WO2011070926A1 - Appareil générateur d'ozone - Google Patents

Appareil générateur d'ozone Download PDF

Info

Publication number
WO2011070926A1
WO2011070926A1 PCT/JP2010/071159 JP2010071159W WO2011070926A1 WO 2011070926 A1 WO2011070926 A1 WO 2011070926A1 JP 2010071159 W JP2010071159 W JP 2010071159W WO 2011070926 A1 WO2011070926 A1 WO 2011070926A1
Authority
WO
WIPO (PCT)
Prior art keywords
exchange membrane
fluororesin
anode
cation exchange
conductive diamond
Prior art date
Application number
PCT/JP2010/071159
Other languages
English (en)
Japanese (ja)
Inventor
昌明 加藤
理恵 川口
剛陸 岸
Original Assignee
クロリンエンジニアズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by クロリンエンジニアズ株式会社 filed Critical クロリンエンジニアズ株式会社
Priority to CN201080055426.7A priority Critical patent/CN102648308B/zh
Priority to KR1020127014722A priority patent/KR101340239B1/ko
Priority to US13/393,484 priority patent/US8815064B2/en
Publication of WO2011070926A1 publication Critical patent/WO2011070926A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/10—Preparation of ozone
    • C01B13/11—Preparation of ozone by electric discharge
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/13—Ozone
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2201/00—Preparation of ozone by electrical discharge
    • C01B2201/20—Electrodes used for obtaining electrical discharge
    • C01B2201/24—Composition of the electrodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2201/00—Preparation of ozone by electrical discharge
    • C01B2201/30—Dielectrics used in the electrical dischargers
    • C01B2201/34—Composition of the dielectrics
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • an anode and a cathode are adhered to both sides of a fluororesin cation exchange membrane, an electrode having conductive diamond on the surface is used as an anode, water is electrolyzed, ozone from the anode, and hydrogen from the cathode.
  • the present invention relates to an ozone generator that generates water.
  • Ozone is known as a substance having extremely strong oxidizing power in nature, and recently, its use is spreading in various industrial fields by utilizing the strong oxidizing power. For example, in water and sewage facilities, a sterilization / decolorization method using ozone is used. Ozone is self-degrading over time and becomes harmless oxygen, so there is no worry of secondary contamination due to residual chemicals or reaction products compared to conventional sterilization and decolorization methods, and post-treatment is easy. Therefore, it is highly appreciated.
  • an ultraviolet lamp method As a method for generating ozone, an ultraviolet lamp method, a silent discharge method, and an electrolysis method are known.
  • the ultraviolet lamp method is a method in which oxygen is excited by ultraviolet rays to produce ozone, and ozone can be generated with relatively simple equipment, but the amount of generation is small, and the field of use is indoors and in cars. Limited to deodorization.
  • the silent discharge method is the most popular general ozone generation method, and uses a large generator of several tens of kg / h for simple purposes such as indoor deodorization using a small amount of ozone generator. It is used for various purposes up to large-scale water treatment.
  • the silent discharge method is a method in which oxygen gas or oxygen in the air is used as a raw material, and oxygen is excited by a discharge to react with ozone.
  • the electrolysis method is a method of obtaining ozone in the anodic gas by electrolyzing water.
  • Ozone is also generated by electrolyzing an aqueous solution such as an aqueous sulfuric acid solution, but when ultrapure water electrolysis is performed using a fluororesin-based cation exchange membrane as an electrolyte, high-concentration and high-purity ozone can be obtained. ing.
  • ultrapure water is used as a raw material and the impurities in the generated gas are extremely small, ultrapure water electrolysis ozone water production equipment is widely used in the precision cleaning field for cleaning semiconductor wafers and LCD substrates. Yes.
  • the anode used in the ozone generation method by electrolysis has excellent ozone gas generation current efficiency, so lead dioxide (PbO 2 ) supported by a method such as electrolytic plating on a conductive porous metal such as titanium.
  • PbO 2 lead dioxide
  • the ozone generation current efficiency was normally 10-15%, and at high current density, 20%. %.
  • the perfluorosulfonic acid ion exchange membrane is consumed over time, the consumption is small and stable ozone generation and safety can be maintained even after continuous electrolysis for 2 years or more.
  • the lead dioxide anode has high ozone generation current efficiency and excellent stability over time under high current density and continuous electrolysis, but this lead dioxide anode is reduced and altered in a reducing environment. It has easy characteristics. For example, when the electrolysis is stopped, the lead dioxide on the electrode surface is easily converted to lead hydroxide (Pb) by reaction with a reducing substance such as hydrogen remaining in the electrolysis cell or by electroreduction reaction by negative polarization of the lead dioxide anode. (OH) 2 ), lead oxide (PbO), and lead ions (Pb 2+ ). Since neither of these has an ozone generating ability or electronic conductivity, a phenomenon occurs in which the ozone generating ability is reduced during re-operation after the electrolysis is stopped.
  • Pb lead hydroxide
  • a protective current that is 1/10 to 1/1000 of the normal electrolytic current is applied to the electrolytic cell. It has a supply mechanism.
  • This mechanism is composed of a direct current power source for protection current, a storage battery, and a control system, and constantly monitors the status of the apparatus so that an instantaneous non-energized state does not occur in the electrolysis cell.
  • This mechanism protects the lead dioxide anode without being exposed to the reducing environment even when electrolysis is stopped.
  • the existence of this mechanism complicates the operation mechanism and configuration of the electrolytic ozone generator and increases the price of the apparatus. ing.
  • the lead dioxide anode contains a lot of lead, and in recent years, the use of lead tends to be reduced in all industrial products due to the toxicity and legal regulations of lead, such as the ROHS guidelines (Non-patent Document 1). reference).
  • the ozone generation current efficiency is about 40% much higher than that of the lead dioxide anode. I know I can get it.
  • the conductive diamond anode is excellent in chemical and electrochemical stability, it does not change in properties and electrolytic characteristics even in a reducing environment in which lead dioxide is altered or deteriorated by reduction. Therefore, the protective current mechanism which is essential in the electrolytic ozone generator using the lead dioxide anode is not necessary, and the apparatus is simplified.
  • carbon and boron constituting the conductive diamond are not subject to the ROHS guidelines.
  • the conductive diamond electrode has a very strong oxidizing ability, water electrolysis can be performed while contacting the conductive diamond electrode and the perfluorosulfonic acid ion exchange membrane in the same manner as the conventional electrolytic ozone generation cell.
  • rate of a perfluorosulfonic-acid ion exchange membrane was 100 times or more large compared with the case of a lead dioxide electrode.
  • the rapid thinning of the membrane by electrolysis causes a rapid increase in the amount of hydrogen gas generated in the cathode chamber to the anode chamber, and the hydrogen concentration in the anode gas exceeds the lower limit of hydrogen explosion even in short-time electrolysis.
  • An electrolysis cell having a very short period during which stable electrolysis can be performed is obtained. Therefore, although the conductive diamond electrode has an excellent ozone generation capability, it has been difficult to commercially use it as an electrolytic cell in an ozone generator or the like.
