US20030168348A1 - Method and apparatus for generating ozone by electrolysis - Google Patents

Method and apparatus for generating ozone by electrolysis Download PDF

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Publication number
US20030168348A1
US20030168348A1 US10/239,171 US23917103A US2003168348A1 US 20030168348 A1 US20030168348 A1 US 20030168348A1 US 23917103 A US23917103 A US 23917103A US 2003168348 A1 US2003168348 A1 US 2003168348A1
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United States
Prior art keywords
platinum
treatment water
ozone
coated
anode
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Abandoned
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US10/239,171
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English (en)
Inventor
Yasuhito Kondo
Naoki Hiro
Kazuo Ikegami
Yasuhiko Shimizu
Masahiro Iseki
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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Assigned to SANYO ELECTRIC CO., LTD. reassignment SANYO ELECTRIC CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HIRO, NAOKI, SHIMIZU, YASUHIKO, IKEGAMI, KAZUO, ISEKI, MASAHIRO, KONDO, YASUHITO
Publication of US20030168348A1 publication Critical patent/US20030168348A1/en
Abandoned legal-status Critical Current

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    • 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
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/305—Endocrine disruptive agents
    • 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
    • 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
    • C02F2201/46155—Heating or cooling
    • 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
    • C02F2303/04—Disinfection

