US20160186337A1 - Electrolytic device and electrode - Google Patents

Electrolytic device and electrode Download PDF

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Publication number
US20160186337A1
US20160186337A1 US15/062,619 US201615062619A US2016186337A1 US 20160186337 A1 US20160186337 A1 US 20160186337A1 US 201615062619 A US201615062619 A US 201615062619A US 2016186337 A1 US2016186337 A1 US 2016186337A1
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United States
Prior art keywords
recess portions
electrode
electrolytic device
recess
holes
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Abandoned
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US15/062,619
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English (en)
Inventor
Masahiro Yokota
Hideo Oota
Katsuyuki Naito
Norihiro Yoshinaga
Wu Mei
Norihiro Tomimatsu
Ryosuke YAGI
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Toshiba Corp
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Toshiba Corp
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Assigned to KABUSHIKI KAISHA TOSHIBA reassignment KABUSHIKI KAISHA TOSHIBA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MEI, WU, NAITO, KATSUYUKI, TOMIMATSU, NORIHIRO, YOSHINAGA, NORIHIRO, OOTA, HIDEO, YOKOTA, MASAHIRO, YAGI, RYOSUKE
Publication of US20160186337A1 publication Critical patent/US20160186337A1/en
Abandoned legal-status Critical Current

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    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • 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
    • 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
    • C02F1/46—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
    • C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
    • C25B9/08—
    • 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
    • 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
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46157—Perforated or foraminous electrodes
    • 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
    • C02F2001/4619—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water only cathodic or alkaline water, e.g. for reducing
    • 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

Definitions

  • Embodiments described herein relate generally to an electrolytic device and an electrode used for the electrolytic device.
  • an electrolytic device an electrolyzed-water production device for producing ionized alkaline water, ozone water, aqueous hypochlorous acid or the like is conventionally known.
  • a device comprising a three-chamber electrolytic tank (electrolytic cell) has been proposed.
  • the three-chamber cell includes an electrolytic container divided into three chambers, that is, an anode chamber, an intermediate chamber and a cathode chamber by diaphragms.
  • salt water is introduced into the intermediate chamber, and water is introduced into the cathode chamber and the anode chamber on the right and left sides.
  • the salt water in the intermediate chamber is electrolyzed by the anode and the cathode to produce aqueous hypochlorous acid from gaseous chlorine produced in the anode chamber and sodium hydroxide solution in the cathode chamber.
  • Hypochlorous acid thus produced can be utilized as sterilizing solution and sodium hydroxide solution as a cleaning solution.
  • an electrolytic device having such a three-chamber cell involves reactions in a complicated way around the anode, which proceed from chlorine ions to gaseous chloride and then to hypochlorous acid.
  • the reaction system does not take place appropriately, competitive gaseous oxygen is produced and thus the productivity of hypochlorous acid is reduced.
  • gaseous chloride and hypochlorous acid produced here are strong oxidizers, which may cause deterioration of diaphragms.
  • FIG. 1 is a block diagram schematically showing an electrolytic device according to a first embodiment.
  • FIG. 2 is an exploded perspective view showing an electrolytic cell of the electrolytic device according to the first embodiment.
  • FIG. 3 is a sectional view of the electrolytic cell.
  • FIG. 4 is an expanded perspective view showing a first electrode and an anode cover of the electrolytic cell.
  • FIG. 5 is a perspective view showing a first surface side of the first electrode.
  • FIG. 6 is a perspective view showing a second surface side of the first electrode.
  • FIG. 7 is a partially expanded perspective view showing the first electrode.
  • FIG. 8 is a plan view of the first electrode as viewed from the first surface side.
  • FIG. 9 is a sectional view of the first electrode and an anion-exchange membrane, taken along line A-A of FIG. 8 .
  • FIG. 10 is a sectional view of the first electrode and the anion-exchange membrane, taken along line B-B of FIG. 8 .
  • FIG. 11 is a partially expanded perspective view showing a first electrode of an electrolytic device according to a first modification.
  • FIG. 12 is a plan view of the first electrode according to the first modification as viewed from the first surface side.
  • FIG. 13 is a sectional view of the first electrode and an anion-exchange membrane, taken along line C-C of FIG. 12 .
  • FIG. 14 is a sectional view of the first electrode and an anion-exchange membrane, taken along line D-D of FIG. 12 .
  • FIG. 15 is a partially expanded perspective view showing a first electrode of an electrolytic device according to a second modification.
  • FIG. 16 is a plan view of the first electrode according to the second modification as viewed from the first surface side.
  • FIG. 17 is a sectional view of the first electrode and an anion-exchange membrane, taken along line E-E of FIG. 16 .
  • FIG. 18 is a sectional view of the first electrode and an anion-exchange membrane, taken along line F-F of FIG. 16 .