  • an ozone generation method in which an anode and a cathode are in close contact with both sides of a fluororesin-based cation exchange membrane, a conductive diamond electrode is used as the anode, and water is electrolyzed to generate ozone from the anode and hydrogen from the cathode.
  • a method of suppressing the consumption of the fluororesin cation exchange membrane the consumption of the fluororesin cation exchange membrane can be suppressed by adjusting the current value to be energized or by including a reinforcing material in the fluororesin cation exchange membrane. (See Patent Document 1).
  • the supply current value to the electrolysis cell is limited to the current value or less that maximizes the ozone generation efficiency, so the apparatus using this electrolysis method has a problem that the adjustment range of the ozone generation amount becomes narrow. Occurs.
  • the reinforcing material is Since it does not have electrical conductivity, there is a problem that ozone cannot be generated because it cannot be energized at that time.
  • the lifetime of the electrolytic cell is the time when the thickness of the fluororesin cation exchange membrane from the surface of the fluororesin cation exchange membrane to the reinforcing material is consumed.
  • the present invention eliminates the drawbacks of the above conventional methods, adheres the anode and cathode to both sides of the fluororesin cation exchange membrane, uses a conductive diamond electrode as the anode, electrolyzes water, To provide an ozone generating apparatus capable of generating ozone stably, for a long period of time with high current efficiency, in a ozone generating apparatus that generates hydrogen from ozone and a cathode, suppressing consumption of a fluororesin cation exchange membrane. With the goal.
  • the present invention uses a conductive diamond electrode provided with anodes and cathodes on both sides of a fluororesin-based cation exchange membrane and having conductive diamond on the surface as the anode, and the anode chamber is pure.
  • the conductive diamond electrode A conductive diamond electrode comprising a substrate having a large number of convex and concave portions and a conductive diamond film coated on the surface of the substrate, and a fluororesin-based cation exchange membrane having no notch is in close contact with the cathode surface, and an electrolytic cell A packed bed closely packed with ion-exchange resin particles is adhered to the anode-side surface of the fluororesin-based cation exchange membrane without being cut. It lies in the configuration of an ozone generating apparatus Te.
  • an ozone generating device is configured by bringing a notched fluororesin cation exchange membrane into close contact with the anode side surface of the packed bed.
  • a third solution according to the present invention is that a positive electrode and a negative electrode are provided on both sides of a fluororesin cation exchange membrane, a conductive diamond electrode having a conductive diamond on the surface is used as the anode, and the anode chamber is pure.
  • the conductive diamond electrode for electrolyzing water by supplying water and supplying a direct current between the positive and negative electrodes, generating ozone from the anode chamber, and generating hydrogen from the cathode chamber
  • a conductive diamond electrode comprising a substrate having a number of convex and concave portions and a conductive diamond film coated on the surface of the substrate is used, and a fluororesin-based cation exchange membrane having no notch is brought into close contact with the cathode surface, and an electrolytic cell Fluorine resin-based cation exchange membrane with a notch on the anode side surface of the fluororesin-based cation exchange membrane Lies in the configuration of the ozone generator is brought into close contact more becomes an ion exchange membrane layer.
  • the fourth solution according to the present invention is a fluororesin-based cation exchange membrane having a notch on the outermost surface on the anode side of the ion exchange membrane layer comprising the plurality of notched fluororesin-based cation exchange membranes. Is fixed to the electrolytic cell to constitute an ozone generator.
  • an ozone generator is configured using a perfluorosulfonic acid cation exchange membrane as the fluororesin cation exchange membrane.
  • an ozone generating device is configured by using fluororesin-based ion exchange resin particles as the ion exchange resin particles.
  • the ozone generator according to the present invention it is possible to suppress the consumption of the fluororesin cation exchange membrane and generate ozone stably for a long period of time.
  • Example 1 the schematic diagram which shows the structure of one example of the electrolysis cell for implementing the ozone generator by this invention.
  • Example 2 the schematic diagram which shows the structure of the other example of the electrolytic cell for implementing the ozone generator by this invention.
  • Example 3 the schematic diagram which shows the structure of the further another example of the electrolytic cell for implementing the ozone generator by this invention.
  • Example 4 the schematic diagram which shows the structure of the further another example of the electrolytic cell for implementing the ozone generator by this invention.
  • Example 2 the figure which shows an example of the fluorine resin type
  • Example 4 the figure which shows the other example of the fluororesin type
  • the surface view which shows the structure of an example of the board
  • Sectional drawing which shows the structure of one example of the board
  • the block diagram which shows one Example of the ozone generator by this invention.
  • FIG. 1-1 is a schematic diagram showing a configuration of an example of an electrolysis cell for carrying out an ozone generator according to the present invention.
  • 1 is an anode chamber discharge port
  • 2 is a cathode chamber discharge port
  • 3 is an anode chamber
  • 4 is a cathode chamber
  • 5 is an anode feeding terminal
  • 6 is a cathode feeding terminal
  • 7 is an anode chamber feeding port
  • 8 is a cathode chamber supply port
  • 9 is a non-cut fluororesin cation exchange membrane
  • 10 is a conductive diamond film
  • 11 is a p-type silicon substrate with irregularities
  • 12 is a through-hole
  • 13 is a cathode.
  • a sheet, 14 is a cathode current collector, 15 is a sealing material, 16 is a fastening bolt, 17 is a nut, and 18 is a press plate.
  • Reference numeral 19 denotes a packed bed in which ion-exchange resin particles are closely packed.
  • the anode has a conductive diamond film 10 on the surface of the p-type silicon substrate 11 with unevenness, the through-hole 12 is perforated, and the cathode consists of a cathode sheet 13.
  • the fluororesin-based cation exchange membrane 9 having no notch is in close contact with the surface of the cathode sheet 13.
  • the fluororesin cation exchange membrane 9 having no cut is fixed to the electrolysis cell by a sealing material 15.
  • a filling layer 19 tightly filled with ion exchange resin particles is in close contact with the anode side surface of the fluororesin cation exchange membrane 9 without being cut.
  • the anode and cathode are housed in an anode chamber 3 and a cathode chamber 4, respectively.
  • the anode chamber 3 and the cathode chamber 4 have an anode chamber discharge port 1, a cathode chamber discharge port 2, an anode chamber supply port 7 and a cathode chamber supply port 8, respectively. is doing.
  • the membrane 9 was joined by pressing with a torque using a tightening bolt 16, a nut 17, and a press plate 18.
  • the torque to the bolt and nut was 3 N ⁇ m.
  • the pure water When pure water is supplied into the anode chamber 3 from the anode chamber supply port 7, the pure water passes through the through-hole 12 and the like, and the ion exchange is performed on the surface of the conductive diamond film 10 and the fluororesin cation exchange membrane 9 without being cut. It is supplied to the contact surface of the filling layer 19 tightly filled with resin particles, an electrolytic reaction occurs, ozone gas, oxygen gas, and hydrogen ions are generated in the anode chamber 3, and the ozone gas and oxygen gas pass through the anode chamber outlet 1.
