WO2011016206A1 - Procédé et dispositif de génération d’un principe actif, filtre à air et humidificateur équipés tous deux dudit dispositif - Google Patents

Procédé et dispositif de génération d’un principe actif, filtre à air et humidificateur équipés tous deux dudit dispositif Download PDF

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WO2011016206A1
WO2011016206A1 PCT/JP2010/004831 JP2010004831W WO2011016206A1 WO 2011016206 A1 WO2011016206 A1 WO 2011016206A1 JP 2010004831 W JP2010004831 W JP 2010004831W WO 2011016206 A1 WO2011016206 A1 WO 2011016206A1
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active substance
photocatalyst
air
halogen
light
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PCT/JP2010/004831
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English (en)
Japanese (ja)
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茂俊 堀切
純 稲垣
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パナソニック株式会社
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Priority claimed from JP2009182160A external-priority patent/JP5845383B2/ja
Priority claimed from JP2009207705A external-priority patent/JP5845384B2/ja
Priority claimed from JP2009211408A external-priority patent/JP5845385B2/ja
Priority claimed from JP2009211409A external-priority patent/JP2011058766A/ja
Application filed by パナソニック株式会社 filed Critical パナソニック株式会社
Publication of WO2011016206A1 publication Critical patent/WO2011016206A1/fr

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    • 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
    • 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
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20—Gaseous substances, e.g. vapours
    • 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
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20—Gaseous substances, e.g. vapours
    • A61L2/208—Hydrogen peroxide
    • 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
    • A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
    • A61L9/18—Radiation
    • A61L9/20—Ultraviolet radiation
    • A61L9/205—Ultraviolet radiation using a photocatalyst or photosensitiser
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • C01B11/04—Hypochlorous acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C02F1/325—Irradiation devices or lamp constructions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • A61L2209/211—Use of hydrogen peroxide, liquid and vaporous
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/02—Odour removal or prevention of malodour
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Definitions

  • the present invention relates to an active substance generating method and an active substance generating apparatus for generating active substances such as active oxygen species and halogen oxides having an ability to oxidize organic substances, and diffusing them in the gas phase or liquid phase and releasing them.
  • the present invention relates to an air purifier and a humidifier used.
  • Titanium oxide is known to have a photocatalytic action, and deodorization or antibacterial action can be exhibited by irradiating titanium oxide with light such as ultraviolet rays.
  • light such as ultraviolet rays.
  • hydroxyl radicals known as active substances having high oxidizing power are generated on titanium oxide.
  • the generated hydroxyl radicals are decomposed by oxidizing the odor components and microorganisms adsorbed on the filter.
  • the photocatalyst is processed into a filter shape such as a honeycomb, and the air is deodorized or antibacterial by aeration through the filter while irradiating with ultraviolet rays.
  • FIG. 13 is a perspective view schematically showing a conventional deodorizing apparatus.
  • a device in which a photocatalyst 502 is kneaded into an adsorbent 501 and formed into a honeycomb shape is known.
  • air containing odor is passed through the honeycomb holes 503, a lamp 504 as an excitation light source of the photocatalyst is turned on, and light 504a such as ultraviolet rays from the lamp 504 is irradiated.
  • the photocatalyst 102 is excited and the odor is decomposed and deodorized.
  • FIG. 14 is a block diagram showing a conventional hydrogen peroxide generator.
  • a generator for hydrogen peroxide which is one of active oxygen species is known.
  • This generator generates hydrogen peroxide by discharge using a mixed gas containing hydrogen and oxygen as a source gas.
  • the source gas 505, hydrogen and oxygen are introduced into the first discharge unit 506 while being adjusted to a predetermined concentration that does not explode, and discharge is performed.
  • the material gas 505 is introduced into the second discharge part 508 to perform discharge, and a mixture of hydrogen peroxide, hydrogen, oxygen, and water is obtained. .
  • 13 is a filter-shaped structure in which a photocatalyst 502 is kneaded, and can act on a substance adsorbed on the filter by aeration.
  • a photocatalyst 502 is kneaded, and can act on a substance adsorbed on the filter by aeration.
  • an effect cannot be obtained for a filter that is not adsorbed on a filter or that is not adsorbed on the surface of an object and scattered in the air. This is because hydroxyl radicals generated on titanium oxide are unstable and have a very short lifetime, so that they are hardly released from the filter and the effect is limited to the vicinity of the filter.
  • FIG. 15 is a cross-sectional view showing a schematic configuration of a radical generator which is an example of a conventional active substance generator.
  • a method is known in which a photocatalyst 601 is attached to the surface of a glass tube 602 using a radical generator shown in FIG. 15 and light is emitted from the outside by a light source 603 to decolorize the pigment (see, for example, Patent Document 3). ). Even when the glass tube 602 is in slight contact with the dye solution 604, the active substance is generated in the vicinity and the dye can be decomposed.
  • FIG. 16 is a cross-sectional view showing a main manufacturing process of a lithography method using an active substance as a method using an active substance generating apparatus.
  • a technique applied to the photolithography method using generation of an active substance similar to that in FIG. 15 is known (see, for example, Patent Document 4).
  • the active substance generated in the vicinity of the photocatalyst 606 is generated at a position within 3 mm from the object 605, the object 605 has an oxidizing action.
  • the object 605 to be patterned and the photocatalyst 606 are arranged at a distance of 3 mm or less, and the object 605 is partially oxidized by irradiating the ultraviolet ray 608 through the mask pattern 607, so that the pattern shape is It is formed.
  • the active substance generator shown in FIG. 15 has a problem that the effect is limited to the vicinity of the photocatalyst 601 and that the entire object must be irradiated with ultraviolet rays. This is because the hydroxyl radical generated on the photocatalyst is unstable and has a very short lifetime, so that it can exist only in the vicinity of the photocatalyst, and the effect is limited to the vicinity of the photocatalyst. If the action of directly decomposing the dye with ultraviolet light is not used, almost no decoloring effect can be obtained, but depending on the object, it may not be possible to irradiate the ultraviolet light or it may be difficult to hit the ultraviolet light. Instead, it is required to obtain an oxidizing action with an active substance.
  • the active substance generator shown in FIG. 16 has a problem that the distance between the object 605 and the photocatalyst 606 needs to be arranged within 3 mm. This is because the hydroxyl radical generated on the photocatalyst is unstable and has a very short life, and in order for the active substance to reach further distance and have an effect, it is required to convert the active substance into a stable one. ing.
  • FIG. 17 is a cross-sectional view showing a schematic configuration of a conventional humidifier using the above-described active substance generator.
  • a humidifying device 702 provided with a generating unit 701 that generates mist or water vapor
  • an active substance generating device having a photocatalytic function is incorporated in a member 703 that forms a discharge port.
  • the organic matter adhering to the member 703 forming the discharge port is decomposed to suppress generation of mold and bacteria.
  • the effect is limited to the surface of the member, and there is a problem that the effect cannot be obtained for a member that does not adhere to the member 703 that forms the discharge port or that is floating in the air.
  • JP-A-1-189322 Japanese Patent Laid-Open No. 4-130002 JP 2003-335505 A JP 2003-236390 A Japanese Patent Laid-Open No. 10-132340
  • the present invention solves the above-described conventional problems, is stable and has a long life, can be released from titanium oxide to the gas phase, and has a low irritating odor or activity such as a halogen oxide.
  • Methods and apparatus for selectively generating materials are provided.
  • the present invention also provides an air cleaning device and a humidifying device using such a method and apparatus for generating an active substance.
  • the active substance generating method of the present invention comprises a method of irradiating a photocatalyst containing at least oxo acid with light containing ultraviolet rays and releasing the active substance from the photocatalyst.
  • This method has an action of converting an active substance generated on the surface of titanium oxide, for example, a hydroxyl radical into an active oxygen species having a relatively long life such as hydrogen peroxide.
  • an active substance generated on the surface of titanium oxide for example, a hydroxyl radical
  • an active oxygen species having a relatively long life such as hydrogen peroxide.
  • the active substance generator of the present invention comprises a photocatalyst containing at least an oxo acid, and a light source for irradiating the photocatalyst with excitation light, and generates an active substance by irradiating the photocatalyst with the excitation light.
  • This structure has an effect of converting an active substance generated on the surface of titanium oxide, for example, a hydroxyl radical into an active oxygen species having a relatively long life such as hydrogen peroxide.
  • an active substance generated on the surface of titanium oxide for example, a hydroxyl radical
  • an active oxygen species having a relatively long life such as hydrogen peroxide.
  • the air cleaning device of the present invention includes a photocatalyst containing at least oxo acid and a light source for irradiating the photocatalyst with excitation light in a main body having a suction port and a blowout port, and using the excitation light as a photocatalyst. It comprises an active substance generator that irradiates and generates an active substance, an air purifier, and a blower that blows out at least a portion of the air sucked from the inlet through the outlet.
  • an air purifier that can generate an active substance that is stable, has a long life, can be released from the photocatalyst into the gas phase, and can react with an object to be processed such as germs and organic substances in a remote place. Can be provided.
  • the humidifying device of the present invention includes a photocatalyst containing at least oxo acid and a light source for irradiating the photocatalyst with excitation light, and irradiating the photocatalyst with excitation light in a main body having a suction port and a blowout port.
  • An active substance generating device that generates an active substance, a humidifying unit that generates mist or water vapor, a water supply unit that supplies water to the humidifying unit, and an air blowing unit, the active material generating
  • the active substance generated from the apparatus and the air containing mist or water vapor are configured to be blown out from the outlet by the blower.
  • This configuration provides a humidifier that can generate an active substance that is stable, has a long life, and can be released from the photocatalyst into the gas phase, and can react with an object to be treated such as germs and organic substances in a remote location. can do.
  • FIG. 1 is a diagram showing the measurement result of hydrogen peroxide in an example of the active substance generation method according to the first embodiment of the present invention.
  • FIG. 2 is a diagram showing the amount of hypochlorous acid generated with respect to time in the example of the active substance generation method according to the first embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing a schematic configuration of the active substance generator according to Embodiment 2 of the present invention.
  • FIG. 4 is a diagram showing a measurement result of the concentration of hydrogen peroxide with respect to temperature in the example of the active substance generating apparatus according to the second embodiment of the present invention.
  • FIG. 1 is a diagram showing the measurement result of hydrogen peroxide in an example of the active substance generation method according to the first embodiment of the present invention.
  • FIG. 2 is a diagram showing the amount of hypochlorous acid generated with respect to time in the example of the active substance generation method according to the first embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing a schematic
  • FIG. 5 is a diagram showing a measurement result of an effective chlorine concentration with respect to temperature in the example of the active substance generating apparatus according to the second embodiment of the present invention.
  • FIG. 6 is sectional drawing which shows schematic structure of the air purifying apparatus concerning Embodiment 3 of this invention.
  • FIG. 7 is sectional drawing which shows schematic structure of the air purifying apparatus concerning Embodiment 4 of this invention.
  • FIG. 8 is sectional drawing which shows schematic structure of the air purifying apparatus concerning Embodiment 5 of this invention.
  • FIG. 9 is sectional drawing which shows schematic structure of the air purifying apparatus concerning Embodiment 6 of this invention.
  • FIG. 10 is sectional drawing which shows schematic structure of the humidification apparatus concerning Embodiment 7 of this invention.
  • FIG. 11 is sectional drawing which shows schematic structure of the humidification apparatus concerning Embodiment 8 of this invention.
  • FIG. 12 is sectional drawing which shows schematic structure of the humidification apparatus concerning Embodiment 9 of this invention.
  • FIG. 13 is a perspective view schematically showing a conventional deodorizing apparatus.
  • FIG. 14 is a block diagram showing a conventional hydrogen peroxide generator.
  • FIG. 15 is a cross-sectional view showing a schematic configuration of a conventional radical generator.
  • FIG. 16 is a sectional view showing a main manufacturing process of a lithography method using a conventional active substance.
  • FIG. 17 is a cross-sectional view showing a schematic configuration of a conventional humidifier.
