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WO2017090431A1 - Dispositif de production d'eau réduite et procédé de production d'eau réduite - Google Patents

Dispositif de production d'eau réduite et procédé de production d'eau réduite Download PDF

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Publication number
WO2017090431A1
WO2017090431A1 PCT/JP2016/083245 JP2016083245W WO2017090431A1 WO 2017090431 A1 WO2017090431 A1 WO 2017090431A1 JP 2016083245 W JP2016083245 W JP 2016083245W WO 2017090431 A1 WO2017090431 A1 WO 2017090431A1
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Prior art keywords
cathode
chamber
water
diaphragm
cathode electrode
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PCT/JP2016/083245
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English (en)
Japanese (ja)
Inventor
修生 澄田
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Priority to KR1020187005674A priority Critical patent/KR102616663B1/ko
Priority to JP2017552346A priority patent/JP6869188B2/ja
Publication of WO2017090431A1 publication Critical patent/WO2017090431A1/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
    • 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
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • 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
    • 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
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • 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
    • 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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • 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
    • C02F2201/4616—Power supply
    • 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

  • the present invention relates to reduced water (hydrogen water) containing hydrogen obtained by electrolytic reduction, and more particularly, to an apparatus and method capable of suppressing a decrease in dissolved hydrogen molecule concentration in the reduced water.
  • Examples of a method for generating hydrogen water include an electrolytic reduction method in which water is electrolytically reduced to directly generate dissolved hydrogen molecules in water, and a method in which hydrogen gas is bubbled into water to dissolve hydrogen molecules.
  • a hydrogen gas pressure dissolution method in which hydrogen gas is dissolved in water under pressure is known.
  • the equilibrium solubility of hydrogen gas is 1.5 to 1.6 ppm. Since the reduced water produced by electrolytic reduction is in contact with the atmosphere, the concentration of dissolved hydrogen molecules in the water is considerably lower than 1.5 ppm. For example, when electrolytically reduced water is stored in a PET bottle or the like, the concentration of dissolved hydrogen molecules in the water becomes 0.5 ppm or less after a lapse of a certain time. Thus, when hydrogen water is stored in contact with the atmosphere, some dissolved hydrogen molecules are volatilized in the atmosphere, so the dissolved hydrogen molecule concentration decreases. Therefore, for example, a technique described in Patent Document 1 has been proposed for the purpose of suppressing a decrease in dissolved hydrogen molecule concentration in the obtained hydrogen water.
  • An object of this invention is to provide the novel technique which can suppress the fall of dissolved hydrogen molecule concentration in the reducing water obtained by electrolytic reduction.
  • the present inventor conducted electrolytic reduction by applying a predetermined current to the cathode electrode in the electrolytic cell involved in the reduction reaction when electrolyzing to generate hydrogen, or electrolytic reduction It was found that the decrease in dissolved hydrogen molecule concentration can be suppressed by generating hydrogen in the vicinity of the cathode electrode and applying vibration to the cathode electrode with a predetermined ultrasonic wave, thereby completing the present invention.
  • the gist of the present invention is as follows. [1] An anode chamber, a cathode chamber, a diaphragm that is a fluorine-based ion exchange membrane disposed between the anode chamber and the cathode chamber, and a porosity that is disposed in contact with the diaphragm in the anode chamber An electrolytic cell comprising an anode electrode and a cathode electrode disposed in the cathode chamber; Applying an electric current having an alternating current component with an average current value of 10 kHz or less to zero or more to the cathode electrode to generate hydrogen by electrolytic reduction of water supplied between the diaphragm and the cathode electrode And applying a current having a direct current component to the cathode electrode to perform electroreduction of water supplied between the diaphragm and the cathode electrode to generate hydrogen, and at least 30 kHz to 10 MHz on the surface of the cathode electrode.
  • a reduced water production apparatus comprising: a concentration reduction suppressing unit that performs at least one of applying mechanical vibration in the following ultrasonic region.
  • a concentration reduction suppressing unit that performs at least one of applying mechanical vibration in the following ultrasonic region.