  • the hydrogen ions are discharged from the electrolysis cell to the surface of the cathode sheet 13 through the fluororesin-based cation exchange membrane 9 without being cut, and are combined with electrons to become hydrogen gas, from the cathode chamber outlet 2. It is discharged out of the electrolysis cell.
  • the cathode sheet 13 was manufactured as follows. PTFE dispersion (Mitsui Dupont Fluorochemical Co., Ltd. 31-J) and a dispersion of platinum-supported carbon catalyst dispersed in water were mixed, dried, kneaded with solvent naphtha added thereto, Through the drying step and the firing step, the cathode sheet 13 was obtained with PTFE 40%, platinum-supported carbon catalyst 60% in film thickness, and porosity of 55%. Moreover, a 2.5 mm thick stainless steel fiber sintered body (Tokyo Seizuna Co., Ltd.) was used as the cathode current collector.
  • PTFE dispersion Mitsubishi Dupont Fluorochemical Co., Ltd. 31-J
  • a dispersion of platinum-supported carbon catalyst dispersed in water were mixed, dried, kneaded with solvent naphtha added thereto, Through the drying step and the firing step, the cathode sheet 13 was obtained with PTFE 40%, platinum-supported carbon catalyst 60% in film thickness
  • the ion exchange resin particles used for the packed layer 19 tightly filled with ion exchange resin particles are preferably fluororesin ion exchange resin particles in view of resistance to ozone generated by electrolysis.
  • the filling amount of the packed layer 19 tightly filled with ion-exchange resin particles determines the filling amount of the ion-exchange resin from the consumption rate of the fluororesin cation exchange membrane by electrolysis and the expected electrolytic cell life, It is necessary to configure the electrolytic cell.
  • the exhaustion of the fluororesin cation exchange membrane 9 with no cut on the most cathode side is started, and the hydrogen concentration permeating into the anode gas is 4.5 vol%, which is the lower limit of explosion.
  • the life is reached when it becomes 1% by volume or more, which is a quarter, but by obtaining the required amount of ion exchange resin from the product of the consumption rate of the membrane and the expected life time in advance, the electrolytic cell is constructed. An electrolytic cell that can achieve the expected life can be obtained.
  • FIG. 1-2 is a schematic diagram showing the structure of another example of the electrolytic cell for carrying out the ozone generating apparatus according to the present invention, on the surface on the anode side of the packed layer 19 in which ion-exchange resin particles are closely packed.
  • FIG. 2A shows an example in which a fluororesin cation exchange membrane 21 having a notch 20 is closely attached. The fluororesin cation exchange membrane 21 with the cut 20 is fixed to the electrolytic cell by the sealing material 15.
  • a plurality of fluororesin-based cation exchange membranes 21 in contact with the anode can be provided, but they are arranged on the cathode side. Except for the fluororesin-based cation exchange membrane 9, any membrane is provided with a cut 20 so that no liquid or gas stays in the anode chamber 3.
  • hydrogen gas or oxygen gas that has permeated the fluororesin-based cation exchange membrane 21 stays in the ion exchange resin filling layer 19, the internal pressure in the anode chamber 3 rises, and the ions filled in the anode chamber 3.
  • a plurality of the cuts 20 of the fluororesin ion exchange membrane 21 containing the cuts 20 may be formed in the lateral direction, but the shape of the cuts 20 is formed on a part or the whole of the surface.
  • a plurality of the slits 20 are formed in a straight line or a circle in the vertical direction, the horizontal direction, the concentric circles, or irregularly, and the above effect can be further improved.
  • the hydrogen concentration in the ozone-containing gas generated from the previous anode chamber can be further reduced. At the same time, an increase in cell voltage can be prevented.
  • FIG. 1-3 is a schematic view showing the configuration of still another example of an electrolysis cell for carrying out the ozone generator according to the present invention, in which an anode and a cathode are provided on both sides of a fluororesin cation exchange membrane.
  • the ion exchange membrane layer 22 composed of a plurality of cut fluororesin cation exchange membranes has the same effect as the packed layer 19 in which the ion exchange resin particles shown in FIGS. 1-1 and 1-2 are closely packed. Can be played. The notch of the ion exchange membrane layer 22 is not shown.
  • the number of ion exchange membrane layers 22 made of a plurality of cut fluororesin cation exchange membranes is determined from the consumption rate of the fluororesin cation exchange membrane by electrolysis and the expected electrolytic cell lifetime. Configuration is required.
  • this electrolytic cell the consumption of the fluororesin cation exchange membrane 9 with no notch on the cathode side is started, and the hydrogen concentration permeating into the anode gas is the lower limit of explosion, 4.5 vol% 4
  • the life is reached when the volume is 1% by volume or more, which is a fraction, but the ion exchange membrane layer 22 is composed of a plurality of fluororesin-based cation exchange membranes required in advance from the product of the membrane consumption rate and the expected life time.
  • an electrolytic cell that can achieve the expected life can be obtained by configuring the electrolytic cell.
  • the fluororesin cation exchange membrane 9 having no cut As the fluororesin cation exchange membrane 9 having no cut, the fluororesin ion exchange membrane 21 having a cut and the plurality of fluororesin cation exchange membranes having a cut constituting the ion exchange membrane layer 22, A perfluorosulfonic acid cation exchange membrane is preferable, and a commercially available perfluorosulfonic acid type cation exchange membrane (trade name: Nafion 117, manufactured by DuPont, catalog thickness: 175 ⁇ m) is used and immersed in boiling pure water for 30 minutes. Those subjected to swelling treatment with water can be used.
  • FIG. 1-4 is a schematic view showing the configuration of still another example of an electrolysis cell for carrying out the ozone generating apparatus according to the present invention, which is composed of a plurality of fluororesin cation exchange membranes having notches 20.
  • This shows an example in which a fluororesin cation exchange membrane 21 having a single notch 20 is fixed to the sealing material 15 of the electrolytic cell on the outermost surface on the anode side of the ion exchange membrane layer 22.
  • FIG. 2-2 is a view of the configuration of the fluororesin cation exchange membrane in FIG. 1-4 as viewed from the anode side.
  • FIGS. 3A and 3B are diagrams showing an example of the structure of an anode having conductive diamond on the surface used for the ozone generation method and the ozone generation apparatus according to the present invention.
  • a large number of irregularities with a pitch of 0.5 mm were formed on the surface of the surface of 3 mmt) 11 by dicing, and then drilled from the back surface to obtain a plurality of through holes 12.
  • a hydrofluoric acid solution prepared by mixing 35% hydrofluoric acid and 70% nitric acid at 1: 1 at room temperature for 5 minutes, and further 10% potassium hydroxide aqueous solution at 60 ° C. For 5 minutes.
  • Reference numeral 23 denotes a convex portion
  • 24 denotes a concave portion.
  • diamond powder was placed in isopropyl alcohol, a substrate was placed, and ultrasonic waves were applied to perform seeding treatment.
  • a microwave plasma CVD method at 2.45 GHz was used.
  • H 2 , CH 4 , and B 2 H 6 were used as gases, and the flow rates were 800 sccm, 20 sccm, and 0.2 sccm, respectively, and the gas pressure was 3.2 kPa.
  • a conductive diamond film 10 containing boron as a dopant was formed by microwave plasma CVD.
  • the total area of the convex part top part used as an actual electrolysis area is 6.25 cm ⁇ 2 >.