  • the active substance generated by the method for generating an active substance of the present invention is an oxidizing agent having an action of oxidizing by reacting with an organic substance or an action of modifying a higher order structure of the organic substance.
  • active oxygen species and halogen oxidation There are things.
  • Activating oxygen species include hydroxyl radicals, superoxide radicals, singlet oxygen, hydrogen peroxide, and ozone. These are a C—C bond (bond energy of about 347 kJ / mol), a C—H bond (bond energy of about 415 kJ / mol), or a C ⁇ C bond ⁇ bond (bond energy of about 285 kJ), which is a basic skeleton of organic matter. It is known that bonds such as / mol) are cleaved by an oxidation reaction.
  • the oxidation potential of hydroxyl radical which is a strong active oxygen species, is approximately 2.8 V, and the dissociation energy is approximately 504 kJ / mol. Therefore, the CC bond can be cleaved to oxidatively decompose.
  • Such an oxidant has high energy, but is unstable and has a very short life of about 1 millisecond or less.
  • the oxidation potential is 1.77 V
  • the dissociation energy is 319 kJ / mol.
  • the ⁇ bond of the C ⁇ C double bond can be cut.
  • organic substances having a relatively large molecular weight such as proteins and enzymes
  • a three-dimensional higher order structure is important in order to perform the original function.
  • active substances such as hydrogen peroxide can denature their higher-order structures by strong oxidizing power and lose their original functions, and can obtain a sterilizing action and an antiviral action.
  • hydrogen peroxide has a lower oxidation potential and is more stable than the hydroxyl radical, it has a property that its life is extended to about 1 hour or more.
  • the active substance is allowed to act on a remote position such as the gas phase or the liquid phase, such a substance as hydrogen peroxide is suitable.
  • Halogen oxides include chlorine oxides (for example, hypochlorous acid, chlorous acid, perchloric acid, chlorine dioxide), bromine oxides (for example, bromic acid, hypobromous acid, perbromic acid, etc.) ), And iodine oxide (eg, iodic acid, periodic acid, etc.) can be used. These have oxidizing power.
  • the oxidation potential of hypochlorous acid is 1.5 V
  • the dissociation energy is about 268 kJ / mol.
  • it is lower than the C—C bond cleavage energy, it breaks hydrogen bonds and van der Waals bonds to denature higher-order structures of relatively high molecular weight organic substances such as proteins and enzymes. Thereby, the original function can be lost, and a disinfection action, an antifungal action, and an antiviral action can be obtained. Further, it can affect the light absorption structure such as a dye, and can obtain a decoloring action.
  • the term “antibacterial” refers to sterilizing or decomposing gas phase bacteria, and preferably performing at least one of reducing gas phase bacteria concentration or inhibiting bacteria growth.
  • “antibacterial” means that the concentration of the bacterium in contact can be reduced by two orders of magnitude or more from the initial concentration.
  • the target of antibacterial activity is not particularly limited, and examples thereof include bacteria, molds, viruses, and the like. From the viewpoint of antibacterial activity, bacteria are preferable. Examples of bacteria include Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, MRSA, Bacillus cereus, and Klebsiella pneumoniae.
  • an “oxo acid” is a compound having a hydroxyl group (OH) and an oxo group (C ⁇ O).
  • oxo acid a compound having a hydroxyl group (OH) and an oxo group (C ⁇ O).
  • those that are not oxidatively decomposed by a photocatalyst are preferable, and examples thereof include phosphoric acid, sulfuric acid, carbonic acid, nitric acid, boric acid, and at
  • phosphoric acid when used as the oxo acid, it can be used as an aqueous solution having an appropriate concentration using a phosphate or hydrogen phosphate.
  • phosphoric acid compounds such as polyphosphoric acid and metaphosphoric acid, can be used similarly. All of these have a plurality of oxo groups in their structures.
  • the type of active substance to be generated can be selectively generated according to the type and amount of oxo acid and halogen contained.
  • oxo acid when phosphate is used as an oxo acid, it has been confirmed that hydrogen peroxide is generated as an active substance. It has also been confirmed that hypochlorous acid is generated when fluorine and chlorine are used as the halogen.
  • the halogen content is not uniform, and when halogen is chemically bonded to a photocatalyst, for example, titanium (IV) oxide, the amount of active oxygen generated can be improved.
  • a part of the halogen that is not bonded is released in the form of an active substance having a high antibacterial property such as a chloric acid type active substance.
  • “at least a part of halogen is chemically bonded to a photocatalyst such as titanium oxide” means that titanium oxide and at least a part of halogen are chemically bonded. Preferably, it refers to a state where titanium oxide and halogen are bonded at an atomic level, not supported or mixed, and more preferably that titanium oxide and halogen are ionically bonded.
  • “chemically bonded halogen” refers to, for example, a halogen that is difficult to elute in water among the halogens contained in the halogen-containing titanium oxide. In addition, when two or more types of halogens are contained, the effect can be obtained as long as one or more of them are chemically bonded.
  • the halogen includes fluorine, iodine, bromine and chlorine, and is at least one selected from the group consisting of fluorine, chlorine, bromine and iodine.
  • the fluorine content is 1.25 wt% or more and 4.0 wt% or less from the viewpoint of enhancing the amount of active substance generated and antibacterial performance during light irradiation. It is preferable.
  • the fluorine content in the fluorine-containing titanium oxide can be determined by an absorptiometric analysis method (JISK0102).
  • a pH adjuster for example, hydrochloric acid or ammonia water
  • the chemical bond is preferably an ionic bond.
  • the chemical bond is an ionic bond
  • the halogen and titanium oxide are strongly bonded, and for example, the antibacterial activity and the photocatalytic reaction can be improved.
  • the ionic bond between titanium oxide and halogen is analyzed by a photoelectron spectrometer. it can.
  • the halogen is fluorine
  • the halogen-containing titanium oxide is analyzed with a photoelectron spectrometer
  • the peak top of the fluorine 1s orbital (F1s) shows a spectrum in the range of 683 eV or more and 686 eV or less. . This is because the value of the peak top of titanium fluoride in which fluorine and titanium are ion-bonded is within the above range.
  • titanium oxide examples include anatase-type titanium oxide, rutile-type titanium oxide, and brookite-type titanium oxide, and it is preferable to select anatase-type titanium oxide because high photocatalytic activity can be obtained.
  • titanium oxide examples include titanium dioxide, hydrous titanium oxide, hydrated titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide, oxygen-deficient titanium oxide, nitrogen-substituted titanium oxide, and sulfur-substituted titanium oxide. It is done.
  • the crystal form is not particularly limited as long as it has photocatalytic activity, and any of amorphous, anatase, rutile, and brookite forms may be used. There is no problem even if components having different crystal forms such as a combination of rutile type and anatase type titanium oxide are combined.
  • Titanium oxide is often powdery, but a titanium oxide thin film may be formed by oxidizing a metal surface such as a titanium plate.
  • a titanium thin film may be formed by coating titanium alkoxide or the like and performing heat treatment.
  • a titanium oxide film may be formed by spraying titanium powder on a metal surface or the like.
  • a metal such as is not limited. Further, it is not limited at all to use a photocatalyst whose surface has an impurity metal such as Cr (chromium) or V (vanadium) and whose light absorption wavelength is expanded.
  • the specific surface area of titanium oxide is preferably 200 m 2 / g or more and 350 m 2 / g or less, more preferably 250 m 2 / g or more and 350 m 2 / g or less.
  • the specific surface area in the present invention is a surface area value per gram of titanium oxide powder measured by a BET method (nitrogen adsorption / desorption method). When the specific surface area is 200 m 2 / g or more, the contact area with the object to be decomposed can be increased.
  • titanium oxide and halogen may be chemically bonded, and oxo acid and halogen different from the above halogen may be attached.
  • it can be produced by preparing a halogen-containing titanium oxide in the first step and further adding oxo acid and other halogens in the second step.
  • titanium oxide chemically bonded with halogen it can be carried out only in the second step.
  • the halogen-containing titanium oxide can be produced by a production method including a step of reacting titanium oxide with a halogen compound and a step of obtaining a halogen-containing titanium oxide.
  • the step of reacting titanium oxide and the halogen compound when the pH of the mixed liquid in which the titanium oxide aqueous dispersion and the halogen compound are mixed exceeds 3, the pH is adjusted to 3 or less using an acid. In this step, titanium oxide and a halogen compound are reacted in this mixed solution.
  • the step of obtaining the halogen-containing titanium oxide is performed by washing a reaction product obtained by reacting titanium oxide with a halogen compound, whereby at least a part of the halogen is chemically bonded to the titanium oxide. It is the process of obtaining.
  • anatase type titanium oxide having an adsorption amount of n-butylamine of 8 ⁇ mol / g or less for example, SSP-25 manufactured by Sakai Chemical Industry Co., Ltd. can be used.
  • CSB-M manufactured by Co., Ltd. can be used as anatase type titanium oxide having an adsorption amount of n-butylamine of 8 ⁇ mol / g or less.
  • the halogen compound is not particularly limited, but a general halogen compound can be used.
  • the halogen compound is a fluorine compound, examples thereof include ammonium fluoride, potassium fluoride, sodium fluoride, and hydrofluoric acid. Among these, ammonium fluoride, potassium fluoride, and hydrofluoric acid are preferable.
  • the halogen compound is an iodine compound, examples thereof include hydrogen iodide, periodic acid, and ammonium iodide.
  • the halogen compound is a bromine compound, examples thereof include hydrobromic acid and ammonium bromide.
  • a halogen compound is a chlorine compound, hydrochloric acid, sodium chloride, and hypochlorous acid are mentioned.
  • the method for measuring the amount of n-butylamine adsorbed per gram of titanium oxide is as follows. That is, 1 g of titanium oxide sample dried at 130 ° C. for 2 hours is precisely weighed in a 50 mL conical flask with a stopper, and 30 mL of 0.003 normal concentration n-butylamine solution diluted with methanol is added thereto. Next, this is subjected to ultrasonic dispersion for 1 hour and then allowed to stand for 10 hours, and 10 mL of the supernatant is collected.
  • the collected supernatant is subjected to potentiometric titration using a 0.003 normal concentration perchloric acid solution diluted with methanol, and the adsorption amount of n-butylamine can be determined from the titration amount at the neutralization point at that time. .
  • titanium oxide can be effectively carried out on the substrate to prevent light irradiation and photocatalyst scattering.
  • titanium oxide When supported on a substrate, titanium oxide is prepared by first preparing a halogen-containing titanium oxide and supporting it on the substrate, and then attaching an oxo acid and an additional halogen.
  • the substrate is not particularly limited, but a general filter substrate can be used, and examples thereof include metals, plastics, synthetic resin fibers, natural fibers, wood, paper, glass, ceramics, and metals, ceramics, and glass. Is suitable.
  • plastic or paper is used as a base material, titanium oxide may be supported by coating the surface of the base material with silicone, a fluororesin, silica, or the like.
  • the shape of the substrate is not particularly limited, but if it is formed into a filter shape such as a plate shape, a net shape, a honeycomb shape, a fiber shape, a bead shape, a slit shape, or a foam shape, light irradiation and air contact can be efficiently performed. it can.
  • a plate-like filter is preferably provided with an opening such as a punching shape in which holes are formed in a plate, a knitted shape in which fibers are knitted, and a non-woven shape in which fibers are bonded. If it is plate-shaped, pressure loss may be reduced by expanding the surface area of the filter by folding the plate into a pleat shape.
  • glass fiber woven fabric When a glass fiber woven fabric is used for the base material, durability against light and radiation is strong, and it is less susceptible to chemical corrosion due to acidic binders than organic synthetic fibers and paper. Moreover, since glass fiber has a light transmittance and light scattering property, when irradiating light to a halogen containing titanium oxide, light can be irradiated efficiently.
  • the material of the glass fiber include quartz glass, E glass, C glass, S glass, and A glass.
  • the fiber shape is not particularly limited, but it is preferably formed by a fiber bundle in which a plurality of short fiber glasses having a diameter of 4 ⁇ m or more and 9 ⁇ m or less are bundled rather than a single fiber.