  • the concentration decrease suppression unit applies an AC current of 10 kHz or less subjected to half-wave rectification or full-wave rectification to the cathode electrode to perform electrolytic reduction of water, and has a surface of the cathode electrode with a frequency of 30 kHz to 10 MHz.
  • a device for producing reduced water that imparts mechanical vibration in the ultrasonic region. [5] In the device according to any one of [1] to [4], An apparatus for producing reduced water in which an ion exchange resin is filled between the diaphragm and the cathode electrode.
  • the concentration reduction suppressing unit has an ultrasonic vibrator embedded in the ion exchange resin,
  • the concentration reduction suppressing unit is a device for producing reduced water that imparts mechanical vibration in an ultrasonic region of 30 kHz to 10 MHz from the ultrasonic vibrator to the surface of the cathode electrode.
  • the cathode chamber has a plurality of protrusions on a surface facing the diaphragm, and the cathode electrode is disposed at the tip of the protrusion so as to be in contact with the protrusion, and between the cathode electrode and the diaphragm.
  • the cathode is a porous cathode;
  • the cathode chamber includes a plurality of raw water supply units that allow water to flow in from the cathode chamber, and a plurality of reduced water discharge units that discharge electrolytically reduced water from the cathode chamber, and the raw water supply unit and the
  • the reduced water discharge unit is a reduced water production apparatus disposed with the protruding portion interposed therebetween.
  • the electrolytic cell is a three-chamber electrolytic cell that is disposed between the anode chamber, the cathode chamber, the anode chamber and the cathode chamber, and has an intermediate chamber separated from the anode chamber and the cathode chamber by the diaphragm.
  • a reducing water production apparatus in which a reducing substance is present in the intermediate chamber.
  • Supplying water between the diaphragm and the cathode in an electrolytic cell comprising an anode and a cathode disposed in the cathode chamber Applying an electric current having an alternating current component having an average current value of 10 kHz or less to zero or more to the cathode electrode to generate hydrogen by electrolytic reduction of water, and an electric current having a direct current component to the cathode electrode
  • a method for producing reduced water wherein an electric current having an alternating current component having an average current value of 10 kHz or less being zero or more is an electric current having an alternating current component having a minimum current value of zero or more.
  • a method for producing reduced water wherein the current having an alternating current component with an average current value of 10 kHz or less being zero or more is an alternating current obtained by half-wave rectification or full-wave rectification.
  • the manufacturing method of the reduced water which supplies water between the said diaphragm in the said electrolytic cell and the said cathode electrode whose distance in the direction orthogonal to the said diaphragm is 1 mm or less.
  • the cathode is a porous cathode;
  • the cathode chamber includes a plurality of raw water supply units that allow water to flow in from the cathode chamber, and a plurality of reduced water discharge units that discharge electrolytically reduced water from the cathode chamber, and the raw water supply unit and the
  • the reduced water discharge part is a method for producing reduced water disposed with the protruding part interposed therebetween.
  • the electrolytic cell is a three-chamber electrolytic cell that is disposed between the anode chamber, the cathode chamber, the anode chamber and the cathode chamber, and has an intermediate chamber separated from the anode chamber and the cathode chamber by the diaphragm.
  • a method for producing reduced water in which a reducing substance is present in the intermediate chamber is a three-chamber electrolytic cell that is disposed between the anode chamber, the cathode chamber, the anode chamber and the cathode chamber, and has an intermediate chamber separated from the anode chamber and the cathode chamber by the diaphragm.
  • the first embodiment includes an anode chamber, a cathode chamber, a diaphragm that is a fluorine-based ion exchange membrane disposed between the anode chamber and the cathode chamber, and a porosity that is disposed in contact with the diaphragm in the anode chamber.
  • An electrolytic cell comprising an anode electrode and a cathode electrode disposed in the cathode chamber; Concentration reduction suppressing unit that generates hydrogen by performing electrolytic reduction of water supplied between the diaphragm and the cathode electrode by applying an electric current having an AC component whose average current value of 10 kHz or less to zero or more to the cathode electrode It is related with the reduced water manufacturing apparatus provided with.
  • FIG. 1 is a diagram showing an outline of the configuration of the system.