  • the convex portion 23 on the surface of the conductive diamond film 10 is in contact with both the perfluorosulfonic acid cation exchange membrane 9 and the aqueous phase, and these form a three-phase interface. Further, since the entire contact surface between the convex portion 23 and the perfluorosulfonic acid type cation exchange membrane 9 has a three-phase interface, it has a fine structure, and water penetrates the entire surface of the convex portion 23 so that the electrolytic gas quickly flows. In order to be discharged from the electrolysis field, the width of the projection 23 must be 1 mm or less and the entire surface of the electrode must be present.
  • the three-phase interface also increases the number of flow paths for the electrolytic solution and the generated gas, thereby facilitating fluid flow.
  • the width of the convex portion 23 is 2 mm or more, water does not always enter the intermediate portion of the convex portion 23 even though the convex portion 23 is in contact with the perfluorosulfonic acid cation exchange membrane 9, and electrolysis is performed. An impossible part is formed.
  • the portion formed in the intermediate portion of the convex portion 23 that cannot be electrolyzed because water does not always enter is such that the bubble covers the entire surface of the conductive diamond film 10 after the start of electrolysis, and the portion of the three-phase interface Almost disappears and electrolysis cannot be performed.
  • the convex portion 23 is too fine, in the zero gap structure in which the ion exchange membrane and the electrode are brought into contact with each other by pressing pressure to obtain a three-phase interface, the convex portion 23 is easily damaged.
  • the width of the convex portion 23 is required to be 0.2 mm or more so that the entire surface of the convex portion 23 exists on the electrode surface.
  • the surface of the convex portion 23 needs to have an appropriate surface roughness.
  • the surface roughness Ra needs to be 0.1 ⁇ m or more.
  • the surface roughness Ra is preferably 0.2 to 0.5 ⁇ m.
  • the conductive diamond electrode according to the present invention needs to use machining such as dicing or drilling that can produce an uneven structure without using a plurality of high-precision processing devices in order to reduce costs.
  • each convex portion 23 of the convex concave portion a conductive diamond electrode having a circular shape, an elliptical shape, a polygonal shape or other shapes can be used.
  • a large number of strip-shaped substrates are arranged across the entire surface of the conductive diamond electrode with a gap between each of the strip-shaped substrates.
  • a substrate that is vertically, horizontally and vertically shaped like a projection in a square shape, a circular shape, or other shapes may be used.
  • the anode having the conductive diamond film 10 on its surface is manufactured by supporting diamond, which is a reduced precipitate of an organic compound serving as a carbon source, on an electrode substrate.
  • the material and shape of the electrode substrate are not particularly limited as long as the material is conductive.
  • the electrode substrate is plate-like, mesh-like, or porous, for example, a vibrant fiber sintered body made of conductive silicon, silicon carbide, titanium, niobium, molybdenum or the like. It is particularly preferable to use conductive silicon or silicon carbide having a thermal expansion coefficient that can be used.
  • the substrate surface has a certain degree of roughness.
  • the film thickness be 10 ⁇ m to 50 ⁇ m in order to reduce durability and occurrence of pinholes.
  • a self-supporting film having a thickness of 100 ⁇ m or more can be used from the viewpoint of durability, it is not preferable because the cell voltage becomes high and the control of the electrolyte temperature becomes complicated.
  • the method for supporting the conductive diamond on the substrate is not particularly limited, and any conventional method can be used.
  • Typical conductive diamond production methods include a hot filament CVD (chemical vapor deposition) method, a microwave plasma CVD method, a plasma arc jet method, and a physical vapor deposition (PVD) method.
  • the use of a microwave plasma CVD method is desirable because it is easy to obtain a uniform film.
  • a diamond electrode in which a synthetic diamond powder produced at an ultrahigh pressure is supported on a substrate by using a binder such as a resin can also be used.
  • the microwave plasma CVD method uses a mixed gas obtained by diluting a carbon source such as methane and a dopant source such as borane with hydrogen as a conductive material such as conductive silicon, alumina, or silicon carbide connected to a microwave transmitter through a waveguide.
  • a conductive diamond film is introduced into a reaction chamber provided with a substrate, plasma is generated in the reaction chamber, and conductive diamond is grown on the substrate.
  • ions hardly vibrate, and a pseudo high temperature is achieved in a state where only electrons are vibrated, and the chemical reaction is promoted.
  • the plasma output is 1 to 5 kW. The larger the output, the more active species can be generated, and the diamond growth rate increases.
  • the advantage of using plasma is that diamond can be deposited at high speed using a substrate with a large surface area.
  • the content of boron or phosphorus is preferably 1 to 100,000 ppm, more preferably 100 to 10,000 ppm.
  • boron oxide, diphosphorus pentoxide, or the like having a low toxicity can be used as a raw material for this additive element.
  • the conductive diamond supported on the substrate thus manufactured is a flat plate, stamped plate, wire mesh, powder sintered body made of a conductive material such as titanium, niobium, tantalum, silicon, carbon, nickel, tungsten carbide. In addition, it can be connected to a power feeding body having a form such as a metal fiber body or a metal fiber sintered body.
  • the cathode sheet 13 was manufactured as follows. PTFE dispersion (Mitsui Dupont Fluorochemical Co., Ltd. 31-J) and a dispersion of platinum-supported carbon catalyst dispersed in water were mixed, dried, kneaded with solvent naphtha added thereto, Through the drying step and the firing step, a cathode sheet 13 having a PTFE of 40%, a platinum-supported carbon catalyst of 60%, a film thickness of 120 ⁇ m, and a porosity of 55% was obtained. Moreover, a 2.5 mm thick stainless steel fiber sintered body (Tokyo Seizuna Co., Ltd.) was used as the cathode current collector.
  • Example 1 An electrolytic cell was constructed as shown in FIG. A fluororesin-based cation exchange membrane 9 having no cuts is brought into close contact with the surface of the cathode sheet 13 and fixed to the sealing material 15 of the electrolysis cell, and ions are formed on the anode-side surface of the fluororesin-based cation exchange membrane 9 having no cuts.
  • the packed bed 19 closely packed with exchange resin particles was brought into close contact to constitute an electrolytic cell.
  • the anode and the cathode are housed in an anode chamber 3 and a cathode chamber 4, respectively.
  • the anode chamber 3 and the cathode chamber 4 have supply ports 7 and 8 and discharge ports 1 and 2, respectively.
  • the ion exchange resin particles filled in the packed layer 19 were prepared by boiling a product name: NR50, an ion exchange resin manufactured by DuPont, and immersing in pure water for 30 minutes to perform a swelling treatment with water.
  • the anode made of a conductive diamond electrode is a hydrofluoric acid solution prepared by mixing 35% hydrofluoric acid and 70% nitric acid at a ratio of 1: 1 for texture processing on the surface of a 5 cm square p-type silicon substrate (3 mmt). For 5 minutes at room temperature, and further immersed in a 10% aqueous potassium hydroxide solution at 60 ° C. for 5 minutes. At this time, the surface roughness Ra of the silicon substrate was 0.1 to 4 ⁇ m although there was unevenness depending on the location. Next, many irregularities were produced on the surface by dicing using a diamond saw. Note that the thickness of the diamond saw used for the preparation of each sample is 20 ⁇ m.