  • the fiber bundle can be used by bundling an arbitrary number of fiber bundles of about 50 or more and 6400 or less.
  • titanium oxide particles are fixed by entering or adhering between the fibers.
  • titanium oxide can be held between the fibers, so that the supported amount can be increased.
  • the titanium oxide particles that have entered between the fibers are firmly fixed by being sandwiched between the fibers. At the same time, even when an impact is applied from the outside, the impact is transmitted through the fiber, so that it is difficult to drop off.
  • alkali silicates composed of silicates such as Na 2 O, K 2 O and LiO 2 , inorganic colloids such as silica sol, alumina sol and zirconia sol, alkoxides such as silica, silicon and titanium and their hydrolysis Such as things.
  • alkali components such as Na (sodium) may reduce the crystallinity of titanium oxide and may reduce performance. Therefore, the binder is preferably SiO 2 as a main component, and a silica sol or a hydrolyzate of silica alkoxides is preferable.
  • silicon alkoxides include tetraethoxysilane and its polymer methoxypolysiloxane, ethoxypolysiloxane, butoxypolysiloxane, and lithium silicate.
  • titanium alkoxides include tetrapropoxy titanium and polymers thereof. These metal alkoxides are hydrolyzed with water and acid and can be used as a binder. In the case of titanium alkoxide, it can have a photocatalytic action by heat treatment.
  • the binder is preferably acidic, and examples thereof include a product obtained by hydrolyzing silicon, titanium and the like with an acid, acidic silica sol, alumina sol and the like.
  • the pH may be adjusted to 1 or more and 5 or less using hydrochloric acid, sulfuric acid, or the like.
  • silica sol those having a pH of 2 or more and 4 or less and a particle diameter of 10 nm or more and 50 nm or less are suitable.
  • a neutral or alkaline silica sol having a pH is used, gelation is often caused when a halogen-containing titanium oxide is added, and it is often difficult to uniformly support the titanium oxide on the substrate.
  • the binder contains cation components such as Na (sodium), K (potassium), NH 4 (ammonia), the antibacterial performance is degraded due to the progress of the reaction with halogen and adsorption onto the titanium oxide surface.
  • the cation component should be as small as possible.
  • the Na concentration is preferably greater than 0 wt% and not more than 0.05 wt% as Na 2 O.
  • the basis weight of the glass fiber woven fabric is preferably 10 g / m 2 or more and 900 g / m 2 or less, and in order to facilitate the production, one having a weight of 100 g / m 2 or more and 400 g / m 2 or less may be selected.
  • the weaving method may be any weaving method such as plain weaving, twill weaving, satin weaving, tangle weaving or imitation weaving, but imitation weaving is preferred from the viewpoint of shape stability.
  • the yarn density is preferably 20/25 mm or more and 40/25 mm or less for the fiber bundle of warp and width, the thickness is 0.1 mm or more and 2 mm or less, and the tensile strength is 100 N / 25 mm or more.
  • the method of supporting the halogen-containing titanium oxide on the substrate examples include dip coating and spraying, but any means may be used as long as the halogen-containing titanium oxide can be immobilized on the substrate. If the carrying amount is not enough in one treatment, a plurality of treatment steps may be repeated.
  • the binder may be contracted by heating at a temperature of about 50 ° C. or more and 700 ° C. or less for about 0.01 hour or more and 5 hours or less with a dryer, and may be firmly fixed to the substrate. Heating for 0.1 hour at a temperature of 150 ° C. or higher is more preferable. In the case of performing such heat drying treatment, it is desirable that the main component of the base material is composed of glass or ceramics.
  • the particle diameter of the halogen-containing titanium oxide is preferably smaller than the fiber diameter. Since the halogen-containing titanium oxide is smaller than the diameter of the fiber, the halogen-containing titanium oxide can easily enter the stitches or overlapping portions between the fibers and can be firmly fixed. As a result, the amount of halogen-containing titanium oxide supported can be increased.
  • the particle size of the halogen-containing titanium oxide is about 6 nm or more and 100 nm or less as the primary particle size, but in practice, the primary particles often aggregate to form secondary particles of about 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the particle diameter of the halogen-containing titanium oxide here indicates a state of secondary particles, and when the halogen-containing titanium oxide is dispersed in the knitted fabric, it is necessary to easily enter the fiber stitches or overlapping portions.
  • the halogen-containing titanium oxide prepared in the first step is brought into contact with an aqueous solution containing an oxo acid or a halogen of a type different from the above halogen. Can be produced.
  • the oxo acid is not particularly limited, but a general oxo acid compound can be used.
  • the oxo acid is at least one compound selected from compounds containing phosphoric acid, sulfuric acid, carbonic acid, nitric acid, or boric acid.
  • the oxo acid is a phosphate compound
  • the oxo acid is a carbonate compound
  • Examples include strontium carbonate, cesium carbonate, cerium carbonate, iron carbonate, and copper carbonate.
  • the oxo acid is a sulfuric acid compound
  • sulfuric acid zinc sulfate, aluminum sulfate, ammonium sulfate, potassium sulfate, calcium sulfate, ammonium hydrogen sulfate, potassium hydrogen sulfate, sodium hydrogen sulfate, tin (II) sulfate, strontium sulfate, cesium sulfate , Ferrous sulfate, ferrous sulfate, ferric sulfate, ferric sulfate, titanium sulfate, copper (II) sulfate, sodium sulfate, magnesium sulfate, manganese sulfate, lithium sulfate and the like.
  • the oxo acid is a nitrate compound, nitric acid, zinc nitrate, ammonium nitrate, potassium nitrate, chromium nitrate (III), cobalt nitrate (II), cesium nitrate, iron (II) nitrate, copper (II) nitrate, nickel nitrate, Examples thereof include barium nitrate, magnesium nitrate, manganese nitrate, and lithium nitrate.
  • the oxo acid is a boric acid compound
  • boric acid zinc borate, ammonium borate, potassium borate, calcium borate, barium borate, magnesium borate, manganese (II) borate and the like can be mentioned.
  • Oxo acid is mixed with a concentration that can be dissolved in an appropriate solvent and used for the addition.
  • a concentration that can be dissolved in an appropriate solvent For example, it is used by dissolving in purified water to a concentration of about 0.01% to 10% by weight.
  • halogen compounds as the halogen to be chemically bonded can be mixed and simultaneously added to the solution.
  • the halogen at this time include chlorides such as sodium chloride, potassium chloride, and magnesium chloride in the case of chlorine compounds.
  • iodine compounds include potassium iodide and sodium iodide.
  • bromine compounds include bromides such as potassium bromide, calcium bromide, ammonium bromide, and sodium bromide.
  • These halogen compounds are also used by mixing and dissolving them in an oxo acid solution. For example, it can be dissolved and used at a concentration of about 0.01% to 10% by weight.
  • Examples of the method of adding oxo acid to titanium oxide or halogen-containing titanium oxide include dip coating and spraying, but any means may be used as long as it can be contained in titanium oxide. After the titanium oxide is brought into contact with the oxo acid solution, if the titanium oxide is a powder, it is dried after being centrifuged or filtered. If the titanium oxide is fixed to the base material, the titanium oxide is brought into contact with the oxo acid solution and pulled up, and then dried at a low temperature of 100 ° C. or less in order to eliminate the residual liquid. It is presumed that the oxo acid and halogen adsorbed in this way are in a state of being adsorbed or chemically bonded to the pores of the titanium oxide or the surface at random.
  • the light source for irradiating titanium oxide is not particularly limited as long as it has light having a wavelength capable of activating titanium oxide.
  • the light source having a strong emission peak in the wavelength range of 350 nm or more and 450 nm or less can excite titanium oxide more efficiently with respect to the input power.
  • a straight tube type fluorescent lamp type black light it can be used suitably when the area of the base material is large because it contains many wavelengths around 380 nm and can irradiate strong light efficiently over a wide range.
  • a light source such as a halogen lamp, a xenon lamp, or a mercury lamp may be arranged so that a large area can be irradiated by a mirror or a lens that absorbs less ultraviolet light.
  • a light source using a semiconductor element as a light source having a strong emission peak in the above wavelength range.
  • a light emitting diode or a semiconductor laser can be used. These are suitable for locally irradiating a small portion because the irradiation area is small and the size of the light source is small.
  • an active substance can be generated and diffused and released into the space.
  • Example 1 ⁇ 1>.
  • Preparation of oxo acid and halogen-containing titanium oxide Titanium oxide as a photocatalyst (trade name: SSP-25, manufactured by Sakai Chemical Industry Co., Ltd., anatase type, particle size: 5 nm to 10 nm, specific surface area: 270 m 2 / g or more)
  • Pure water was added to titanium oxide so as to have a concentration of 150 g / L, and this was stirred to prepare a titanium oxide dispersion.
  • titanium oxide dispersion hydrofluoric acid equivalent to 3% by weight in terms of fluorine (element) with respect to titanium oxide (made by Wako Pure Chemical Industries, special grade) was added, and the added titanium oxide dispersion was kept at pH 3 and reacted at 25 ° C. for 60 minutes.
  • the obtained reaction product was washed with water. The washing with water was performed until the electric conductivity of the filtrate collected by filtering the reaction product was 1 mS / cm or less. And this was dried in air at 130 degreeC for 5 hours, and the fluorine-containing titanium oxide was prepared.
  • the glass fiber woven fabric used as the base material of the glass fiber woven fabric has a weight per unit area of 354 g / m 2 , a yarn density of 11 ⁇ 3/25 mm (same for vertical and horizontal), and a thickness of 0.42 mm. It was.
  • the aperture ratio of the prepared glass fiber fabric was about 15%.
  • the obtained active material generating material for example, a halogen-containing titanium oxide filter, is impregnated with 50 mM phosphate buffered saline which is a source of oxo acid and halogen. After that, it was pulled up, allowed to stand for 2 hours in a drying oven at 50 ° C. and dried to produce an active material generating material containing oxo acid and halogen-containing titanium oxide.
  • the produced active substance generating material for example, a titanium oxide filter
  • a glass-made gas sampling tube (impinger) was connected to the downstream side, and 20 ml of distilled water as a collection liquid was placed inside. The black light was irradiated so as to be 5 mW / cm 2 so as to sandwich the quartz tube, and the gas was circulated for 24 hours to collect and collect the active substance generated from the active substance generating material in distilled water.
  • FIG. 1 is a diagram showing measurement results of hydrogen peroxide in Examples and Comparative Examples of the active substance generation method according to Embodiment 1 of the present invention.
  • FIG. 2 is a diagram showing the amount of hypochlorous acid generated with respect to time in Examples and Comparative Examples of the active substance generation method according to Embodiment 1 of the present invention.
  • Example 2 As Example 2, a filter was prepared using anatase-type titanium oxide (trade name: SSP-25, manufactured by Sakai Chemical Industry Co., Ltd.) that does not contain halogen and has photocatalytic activity instead of halogen-containing titanium oxide. Otherwise, the amount of active substance generated was measured in the same manner as in Example 1. The results are shown in FIG. 1 and FIG.
  • Comparative Example 1 As Comparative Example 1, a filter using a halogen-containing titanium oxide not containing an oxo acid instead of the oxo-acid halogen-containing titanium oxide was used. Otherwise, the amount of active substance generated was measured in the same manner as in Example 1. The results are shown in FIG. 1 and FIG.
  • Comparative Example 2 As Comparative Example 2, in the same manner as in Example 1, the amount of active substance generated was measured in the dark without being irradiated with ultraviolet rays. The results are shown in FIG. 1 and FIG. In addition, the generation amount of hypochlorous acid with respect to the time of Examples 1 and 2 and Comparative Examples 1 and 2 is shown in FIG.
  • Example 1 residual chlorine was detected from the filter of Example 1 at 23.6 ⁇ g / m 3 (concentration 1.7 mg / L).
  • Example 1 1.3 ⁇ g / m 3 (concentration 0.09 mg / L) was detected as residual oxygen.
  • Comparative Examples 1 and 2 the residual oxygen was below the lower limit of detection (0.1 ⁇ g / m 3 or less).