  • FIG. 19 is a partially expanded perspective view showing a first electrode of an electrolytic device according to a third modification.
  • FIG. 20 is a plan view of the first electrode according to the third modification as viewed from the first surface side.
  • FIG. 21 is a sectional view of the first electrode and an anion-exchange membrane, taken along line G-G of FIG. 20 .
  • FIG. 22 is a sectional view of the first electrode and an anion-exchange membrane, taken along line H-H of FIG. 20 .
  • FIG. 23 is a partially expanded perspective view showing a first electrode of an electrolytic device according to a fourth modification.
  • FIG. 24 is a partially expanded perspective view showing a first electrode of an electrolytic device according to a fifth modification.
  • FIG. 25 is a partially expanded perspective view showing a first electrode of an electrolytic device according to a sixth modification.
  • FIG. 26 is a partially expanded perspective view showing a first electrode of an electrolytic device according to a seventh modification.
  • FIG. 27 is a plan view of the first electrode according to the seventh modification as viewed from the first surface side.
  • FIG. 28 is a sectional view of the first electrode and an anion-exchange membrane, taken along line I-I of FIG. 27 .
  • FIG. 29 is a partially expanded perspective view showing a first electrode of an electrolytic device according to an eighth modification.
  • FIG. 30 is a plan view of the first electrode according to the eighth modification as viewed from the first surface side.
  • FIG. 31 is a sectional view of the first electrode and an anion-exchange membrane, taken along line J-J of FIG. 30 .
  • an electrolytic device comprises an electrolytic cell comprising a first electrode, a second electrode opposing the first electrode and at least one diaphragm provided between the first electrode and the second electrode.
  • the first electrode is formed of a plate comprising a first surface opposing the diaphragm, a second surface located on an opposite side to the diaphragm, and first recess portions formed in the first surface with a first pattern.
  • the first recess portions include a bottom surface apart from the first surface and through-holes each opening to the second surface of the first electrode and to a part of the bottom surface.
  • FIG. 1 is a diagram briefly showing an electrolytic device according to the first embodiment.
  • the electrolytic device 10 is constituted as an electrolysis water production device.
  • the electrolytic device 10 comprises, as shown in FIG. 1 , a three-chamber electrolytic cell 11 .
  • the electrolytic cell 11 is formed into a flat rectangle box, inside of which is divided by an anion-exchange membrane 16 as a first diaphragm and a cation-exchange membrane 18 as a second diaphragm into an intermediate chamber 15 a , and also an anode chamber 15 b and a cathode chamber 15 c located on both sides of the intermediate chamber 15 a .
  • a first electrode (anode) 14 is provided in the anode chamber 15 b so as to oppose the anion-exchange membrane 16 .
  • a second electrode (cathode) 20 is provided in the cathode chamber 15 c so as to oppose the cation-exchange membrane 18 .
  • the electrolytic device 10 comprises an electrolyte supplier 19 which supplies an electrolyte, for example, saturated salt water, to the intermediate chamber 15 a of the electrolytic cell 11 , a water supplier 21 which supplies a solution to be electrolyzed, for example, water, to the anode chamber 15 b and the cathode chamber 15 c and a power supply 23 that applies positive and negative voltages respectively to the first and second electrodes 14 and 20 .
  • an electrolyte supplier 19 which supplies an electrolyte, for example, saturated salt water, to the intermediate chamber 15 a of the electrolytic cell 11
  • a water supplier 21 which supplies a solution to be electrolyzed, for example, water
  • a power supply 23 that applies positive and negative voltages respectively to the first and second electrodes 14 and 20 .
  • the electrolyte supplier 19 comprises a salt water tank 25 to produce saturated salt water, a supply pipe 19 a which conveys saturated salt water from the salt water tank 25 to a lower portion of the intermediate chamber 15 a , a liquid feed pump 29 provided in the supply pipe 19 a and a drainage pipe 19 b which sends the electrolyte which has flowed through the inside of the intermediate chamber 15 a from an upper portion of the intermediate chamber 15 a to the salt water tank 25 .
  • the water supplier 21 comprises a water supply source (not shown) which supplies water, a water supply pipe 21 a which guides water to lower portions of the anode chamber 15 b and the cathode chamber 15 c from the water supply source, a first drainage pipe 21 b to discharge the water which has flowed through the anode chamber 15 b from an upper portion of the anode chamber 15 b , a second drainage pipe 21 c to discharge the water which has flowed through the cathode chamber 15 c from an upper portion of the cathode chamber 15 c and a gas-liquid separator 27 provided in the second drainage pipe 21 c.