  • the produced uneven silicon plate was washed with water and dried, and then, as a pretreatment, diamond powder was placed in isopropyl alcohol, a substrate was placed, and ultrasonic waves were applied to perform seeding treatment.
  • a microwave plasma CVD method at 2.45 GHz was used.
  • H 2 , CH 4 , and B 2 H 6 were used as gases, and the flow rates were 800 sccm, 20 sccm, and 0.2 sccm, respectively, and the gas pressure was 3.2 kPa.
  • a conductive diamond film containing boron as a dopant was formed by microwave plasma CVD.
  • the conductive diamond electrode is obtained by coating the surface of a substrate 11 having a large number of convex and concave portions over the entire surface with a diamond film 10.
  • the shape of the part 23 was formed in a square shape.
  • the substrate 11 was provided with a plurality of through holes 12 so that the gas discharged from the surface of the convex portion 23 to the concave portion 24 and the water supplied to the surface of the convex portion 23 can circulate quickly from the back surface of the electrode.
  • the total area of the protrusions that was the actual electrolysis area was 6.25 cm 2 .
  • the total area of the openings of the through holes was 10% with respect to the projected area of the electrode structure.
  • the surface roughness Ra of each convex portion was 0.2 to 0.5 ⁇ m.
  • PTFE dispersion Mitsubishi DuPont Fluorochemical Co., Ltd. 31-J
  • a dispersion of platinum-supported carbon catalyst dispersed in water are mixed, dried, kneaded with solvent naphtha, and then rolled.
  • a drying step and a firing step a cathode sheet 13 having a film thickness of 120 ⁇ m and a porosity of 55% at a mixing ratio of 40% PTFE and 60% platinum-supported carbon catalyst was obtained.
  • a 2.5 mm-thick stainless steel sintered body (Tokyo Steel Line Co., Ltd.) was used as the cathode current collector 14.
  • the electrolysis cell 25 was connected with the anode side gas-liquid separator 26, the cathode side gas-liquid separator 27, and the DC power supply 28, and water electrolysis was performed.
  • the electrolytic current was 6.25A.
  • the temperature at the start of operation of pure water as an electrolytic solution was 23 ° C., and water electrolysis was performed without cooling.
  • the results shown in Table 1 were obtained.
  • the ozone generation current efficiency is 20%
  • the hydrogen gas concentration contained in the anode gas is 0.1 Vol%
  • the cell voltage is 11.8 V
  • the ozone generation current efficiency is 18% even on the 10th day of continuous electrolysis.
  • the hydrogen gas concentration contained in the anode gas was 0.1 Vol% and the cell voltage was 11.7 V, and no significant change was observed.
  • Example 2 The electrolytic cell shown in FIG. 1-2 was assembled and an electrolytic test was conducted. That is, as shown in FIG. 2-1, a fluororesin cation exchange membrane 21 having a notch 20 was brought into close contact with the anode side surface of the packed layer 19 in which the ion exchange resin particles were closely packed. The fluororesin cation exchange membrane 21 with the cut 20 is fixed to the electrolytic cell by the sealing material 15.
  • fluororesin-based cation exchange membranes 9 and 21 commercially available fluororesin-based cation exchange membranes (trade name: Nafion 117, manufactured by DuPont, catalog thickness: 175 ⁇ m) are used and immersed in boiling pure water for 30 minutes. Then, a swelling treatment with water was performed.
  • PTFE dispersion Mitsubishi Dupont Fluorochemical Co., Ltd. 31-J
  • a dispersion of platinum-supported carbon catalyst dispersed in water are mixed, dried, mixed with solvent naphtha, kneaded, and rolling step
  • a cathode sheet 13 having a PTFE of 40%, a platinum-supported carbon catalyst of 60% and a film thickness of 120 ⁇ m and a porosity of 55% was obtained.
  • a 2.5 mm-thick stainless steel sintered body (Tokyo Steel Line Co., Ltd.) was used as the cathode current collector 14.
  • the ion exchange resin particles filled in the packed layer 19 were prepared by boiling a product name: NR50, an ion exchange resin manufactured by DuPont, and immersing in pure water for 30 minutes to perform a swelling treatment with water.
  • Example 1 As the anode, the same conductive diamond electrode as in Example 1 was used, and an electrolytic test was conducted in the same manner as in Example 1.
  • the results shown in Table 1 were obtained.
  • the ozone generation current efficiency is 20%
  • the hydrogen gas concentration contained in the anode gas is 0.1 Vol%
  • the cell voltage is 12V
  • the ozone generation current efficiency is 18% even on the 10th day of continuous electrolysis.
  • the concentration of hydrogen gas contained in the gas was 0.1 Vol% and the cell voltage was 11.9 V, and no significant change was observed.
  • Example 3 The electrolytic cell shown in FIG. 1-3 was assembled and an electrolytic test was performed. That is, the fluororesin cation exchange membrane 9 having no notch is brought into close contact with the cathode surface and fixed to the sealing material 15 of the electrolysis cell, and the notch is formed on the anode side surface of the fluororesin cation exchange membrane 9 having no notch. A certain 15 sheets of an ion exchange membrane layer 22 made of a fluororesin cation exchange membrane were adhered.
  • the results shown in Table 1 were obtained.
  • the ozone generation current efficiency is 20%
  • the hydrogen gas concentration contained in the anode gas is 0.1 Vol%
  • the cell voltage is 11.8 V
  • the ozone generation current efficiency is 18% even on the 10th day of continuous electrolysis.
  • the hydrogen gas concentration contained in the anode gas was 0.1 Vol% and the cell voltage was 11.7 V, and no significant change was observed.
  • Example 4 The electrolytic cell shown in FIG. 1-4 was assembled and an electrolytic test was performed. That is, the fluororesin-based cation exchange having notches 20 on the outermost surface on the anode side of the ion exchange membrane layer 22 made of a plurality of fluororesin-based cation exchange membranes having notches 20 in the electrolytic cell used in Example 3. The membrane 21 was fixed to the sealing material 15 of the electrolytic cell.
  • the results shown in Table 1 were obtained.
  • the ozone generation current efficiency is 20%
  • the hydrogen gas concentration contained in the anode gas is 0.1 Vol%
  • the cell voltage is 12.1 V
  • the ozone generation current efficiency is 18% even on the 10th day of continuous electrolysis.
  • the hydrogen gas concentration contained in the anode gas was 0.1 Vol% and the cell voltage was 11.9 V, and no significant change was observed.
  • Comparative Example 2 In Comparative Example 2, the electrolytic cell shown in FIG. 5 was configured. In this comparative example 2, two fluororesin cation exchange membranes 9 and 21 were brought into close contact with each other to constitute an electrolytic cell. The fluororesin-based cation exchange membrane 21 in contact with the anode was formed with a notch 20.
  • the ozone generator according to the present invention it is possible to suppress the consumption of the fluororesin cation exchange membrane, stably generate ozone for a long period of time, and the sterilization / decolorization method using ozone is used in water and sewage facilities. be able to.
  • Anode chamber discharge port 2 Cathode chamber discharge port 3: Anode chamber 4: Cathode chamber 5: Anode feed terminal 6: Cathode feed terminal 7: Anode chamber feed port 8: Cathode chamber feed port 9: Fluorine resin system without cut Ion exchange membrane 10: Conductive diamond film 11: P-type silicon substrate 12 with unevenness 12: Through hole 13: Cathode sheet 14: Cathode collector 15: Sealing material 16: Tightening bolt 17: Nut 18: Press plate 19: Ion Packing layer 20 closely packed with exchange resin particles 20: notch 21: notched fluororesin ion exchange membrane 22: notched ion exchange membrane layer 23 made of a plurality of fluororesin cation exchange membranes: convex portion 24 : Recess 25: Electrolytic cell 26: Anode-side gas-liquid separator 27: Cathode-side gas-liquid separator 28: DC power supply 29 for electrolysis: Heat exchanger