  • hydrogen peroxide it contained oxoacid, and it was confirmed that hypochlorous acid was released by light irradiation. It was also confirmed that the amount of hypochlorous acid generated was increased about 20 times by using halogen-containing titanium oxide.
  • the active substance generating method of the present invention comprises a method of irradiating a photocatalyst containing at least oxo acid, for example, titanium oxide with light containing ultraviolet rays and releasing the active substance from the photocatalyst.
  • hydroxyl radicals generated on the surface of titanium oxide by the light irradiation reaction can be converted into active substances such as active oxygen species having a long lifetime, and the active substance can be converted into the gas phase.
  • the photocatalyst may be a method containing at least halogen.
  • the activity of titanium oxide can be improved and the generation of active substances can be increased.
  • a method in which at least a part of the halogen is chemically bonded to the photocatalyst may be used.
  • the chemical bond is an ionic bond
  • the halogen and titanium oxide are firmly bonded, and for example, the generation amount of the active substance can be improved.
  • halogen is at least one selected from the group consisting of fluorine, chlorine, bromine and iodine.
  • halogen can generate an active substance stably because the chemical bond of the photocatalyst is stable.
  • the oxo acid may be at least one compound selected from compounds containing phosphoric acid, sulfuric acid, carbonic acid, nitric acid, or boric acid.
  • This method is stable without being decomposed by the photocatalytic reaction, and can be easily contained in titanium oxide, so that the active substance can be generated stably.
  • the halogen is at least one of fluorine and chlorine
  • the active substance can be stably generated by containing fluorine or chlorine.
  • an active substance having high antibacterial properties such as a chloric acid-based active substance can be selectively generated.
  • a method in which the oxo acid is phosphoric acid may be used.
  • hydrogen peroxide having a relatively long life and high activity can be generated in the active substance, and the active substance can be generated stably.
  • a method in which the fluorine content is 1.25% by weight or more and less than 4.0% by weight with respect to the photocatalyst may be used. By this method, it is possible to secure an amount of halogen necessary and sufficient to generate the active substance and generate the active substance.
  • a method of irradiating the photocatalyst with light containing ultraviolet rays using a light source may be used.
  • a necessary amount of the active substance can be generated by causing a light irradiation reaction locally on the titanium oxide and limited to a necessary time.
  • the light source may be black light.
  • the light source may be a light emitting diode.
  • a method in which the photocatalyst is immobilized on a substrate may be used.
  • this method scattering of the photocatalyst powder can be prevented, and the photocatalyst and the active substance can be easily separated.
  • the active substance can be stably generated with the optimum shape.
  • FIG. 3 is a sectional view showing a schematic configuration of the active substance generator 1 according to the second embodiment of the present invention.
  • the active substance generator 1 according to the second embodiment includes a photocatalyst 2 containing at least an oxo acid, and a light source 3 for irradiating the photocatalyst 2 with excitation light.
  • the photocatalyst 2 is irradiated to generate an active substance.
  • This structure has an effect of converting an active substance generated on the surface of titanium oxide, for example, a hydroxyl radical, into an active oxygen species having a relatively long life, such as hydrogen peroxide, as will be described later.
  • an active substance generated on the surface of titanium oxide for example, a hydroxyl radical
  • an active oxygen species having a relatively long life such as hydrogen peroxide
  • the active substance generator 1 shown in FIG. 3 includes a casing 4, a fan 5, a reflector 6, an air passage 7, a louver 8, a prefilter 9, a humidifying unit 10, and a heater 11.
  • the photocatalyst 2 contains an oxo acid and a halogen.
  • the light source 3 performs photocatalytic reaction by irradiating the photocatalyst 2 with excitation light.
  • the casing 4 has a blowout port 12 and a suction port 13 as at least one opening, and covers the photocatalyst 2 and the light source 3.
  • the fan 5 is a transport unit that transports air to the photocatalyst 2 and volatilizes the active substance generated by the photocatalytic reaction from the photocatalyst 2.
  • the reflection plate 6 is disposed around the photocatalyst 2 and the light source 3, reflects the leaked light, and irradiates the photocatalyst with light.
  • the air path 7 guides the airflow along the long axis direction of the light source.
  • the louver 8 is a transport direction control unit that is provided in the opening of the casing 4 and controls the transport direction of the active substance.
  • the prefilter 9 is provided on the upstream side of the photocatalyst 2 and removes coarse dust contained in the air supplied to the photocatalyst 2.
  • the humidifying unit 10 humidifies the air supplied to the photocatalyst 2.
  • the heater 11 is a heating unit that is located at the rear stage of the fan 5 and heats the air to raise the temperature of the photocatalyst.
  • an active substance is generated by performing a photocatalytic reaction with excitation light emitted from the light source 3, and is transported by a fan 5 to a place away from the photocatalyst 2. It oxidizes things.
  • Examples of the photocatalyst 2 include titanium oxide, tungsten oxide, strontium titanate, niobium oxide, and tantalum oxide. Of these, tetravalent titanium (IV) oxide is preferable from the viewpoint of stability and strength of activity.
  • titanium oxide (IV) examples include anatase-type titanium oxide, rutile-type titanium oxide, and brookite-type titanium oxide. In addition to obtaining an antibacterial effect in the dark, anatase-type is obtained. Titanium oxide is preferred.
  • titanium oxide examples include titanium dioxide, hydrous titanium oxide, hydrated titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide, oxygen-deficient titanium oxide, nitrogen-substituted titanium oxide, and sulfur-substituted titanium oxide. It is done.
  • the crystal form is not particularly limited as long as it has photocatalytic activity, and any of amorphous, anatase, rutile, and brookite forms may be used. There is no problem even if components having different crystal forms such as a combination of rutile type and anatase type titanium oxide are combined.
  • Titanium oxide is often powdery, but a titanium oxide thin film may be formed by oxidizing a metal surface such as a titanium plate.
  • a titanium thin film may be formed by coating titanium alkoxide or the like and performing heat treatment.
  • a titanium oxide film may be formed by spraying titanium powder on a metal surface or the like.
  • titanium oxide it is not limited at all to coat the surface of titanium oxide with a metal such as Pt, Pd, Rh, Ru, Au, Ag, Cu, Fe, or Ni. Further, there is no limitation to using a photocatalyst whose surface has an impurity metal such as Cr or V to increase the absorption wavelength of light.
  • Titanium oxide has a specific surface area of preferably 200 m 2 / g or more and 350 m 2 / g or less, more preferably 250 m 2 / g or more and 350 m 2 / g or less.
  • the specific surface area in the present invention is a surface area value per gram of titanium oxide powder measured by a BET method (nitrogen adsorption / desorption method).
  • the specific surface area is 200 m 2 / g or more, the contact area with the object to be decomposed can be increased.
  • anatase type titanium oxide when the specific surface area is 350 m 2 / g or less, a photocatalytic reaction can be performed with higher efficiency than when amorphous titanium oxide is used.
  • an “oxo acid” is a compound having a hydroxyl group (OH) and an oxo group (C ⁇ O).
  • oxo acid a compound having a hydroxyl group (OH) and an oxo group (C ⁇ O).
  • those that are not oxidatively decomposed by the photocatalyst are preferable, and phosphoric acid, sulfuric acid, carbonic acid, nitric acid, and boric acid are exemplified
  • phosphoric acid when used as the oxo acid, it can be used as an aqueous solution having an appropriate concentration using a phosphate or hydrogen phosphate.
  • phosphoric acid compounds such as polyphosphoric acid and metaphosphoric acid, can be used similarly. Each of these phosphate compounds has a plurality of oxo groups in its structure.
  • radical substances are converted to stable compounds by oxoacids.
  • a structure containing a large amount of oxygen such as oxo acid is coordinated to a radical and converted into a more stable active substance.
  • examples of the halogen include fluorine, iodine, bromine and chlorine.
  • the fluorine content is 1.25 wt% or more and 4.0 wt% or less from the viewpoint of enhancing the amount of active substance generated and antibacterial performance during light irradiation. It is preferable.
  • the fluorine content in the fluorine-containing titanium oxide (IV) can be determined by an absorptiometric analysis method (JIS K 0102).
  • “at least a part of the halogen is chemically bonded to the photocatalyst” means that the photocatalyst, for example, titanium (IV) oxide, and at least a part of the halogen are chemically bonded. Preferably, it refers to a state where titanium oxide and halogen are bonded at an atomic level, not supported or mixed, and more preferably that titanium oxide and halogen are ionically bonded.
  • “chemically bonded halogen” refers to, for example, a halogen that is difficult to elute in water among the halogens contained in titanium oxide. In addition, when two or more types of halogens are contained, the effect can be obtained as long as one or more of them are chemically bonded.
  • the amount can be calculated by measuring the amount by colorimetric titration or the like and subtracting the elution amount from the total amount of halogen contained in the photocatalyst.
  • the chemical bond is preferably an ionic bond.
  • the chemical bond is an ionic bond
  • the halogen and the photocatalyst are firmly bonded, and for example, the antibacterial activity and the promoting action of the photocatalytic reaction can be improved.
  • the ionic bond between the photocatalyst and the halogen can be analyzed by a photoelectron spectrometer.
  • the halogen is fluorine and the photocatalyst is titanium oxide (IV)
  • the peak top of the fluorine 1s orbital (F1s) is 683 eV or more and 686 eV or less. This refers to the case of showing a spectrum as a range. This is because the value of the peak top of titanium fluoride in which fluorine and titanium are ion-bonded is within the above range.
  • the light source 3 for irradiating the excitation light is not particularly limited as long as it has an intensity at a wavelength of 370 nm or more and 400 nm or less.
  • strong light can be irradiated over a wide range, and therefore it can be suitably used when the substrate has a large area.
  • the light source 3 having a strong emission peak at the above wavelength there is one using a semiconductor element.
  • a semiconductor element for example, a light emitting diode or a semiconductor laser can be used. These are suitable for locally irradiating a small portion because the irradiation area is small and the size of the light source is small.
  • the active substance generated by the active substance generating apparatus of the present invention is the same as the active substance described in the first embodiment, and a description thereof will be omitted.
  • the photocatalyst 2 is arranged so as to surround the light source 3 formed of a glass tube, and the light from the light source is efficiently used as the photocatalyst. Can be irradiated. Further, when the photocatalyst 2 surrounding the light source 3 is made thick to prevent the excitation light from passing therethrough, it is possible to prevent the peripheral members from being deteriorated by the excitation light including ultraviolet rays.
  • the reflection plate 6 whose surface is made of metal is used, so that the excitation light from the light source 3 is reflected by the reflection plate 6 and the excitation light is re-appeared on the surface of the photocatalyst 2 again. Let it be irradiated.
  • the photocatalyst 2 preferably has a certain gap and opening as a porous body in order to ventilate around or inside.
  • the photocatalyst 2 is made porous, the surface area increases, the number of active substance generation sites increases, and the amount of active substance generation can be increased. Furthermore, since the contact efficiency with air improves, the quantity generated in the air can be increased.
  • a casing 4 can be provided.
  • the generation of the active substance is not directly related to the presence or absence of the casing. However, by providing the casing 4, leakage of light to the surroundings and loss of active substances due to natural diffusion can be prevented.
  • the casing 4 can be made of resin, metal, ceramic, or the like, but is preferably formed of a metal that is less deteriorated by the light source 3.
  • an air passage 7 including a photocatalyst 2 and a light source 3 is provided in the casing 4.
  • the air path 7 is disposed along the light source 3 so as to guide the airflow in the long axis direction of the light source 3.
  • the air path 7 is directly irradiated with light from the light source 3 or is in contact with an active substance generated from the photocatalyst 2, so that resin, metal, ceramic, etc. can be used, but preferably formed of metal. It is better.
  • the light source 3 when the light source 3 is a black light or a light emitting diode, the light emission intensity may be attenuated as the usage time elapses, and the photocatalytic reaction may be reduced. Therefore, it is preferable that the light source 3 has a detachable structure and can be replaced with a new light source 3 even when the light emission intensity is reduced.