Definitions

  • the present invention relates to a method and apparatus for producing ozone in water to be treated (hereinafter, “water to be treated” will be referred to as “for-treatment water”) through electrolysis by passing current between an anode and a cathode.
  • sterilization and purification of the water are performed by, for example, applying a high voltage between electrodes in an atmosphere by means of a separate device so as to cause surface creepage on surfaces of the electrodes, producing ozone from oxygen by the creepage, and dissolving the produced ozone in the for-treatment water reserved in a treatment tank or the like.
  • the ozone producing method in the foregoing method has a problem that it is not suitable for practical use since its energy consumption is significant.
  • An object of the present invention is to provide an ozone producing method and apparatus which are capable of significantly increasing an amount of ozone produced in for-treatment water.
  • a method for producing ozone by electrolysis is a method for producing ozone in for-treatment water through electrolysis by passing current between an anode and a cathode, wherein a noble metal is used as a material constituting the anode, and the for-treatment water contains halogen ions or a compound containing halogen ions.
  • the halogen ions are chloride ions.
  • the anode is made of platinum, platinum-coated titanium, a platinum-coated titanium alloy, titanium coated with a platinum-iridium alloy, a titanium alloy coated with a platinum-iridium alloy, titanium coated with a platinum-iridium-tantalum alloy, or a titanium alloy coated with a platinum-iridium-tantalum alloy.
  • a cation exchange film is disposed between the anode and the cathode.
  • the for-treatment water is cooled.
  • a value of the current passed between the anode and the cathode is controlled.
  • An apparatus for producing ozone is an ozone producing apparatus having an anode and a cathode which are immersed in for-treatment water in an electrolysis vessel, wherein the anode is made of a noble metal, and current is passed between the anode and the cathode so as to electrolyze the for-treatment water containing halogen ions or a compound containing halogen ions, thereby producing ozone in the for-treatment water.
  • the halogen ions are chloride ions.
  • the anode is made of platinum, platinum-coated titanium, a platinum-coated titanium alloy, titanium coated with a platinum-iridium alloy, a titanium alloy coated with a platinum-iridium alloy, titanium coated with a platinum-iridium-tantalum alloy, or a titanium alloy coated with a platinum-iridium-tantalum alloy.
  • a cation exchange film is disposed between the anode and the cathode.
  • the ozone producing apparatus in addition to the ozone producing apparatuses of above inventions, has cooling means for cooling the for-treatment water.
  • the ozone producing apparatus in addition to the ozone producing apparatuses of above inventions, has a controller for controlling a value of the current passed between the anode and the cathode.
  • FIG. 1 is a schematic explanatory diagram of an ozone producing apparatus of the present invention.
  • FIG. 2 is a diagram showing potentials with respect to currents when a platinum-coated titanium electrode is used.
  • FIG. 3 is a diagram showing potentials with respect to currents when an electrode made of titanium coated with platinum and iridium is used.
  • FIG. 4 is a diagram showing potentials with respect to currents when an electrode made of titanium coated with platinum, iridium and tantalum is used.
  • FIG. 5 is a diagram showing amounts of contained ozone with respect to for-treatment water temperatures.
  • FIG. 6 is a diagram showing effective chlorine concentrations on the above electrodes with respect to for-treatment water temperatures.
  • FIG. 7 is a diagram showing a decrease in concentration of an endocrine disruptor by electrolysis.
  • FIG. 1 is an explanatory diagram showing an outline of an ozone producing apparatus 1 for implementing an ozone producing method of the present invention.
  • the ozone producing apparatus 1 in the present embodiment comprises an electrolysis vessel 2 which constitutes a treating chamber 4 having an inlet and an outlet for for-treatment water therein, the inlet and the outlet being not shown, a pair of electrodes, i.e., an anode 5 and a cathode 6 , which are opposed to each other such that at least portions thereof are immersed in for-treatment water in the treating chamber 4 , a power supply 7 for energizing the electrodes 5 and 6 , and a controller 8 for controlling the electrodes 5 and 6 and an electric current value.
  • reference numeral 9 denotes a cation exchange film disposed between the anode 5 and the cathode 6 in the electrolysis vessel 2
  • reference numerals 10 denote cooling devices for cooling the for-treatment water in the electrolysis vessel 2 which are disposed, for example, at the bottom of the electrolysis vessel 2 .
  • the anode 5 is made of a noble metal such as platinum, platinum-coated titanium, a platinum-coated titanium alloy, titanium coated with a platinum-iridium alloy, a titanium alloy coated with a platinum-iridium alloy, titanium coated with a platinum-iridium-tantalum alloy, or a titanium alloy coated with a platinum-iridium-tantalum alloy.
  • the cathode 6 is made of the same noble metals as can be used in the anode 5 or an insoluble material or carbon.
  • tap water containing chloride ions is used, for example.
  • for-treatment water is reserved in the treating chamber 4 in the electrolysis vessel 2 , and the controller 8 turns on the power supply 7 so as to energize the anode 5 and the cathode 6 .