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention concerne un appareil générateur d'ozone comprenant une anode et une cathode disposées sur les deux faces d'une membrane d'échange cationique à base de résine fluorée, l'anode étant en diamant conducteur. En alimentant en eau pure la chambre d'anode, et en appliquant entre anode et cathode un courant continu, on réalise une électrolyse de l'eau aboutissant à une production d'ozone dans la chambre d'anode et d'hydrogène dans la chambre de cathode. L'anode en diamant conducteur est constituée, d'une part d'un substrat présentant un grand nombre de parties inégales, et d'autre part un film en diamant conducteur qui couvre la surface du substrat. En l'occurrence, la surface anodique de la membrane d'échange cationique à base de résine fluorée est garnie, soit d'une couche compacte dans laquelle des particules de résine d'échange d'ions sont densément enserrées, soit d'une couche de membrane d'échange cationique à base de résine fluorée présentant un gaufrage.
PCT/JP2010/071159 2009-12-07 2010-11-26 Appareil générateur d'ozone WO2011070926A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201080055426.7A CN102648308B (zh) 2009-12-07 2010-11-26 臭氧发生器
KR1020127014722A KR101340239B1 (ko) 2009-12-07 2010-11-26 오존 생성 장치
US13/393,484 US8815064B2 (en) 2009-12-07 2010-11-26 Ozone generator