  • the photocatalyst 2 is also preferably configured to be detachable because the inorganic component adsorbed on the surface accumulates as the usage time elapses and the photocatalytic reaction may decrease.
  • the casing 4 considering such attachment and detachment, a structure that can be divided so that it can be easily removed, or a structure that includes an opening that can be opened and removed is provided. Also good.
  • the active substance generated in the photocatalyst 2 is separated from the photocatalyst by heat, air current, etc., and is scattered far away by the transport unit.
  • a blower, a pressurization pump, a suction pump, etc. are used, and it disperses with the flow of air or compressed air.
  • compressed air such as a gas cylinder can be used for scattering of the active substance.
  • it is also effective to combine a mechanism for moving the photocatalyst 2 such as rotation and vibration in that the active substance is separated from the vicinity of the photocatalyst 2.
  • a fan 5 As a blower as shown in FIG.
  • an air volume, a wind speed, etc. can be set easily.
  • the casing 4 has at least one opening 4a from which the active substance can be released.
  • the louver 8 which is a conveyance direction control part for controlling the direction which conveys an active substance from the opening part 4a can be provided.
  • a stepping motor or the like whose angle is electrically adjusted by power, or one that manually switches the angle can be used.
  • the conveying direction of the active substance can be controlled by providing the louver 8 on the downstream side in the conveying direction of the photocatalyst 2.
  • the opening 4a is provided with a blowout port 12 for releasing the active substance, but another opening 4a may be provided and a suction port 13 for sucking the air supplied to the photocatalyst 2 into the casing 4 may be provided. . Further, when the pre-filter 9 is provided in the suction port 13, coarse dust can be removed, and performance degradation due to coarse dust adhering to the photocatalyst 2 and the light source 3 can be prevented.
  • a humidifying unit 10 for humidifying the air supplied to the photocatalyst 2 can be provided on the downstream side of the fan 5.
  • the humidification part 10 what can contain much water vapor
  • the prefilter 9 that attaches and ventilates water the one that sprays fine water droplets with pressure applied from the nozzle, or the water tank is provided and the water is refined by an ultrasonic vibrator.
  • a method etc. are used, if it can contain much water vapor
  • Adsorption of moisture in the air is indispensable for the photocatalytic reaction, but when the humidity is extremely low, the photocatalytic reaction may hardly occur. Therefore, by providing the humidification part 10 upstream of the photocatalyst 2 and supplying moisture, the photocatalytic reaction can be stably performed and the active substance can be generated stably.
  • the humidifying unit 10 is disposed so as to be adjacent to the photocatalyst 2, and the photocatalyst 2 is humidified by placing the steam at a distance that can be reached by natural diffusion. be able to.
  • a heater 11 that is a heating unit for heating the air supplied to the photocatalyst 2 can be provided on the downstream side of the fan 5. It is known that the activity of the photocatalytic reaction increases as the temperature increases, and the amount of active substance generated increases.
  • a nichrome wire, a PTC heater, a Peltier element, a refrigeration cycle, a hot water coil, a coil that recovers waste heat, or the like can be used.
  • the temperature heated by the heater 11 is preferably in a range not exceeding 100 ° C at which water is completely vaporized, preferably 10 ° C or more and 100 ° C or less, and preferably 20 ° C or more and 80 ° C or less, More preferably, it is 40 degreeC or more and 60 degrees C or less.
  • the heater 11 that is a heating unit and the humidifying unit 10 are both provided on the downstream side of the fan 5 and on the upstream side of the photocatalyst 2, but the amount of humidification increases when the heater 11 is on the upstream side of the humidifying unit 10. It is preferable from the point which can be made.
  • the photocatalyst 2 can be heated to a target temperature by arranging the heater 11 adjacent to the photocatalyst 2 together with the humidifying unit 10.
  • Examples 1 and 2 and Comparative Examples 1 and 2 shown in FIG. 1 and FIG. 2 and Table 1 is the same in Embodiment 2, and is described in detail in Embodiment 1. Description is omitted.
  • Example 3 An oxoacid and halogen-containing titanium oxide filter produced in the same manner as in Example 1 is a petri dish containing an ultraviolet light emitting diode (center wavelength of about 370 nm) and a circuit as an excitation light source and 20 mL of distilled water for trapping an active substance. And enclosed in a 6.7 L resin box. With the light emitting diode, the titanium oxide filter was irradiated with ultraviolet rays so as to be about 0.85 mW / cm 2. Boxes produced in the same manner were allowed to stand at 15 ° C., 30 ° C., and 40 ° C. After 15 hours, distilled water was taken out, and dissolved hydrogen peroxide and effective chloric acid concentrations were measured. The measurement was performed in the same manner as in Example 1.
  • FIG. 4 is a diagram showing a measurement result of the concentration of hydrogen peroxide with respect to temperature in the example of the active substance generating apparatus according to the second embodiment of the present invention.
  • FIG. 5 is a diagram showing a measurement result of an effective chlorine concentration with respect to temperature in the example of the active substance generating apparatus according to the second embodiment of the present invention.
  • the concentration of hydrogen peroxide trapped in distilled water was relatively low at 0.05 ⁇ M at 15 ° C., but it was 0.18 ⁇ M at 30 ° C., which was tripled. Furthermore, when it reached 40 ° C., it became 0.75 ⁇ M, an increase of 15 times compared with 15 ° C.
  • the concentration of hypochlorous acid which is available chlorine, also tended to increase as the temperature increased to 15 ° C., 30 ° C., and 40 ° C., as shown in FIG. Although there may be a slight difference in the suitable temperature depending on the type of active substance to be generated, it has been clarified that the amount of active substance generated increases by increasing the temperature.
  • the active substance generator of the present invention comprises a photocatalyst 2 containing at least oxo acid and a light source 3 for irradiating the photocatalyst 2 with excitation light, and irradiates the photocatalyst 2 with the excitation light to generate an active substance. Consists of configuration.
  • This structure has an effect of converting an active substance generated on the surface of titanium oxide, for example, a hydroxyl radical into an active oxygen species having a relatively long life such as hydrogen peroxide.
  • an active substance generated on the surface of titanium oxide for example, a hydroxyl radical
  • an active oxygen species having a relatively long life such as hydrogen peroxide.
  • the photocatalyst 2 may be configured to contain at least a halogen. With this configuration, the activity of the photocatalyst 2 can be improved and the generation of active substances can be increased.
  • a configuration in which at least a part of the halogen is chemically bonded to the photocatalyst 2 may be employed. With this configuration, the halogen and the photocatalyst 2 are firmly bonded, and for example, the amount of active substance generated can be improved.
  • the photocatalyst 2 may include titanium (IV) oxide. With this configuration, ultraviolet light having high energy can be used as excitation light, and the amount of active substance generated can be increased.
  • the photocatalyst 2 may be a porous body.
  • the amount of active substance generated can be increased by increasing the surface area of the photocatalyst 2 and increasing the photocatalytic reaction.
  • the efficiency of contact with the air current is improved, and the efficiency in which the generated active substance is volatilized in the air from the vicinity of the photocatalyst 2 and is transported out of the active substance generator 1 can be improved.
  • the photocatalyst 2 may be fixed to the base material. With this configuration, scattering of the photocatalyst powder can be prevented, and the photocatalyst 2 and the active substance can be easily separated. Furthermore, since the photocatalyst 2 can be formed into a free shape in accordance with the base material, the active substance can be effectively generated with the optimum shape.
  • the base material may be at least one of ceramic, glass, and metal.
  • the photocatalyst 2 may be arranged so as to surround the light source 3. With this configuration, excitation light that is not irradiated onto the photocatalyst 2 can be reduced, and an active substance can be generated efficiently.
  • the light source may be a black light or a semiconductor element. With this configuration, it is possible to efficiently irradiate a large area with ultraviolet rays and increase the amount of active substance generated.
  • an air passage 7 for guiding an air flow along the long axis direction of the light source 3 may be provided.
  • the length of passage through the region where the active substance is generated can be increased, and the concentration of the active substance in the air can be increased by continuously generating the active substance in the passing air.
  • the light source 3 may be a semiconductor element. With this configuration, it is possible to irradiate light locally to a minute region and further reduce the size of the whole.
  • a configuration including a reflection plate 6 that reflects light from the light source 3 may be employed.
  • this configuration when the excitation light emitted from the light source 3 leaks without being irradiated to the photocatalyst 2, it can be reflected and re-irradiated to the photocatalyst 2, and the amount of active substance generated can be increased.
  • a configuration may be provided in which a transport unit that transports the active substance generated from the photocatalyst 2 is provided.
  • the active substance can be transported to the object, and the generation efficiency of the active substance on the surface of the photocatalyst 2 can be increased.
  • the transport unit may be configured to blow air to the photocatalyst 2 and transport the active substance from the photocatalyst 2.
  • the generated active substance does not come into contact with the transport unit and is not decomposed, so that the active substance is less likely to decrease, and more active substance can be released.
  • it can prevent that a conveyance part deteriorates by corrosion etc. with an active substance.
  • the conveyance unit may be a fan 5.
  • a configuration may be adopted in which a casing 4 having at least one opening 4 a is provided, and the photocatalyst 2 and the light source 3 are housed in the casing 4.
  • the generated active substance can be released from the opening 4a, and is prevented from being attenuated by natural diffusion.
  • a high concentration active substance can be supplied to the target site.
  • harmful rays such as ultraviolet rays emitted from the light source 3 can be prevented from being emitted to the surroundings.
  • the photocatalyst 2 and the light source 3 may be detachable from the casing 4.
  • the light source 3 whose light amount has decreased due to aging and the photocatalyst 2 that has deteriorated due to adsorption of inorganic salts or the like can be replaced with a new light source 3 and photocatalyst 2, and the performance that has deteriorated over time can be recovered by replacement. can do.
  • the active substance generated inside the casing 4 can be efficiently conveyed by the air current to the vicinity of the object to be decomposed, and the oxidation reaction can be performed efficiently.
  • a prefilter may be provided upstream of the photocatalyst 2 in the transport direction.
  • a configuration in which a humidifying unit 10 for humidifying the photocatalyst 2 may be provided. With this configuration, even when the air condition is low, by supplying water necessary for the photocatalytic reaction, the photocatalytic reaction can be stably performed, and the active substance can be stably generated.
  • a heating part for heating the photocatalyst 2 for example, a heater 11 may be provided.
  • the photocatalyst 2 or the surrounding air can be heated, the photocatalytic reaction can be improved, and the amount of active substance generated can be increased.
  • FIG. 6 is sectional drawing which shows schematic structure of the air purifying apparatus concerning Embodiment 3 of this invention.
  • the air purifying apparatus according to the third embodiment includes a photocatalyst 105 as an active substance generating material, a light source 104, and air purification in a main body 103 having a suction port 101 and a blowout port 102. It is set as the structure provided with the part 112 and the ventilation part 113.
  • the photocatalyst 105 contains at least oxo acid
  • the light source 104 is for irradiating the photocatalyst 105 with excitation light 104a.
  • the active substance generator is, for example, the apparatus shown in FIG.
  • the purification unit 112 includes a dust collection filter 106 and a deodorizing filter 107
  • the air blowing unit 113 includes a fan 108 that blows out at least a part of the air sucked from the suction port 101 from the blowout port 102.
  • the air containing the active substance generated from the active substance generator including the photocatalyst 105 as the active substance generating material moves to the dust collection filter 106 or the deodorizing filter 107 as the purification unit 112.
  • the air containing the active substance reacts with bacteria, molds, viruses, allergens, odor components, organic substances, etc. adhering to or adsorbing to the purification unit 112, and has the effect of decomposing or reducing the activity.
  • the active substance is released into the room from the main body 103 of the air purifier, and reacts with germs, molds, viruses, allergens, odor components, organic substances, etc. adhering to the air or on the wall surface, thereby decomposing / antibacterial or reducing the activity. The effect is obtained.
  • the photocatalyst 105 is arranged so as to surround the light source 104 and efficiently irradiates the photocatalyst 105 with light from the light source 104. can do. Further, when the thickness of the photocatalyst 105 surrounding the light source 104 is increased to prevent light from being transmitted, peripheral members can be prevented from being deteriorated by light such as ultraviolet rays.