  • the system according to the first embodiment includes an electrolytic cell 100 and a raw material water generating and feeding unit 200 that supplies water as a raw material to the cathode chamber 3 of the electrolytic cell 100.
  • a raw material water generating and feeding unit 200 that supplies water as a raw material to the cathode chamber 3 of the electrolytic cell 100.
  • the case where water having an electric conductivity of 200 ⁇ S / cm or less is supplied to the electrolytic cell 100 is taken as an example.
  • the present invention is not limited to this.
  • the raw material water generation / feeding unit 200 can be configured by a reverse osmosis membrane filter 140 and a water supply pump 130.
  • the reverse osmosis membrane filter 140 increases the purity of tap water sent from the tap water line 150 and has an electric conductivity of 200 ⁇ S / cm or less (hereinafter also referred to as raw water. The water is 20 ⁇ S / cm or less). More preferred).
  • the feed water pump 130 supplies the raw water generated in the reverse osmosis membrane filter 140 to the cathode chamber 3 of the electrolytic cell 100.
  • a well-known thing can be used for the feed pump 130, the reverse osmosis membrane filter 140, and the water supply line 150, and it is not specifically limited.
  • generation liquid feeding part 200 is an example, and you may make it supply raw material water to the electrolytic cell 100 by another structure.
  • the electrolytic cell 100 can be a two-chamber electrolytic cell described in Patent Document 1, for example.
  • the electrolytic cell 100 has an anode chamber 1 and a cathode chamber 3.
  • a diaphragm 5 that is a fluorine ion exchange membrane is disposed between the anode chamber 1 and the cathode chamber 3, and separates the anode chamber 1 and the cathode chamber 3.
  • a porous anode 21 is arranged in the anode chamber 1, and a cathode 4 is arranged in the cathode chamber 3.
  • the porous anode 21 is disposed at a position in contact with the diaphragm 5 in the anode chamber 1.
  • the cathode electrode 4 is arranged so as to form a wall portion facing the diaphragm 5 of the cathode chamber 3. Further, in the first embodiment, water having an electric conductivity of 200 ⁇ S / cm or less (preferably water having a value of 20 ⁇ S / cm or less) is used between the diaphragm 5 and the cathode electrode 4 in the cathode chamber. As a preferable configuration in the reduction, the ion exchange resin 31 is filled. In addition, each capacity
  • a voltage is applied to the anode electrode 21 and the cathode electrode 4 by supplying a current from the power source 110.
  • a current is applied to the anode electrode 21 and the cathode electrode 4 by supplying a current from the power source 110.
  • water is electrolyzed in the electrolytic cell 100, and in the cathode chamber 3, a reduction reaction proceeds to generate hydrogen.
  • an oxidation reaction is performed in the anode chamber 1 (a detailed description and illustration are omitted because a known configuration can be used).
  • Reduced water containing hydrogen generated in the cathode chamber 3 of the electrolytic cell 100 is sent to the water storage tank 120 and stored.
  • the inflow into the water storage tank 120 can be controlled by a valve 160. Further, it is possible to control the pressure state in the cathode chamber 3 by operating the valve 160.
  • a current having an alternating current component having an average current value of 10 kHz or less from the power source 110 (corresponding to the concentration reduction suppressing unit in the first embodiment) of 10 kHz or less is zero or more from the cathode electrode 4.
  • half-wave rectification or full-wave rectification of an alternating current of 10 kHz or less is applied to the cathode electrode 4 to perform electrolytic reduction of water to generate hydrogen.
  • half-wave rectification and full-wave rectification refer to processing for converting a current / voltage component in a negative direction to zero or a positive side larger than zero in alternating current / voltage.
  • the current having an alternating current component whose current average value is zero or more is not limited to the half-wave rectified or full-wave rectified alternating current, and may be, for example, a pulse current.
  • the water supplied to the cathode chamber is subjected to electrolytic reduction by applying an electric current having an alternating current component having an average current value of 10 kHz or less to zero or more to the cathode electrode.
  • High dissolved hydrogen molecule concentration can be obtained.
  • the power source 110 and the mechanical vibration applying unit 8 correspond to a concentration reduction suppressing unit.