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-277373 2009-12-07
JP2009277373A JP5457810B2 (ja) 2009-12-07 2009-12-07 オゾン生成装置

Publications (1)

Publication Number Publication Date
WO2011070926A1 true WO2011070926A1 (fr) 2011-06-16

Family

ID=44145473

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/071159 WO2011070926A1 (fr) 2009-12-07 2010-11-26 Appareil générateur d'ozone

Country Status (6)

Country Link
US (1) US8815064B2 (fr)
JP (1) JP5457810B2 (fr)
KR (1) KR101340239B1 (fr)
CN (1) CN102648308B (fr)
TW (1) TWI484070B (fr)
WO (1) WO2011070926A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012144779A (ja) * 2011-01-12 2012-08-02 Kobe Steel Ltd 電解用電極の製造方法
JP2012144778A (ja) * 2011-01-12 2012-08-02 Kobe Steel Ltd 電解用電極及びその電解用電極を用いたオゾン生成装置
US20140076724A1 (en) * 2012-09-14 2014-03-20 Cashido Corporation Cell module, ozone generator thereof and methods for generating ozone using the same
JP2019202295A (ja) * 2018-05-25 2019-11-28 パナソニックＩｐマネジメント株式会社 電解水生成装置および電解水生成システム
WO2019225414A1 (fr) * 2018-05-25 2019-11-28 パナソニックＩｐマネジメント株式会社 Dispositif et système de génération d'eau électrolysée
JP2019202296A (ja) * 2018-05-25 2019-11-28 パナソニックＩｐマネジメント株式会社 電解水生成装置
JP2019202297A (ja) * 2018-05-25 2019-11-28 パナソニックＩｐマネジメント株式会社 電解水生成システム
US11975992B2 (en) * 2018-03-27 2024-05-07 Lam Research Ag Method of producing rinsing liquid

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2697730A4 (fr) 2011-04-15 2015-04-15 Advanced Diamond Technologies Inc Système et procédé électrochimiques destinés à une génération sur site d'oxydants sous une densité de courant élevée
US9380920B2 (en) * 2011-10-18 2016-07-05 Minuteman International, Inc. Ozone injection for continuous flow cleaning systems
JP5069379B1 (ja) * 2012-02-15 2012-11-07 日科ミクロン株式会社 オゾン水生成装置
JP5069380B1 (ja) * 2012-03-16 2012-11-07 日科ミクロン株式会社 オゾン水生成装置
CN103588258B (zh) * 2012-08-14 2016-01-20 虞文豪 一种水产养殖的杀菌系统
US10662523B2 (en) 2015-05-27 2020-05-26 John Crane Inc. Extreme durability composite diamond film
US10239772B2 (en) 2015-05-28 2019-03-26 Advanced Diamond Technologies, Inc. Recycling loop method for preparation of high concentration ozone
US10907264B2 (en) 2015-06-10 2021-02-02 Advanced Diamond Technologies, Inc. Extreme durability composite diamond electrodes
JP6096258B1 (ja) * 2015-09-11 2017-03-15 株式会社ウォーターエージェンシー オゾン水製造装置
CN105112937A (zh) * 2015-09-30 2015-12-02 广州市德百顺电气科技有限公司 一种直接连接镀膜电极的电解臭氧水装置
WO2018075920A1 (fr) 2016-10-20 2018-04-26 Advanced Diamond Technologies, Inc. Générateurs d'ozone, procédés de fabrication de générateurs d'ozone et procédés de génération d'ozone
US10662550B2 (en) 2016-11-03 2020-05-26 John Crane Inc. Diamond nanostructures with large surface area and method of producing the same
GB2557182B (en) * 2016-11-29 2020-02-12 Roseland Holdings Ltd Electrode and electrochemical cell comprising the same
JP6220957B1 (ja) * 2016-12-12 2017-10-25 日科ミクロン株式会社 ダイヤモンド電極、ダイヤモンド電極の製造方法及び電解水生成装置
CN108034960A (zh) * 2017-12-29 2018-05-15 唐锋机电科技（深圳）有限公司 臭氧发生系统及便携式臭氧发生器
WO2019127527A1 (fr) * 2017-12-29 2019-07-04 唐锋机电科技（深圳）有限公司 Système de génération d'ozone et générateur d'ozone portable
CN108330503B (zh) * 2018-02-11 2019-08-02 中氧科技（广州）有限公司 一种电解臭氧发生器
CN110123472B (zh) * 2019-04-18 2021-08-03 湖州中科水滴石科技有限公司 一种可监视的臭氧水冲牙器
CN111304678A (zh) * 2020-04-22 2020-06-19 广州市德百顺电气科技有限公司 一种电解式臭氧发生器
US11875974B2 (en) 2020-05-30 2024-01-16 Preservation Tech, LLC Multi-channel plasma reaction cell
US12012661B2 (en) 2020-06-27 2024-06-18 Aquamox Inc. Electrolytic generators
TWI766780B (zh) * 2021-07-29 2022-06-01 鄭益 可分離氫氣與氧氣之電解槽裝置
CN114990595A (zh) * 2022-05-27 2022-09-02 国网江苏电力设计咨询有限公司 一种制氢系统
CN117418247B (zh) * 2023-12-18 2024-03-15 中国科学院生态环境研究中心 电化学耦合氧气解离的臭氧生成装置及生成方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005240074A (ja) * 2004-02-24 2005-09-08 Permelec Electrode Ltd 導電性ダイヤモンド電極及びその製造方法
JP2007070701A (ja) * 2005-09-08 2007-03-22 Ebara Corp 固体高分子電解質型オゾン生成装置
JP2009007655A (ja) * 2007-06-29 2009-01-15 Central Japan Railway Co オゾン生成方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5140218B2 (ja) * 2001-09-14 2013-02-06 有限会社コヒーレントテクノロジー 表面洗浄・表面処理に適した帯電アノード水の製造用電解槽及びその製造法、並びに使用方法
JP4220978B2 (ja) * 2004-04-28 2009-02-04 東海旅客鉄道株式会社 電極、オゾン生成装置、及び、オゾン生成方法
JP4903405B2 (ja) * 2005-08-10 2012-03-28 東海旅客鉄道株式会社 オゾン水生成方法及びオゾン水生成装置
EP1953271A4 (fr) * 2005-11-24 2011-08-31 Sumitomo Elec Hardmetal Corp Électrode en diamant, procédé pour sa fabrication et cellule électrolytique
HUP0501204A2 (en) * 2005-12-23 2007-07-30 Thales Rt Ozone generating electrolytic cell
JP4598698B2 (ja) * 2006-03-13 2010-12-15 クロリンエンジニアズ株式会社 オゾン製造方法
GB0612094D0 (en) * 2006-06-19 2006-07-26 Clarizon Ltd Electrode, method of manufacture and use thereof
GB0622482D0 (en) * 2006-11-10 2006-12-20 Element Six Ltd Diamond electrode
JP4323535B2 (ja) * 2007-04-26 2009-09-02 クロリンエンジニアズ株式会社 水電解装置
CN101250710B (zh) * 2008-03-28 2010-06-09 陕西科技大学 电解式臭氧发生器及其阴极催化层的制备工艺
JP5480542B2 (ja) * 2009-06-23 2014-04-23 クロリンエンジニアズ株式会社 導電性ダイヤモンド電極並びに導電性ダイヤモンド電極を用いたオゾン生成装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005240074A (ja) * 2004-02-24 2005-09-08 Permelec Electrode Ltd 導電性ダイヤモンド電極及びその製造方法
JP2007070701A (ja) * 2005-09-08 2007-03-22 Ebara Corp 固体高分子電解質型オゾン生成装置
JP2009007655A (ja) * 2007-06-29 2009-01-15 Central Japan Railway Co オゾン生成方法

