WO2020090538A1 - 二酸化塩素発生装置 - Google Patents

二酸化塩素発生装置 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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WO
WIPO (PCT)
Prior art keywords
chlorine dioxide
catalyst
chlorite
aqueous solution
air
Prior art date
Application number
PCT/JP2019/041276
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
翔平 辻本
Original Assignee
大幸薬品株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 大幸薬品株式会社 filed Critical 大幸薬品株式会社
Priority to JP2020553796A priority Critical patent/JP7401103B2/ja
Priority to CN201980059166.1A priority patent/CN112672770A/zh
Priority to KR1020217007121A priority patent/KR102720554B1/ko
Publication of WO2020090538A1 publication Critical patent/WO2020090538A1/ja

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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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
PCT/JP2019/041276 2018-10-29 2019-10-21 二酸化塩素発生装置 WO2020090538A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2020553796A JP7401103B2 (ja) 2018-10-29 2019-10-21 二酸化塩素発生装置
CN201980059166.1A CN112672770A (zh) 2018-10-29 2019-10-21 二氧化氯产生装置
KR1020217007121A KR102720554B1 (ko) 2018-10-29 2019-10-21 이산화 염소 발생 장치

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018202564 2018-10-29
JP2018-202564 2018-10-29

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WO2020090538A1 true WO2020090538A1 (ja) 2020-05-07

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JP (1) JP7401103B2 (zh)
KR (1) KR102720554B1 (zh)
CN (1) CN112672770A (zh)
TW (1) TWI813799B (zh)
WO (1) WO2020090538A1 (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5008096A (en) * 1990-04-03 1991-04-16 Bio-Cide International, Inc. Catalyst enhanced generation of chlorine dioxide
JPH10192377A (ja) * 1997-01-14 1998-07-28 Chisso Corp 二酸化塩素ガスによる環境殺菌の方法
WO2009154143A1 (ja) * 2008-06-19 2009-12-23 大幸薬品株式会社 １液型電解式の二酸化塩素製造方法
JP2010057429A (ja) * 2008-09-04 2010-03-18 Okuno Chem Ind Co Ltd 食品の殺菌処理方法
JP2014014589A (ja) * 2012-07-11 2014-01-30 Fumakilla Ltd 気体放散装置

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6265343B1 (en) * 1994-03-07 2001-07-24 Degussa Corporation Catalyst and method for the synthesis of chlorine dioxide, and method of making catalyst for the synthesis of chlorine dioxide
JP4125103B2 (ja) * 2002-12-10 2008-07-30 第一制電機株式会社 二酸化塩素ガス発生装置
US20050079123A1 (en) * 2003-10-10 2005-04-14 Shuler Robert K. Method and apparatus for microbial decontamination
CN1295142C (zh) * 2003-12-15 2007-01-17 深圳市聚源科技有限公司 用二氧化碳和亚氯酸钠生产二氧化氯的方法
JP2007217239A (ja) * 2006-02-17 2007-08-30 Taiko Pharmaceutical Co Ltd 二酸化塩素発生組成物
CN104705342B (zh) 2007-03-15 2019-01-25 大幸药品株式会社 纯二氧化氯液剂、含有其的凝胶状组合物及发泡性组合物
JP2011093737A (ja) * 2009-10-29 2011-05-12 Csl:Kk 亜塩素酸化合物水溶液組成物及び二酸化塩素ガスの発生方法
JP5670383B2 (ja) * 2011-12-15 2015-02-18 株式会社ウオーターテクノカサイ 透析用水供給装置、及び、透析用水供給方法
EP2662328B1 (de) * 2012-05-07 2018-08-15 Erich Schmid Verfahren und Vorrichtung zur Erzeugung von Chlordioxid
JP6537451B2 (ja) 2013-12-27 2019-07-03 大幸薬品株式会社 可視光を照射することにより二酸化塩素を発生させるための組成物
JP6317623B2 (ja) * 2014-05-16 2018-04-25 セントラルフィルター工業株式会社 亜塩素酸および二酸化塩素を含有した殺菌水の生成装置
KR102369884B1 (ko) 2016-09-05 2022-03-04 가부시키가이샤 오사카소다 이산화염소 발생 장치 및 이산화염소 발생 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5008096A (en) * 1990-04-03 1991-04-16 Bio-Cide International, Inc. Catalyst enhanced generation of chlorine dioxide
JPH10192377A (ja) * 1997-01-14 1998-07-28 Chisso Corp 二酸化塩素ガスによる環境殺菌の方法
WO2009154143A1 (ja) * 2008-06-19 2009-12-23 大幸薬品株式会社 １液型電解式の二酸化塩素製造方法
JP2010057429A (ja) * 2008-09-04 2010-03-18 Okuno Chem Ind Co Ltd 食品の殺菌処理方法
JP2014014589A (ja) * 2012-07-11 2014-01-30 Fumakilla Ltd 気体放散装置

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Publication number Publication date
JPWO2020090538A1 (ja) 2021-09-24
TW202034966A (zh) 2020-10-01
JP7401103B2 (ja) 2023-12-19
KR20210082433A (ko) 2021-07-05
TWI813799B (zh) 2023-09-01
KR102720554B1 (ko) 2024-10-23
CN112672770A (zh) 2021-04-16

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