  • the current applied to the cathode electrode 4 is not particularly limited as long as it is a current having a direct current component.
  • a direct current etc. It may be.
  • the current applied to the cathode electrode 4 is preferably an alternating current of 10 kHz or less subjected to half-wave rectification or full-wave rectification.
  • FIG. 2 illustrates a case where an alternating current of 10 kHz or less subjected to half-wave rectification or full-wave rectification is applied.
  • an ultrasonic vibrator can be used as the mechanical vibration applying unit 8.
  • the position where the mechanical vibration applying unit 8 is disposed is not particularly limited and can be set as appropriate. For example, it can be disposed at the position shown in FIGS.
  • the mechanical vibration applying unit 8 is disposed at a position in contact with the cathode electrode 4 outside the electrolytic cell 100.
  • the mechanical vibration applying unit 8 is embedded in the ion exchange resin 31 in the cathode chamber 3 and disposed in the vicinity of the surface of the cathode electrode 4.
  • FIG. 2 illustrates the case where the mechanical vibration applying unit 8 is embedded in the ion exchange resin 31 in the cathode chamber 3.
  • a mechanical vibration applying unit 8 is installed in the cathode chamber as illustrated in FIG. It is preferable.
  • the electrolytic reduction of water in the cathode chamber is performed to generate hydrogen
  • the mechanical vibration applying unit 8 causes the surface of the cathode electrode 4 in the cathode chamber 3 to exceed 30 kHz to 10 MHz.
  • FIG. 5 shows an outline of a system according to the third embodiment.
  • the system according to the third embodiment includes a three-chamber electrolytic cell 300 instead of the two-chamber electrolytic cell 100 according to the first embodiment.
  • the three-chamber electrolytic cell 300 is disposed between the anode chamber 1 and the cathode chamber 3 and is separated from the anode chamber 1 and the cathode chamber 3 by the diaphragms 51 and 52.
  • the electrolytic cell 300 can be a three-chamber electrolytic cell described in Patent Document 1, for example.
  • the intermediate chamber 6 is filled with an ion exchange resin, and purified water from which divalent or higher metal ions including alkaline earth metals such as calcium ions are removed can be supplied (anode chamber 1).
  • an oxidizing substance such as oxygen generated in the anode chamber 1 from moving to the cathode chamber 3.
  • FIGS. 6 and 7 are diagrams showing an outline of an electrolytic cell 300 according to the fourth embodiment.
  • the position at which the mechanical vibration applying unit 8 is disposed is not particularly limited and can be set as appropriate.
  • the mechanical vibration imparting unit 8 is disposed at the position illustrated in FIGS. can do.
  • the mechanical vibration applying unit 8 is disposed at a position in contact with the cathode electrode 4 outside the electrolytic cell 300.
  • the mechanical vibration applying unit 8 is embedded in the ion exchange resin 31 in the cathode chamber 3 and disposed in the vicinity of the surface of the cathode electrode 4.
  • FIG. 8 shows an outline of a system according to the fifth embodiment.
  • the organic acid reducing aqueous solution is passed through the intermediate chamber 6, and the reducing aqueous solution discharged from the outlet of the intermediate chamber 6 is led to the intermediate chamber 6 to circulate the reducing aqueous solution.
  • the intermediate chamber 6 is filled with an organic acid reducing aqueous solution.
  • the reducing substance is present in the intermediate chamber 6.
  • a circulation line 190 is provided to circulate the organic acid reducing aqueous solution.
  • An intermediate chamber liquid circulation pump 180 and an intermediate chamber liquid storage tank 170 are provided in the circulation line 190 to circulate a reducing aqueous solution.
  • the organic acid reducing substance include ascorbic acid, lactic acid, and gluconic acid. In this embodiment, these aqueous solutions can be circulated.
  • the present invention has been described with reference to some embodiments, but other embodiments may be used.
  • the electrolytic cell is filled with an ion exchange resin between the cathode electrode and the diaphragm in the cathode chamber. It has the composition which is.
  • another configuration may be used.
  • an improved cathode electrode that enables both water flow and low-voltage electrolysis without filling with an ion exchange resin can be used.
