide generator according to claim 7,
    The catalyst is a metal-based catalyst, a mineral-based catalyst, a carbon-based catalyst, or a combination thereof,
    apparatus.
  9. 　請求項８に記載の二酸化塩素発生装置であって、
    　前記金属触媒が、白金（Ｐｔ）、ルテニウム（Ｒｈ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、イリジウム（Ｉｒ）、オスミウム（Ｏｓ）、鉄（Ｆｅ）、銅（Ｃｕ）、マンガン（Ｍｎ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、モリブデン（Ｍｏ）、または、これらの金属の化合物、を含む触媒であり、
    　前記鉱物系触媒が、シリカ（Ｓｉ）、または、シリカを含む化合物、を含む触媒であり、
    　前記炭素系触媒が、活性炭を含む触媒、
    であることを特徴とする、
    装置。     The chlorine dioxide generator according to claim 8, wherein:
    The metal catalyst is platinum (Pt), ruthenium (Rh), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), copper (Cu), manganese (Mn), A catalyst containing cobalt (Co), nickel (Ni), molybdenum (Mo), or a compound of these metals,
    The mineral-based catalyst is a catalyst containing silica (Si) or a compound containing silica,
    The carbon-based catalyst is a catalyst containing activated carbon,
    Is characterized by
    apparatus.
  10. 　請求項１に記載の二酸化塩素発生装置であって、
    　前記触媒が、担体に担持されていることを特徴とする、
    装置。     The chlorine dioxide generator according to claim 1, wherein
    The catalyst is supported on a carrier,
    apparatus.
  11. 　請求項１０に記載の二酸化塩素発生装置であって、
    　前記担体が、チタン、バルブ金属、ステンレス、ニッケル、セラミックス、炭素、および、多孔質物質からなる群から選択される材料を含む担体であることを特徴とする、
    装置。     The chlorine dioxide generator according to claim 10, wherein
    The carrier is a carrier containing a material selected from the group consisting of titanium, valve metal, stainless steel, nickel, ceramics, carbon, and a porous material,
    apparatus.
  12. 　請求項１に記載の二酸化塩素発生装置であって、
    　前記空気導入装置が、前記二酸化塩素発生装置の流路の始点から前記流路内へ空気を導入する装置、または、前記二酸化塩素発生装置の流路の終点から前記流路内の空気を吸引する装置、であることを特徴とする、
    装置。     The chlorine dioxide generator according to claim 1, wherein
    The air introduction device is a device that introduces air into the flow passage from the start point of the flow passage of the chlorine dioxide generation device, or sucks air in the flow passage from the end point of the flow passage of the chlorine dioxide generation device. A device,
    apparatus.
  13. 　請求項１２に記載の二酸化塩素発生装置であって、
    　前記空気導入装置が、電動式のエアポンプであることを特徴とする、
    装置。     The chlorine dioxide generator according to claim 12,
    The air introduction device is an electric air pump,
    apparatus.
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