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012144779A (ja) * 2011-01-12 2012-08-02 Kobe Steel Ltd 電解用電極の製造方法
JP2012144778A (ja) * 2011-01-12 2012-08-02 Kobe Steel Ltd 電解用電極及びその電解用電極を用いたオゾン生成装置
US20140076724A1 (en) * 2012-09-14 2014-03-20 Cashido Corporation Cell module, ozone generator thereof and methods for generating ozone using the same
US11975992B2 (en) * 2018-03-27 2024-05-07 Lam Research Ag Method of producing rinsing liquid
JP2019202295A (ja) * 2018-05-25 2019-11-28 パナソニックＩｐマネジメント株式会社 電解水生成装置および電解水生成システム
WO2019225414A1 (fr) * 2018-05-25 2019-11-28 パナソニックＩｐマネジメント株式会社 Dispositif et système de génération d'eau électrolysée
JP2019202296A (ja) * 2018-05-25 2019-11-28 パナソニックＩｐマネジメント株式会社 電解水生成装置
JP2019202297A (ja) * 2018-05-25 2019-11-28 パナソニックＩｐマネジメント株式会社 電解水生成システム
CN112154124A (zh) * 2018-05-25 2020-12-29 松下知识产权经营株式会社 电解水生成装置和电解水生成系统
US11795072B2 (en) 2018-05-25 2023-10-24 Panasonic Intellectual Property Management Co., Ltd. Electrolyzed water generator and electrolyzed water generation system

Also Published As

Publication number Publication date
TWI484070B (zh) 2015-05-11
JP2011117052A (ja) 2011-06-16
KR101340239B1 (ko) 2013-12-10
CN102648308A (zh) 2012-08-22
CN102648308B (zh) 2014-07-02
KR20120091322A (ko) 2012-08-17
US8815064B2 (en) 2014-08-26
TW201129723A (en) 2011-09-01
JP5457810B2 (ja) 2014-04-02
US20120168302A1 (en) 2012-07-05

Similar Documents

Publication Publication Date Title
JP5457810B2 (ja) オゾン生成装置
JP5480542B2 (ja) 導電性ダイヤモンド電極並びに導電性ダイヤモンド電極を用いたオゾン生成装置
JP2011117052A5 (fr)
CA2630792C (fr) Electrode a diamant, methode de production et cellule electrolytique
US6855242B1 (en) Electrochemical production of peroxopyrosulphuric acid using diamond coated electrodes
JP2007242433A (ja) 電気化学反応用電極触媒、その製造方法及び前記電極触媒を有する電気化学用電極
TWI453302B (zh) 硫酸電解方法
WO2016047629A1 (fr) Cellules électrolytique pour la production d'hydrures chimiques organiques
CN108611655B (zh) 一种电极单元及其组成的电极
TW201347282A (zh) 使用於液體中之碳電極裝置及相關方法
JP2007332441A (ja) 過硫酸の製造方法及び製造用電解槽
TWI467058B (zh) 硫酸電解槽及使用硫酸電解槽之硫酸循環型清洗系統
JP5408653B2 (ja) オゾン生成方法及びオゾン生成装置
KR20130108435A (ko) 도전성 다이아몬드 전극, 이것을 이용한, 황산 전해방법 및 황산 전해장치
JP2004332108A (ja) 電解用ダイヤモンド電極
EP4392380A1 (fr) Électrode au diamant avec une surface ayant subi une ablation
JP2010053400A (ja) 電解装置用多孔質導電体の製造方法
JP2004115825A (ja) 水電解装置用セパレータの製造方法
JP2007146255A (ja) ダイヤモンド被覆基板及び電極
JPH11333457A (ja) 電解水の製造方法
TWM478024U (zh) 石墨烯生成裝置

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080055426.7

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10835848

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 13393484

Country of ref document: US

ENP Entry into the national phase

Ref document number: 20127014722

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10835848

Country of ref document: EP

Kind code of ref document: A1