  • microorganisms contained in the for-treatment water are attracted to the anode 5 which is positively charged since the microorganisms are generally negatively charged.
  • chloride ions contained in the for-treatment water produce chlorine by discharging electrons. Thereafter, the chlorine dissolves in the water so as to produce hypochlorous acid.
  • microorganisms in the for-treatment water which are present in the vicinity of the anode 5 are sterilized by the chlorine or hypochlorous acid.
  • the anode 5 is made of platinum, platinum-coated titanium, a platinum-coated titanium alloy, titanium coated with a platinum-iridium alloy, a titanium alloy coated with a platinum-iridium alloy, titanium coated with a platinum-iridium-tantalum alloy, or a titanium alloy coated with a platinum-iridium-tantalum alloy as described above and the for-treatment water contains the chloride ions, the potential increases and ozone is produced.
  • FIG. 2 shows potentials with respect to currents when the chloride ions are contained and not contained, with a platinum-coated titanium electrode being used as the electrode.
  • 1M sulfuric acid containing 10% of potassium chloride is used when the chloride ions are contained, and 1M sulfuric acid is used when the chloride ions are not contained.
  • the potential sharply increases from 1.2 V to 1.5 V when a current of 6 to 8 mA is passed, and the potential increases to 2.1 V with a current of 60 mA. Meanwhile, in the case of for-treatment water containing no chloride ions, the potential is gently increased from 0.8 V to 1.8 V as current is gradually increased from 0.1 mA to 60 mA. Thereby, it is understood that when the chloride ions are contained in the for-treatment water, the potential is significantly increased, as compared with when the chloride ions are not contained in the for-treatment water.
  • FIG. 3 is a diagram for illustrating an increase in potential with or without the chloride ions when a titanium electrode coated with platinum and iridium is used.
  • FIG. 3 shows potentials with respect to currents when the chloride ions are contained and not contained, with titanium coated with platinum and iridium being used as the electrode.
  • 1M sulfuric acid containing 10% of potassium chloride is used when the chloride ions are contained, and 1M sulfuric acid is used when the chloride ions are not contained.
  • the potential increases to about 1.48 V when a current of 60 mA is passed, while in the case of for-treatment water containing no chloride ions, the potential is increased to about 1.4 V when a current of 60 mA is passed.
  • the potential is increased, as compared with when the chloride ions are not contained in the for-treatment water.
  • FIG. 4 is a diagram for illustrating an increase in potential with or without the chloride ions when a titanium electrode coated with platinum, iridium and tantalum is used.
  • FIG. 4 shows potentials with respect to currents when the chloride ions are contained and not contained, with titanium coated with platinum, iridium and tantalum being used as the electrode.
  • 1M sulfuric acid containing 10% of potassium chloride is used when the chloride ions are contained, and 1M sulfuric acid is used when the chloride ions are not contained.
  • the potential increases to about 1.7 V when a current of 60 mA is passed, while in the case of for-treatment water containing no chloride ions, the potential is increased to about 1.6 V when a current of 60 mA is passed.
  • a difference in potential between when the chloride ions are contained and when the chloride ions are not contained is not so significant.
  • the potential is increased, as compared with when the chloride ions are not contained in the for-treatment water.
  • ozone when for-treatment water containing the chloride ions is electrolyzed by means of a titanium electrode coated with platinum, a titanium electrode coated with platinum and iridium or a titanium electrode coated with platinum, iridium and tantalum, ozone can be produced with ease by an increase in potential. Thereby, since ozone can be produced with a relatively small current, microorganisms, chlorine-resistant bacteria, spores and protozoans contained in for-treatment water can be eliminated by ozone which exhibits a very powerful sterilizing effect.
  • the electrode used in the present invention is a platinum-coated titanium electrode, chlorine or hypochlorous acid and ozone which exhibit an excellent sterilizing effect can be produced in the same electrolysis vessel 2 , thereby making it possible to sterilize and purify for-treatment water efficiently.
  • for-treatment water can be sterilized and purified while ozone is produced. Therefore, there is no longer need to carry out the step of dissolving ozone produced in a separate device into for-treatment water, and ozone can be contained in the for-treatment water in a significantly larger amount than a conventional amount of dissolved ozone. Thereby, sterilization and purification of for-treatment water can be carried out more securely and more efficiently.
  • ozone is produced without use of lead dioxide. Therefore, sterilized and purified for-treatment water can be directly used for drinking or sterilization of cooking utensils without affecting human bodies.
  • the cation exchange film 9 is disposed between the anode 5 and the cathode 6 in the electrolysis vessel 2 .
  • hydrogen ions produced by electrolysis are transferred from the anode 5 side to the cathode 6 side so as to promote production of hydrogen at the cathode 6 .
  • the potential can be increased, and the amount of ozone produced can also be increased along with an increase in the potential.