  • the reflection plate whose surface is formed of metal or glass around the photocatalyst 105, the reflection plate reflects the light from the light source 104, and the photocatalyst 105 is efficiently formed.
  • the surface can be irradiated with light.
  • the ventilation path (not shown), the purification unit 112, and the air blowing unit 113 constituting the main body 103 is made of a material that is inactive with respect to the active substance.
  • cleaning part 112, and the ventilation part 113 do not deteriorate with an active substance, and can obtain a reliable air cleaner.
  • a material inert to the active substance metals such as stainless steel and aluminum, glass, alumina, mica and the like can be used. A resin may be used as long as the influence of deterioration is small.
  • the ventilation path itself may be formed by the photocatalyst 105, such as coating the metal surface with the photocatalyst 105.
  • a blower As the air blowing unit 113, a blower, a fan 108, a pump, or the like can be used. By using the fan 108, an air volume, a wind speed, etc. can be set easily. Furthermore, a louver that changes the direction of the wind may be used.
  • the dust collection filter 106 There is no particular problem with the dust collection filter 106 as long as dust, fungi, mold, etc. in the air can be collected, and general filter materials such as nets, knitted fabrics / woven fabrics, nonwoven fabrics, and glass fibers should be used. Can do.
  • the deodorizing filter 107 is not particularly limited as long as it can adsorb odorous substances in the air, and it is possible to use a filter in which an adsorbent such as activated carbon, zeolite, silica gel, sepiolite is fixed to fiber or paper. it can. Those that are less likely to deteriorate with respect to the active substance are preferred.
  • the air purifying apparatus of the present invention includes a photocatalyst 105 containing at least oxo acid and a light source 104 for irradiating the photocatalyst 105 with excitation light 104a in a main body 103 having a suction port 101 and a blowout port 102. Yes.
  • the air purifying apparatus irradiates the photocatalyst 105 with the excitation light 104a to generate an active substance, the air purifying unit 112, and at least a part of the air sucked from the suction port 101. It consists of the structure provided with the ventilation part 113 for blowing out from.
  • an air purifier capable of generating an active substance that is stable, has a long life, and can be released from the photocatalyst 105 to the gas phase, etc., and can react with an object to be processed such as germs and organic substances in a remote place. Can be provided.
  • FIG. 7 is sectional drawing which shows schematic structure of the air purifying apparatus concerning Embodiment 4 of this invention.
  • the air cleaning device of the fourth embodiment contains a light emitting diode as a light source 104 for irradiating light and at least an oxo acid in a main body 103 having a suction port 101 and a blowout port 102.
  • Active material generating material for example, photocatalyst 105 is contained.
  • the air purifier includes an active substance generating material 105 that releases an active substance by irradiating light, a dust collection filter 106 and a deodorizing filter 107 as an air purification unit 112, and a fan 108 as a blower 113. It has.
  • the active material generating material 105 containing at least an oxo acid and a photocatalyst and the zeolite as a deodorizing adsorbent are held and integrated on a base material 103a having an opening 104b so that air can pass through.
  • the integrated active material generating material 105 and the adsorbent are mixed so that the blending ratio of the active material generating material 105 becomes higher as the distance from the light emitting diode as the light source 104 is closer, and the base material 103a is mixed. Is held in.
  • the air containing the active substance generated from the active substance generating device including the active substance generating material 105 passes through the dust collection filter 106 or the deodorizing filter 107 as the purification unit 112.
  • the air containing this active substance can react with various bacteria, molds, viruses, allergens, odor components, organic substances, etc. adhering to or adsorbing to the purification unit 112, and can obtain an effect of decomposing or reducing the activity. Since the active substance generating material 105 has a higher blending ratio as the distance from the light emitting diode as the light source 104 is closer, more active substances can be generated. In addition, since the active substance generating material 105 and the adsorbent are mixed, the odor component adsorbed on the adsorbent and the active substance can be reacted in a shorter time.
  • a bypass ventilation path as a ventilation path composed of glass as the light transmissive member 109 and a thin film of the active material generating material 105 a coated on the inner surface of the glass as the light transmissive member 109. 110 is provided.
  • the room light that has passed through the glass as the light transmissive member 109 is irradiated to the active substance generating material 105a to release the active substance, and at the same time, from the outlet 102 of the main body 103 into the room by the action of the fan 108 as the blower 113. Released.
  • the active substance released into the room from the main body 103 of the air cleaning device reacts with germs, molds, viruses, allergens, odor components, organic substances, etc. adhering to the air or on the wall surface, and has the effect of decomposing or reducing the activity. be able to.
  • the air purifying apparatus of the present invention includes a photocatalyst 105 containing at least oxo acid and a light source 104 for irradiating the photocatalyst 105 with excitation light 104a in a main body 103 having a suction port 101 and a blowout port 102. Yes.
  • the air purifying apparatus irradiates the photocatalyst 105 with the excitation light 104a to generate an active substance, the air purifying unit 112, and at least a part of the air sucked from the suction port 101.
  • an air blowing unit 113 for blowing out the air.
  • the purifying unit 112 may include at least one of the dust collection filter 106 and the deodorizing filter 107, and the active substance generated from the active substance generating device may be supplied to the upstream side of the purifying part 112.
  • an air purifier capable of generating an active substance that is stable, has a long life, and can be released from the photocatalyst 105 to the gas phase, etc., and can react with an object to be processed such as germs and organic substances in a remote place.
  • an object to be processed such as germs and organic substances in a remote place.
  • the odorous substance collected by the deodorizing filter 107 and the active substance can be reacted, so that the deodorizing performance of the deodorizing filter 107 can be further improved and the life can be extended.
  • the active substance generated from the active substance generator may be configured to include a bypass ventilation path 110 that is supplied indoors without passing through the purification unit 112.
  • the deodorizing filter may include the photocatalyst and an adsorbent, and the photocatalyst content rate may be increased at a position where a large amount of light is irradiated from the light source to the deodorizing filter.
  • the deodorizing filter includes the adsorbent
  • the content rate of the active substance generating material 105a is relatively increased at the position where the amount of light is large, an effect that more active substances are generated can be obtained.
  • the reaction probability between the odor component collected by the adsorbent and the active substance is increased, the deodorization is efficiently performed, and the adsorbent can be regenerated and used for a long time.
  • FIG. 8 is sectional drawing which shows schematic structure of the air purifying apparatus concerning Embodiment 5 of this invention.
  • the air purifying apparatus according to the fifth embodiment contains a light emitting diode as a light source 104 for irradiating light in a main body 103 having a suction port 101 and a blowout port 102, and at least oxo acid. It has a photocatalyst 105 as an active material generating material.
  • the air purifier includes an active substance generating material 105 that releases an active substance by irradiating light, a dust collection filter 106 and a deodorizing filter 107 as an air purification unit 112, and a fan 108 as a blower 113. It has.
  • the active substance generating material 105 is held on the surface of a fluororesin film as the light transmissive member 109, and transmits light from a room such as a fluorescent lamp (not shown) and light from a light emitting diode as the light source 104 on the front and back surfaces. Can receive a large amount of active substance.
  • the bypass ventilation path 110 is provided with a damper 111 that opens and closes the bypass ventilation path 110. By opening and closing the damper 111 and switching the air flow rate of the bypass ventilation path 110, the air containing the active substance can be supplied to the dust collection filter 106 and the deodorization filter 107 in an arbitrary amount.
  • the generated air containing the active substance passes through the dust collection filter 106 or the deodorization filter 107 as the purification unit 112 by the fan 108, and the bacteria, mold, virus, allergen, odor component, organic matter, etc. adhering to or adsorbing to the purification unit 112 It is possible to obtain the effect of decomposing or reducing the activity. Moreover, it reacts with various germs, molds, viruses, allergens, odorous components, organic substances, etc. released in the room and attached to the air or on the wall surface, thereby obtaining the effect of decomposing / antibacterial or reducing the activity.
  • the air purifying apparatus of the present invention includes a photocatalyst 105 containing at least oxo acid and a light source 104 for irradiating the photocatalyst 105 with excitation light 104a in a main body 103 having a suction port 101 and a blowout port 102. Yes.
  • the air purifying apparatus irradiates the photocatalyst 105 with the excitation light 104a to generate an active substance, the air purifying unit 112, and at least a part of the air sucked from the suction port 101.
  • an air blowing unit 113 for blowing out the air.
  • a part of the main body 103 is constituted by a light transmissive member 109.
  • an air purifier capable of generating an active substance that is stable, has a long life, and can be released from the photocatalyst 105 to the gas phase, etc., and can react with an object to be processed such as germs and organic substances in a remote place. Can be provided. Furthermore, it becomes easier to capture the light of the indoor fluorescent lamp and sunlight through the light transmissive member 109, and more active substances can be generated from the active substance generating material.
  • FIG. 9 is sectional drawing which shows schematic structure of the air purifying apparatus concerning Embodiment 6 of this invention.
  • the air purifying apparatus according to the sixth embodiment includes a black light as a light source 124 for irradiating light in a main body 123 having a suction port 121 and a blowout port 122.
  • the air purifier includes at least an oxo acid and a photocatalyst 125, and releases an active substance when irradiated with light, a humidifying filter 126 as a humidifying unit, a heater 127, and a fan 128. And.
  • the humidifying filter 126 is a humidifying unit that humidifies air and supplies moisture to the active substance generating material 125.
  • the heater 127 is a heating unit for heating the humidification unit, and the fan 128 is a blower unit.
  • the active substance generator 150 includes a light source 124 and an active substance generator 125.
  • the active material generating material 125 is fixed on the surface of a heat transfer plate 129 as a heating unit for heating the active material generating material 125, and the heat transfer plate 129 generates heat using the heat of the heater 127, and the active material The temperature of the generating material 125 can be raised.
  • the humidifying filter 126 is wetted when water 131 is supplied from a water tank 130 as a water supply unit. Moisture can be supplied to the active substance generating material 125 by the air passing through the humidified humidifying filter 126. An active substance can be generated from the active substance generating material 125 by controlling the active substance generating material 125 to an appropriate temperature by the heat transfer plate 129 and irradiating light from the light source 124 while supplying moisture. .
  • the active substance can be generated more efficiently by reflecting the light generated from the light source 124 by the reflecting plate 132.
  • the air containing the generated active substance is released into the room by the fan 128 and reacts with germs, molds, viruses, allergens, odorous components, organic substances, etc. adhering to the air or on the wall surface, decomposing / antibacterial or reducing activity. An effect can be obtained.
  • the air can contain a large amount of water vapor.
  • a nozzle that sprays fine water droplets with pressure applied from a nozzle, or a water tank is provided to refine water with an ultrasonic vibrator. A method or the like is used.
  • this is not limited as long as it can contain a large amount of water vapor in the air.
  • Adsorption of moisture in the air is indispensable for the photocatalytic reaction, but when the humidity is extremely low, the photocatalytic reaction may hardly occur. For this reason, by providing a humidifying section in front of the air supplied to the photocatalyst 125 and supplying moisture, the photocatalytic reaction can be performed stably and the active substance can be generated stably.
  • a heater may be provided as a heating unit for heating the air supplied to the photocatalyst 125. It is known that the activity of the photocatalytic reaction increases as the temperature increases, and the amount of active substance generated increases.
  • the heating unit for heating the active material generating material 125 one that can control the temperature by the amount of electricity or hot water is preferable. For example, nichrome wire, PTC heater, infrared lamp, refrigeration cycle, hot water coil, or waste heat is recovered. Coil, heat transfer plate, etc. can be used.
  • the heating temperature is preferably within a range not exceeding 100 ° C at which water is completely vaporized, preferably 10 ° C or more and 100 ° C or less, preferably 20 ° C or more and 80 ° C or less, Preferably they are 40 degreeC or more and 60 degrees C or less.
  • a light emitting diode is used as a light source, it is preferably used at a temperature of 80 ° C. or lower because deterioration of the element is accelerated by heat and the life is shortened.