  • the cathode chamber has a plurality of protrusions on the surface facing the diaphragm, and the cathode electrode is disposed so as to contact the protrusion at the tip of the protrusion, and between the cathode electrode and the diaphragm.
  • the distance in the direction perpendicular to the diaphragm can be 1 mm or less.
  • Specific examples of such a cathode chamber include a cathode chamber having a corrugated surface and a comb-shaped cathode electrode described in Patent Document 1.
  • FIG. 9 is a diagram showing an outline of the electrolytic cell according to the aspect
  • FIG. 10 is a diagram showing an outline of the system according to the aspect.
  • the porous cathode electrode 4 having a plurality of openings is placed in contact with the cathode chamber frame 400, and the porous cathode electrode 4 and the diaphragm 5 are arranged.
  • the distance in a direction perpendicular to the diaphragm 5 is set to 1 mm or less.
  • the cathode chamber frame 400 has a plurality of protrusions 320 on the surface facing the diaphragm 5, and the porous cathode electrode 4 is in contact with the protrusion 320 at the tip of the protrusion 320. At the same time, it is arranged to face the diaphragm 5.
  • a plurality of raw water supply lines 302 and a plurality of reducing water discharge lines 303 are connected to a non-projecting portion that is not in contact with the cathode electrode 4 on the surface facing the porous cathode electrode 4 of the cathode chamber frame 400.
  • the raw water supply line 302 and the reduced water discharge line 303 are disposed with a protrusion 320 in contact with the porous cathode 4 interposed therebetween.
  • the raw water supply line 302 communicates with the raw water supply manifold 304.
  • Raw material water is supplied from the communicating raw material water inlet 306 to the raw material water supply manifold 304.
  • the raw water flows into the cathode chamber 3 from the raw water supply line 302 via the raw water supply manifold 304 and is porous through an opening in a non-contact portion with the protruding portion 320 of the porous cathode electrode 4. It is supplied to the electrolytic surface 301 on the surface of the cathode electrode 4.
  • the reduced water discharge line 303 communicates with the reduced water discharge manifold 305.
  • the reduced water generated on the electrolytic surface flows into the reduced water discharge manifold 305 through the opening in the non-contact portion with the protrusion 320 of the porous cathode electrode 4 and the reduced water discharge line 303.
  • a reducing water outlet 307 communicates with the reducing water discharge manifold 305, and the reducing water generated from the reducing water outlet 307 is discharged.
  • the reduced water discharge line 303 and the reduced water discharge manifold 305 are not visible in the cross section where the raw water supply line 302 and the raw water supply manifold 304 are visible. Therefore, in FIGS.
  • the reduced water discharge line 303 and the reduced water discharge manifold 305 are indicated by broken lines. That is, in this embodiment, the raw material water that has flowed into the cathode chamber from the raw material water supply line 302 is supplied to the electrolysis surface 301 through an opening in a non-contact portion with the protruding portion 320 of the porous cathode electrode 4. Further, the reduced water generated on the electrolytic surface 301 is discharged from the reduced water drain line 303 to the outside of the cathode chamber through an opening in a non-contact portion with the protruding portion 320 of the porous cathode electrode 4. According to such an aspect, the flow velocity of the cathode electrode surface that is the electrolytic surface can be further increased. As a result, the highly dissolved hydrogen molecule concentration water in the vicinity of the cathode electrode can be more efficiently transferred to the bulk water, so that the decrease in the dissolved hydrogen molecule concentration can be further suppressed.
  • the equilibrium solubility of hydrogen gas is 1.5 to 1.6 ppm under conditions of atmospheric pressure and room temperature.
  • the present inventor applied an electric current having an alternating current component with an average current value of zero or more to the cathode electrode in the electrolytic cell involved in the reduction reaction when generating hydrogen by electrolysis.
  • electrolytic reduction to the cathode electrode by applying a current having a DC component to the cathode electrode to generate hydrogen in the vicinity of the cathode electrode and applying vibrations to the cathode electrode by a predetermined ultrasonic wave
  • the present inventors have found that the decrease in dissolved hydrogen molecule concentration can be suppressed, and have completed the present invention. Hereinafter, this point will be described in detail.