  • the electrolysis vessel 2 electrolyzes for-treatment water while cooling the for-treatment water by means of the conventional cooling devices 10 .
  • FIG. 5 is a diagram showing amounts of contained ozone with respect to a for-treatment water temperature, and electrolysis was carried out with a current of 400 mA by use of a platinum-coated titanium electrode, a titanium electrode coated with platinum and iridium, or a titanium electrode coated with platinum, iridium and tantalum.
  • the concentration of ozone is about 0.48 mg/dm 3 for the platinum-coated titanium electrode, about 0.10 mg/dm 3 for the titanium electrode coated with platinum and iridium, and about 0.18 mg/dm 3 for the titanium electrode coated with platinum, iridium and tantalum.
  • the concentration of ozone is about 0.12 mg/dm 3 for the platinum-coated titanium electrode, about 0.01 mg/dm 3 for the titanium electrode coated with platinum and iridium, and about 0.05 mg/dm 3 for the titanium electrode coated with platinum, iridium and tantalum, at the for-treatment temperature of +22° C. Further, it is observed that as the for-treatment water temperature is further increased for each of the electrodes, ozone hardly exists for any of the electrodes at the for-treatment water temperature of +60° C.
  • FIG. 6 is a diagram showing effective chlorine concentrations on the above electrodes with respect to for-treatment water temperatures and shows the results of experiments conducted under the same conditions as those for the experiments whose results are shown in FIG. 5.
  • effective chlorine concentration for the platinum-coated titanium electrode is significantly lower than effective chlorine concentrations for other electrodes. This is assumed to be because a reaction of producing ozone occurs preferentially.
  • FIG. 7 is a diagram showing a decrease in concentration of an endocrine disrupter by electrolysis, which is currently considered as a problem. It is seen that when an endocrine disruptor such as di-2-ethylhexyl phthalate is contained in the foregoing for-treatment water, di-2-ethylhexyl phthalate is decreased with the passage of electrolysis time by ozone produced as described above. Thus, even if an endocrine disruptor such as di-2-ethylhexyl phthalate is contained in for-treatment water, the endocrine disrupter can be decomposed efficiently by ozone, thereby improving efficiency of purification of the for-treatment water.
  • an endocrine disruptor such as di-2-ethylhexyl phthalate
  • an electric current value can be controlled by the controller 8 . Accordingly, an electric current value is controlled according to quality of for-treatment water, thereby making it possible to produce required ozone.
  • the method of the present invention for producing ozone by means of electrolysis it is a method for producing ozone in for-treatment water through electrolysis by passing current between an anode and a cathode, wherein a noble metal is used as a material constituting the anode, and the for-treatment water contains halogen ions or a compound containing halogen ions.
  • a noble metal is used as a material constituting the anode
  • the for-treatment water contains halogen ions or a compound containing halogen ions.
  • the above halogen ions are chloride ions.
  • hypochlorous acid can be produced along with production of ozone, and the for-treatment water can be sterilized effectively by ozone and hypochlorous acid.
  • the above anode is made of platinum, platinum-coated titanium, a platinum-coated titanium alloy, titanium coated with a platinum-iridium alloy, a titanium alloy coated with a platinum-iridium alloy, titanium coated with a platinum-iridium-tantalum alloy, or a titanium alloy coated with a platinum-iridium-tantalum alloy.
  • a value of the current passed between the above anode and cathode is controlled. Thereby, the amount of ozone contained in the for-treatment water can be controlled.
  • the apparatus of the present invention for producing ozone by electrolysis it is an ozone producing apparatus having an anode and a cathode which are immersed in for-treatment water in an electrolysis vessel, wherein the anode is made of a noble metal, and current is passed between the anode and the cathode so as to electrolyze the for-treatment water containing halogen ions or a compound containing halogen ions, thereby producing ozone in the for-treatment water.
  • ozone can be produced in an electrolysis vessel efficiently so as to sterilize the for-treatment water efficiently.
  • chlorine-resistant bacteria and the like which are conventionally contained in the for-treatment water can be eliminated efficiently, and the resulting treated water can be used also as drinking water or the like.
  • the halogen ions are chloride ions. Therefore, hypochlorous acid can be produced along with production of ozone, and the for-treatment water can be sterilized effectively by ozone and hypochlorous acid contained in the for-treatment water.
  • the above anode is made of platinum, platinum-coated titanium, a platinum-coated titanium alloy, titanium coated with a platinum-iridium alloy, a titanium alloy coated with a platinum-iridium alloy, titanium coated with a platinum-iridium-tantalum alloy, or a titanium alloy coated with a platinum-iridium-tantalum alloy.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
US10/239,171 2001-03-14 2002-03-06 Method and apparatus for generating ozone by electrolysis Abandoned US20030168348A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-71895 2001-03-14
JP2001071895A JP2002263650A (ja) 2001-03-14 2001-03-14 電解によるオゾン発生方法及びオゾン発生装置