  • the heating unit for heating the active substance generating material 125 is not limited as long as the heating unit can be heated to an appropriate temperature, such as a nichrome wire, a PTC heater, an infrared lamp, a refrigeration cycle, a hot water coil, a coil that collects waste heat, A hot plate can be used. Heated air may be blown onto the active substance generating material 125.
  • the reflector 132 is not particularly limited as long as it reflects light, and aluminum, glass, stainless steel, or the like can be used.
  • the reflecting plate 132 is arranged on the side surface of the lamp.
  • a plurality of the reflecting plates 132 or the entire vicinity of the ventilation path where the active substance generating material 125 is fixed may be made of a material having a light reflecting action. Good.
  • Example 4 Example except that an active material generating material containing oxo acid and halogen-containing titanium oxide prepared in the same manner as in Example 1 was used, and dry air (temperature of about 25 ° C., relative humidity of 0%) was supplied from the upstream side. In the same procedure as in No. 1, the amount of active substance generated was measured. In air with a humidity of 0%, the amount of hydrogen peroxide generated was below the detection limit (less than 0.1 nmol) even after 24 hours. From the test of Example 1, it is known that the active substance generating material can generate about 153 nmol of hydrogen peroxide after 24 hours in air of 50% humidity, and the presence of water is necessary for the generation of the active substance. I understood it.
  • the air purifying device of the present invention includes a photocatalyst 125 containing at least oxo acid and a light source 124 for irradiating the photocatalyst 125 with excitation light in a main body 123 having a suction port 121 and a blowout port 122. . Then, the air purifier blows at least a part of the air sucked from the active substance generator, the air purifier, and the air inlet 121 from the air outlet 122 by irradiating the photocatalyst 125 with the excitation light. It consists of the structure provided with the ventilation part 128 for taking out.
  • an air purifier that can generate an active substance that is stable, has a long life, and can be released from the photocatalyst 125 to the gas phase, etc., and can react with an object to be processed such as germs or organic substances in a remote place. Can be provided.
  • the oxo acid may be at least one compound selected from compounds containing phosphoric acid, sulfuric acid, carbonic acid, nitric acid, or boric acid.
  • the active material generating material may contain halogen.
  • halogen the activity of the photocatalyst can be improved and the generation of the active substance can be increased.
  • chlorine compounds such as hypochlorous acid and chlorine, can be produced
  • a structure in which a halogen compound is chemically bonded to the photocatalyst and then an oxo acid is attached may be employed.
  • the halogen radical and the photocatalyst are chemically bonded to increase the amount of hydroxyl radicals generated, and the generated hydroxyl radicals are efficiently converted into hydrogen peroxide, hypochlorous acid, by the action of oxo acids present on the surface. It can be changed to a long-lived active species such as chlorine.
  • At least a part of the ventilation path may be formed of an active material generating material.
  • the purification unit may be composed of an active substance generating material.
  • the content of the active substance generating material at a position where the amount of light irradiated to the purification unit is large may be increased.
  • the content of the active substance generating material is relatively increased at a position where the amount of light is large, an effect that more active substances are generated can be obtained.
  • At least a part of the ventilation path, the purification unit, and the air blowing unit constituting the main body may be made of a material that is inert to the active substance.
  • the active substance generating material may be arranged in the upper part of the main body, and the upper part of the main body may be constituted by a light transmissive member.
  • the light from the indoor fluorescent lamp and sunlight can be easily taken in through the light transmissive member, and more active substances can be generated from the active substance generating material.
  • a configuration including a light source that emits light including ultraviolet rays may be employed.
  • the active substance can be stably generated from the active substance generating material by the ultraviolet rays generated from the light source.
  • the light source may be an ultraviolet lamp. With this configuration, more active substances can be generated from the active substance generating material by the strong ultraviolet rays generated from the ultraviolet lamp.
  • the light source may be a light emitting diode.
  • the light-emitting diode has good light directivity, and it is easy to adjust the direction so that only the active substance generating material is exposed to ultraviolet rays, and the active substance is efficiently utilized by using strong ultraviolet rays generated from the lamp. Can be generated.
  • a configuration may be adopted in which a light reflector is provided around the light source. With this configuration, the ultraviolet rays generated from the light source can be efficiently used by using the reflector.
  • a configuration including a heating unit for heating the active substance generating material may be employed. With this configuration, a large amount of active substance can be generated by heating the active substance generating material.
  • a configuration may be provided that includes a humidifying unit that supplies moisture to the active substance generating material.
  • a humidifying unit that supplies moisture to the active substance generating material.
  • FIG. 10 is sectional drawing which shows schematic structure of the humidification apparatus concerning Embodiment 7 of this invention.
  • the humidifying device of the seventh embodiment includes an ultraviolet lamp as a light source 204 for irradiating light and an active substance generating material 205 in a main body 203 having a suction port 201 and a blowout port 202.
  • the humidifying device includes an active substance generating device 210 including a humidifying unit 211, a water supply unit 212, and a blower unit 213.
  • the humidification apparatus of this Embodiment 7 is set as the structure which blows off the active substance which generate
  • the active substance generating material 205 contains at least an oxo acid and a photocatalyst, and releases the active substance when irradiated with light.
  • the humidifying unit 211 has, for example, an ultrasonic element 206 and humidifies air to supply moisture to the active substance generating material 205.
  • the blower 213 includes a fan 207 as a blower, for example.
  • the ultrasonic element 206 is supplied with water 209 from a water tank 208 serving as a water supply unit 212, and generates humid air in the main body 203 and in the room.
  • the active substance generating material 205 is obtained by fixing an oxo acid and a photocatalyst on a glass fiber woven base material using a binder, and is arranged so as to surround the rod-shaped light source 204.
  • the active substance generating material 205 can generate an active substance by receiving appropriate moisture and light from the light source 204. As shown in FIG. 10, the active substance generating material 205 is provided on the upstream side of the ultrasonic element 206 of the humidifying unit 211. For this reason, the air containing the generated active substance is moved by the fan 207 and reacts with various germs, molds, organic substances, etc. in the water, and the effect of decomposing / antibacterial or reducing the activity can be obtained. Some of them are released indoors and can react with various germs, molds, viruses, allergens, odor components, organic substances, etc. adhering to the air or on the wall surface, and the effect of decomposing / antibacterial or reducing the activity can be obtained. .
  • the photocatalytic reaction In the photocatalytic reaction, adsorption of moisture in the air is indispensable. However, when the humidity is extremely low, the photocatalytic reaction may be difficult to occur. Therefore, by providing the humidification part 211 and sufficiently supplying water to the photocatalyst, the photocatalytic reaction can be performed stably and the active substance can be generated stably.
  • the photocatalyst is efficiently irradiated with light from the light source 204 when arranged so as to surround the light source 204. can do. Further, when the thickness of the photocatalyst surrounding the light source 204 is increased to prevent light from being transmitted, peripheral members can be prevented from being deteriorated by light such as ultraviolet rays. In addition, by using a reflecting plate whose surface is formed of metal or glass around the photocatalyst, the reflecting plate reflects the light from the light source, and the surface of the photocatalyst can be efficiently irradiated with light.
  • the ventilation path 214 is made of a material that is inactive with respect to the active substance.
  • the main body 203, the humidification part 211, and the ventilation part 213 do not deteriorate with an active substance, and a highly reliable humidification apparatus can be obtained.
  • a material inert to the active substance metals such as stainless steel and aluminum, glass, alumina, mica and the like can be used.
  • a resin may be used as long as the influence of deterioration is small.
  • the ventilation path 214 itself may be formed with a photocatalyst, for example, a metal surface is coated with a photocatalyst.
  • a blower As the air blowing unit 213, a blower, a fan, a pump, or the like can be used. By using a fan, an air volume, a wind speed, etc. can be set easily. Furthermore, a louver that changes the direction of the wind may be used.
  • the humidifying unit 211 As the humidifying unit 211, a filter that allows moisture to attach to the filter and aeration, a spray that sprays fine water droplets with pressure applied from a nozzle, or a water tank 208 as shown in FIG.
  • the method of making water fine is mentioned, The method of evaporating water using a humidification filter is preferable. Adsorption of moisture in the air is indispensable for the photocatalytic reaction, but when the humidity is extremely low, the photocatalytic reaction may hardly occur. Therefore, the humidification part 211 is provided in the front stage of the air supplied to the photocatalyst to supply moisture, so that the photocatalytic reaction can be performed stably and the active substance can be generated stably.
  • a dust collection filter that collects dust may be provided in the main body 203 having the suction port 201 and the blowout port 202. There are no particular problems with the dust collection filter as long as dust, fungi, mold, etc. in the air can be collected. Common filter materials such as nets, knitted fabrics / woven fabrics, nonwoven fabrics, and glass fibers can be used. it can.
  • a deodorizing filter for removing odor may be provided in the main body 203 having the suction port 201 and the blowout port 202.
  • the deodorizing filter is not particularly limited as long as it can adsorb odorous substances in the air, and an adsorbent such as activated carbon, zeolite, silica gel, or sepiolite immobilized on fibers or paper can be used. Those that are less likely to deteriorate with respect to the active substance are preferred.
  • the humidifying device of the present invention includes a photocatalyst containing at least oxo acid and a light source for irradiating the photocatalyst with excitation light, and irradiating the photocatalyst with excitation light in a main body having an inlet and an outlet.
  • An active substance generating device that generates an active substance, a humidifying unit that generates mist or water vapor, a water supply unit that supplies water to the humidifying unit, and an air blowing unit, the active material generating The active substance generated from the apparatus and the air containing mist or water vapor are configured to be blown out from the outlet by the blower.
  • This configuration provides a humidifier that can generate an active substance that is stable, has a long life, and can be released from the photocatalyst into the gas phase, and can react with an object to be treated such as germs and organic substances in a remote location. can do.
  • the oxo acid may be at least one compound selected from compounds containing phosphoric acid, sulfuric acid, carbonic acid, nitric acid, or boric acid.
  • the active material generating material may contain halogen.
  • halogen a photocatalyst such as titanium oxide
  • chlorine compounds such as hypochlorous acid and chlorine
  • the configuration with active material generating material on the upstream side of the humidifying part is very good.
  • active substances can be reacted with germs, molds, viruses, organic substances and the like contained in the air sucked into the main body from the suction port, and the air can be humidified while being kept in a cleaner state.
  • FIG. 11 is sectional drawing which shows schematic structure of the humidification apparatus concerning Embodiment 8 of this invention.
  • the humidifier according to the eighth embodiment includes a black light as a light source 224 that irradiates light and an active substance generating material 225 in a main body 223 having an inlet 221 and an outlet 222.
  • a humidifying filter 226 serving as a humidifying unit, and a fan 227 serving as a blowing unit.
  • the active material generating material 225 contains at least an oxo acid and a photocatalyst, and releases the active material when irradiated with light.
  • the humidifying filter 226 humidifies the air and supplies moisture to the active substance generating material 225.
  • the humidifying filter 226 is made of a fibrous nonwoven fabric base material mainly composed of ceramic, and an active material generating material 225 containing an oxo acid and a photocatalyst is fixed on the surface and integrated.
  • an active material generating material 225 containing an oxo acid and a photocatalyst is fixed on the surface and integrated.
  • phosphoric acid as an oxo acid and sodium chloride (NaCl) as a salt containing a halogen are dissolved.
  • the humidifying filter 226 is wetted by supplying water 229 from a water tank 228 serving as a water supply unit, and can supply moisture, oxoacid and halogen salts to the active material generating material 225.
  • the active substance generating material 225 can generate an active substance by receiving moderate moisture and light from the light source 224.
  • the air containing the generated active substance is moved by the fan 227 and reacts with various germs, molds, organic substances, etc. in the water, and the effect of decomposing / antibacterial or reducing the activity can be obtained. Some of them are released indoors and can react with various germs, molds, viruses, allergens, odor components, organic substances, etc. adhering to the air or on the wall surface, and the effect of decomposing / antibacterial or reducing the activity can be obtained. .