  • a water supply source not shown
  • a water supply pipe 21 a which guides water to lower portions of the anode chamber 15 b and the cathode chamber 15 c from the water supply source
  • a first drainage pipe 21 b to discharge the water which has flowed through the anode chamber 15 b from an upper portion of the anode chamber 15 b
  • the liquid feed pump 29 is operated to supply saturated salt water to the intermediate chamber 15 a of the electrolytic cell 11 , and water to the anode chamber 15 b and the cathode chamber 15 c .
  • a positive voltage and a negative voltage are applied to the first electrode 14 and the second electrode 20 , respectively, from the power supply 23 .
  • Sodium ions electrolytically dissociated in the salt water which has flowed into the intermediate chamber 15 a are attracted towards the second electrode 20 , pass through the cation-exchange membrane 18 and flow into the cathode chamber 15 c .
  • the cathode chamber 15 c water is electrolyzed by the second electrode 20 and gaseous hydrogen and an aqueous solution of sodium hydroxide are obtained.
  • the aqueous solution of sodium hydroxide and gaseous hydrogen thus produced flow out of the cathode chamber 15 c into the second drainage pipe 21 c , and are then separated into an aqueous solution of sodium hydroxide and gaseous hydrogen by the gas-liquid separator 27 .
  • the aqueous solution of sodium hydroxide (alkaline water) is discharged through the second drainage pipe 21 c.
  • chlorine ions electrolytically dissociated in the salt water in the intermediate chamber 15 a are attracted towards the first electrode 14 , pass through the anion-exchange membrane 16 and flow into the anode chamber 15 b .
  • the chlorine ions give electrons to the anode with the first electrode 14 to produce gaseous chlorine.
  • the gaseous chlorine reacts with water in the anode chamber 15 b to produce hypochlorous acid and hydrochloric acid.
  • the acidic solution thus produced (aqueous hypochlorous acid and hydrochloric acid) is discharged from the anode chamber 15 b through the first liquid drainage pipe 21 b.
  • FIG. 2 is an exploded perspective view of the electrolytic cell
  • FIG. 3 is a sectional view thereof.
  • the electrolytic cell 11 comprises an intermediate frame 22 of a rectangular frame shape, which functions as a diaphragm, an anode cover (first cover member) 24 of a rectangular plate shape having outer dimensions substantially equal to those of the intermediate frame 22 , which covers one side surface of the intermediate frame, and a cathode cover (second cover member) 26 of a rectangular plate shape having outer dimensions substantially equal to those of the intermediate frame 22 , which covers the other side surface of the intermediate frame.
  • first cover member anode cover
  • second cover member cathode cover
  • the anion-exchange membrane 16 is disposed between the intermediate frame 22 and the anode cover 24 , as a first diaphragm to separate the intermediate chamber 15 a and the anode chamber 15 b from each other, and the first electrode (anode plate) 14 is disposed near the anion-exchange membrane 16 in the anode chamber 15 b .
  • the cation exchange membrane 18 is disposed between the intermediate frame 22 and the cathode cover 26 , as a second diaphragm to separate the intermediate chamber 15 a and the cathode chamber 15 c from each other, and the second electrode (cathode) 20 is disposed near the cation-exchange membrane 18 in the cathode chamber 15 c.
  • a first inlet 34 communicating with the intermediate chamber 15 a is formed in a lower end of the intermediate frame 22 and a first outlet 36 communicating with the intermediate chamber 15 a is provided in an upper end thereof.
  • the supply pipe 19 a and the drainage pipe 19 b are connected to the first inlet 34 and the first outlet 36 , respectively.
  • a plurality of linear ribs 33 are provided on an inner surface of the anode cover 24 , to extend in, for example, the vertical direction (the second direction Y).
  • the ribs 33 are arranged parallel to each other while keeping a predetermined gap between adjacent ones.
  • a circulation groove 32 a is provided between each adjacent pair of the ribs 33 to extend in the vertical direction.
  • a pair of upper and lower side grooves by which ends of each circulation groove 32 a communicate are formed in the inner surface of the anode cover 24 .
  • the anode chamber 15 b is defined by the circulation grooves 32 a , the side grooves and the anion-exchange membrane 16 .
  • the circulation grooves 32 a and the side grooves form flow paths for water.
  • a second inlet 37 communicating with the lower end of the circulation grooves 32 a is formed in a lower portion of the anode cover 24
  • a second outlet 38 communicating with the upper end of the circulation grooves 32 a is formed in an upper portion of the anode cover 24 .
  • the supply pipe 21 a and the first drainage pipe 21 b are connected to the second inlet 37 and the second outlet 38 , respectively.
  • a plurality of ribs 35 , circulation grooves 32 b , and side grooves are each formed on an inner surface of the cathode cover 26 so as to extend in the perpendicular direction (the second direction Y).
  • the circulation grooves 32 b , the side grooves and the cation-exchange membrane 18 defines the cathode chamber 15 c . Further, the circulation grooves 32 b and the side grooves form a flow path for water to flow.