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US (1) US20030168348A1 (de)
EP (1) EP1394119A4 (de)
JP (1) JP2002263650A (de)
WO (1) WO2002072481A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103194765A (zh) * 2012-01-10 2013-07-10 石福金属兴业株式会社 杀菌水生成装置
CN108483586A (zh) * 2018-05-03 2018-09-04 河海大学 一种去除污水厂尾水中雌激素的装置及方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2377187C2 (ru) * 2005-04-26 2009-12-27 Феликс Беттхер Гмбх Унд Ко. Кг Способ и устройство для контроля и ограничения загрязнения микроорганизмами в контурах увлажняющих средств

Citations (6)

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US3234110A (en) * 1959-02-06 1966-02-08 Amalgamated Curacao Patents Co Electrode and method of making same
US4128768A (en) * 1975-05-14 1978-12-05 Mitsubishi Denki Kabushiki Kaisha Ozone generating apparatus
US4236992A (en) * 1979-08-06 1980-12-02 Themy Constantinos D High voltage electrolytic cell
US4316782A (en) * 1980-05-29 1982-02-23 Regents Of The University Of California Electrolytic process for the production of ozone
US4761208A (en) * 1986-09-29 1988-08-02 Los Alamos Technical Associates, Inc. Electrolytic method and cell for sterilizing water
US5427667A (en) * 1992-04-03 1995-06-27 Bakhir; Vitold M. Apparatus for electrochemical treatment of water

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US4171256A (en) * 1978-11-03 1979-10-16 Tim Themy Chlorine generation apparatus
US4316787A (en) * 1979-08-06 1982-02-23 Themy Constantinos D High voltage electrolytic cell
CH667867A5 (de) * 1986-03-11 1988-11-15 Bbc Brown Boveri & Cie Verfahren und vorrichtung zur beladung von leitungswasser mit ozon unter verwendung einer ozonerzeugenden, mit einem feststoffelektrolyten ausgestatteten elektrolysezelle.
JPS6436784A (en) * 1987-04-08 1989-02-07 Nippon Medix Kk Ozone-producing mechanism
US5094734A (en) * 1989-08-03 1992-03-10 Torrado Santiago D Water treatment unit
GB9017404D0 (en) * 1990-08-08 1990-09-19 Johnson Matthey Plc Ozone generation
JP2743823B2 (ja) * 1994-03-25 1998-04-22 日本電気株式会社 半導体基板のウエット処理方法

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Publication number Priority date Publication date Assignee Title
US3234110A (en) * 1959-02-06 1966-02-08 Amalgamated Curacao Patents Co Electrode and method of making same
US4128768A (en) * 1975-05-14 1978-12-05 Mitsubishi Denki Kabushiki Kaisha Ozone generating apparatus
US4236992A (en) * 1979-08-06 1980-12-02 Themy Constantinos D High voltage electrolytic cell
US4316782A (en) * 1980-05-29 1982-02-23 Regents Of The University Of California Electrolytic process for the production of ozone
US4761208A (en) * 1986-09-29 1988-08-02 Los Alamos Technical Associates, Inc. Electrolytic method and cell for sterilizing water
US5427667A (en) * 1992-04-03 1995-06-27 Bakhir; Vitold M. Apparatus for electrochemical treatment of water

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103194765A (zh) * 2012-01-10 2013-07-10 石福金属兴业株式会社 杀菌水生成装置
CN108483586A (zh) * 2018-05-03 2018-09-04 河海大学 一种去除污水厂尾水中雌激素的装置及方法

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WO2002072481A1 (fr) 2002-09-19
EP1394119A1 (de) 2004-03-03
JP2002263650A (ja) 2002-09-17
EP1394119A4 (de) 2009-05-13

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