  • the second active substance generating material 230 may be provided inside the water tank 228. The effect of generating the active substance by reacting the second active substance generating material 230 at a position where light can be received, reacting with various germs, fungi, organic matter, etc. in the water, decomposing / antibacterial or reducing the activity Can be obtained.
  • the composition of the active substance generating material may change.
  • hypochlorous acid and chlorine are generated as active substances
  • the chlorine component may be reduced from the active substance generating material.
  • phosphoric acid as the oxo acid and sodium chloride (NaCl) as the salt containing halogen are dissolved in the water 229 in the water tank 228, so that the chlorine component can be replenished.
  • the active ingredient containing a chlorine component can be released over a long period of time.
  • the air containing the active substance may be brought into contact with water supplied from a water supply unit such as a water tank.
  • a water supply unit such as a water tank.
  • the photocatalyst may be provided at a position in contact with water supplied from the water supply unit.
  • water necessary for generating the active substance can be supplied to the active substance generating material, and the active substance can be stably generated.
  • the water supplied from the water supply unit may include at least one salt of oxo acid and halogen.
  • a chlorine compound such as hypochlorous acid or chlorine
  • a medium such as a gas phase
  • the amount of salt present in the active material generating material decreases. Therefore, the amount and time of generation of the chlorine compound can be increased by bringing the aqueous solution containing at least one of oxo acid and halogen into contact with the active substance generating material.
  • FIG. 12 is sectional drawing which shows schematic structure of the humidification apparatus concerning Embodiment 9 of this invention.
  • the humidifying device of the ninth embodiment includes a light emitting diode as a light source 234 for irradiating light and an active substance generating material 235 in a main body 233 having a suction port 231 and a blowout port 232. It has an active substance generator 250, a humidifying filter 236 as a humidifying unit, and a fan 237 as a blowing unit.
  • the active substance generating material 235 contains at least an oxo acid and a photocatalyst, and releases the active substance when irradiated with light.
  • the humidification filter 236 humidifies the air and supplies moisture to the active substance generating material 235.
  • the humidifying filter 236 is made of a polyester three-dimensional knitted fabric, and an active material generating material 225 in which an oxo acid and a photocatalyst are fixed on a polyester fiber knitted base material using a silicone resin binder on an outer peripheral portion. It has a wound configuration.
  • phosphoric acid as an oxo acid and sodium chloride (NaCl) as a salt containing a halogen are dissolved.
  • the humidification filter 236 is rotatable, and draws water 239 from the water tank 238 as a water supply unit by rotating.
  • the humidifying filter 236 can keep the water 239 on the surface and supply water, oxo acid and halogen salts to the active substance generating material 235.
  • the active substance generating material 235 can generate an active substance by receiving moderate moisture and light from the light source 234.
  • the active substance generating material 235 is rotated integrally with the humidifying filter 236, the light from the light source 234 is irradiated on the entire active substance generating material 235 as it rotates.
  • the upstream side of the active substance generating material 235 is provided with a heater 240 as a heating unit for heating air. It is known that the activity of the photocatalytic reaction increases as the temperature increases, and the amount of active substance generated increases.
  • a heater 240 a nichrome wire, a PTC heater, a Peltier element, a refrigeration cycle, a hot water coil, a coil that recovers waste heat, or the like can be used.
  • the temperature heated by the heater 240 is preferably within a range not exceeding 100 ° C. at which the water 239 is completely vaporized, preferably 10 ° C. or more and 100 ° C. or less, and preferably 20 ° C. or more and 80 ° C. or less.
  • the light emitting diode is used as the light source 234, it is preferable to use the light emitting diode at a temperature of 80 ° C. or lower because deterioration of the element is accelerated by heat and the life is shortened.
  • the air containing the generated active substance is moved by the fan 237 and reacts with various germs, fungi, organic matter, etc. in the water, and the effect of decomposing / antibacterial or reducing the activity can be obtained. Some of them are released indoors and can react with various germs, molds, viruses, allergens, odor components, organic substances, etc. adhering to the air or on the wall surface, and the effect of decomposing / antibacterial or reducing the activity can be obtained. .
  • the active material generating material 235 is coated on the surface of the member constituting the outlet 232, the organic matter adhering to the member forming the outlet 232 is decomposed using the light of indoor lighting (not shown). The effect of suppressing the generation of mold and bacteria can be obtained.
  • the humidification section may be a humidification filter.
  • the humidifying filter expands the contact area between the water supplied from the water supply unit to the humidifying unit and the active substance in the air, and the active substance and the germs, molds, viruses, organic substances, etc. contained in the water The reaction of can be promoted. Thereby, humidification can be performed while keeping water in a cleaner state.
  • the humidification filter may be cylindrical. With this configuration, if the humidifying filter is cylindrical rather than plate-like, the wind speed on the filter surface when the same air volume is allowed to pass can be reduced. As a result, the contact efficiency between the water supplied from the water supply unit to the humidification unit and the active substance in the air is improved, and the reaction between the active substance and various germs, molds, viruses, organic substances, etc. contained in the water is promoted. be able to. Thereby, humidification can be performed while keeping water in a cleaner state.
  • the active material generating material and the humidifying filter may be integrated. With this configuration, the reaction between the active substance and the germs, molds, viruses, organic substances and the like contained in the water supplied from the water supply unit to the humidification unit can be accelerated. Further, by fixing the active substance generating material to the humidifying filter, a base material for fixing the powdery active substance generating material becomes unnecessary.
  • a humidification filter which consists of the water immersion part immersed in the water supplied from a water supply part, and the ventilation part through which air passes, Comprising: It is good also as a structure by which light is irradiated only to the ventilation part of a humidification filter.
  • the intensity of light is attenuated by water in the flooded part, but since the light is less attenuated in the ventilation part, the active substance can be efficiently generated from the humidifying filter.
  • a configuration in which the humidifying filter is rotatable may be employed. With this configuration, when the humidifying filter rotates, the entire humidifying filter can be irradiated with light without bias. Moreover, the whole humidification filter can be efficiently moistened.
  • a light source that irradiates light may be provided to irradiate the active substance generating material with light.
  • the active substance can be stably generated from the active substance generating material by the ultraviolet rays generated from the light source.
  • the light source may be a light emitting diode.
  • the light emitting diode has good light directivity, and it is easy to adjust the direction so that only the active material generating material is exposed to light, and the active material can be generated efficiently.
  • a configuration including a heating unit for heating the active substance generating material may be employed. With this configuration, a large amount of active substance can be generated by heating the active substance generating material.
  • the active substance generating method and active substance generating apparatus of the present invention can provide a method and apparatus for oxidatively decomposing odor components and microorganisms without contact with a photocatalyst, and equipment such as an air purifying apparatus, an air purifying apparatus, and an air conditioner. It can also be applied to.
  • the air purifying device and the humidifying device according to the present invention generate an active substance that is stable and has a long life and can be released from the photocatalyst to the gas phase, etc. Can be reacted. Therefore, the air purifier and the humidifier of the present invention can be used for an air purifier, a humidifier, an air conditioner, an air conditioner, a vacuum cleaner, and the like, and are useful.

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Abstract

Cette invention concerne un procédé et un dispositif de génération d’un principe actif reposant tous deux sur l’emploi, par exemple, d’un oxyde de titane (IV) auquel un halogène est chimiquement lié et renfermant un oxo acide comme photo-catalyseur. Lorsque ce photo-catalyseur est irradié par des ultraviolets au moyen d’une source lumineuse, une variété d’oxygène actif tel qu’un peroxyde d’hydrogène ou un oxyde d’halogène, par exemple un acide hypochloreux, peut être libéré par le photo-catalyseur dans l’atmosphère au moyen d’un ventilateur. Au moment de sa libération, le principe actif réagit avec une substance malodorante flottant dans l’atmosphère ou avec un micro-organisme (tel qu’une bactérie) collée sur une surface solide et exerce par là même une activité déodorante ou microbicide.
PCT/JP2010/004831 2009-08-05 2010-07-30 Procédé et dispositif de génération d’un principe actif, filtre à air et humidificateur équipés tous deux dudit dispositif WO2011016206A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2009-182160 2009-08-05
JP2009182160A JP5845383B2 (ja) 2009-08-05 2009-08-05 活性物質発生方法
JP2009-207705 2009-09-09
JP2009207705A JP5845384B2 (ja) 2009-09-09 2009-09-09 活性物質発生装置
JP2009211408A JP5845385B2 (ja) 2009-09-14 2009-09-14 空気清浄装置
JP2009-211408 2009-09-14
JP2009211409A JP2011058766A (ja) 2009-09-14 2009-09-14 加湿装置
JP2009-211409 2009-09-14

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JP2012176346A (ja) * 2011-02-25 2012-09-13 Panasonic Corp 水処理装置
JP2013230344A (ja) * 2012-11-22 2013-11-14 Marronnier Gijutsu Kenkyusho:Kk 浄化装置及び浄化方法
CN108623089A (zh) * 2018-03-29 2018-10-09 新冶高科技集团有限公司 废水处理装置以及利用该装置处理酚醛树脂废水的方法
US10544574B2 (en) 2015-08-24 2020-01-28 Kohler Co. Clean toilet and accessories
CN111346251A (zh) * 2020-03-09 2020-06-30 南宁师范大学 一种二氧化钛空气净化消毒装置
US10967094B2 (en) 2014-05-05 2021-04-06 Synexis Llc Purified hydrogen peroxide gas generation methods and devices
WO2023110969A1 (fr) * 2021-12-16 2023-06-22 Meudal Nicolas Dispositif de traitement d'effluents aqueux par filtration, uv et ozone et méthode utilisant un tel dispositif

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JP2002143690A (ja) * 2000-11-08 2002-05-21 National Institute Of Advanced Industrial & Technology 高活性光触媒とその製造方法
JP2005289778A (ja) * 2004-04-05 2005-10-20 Oji Paper Co Ltd アパタイト被覆用組成物及びアパタイト被覆二酸化チタンの製造方法

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012176346A (ja) * 2011-02-25 2012-09-13 Panasonic Corp 水処理装置
JP2013230344A (ja) * 2012-11-22 2013-11-14 Marronnier Gijutsu Kenkyusho:Kk 浄化装置及び浄化方法
US10967094B2 (en) 2014-05-05 2021-04-06 Synexis Llc Purified hydrogen peroxide gas generation methods and devices
US11920336B2 (en) 2015-08-24 2024-03-05 Kohler Co. Clean toilet and accessories
US10544574B2 (en) 2015-08-24 2020-01-28 Kohler Co. Clean toilet and accessories
US11873634B2 (en) 2015-08-24 2024-01-16 Kohler Co. Clean toilet and accessories
US11105082B2 (en) 2015-08-24 2021-08-31 Kohler Co. Clean toilet and accessories
US11261592B2 (en) 2015-08-24 2022-03-01 Kohler Co. Clean toilet and accessories
US11542698B2 (en) 2015-08-24 2023-01-03 Kohler Co. Clean toilet and accessories
US11674298B2 (en) 2015-08-24 2023-06-13 Kohler Co. Clean toilet and accessories
US11913211B2 (en) 2015-08-24 2024-02-27 Kohler Co. Clean toilet and accessories
CN108623089A (zh) * 2018-03-29 2018-10-09 新冶高科技集团有限公司 废水处理装置以及利用该装置处理酚醛树脂废水的方法
CN108623089B (zh) * 2018-03-29 2021-10-12 钢研工程设计有限公司 废水处理装置以及利用该装置处理酚醛树脂废水的方法
CN111346251A (zh) * 2020-03-09 2020-06-30 南宁师范大学 一种二氧化钛空气净化消毒装置
CN111346251B (zh) * 2020-03-09 2021-07-02 南宁师范大学 一种二氧化钛空气净化消毒装置
FR3130633A1 (fr) * 2021-12-16 2023-06-23 Nicolas Meudal Dispositif de traitement d’effluents aqueux par filtration, UV et ozone et méthode utilisant un tel dispositif
WO2023110969A1 (fr) * 2021-12-16 2023-06-22 Meudal Nicolas Dispositif de traitement d'effluents aqueux par filtration, uv et ozone et méthode utilisant un tel dispositif

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