  • FIG. 12 shows the state of hydrogen gas generated on the cathode electrode surface.
  • the interface layer of an aqueous solution is composed of a Helmholtz layer 10 and an electric double layer (diffusion layer) 9.
  • the Helmholtz layer 10 is divided into an inner Helmholtz layer and an outer Helmholtz layer.
  • the main molecules of the Helmholtz layer 10 are water molecules that are solvent molecules.
  • Anode 2H 2 O ⁇ O 2 + 4H + + 4e -
  • the cathode 2H + + 2e - ⁇ H 2
  • hydrogen molecules generated in the Helmholtz layer 10 or hydrogen molecular bubbles 11 having a minimum diameter (nm order) move to the electric double layer 9 and have a larger diameter.
  • the hydrogen molecular bubbles 12 are larger than the hydrogen molecular bubbles 13.
  • the dissolved hydrogen concentration is expected to be larger than the value from an equilibrium viewpoint.
  • the amount of hydrogen gas generated when electrolysis is simply performed at a current density of 0.2 A / cm 2 is calculated. Assuming that electrolysis is performed under this condition within 1 ⁇ m of the cathode electrode surface per unit area, about 800 ppm of hydrogen molecules are generated in the cathode electrode surface layer. Assuming that hydrogen molecules are dissolved at this concentration, and based on the AHPray et al. Experiment (HA PRAY et al., IN DUSRIAL AND ENGI NEERING CHEMISTRY Vol. 44, No. 5, 1146) The value when the dissolved hydrogen molecule concentration in is converted to pressure is assumed to be about 1000 HPa or more. In other words, the hydrogen gas dissolves under a high pressure of about 1000 HPa or more.
  • the present invention relates to a method of effectively utilizing dissolved hydrogen molecules on the cathode electrode surface in this non-equilibrium state. Furthermore, the report by Seihara et al. Describes that 200 nm of hydrogen gas was observed on the cathode electrode surface. It has been reported that when the size of the hydrogen gas is 200 nm or less, it becomes transparent and uniform visually, and the stability of the hydrogen gas in the electrolyzed water is improved. This stability is important in terms of the lifetime of residual hydrogen gas in developing the business of water in which hydrogen molecules are dissolved.
  • the present inventor In order to suppress the decrease in the dissolved hydrogen molecule concentration by reducing the dissolved hydrogen molecule concentration by increasing the dissolved hydrogen molecule concentration above the equilibrium concentration value, the present inventor efficiently converts the high dissolved hydrogen molecule concentration water into the bulk water.
  • the present invention relates to a method for efficiently transferring high-dissolved hydrogen molecule concentration water near the cathode electrode to bulk water by applying a dynamic action to the cathode electrode surface.
  • the dissolved hydrogen concentration in the reduced water can be increased by any of the following methods (1) and (2).
  • (1) Ultrasonic application The Helmholtz layer and the electric double layer (diffusion layer) are agitated by ultrasonic vibration, and by this agitation, hydrogen gas bubbles with a small diameter in the Helmholtz layer move to the electric double layer (diffusion layer).
  • the concentration of hydrogen gas bubbles with a small diameter is increased in the double layer.
  • the concentration of hydrogen gas having a small diameter in the bulk water is increased, and the dissolved hydrogen concentration in the obtained reduced water is also increased.
  • FIG. 13 shows a graph as an example of the application of current and the generated hydrogen gas according to the method.
  • FIG. 13 is a graph corresponding to the case where the half-wave rectified current is applied to the cathode electrode in Experimental Example 1 described later. In FIG. 13, the half-wave rectified current is applied to the cathode electrode as indicated by the dotted line current value. Yes.
  • the pressure in the cathode chamber in order to increase the dissolved hydrogen concentration, it is preferable to increase the pressure in the cathode chamber. Specifically, it is preferable to set the pressure in the cathode chamber to 0.01 to 0.1 kg / cm 2 .
  • alternating current is desirable for increasing the dissolved hydrogen concentration.
  • the cathodic electrolysis reaction so using an ordinary alternating current in an alternating current will cause the anodic reaction to mix, increasing the concentration of dissolved hydrogen molecules. becomes difficult. Therefore, it is necessary to reduce the value of the electrolysis current to such a value that hydrogen gas bubbles having a large diameter are hardly visually observed even if the cathode electrolysis current is at least.
  • a current having an alternating current component having an average current value of zero or more can be applied to the cathode electrode, preferably a current having an alternating current component having a minimum current value of zero or more, more preferably A half-wave rectified or full-wave rectified alternating current is applied to the cathode electrode. Therefore, for example, a rectified AC power source or a pulse power source can be used as a power source for an electric current having an AC component whose current average value is zero or more. Since the present invention focuses on efficient movement of hydrogen gas bubbles, there is a limit on the upper frequency limit. In general, when the frequency dependence of a phenomenon involving mass transfer is measured, an effect of alternating current or pulse current appears on electrolysis in a region of about 10 kHz or less.
  • Example 1 A system based on the first embodiment described above was constructed.
  • a reverse osmosis membrane filter manufactured by Seemsbionics was used as the reverse osmosis membrane filter 140.
  • a DC power source or a 50 Hz AC power source was used as the power source.
  • the comparison was made with no rectification, full-wave rectification, or half-wave rectification.
  • the size of the electrolytic cell was 6 ⁇ 8 ⁇ about 1 cm in both the anode chamber and the cathode chamber.
  • the outer dimension of the electrode was 8 ⁇ 6 cm 2 (material: platinum plate applied to titanium plate).
  • the anode was a porous anode having 130 6 mm ⁇ holes at the same interval.
  • the electrolysis current was set to 4A.
  • the current density is 0.83 mA / cm 2 .
  • the dissolved hydrogen molecule concentration in the reduced water was measured with a methylene blue reagent. The results are shown in Table 1.
  • the ultrasonic vibrator is attached at a position in contact with the cathode electrode outside the electrolytic cell, and as shown in FIG. 4, the ultrasonic vibrator is ion-exchanged near the cathode electrode surface in the cathode chamber. Prepared by being embedded in resin.
  • Results are shown in Tables 2 and 3. As shown in Tables 2 and 3, low frequency mechanical vibration (about 250 Hz) had no effect of increasing the dissolved hydrogen concentration. Using a DC power source and ultrasonic vibration (about 2.4 MHz), a dissolved hydrogen molecule concentration of 1.8 ppm was measured transiently, and a result exceeding the equilibrium value was obtained. Furthermore, it was found that the dissolved hydrogen concentration increased transiently when ultrasonic irradiation and rectified alternating current were combined.
  • Example 3 A reduced water production system including the three-chamber electrolytic cell shown in FIG. 7 was configured.
  • the size of the anode chamber, cathode chamber, and intermediate chamber was 6 ⁇ 8 ⁇ about 1 cm.
  • Purified water and 50 g of ascorbic acid were added to the intermediate chamber (concentration: about 5%). This aqueous solution was constantly circulated.
  • Other configurations were the same as in Experimental Example 1.
  • full-wave rectification 50 Hz, 4 A was applied to the cathode electrode, and water flowed at 0.5 l / min.
  • By adjusting the valve at the outlet of the electrolytic cell to adjust the pressure of the cathode chamber to 0.1 kg / cm 2.
  • the measured value of the transient dissolved hydrogen molecule concentration increased by 2.6 ppm compared with 2.3 ppm before the intermediate chamber liquid circulation.
  • electrolytic cell 1 anode chamber 3: cathode chamber 4: cathode electrode 5: diaphragm 51: anode chamber side diaphragm 52: cathode chamber side diaphragm 6: intermediate chamber 8: mechanical vibration applying unit 21: anode electrode 31: ion exchange
  • Power source 120 Reservoir tank 130: Water supply pump 140: Reverse osmosis membrane filter 150: Tap water line 160: Valve 200: Raw material water production and feeding section 301: Electrolytic surface 302: Raw material water supply line 303: Reducing water discharge line 304: Raw material water supply manifold 305: Reducing water discharge manifold 306: Raw material water inlet 307: Reducing water outlet 400: Cathode chamber frame

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

Abstract

La présente invention vise à fournir une nouvelle technique capable d'inhiber une réduction de concentration de molécules d'hydrogène dissoutes dans l'eau réduite obtenue par réduction électrolytique. À cet effet, selon l'invention, dans un bain électrolytique qui est équipé d'une chambre d'anode, d'une chambre de cathode, d'une membrane qui est une membrane d'échange d'ions à base de fluor disposée entre la chambre d'anode et la chambre de cathode, d'une anode poreuse qui est disposée dans la chambre d'anode de façon à entrer en contact avec la membrane, et d'une cathode qui est disposée dans la chambre de cathode, ce procédé de production d'eau réduite contenant de l'hydrogène consiste : à fournir de l'eau entre la membrane et la cathode et à appliquer, sur la cathode, un courant ayant des composantes de courant alternatif dans lesquelles une valeur de courant moyenne inférieure ou égale à 10 kHz est zéro ou plus, pour réaliser une réduction électrolytique de l'eau et, de ce fait, à générer de l'hydrogène ; et à appliquer, sur la cathode, un courant ayant une composante de courant continu pour réaliser une réduction électrolytique de l'eau et, de ce fait, à générer de l'hydrogène et, en même temps, à appliquer, sur la surface de la cathode, des vibrations mécaniques dans une plage ultrasonore de 30 kHz à 10 MHz.
PCT/JP2016/083245 2015-11-25 2016-11-09 Dispositif de production d'eau réduite et procédé de production d'eau réduite Ceased WO2017090431A1 (fr)

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EP3842570A1 (fr) * 2019-12-26 2021-06-30 Vito NV Procédé de génération d'hydrogène et d'oxygène à partir d'un flux d'alimentation liquide comprenant de l'eau et dispositif associé
US20210254227A1 (en) * 2020-02-14 2021-08-19 Hyundai Motor Company Water electrolysis system and control method thereof
WO2023126881A1 (fr) * 2021-12-29 2023-07-06 IDE Water Technologies Ltd Source d'énergie renouvelable utilisant des processus et des systèmes de filtration entraînés par la pression
CN117776346A (zh) * 2024-02-28 2024-03-29 广州市纳爱生物科技有限公司 一种改善视觉疲劳的富氢水的制备方法
US12320015B2 (en) 2023-05-12 2025-06-03 Shaheen Innovations Holding Limited Systems for generating hydrogen

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JP2010094622A (ja) * 2008-10-17 2010-04-30 Spring:Kk 溶存水素飲料水の製造装置及びその製造方法
JP2011006769A (ja) * 2009-06-29 2011-01-13 Mitsubishi Heavy Ind Ltd 水電解装置
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WO2019207092A1 (fr) * 2018-04-26 2019-10-31 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Électrode dotée d'une excitation d'oscillations mécaniques intégrée
EP3842570A1 (fr) * 2019-12-26 2021-06-30 Vito NV Procédé de génération d'hydrogène et d'oxygène à partir d'un flux d'alimentation liquide comprenant de l'eau et dispositif associé
WO2021130261A1 (fr) * 2019-12-26 2021-07-01 Vito Nv Procédé de génération d'hydrogène et d'oxygène à partir d'un courant d'alimentation liquide comprenant de l'eau, et dispositif associé
US20210254227A1 (en) * 2020-02-14 2021-08-19 Hyundai Motor Company Water electrolysis system and control method thereof
WO2023126881A1 (fr) * 2021-12-29 2023-07-06 IDE Water Technologies Ltd Source d'énergie renouvelable utilisant des processus et des systèmes de filtration entraînés par la pression
US12320015B2 (en) 2023-05-12 2025-06-03 Shaheen Innovations Holding Limited Systems for generating hydrogen
US12435435B1 (en) 2023-05-12 2025-10-07 Shaheen Innovations Holding Limited Systems for generating hydrogen
CN117776346A (zh) * 2024-02-28 2024-03-29 广州市纳爱生物科技有限公司 一种改善视觉疲劳的富氢水的制备方法
CN117776346B (zh) * 2024-02-28 2024-05-28 广州市纳爱生物科技有限公司 一种改善视觉疲劳的富氢水的制备方法

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