  • a third inlet 39 communicating with the lower end of the circulation grooves 32 b is formed in a lower portion of the cathode cover 26 , and a third outlet 41 communicating with the upper end of the circulation grooves 32 a is formed in an upper portion thereof.
  • the supply pipe 21 a and the second drainage pipe 21 c are connected to the third inlet 39 and the third outlet 41 , respectively.
  • frame-shaped sealing materials 40 for preventing leakage are disposed respectively between structural components, that is, between the peripheral portion of the anode cover 24 and the peripheral portion of the first electrode 14 ; between the peripheral portions of the first electrode 14 and the anion-exchange membrane 16 and the intermediate frame 22 ; between the intermediate frame 22 and the peripheral portions of the second electrode 20 and the cation-exchange membrane 18 ; and between the peripheral portion of the second electrode 20 and the peripheral portion of the cathode cover 26 .
  • a plurality of fixing bolts 50 are inserted through the peripheral portions of these structural components from, for example, the anode cover 24 side and the tip portions project from the cathode cover 26 .
  • a nut 52 is screwed into the tip portion of each fixing bolt 50 .
  • the anion-exchange membrane 16 and the cation-exchange membrane 18 are each formed into a thin rectangular plate having an outer size substantially equal to that of the intermediate frame 22 and a thickness of about 100 to 200 ⁇ m.
  • the anion-exchange membrane 16 and the cation-exchange membrane 18 each have characteristics of passing only specific ions.
  • a plurality of through-holes through which the fixing bolts 50 are inserted are formed in the peripheral portions of the anion-exchange membrane 16 and the cation-exchange membrane 18 .
  • the anion-exchange membrane 16 is disposed to oppose one surface side of the intermediate frame 22 , and the peripheral portion thereof is tightly attached to the intermediate frame 22 through the sealing material 40 .
  • the cation-exchange membrane 18 is disposed to oppose the other surface side of the intermediate frame 22 and the peripheral portion thereof is tightly attached to the intermediate frame 22 through the sealing material 40 .
  • the first diaphragm and the second diaphragm may be formed from not only an ion-exchange membrane but a porous membrane having water permeability.
  • the first electrode 14 and the second electrode 20 are each formed from a metal plate having a thickness of about 1 mm, formed into a rectangular shape having an outer size substantially equal to that of the intermediate frame 22 .
  • the first electrode 14 and the second electrode 20 each have a central portion (effective region) where micro-through-holes for passing liquid are formed, and a peripheral portion in which a plurality of through-holes through which fixing bolts 50 are inserted are formed.
  • the first electrode 14 includes a contact terminal 14 b projecting from a side edge thereof.
  • the second electrode 20 includes a contact terminal 20 b projecting from a side edge thereof.
  • the first electrode 14 is arranged to oppose to and be tightly contact with the anion-exchange membrane 16 .
  • the second electrode 20 is arranged to oppose to and be tightly contact with the cation-exchange membrane 18 .
  • the structure of the first electrode (anode) 14 will be described in detail as a typical example of the electrodes.
  • FIG. 4 is an expanded perspective view of the first electrode and the anode cover.
  • FIG. 5 is a perspective view of the first surface side of the first electrode.
  • FIG. 6 is a perspective view of the second surface side of the first electrode.
  • FIG. 7 is a partially expanded perspective view of the first electrode.
  • FIG. 8 is a plan view of the first electrode as viewed from the first surface side.
  • FIG. 9 is a sectional view of the first electrode and the anion-exchange membrane, taken along line A-A of FIG. 8 .
  • FIG. 10 is a sectional view of the first electrode and the anion-exchange membrane, taken along line B-B of FIG. 8 .
  • the first electrode 14 has, for example, a porous, mesh structure in which a great number of recesses and through-holes are made in a matrix 17 of a rectangular metal plate.
  • the matrix 17 includes a first surface 17 a and a second surface 17 b opposing substantially parallel to the first surface 17 a .
  • the distance between the first surface 17 a and the second surface 17 b that is, the plate board thickness T, is, for example 0.8 mm.
  • the first surface 17 a opposes the first diaphragm 16 and the second surface 17 b opposes the anode cover 24 .
  • the matrix 17 may be made from a metal such as titanium.
  • a first recess R 1 having a first pattern is formed over the entire surface.
  • a second recess R 2 having a second pattern different from the first pattern is formed over the entire surface.
  • the first recess R 1 of the first pattern comprises a plurality of thin linear first recess portions 42 formed in the first surface 17 a of the matrix 17 and the first recess portions 42 are each opened in the first surface 17 a .
  • Each of the first recess portions 42 includes a bottom surface (bottom portion) 42 a which is apart from the first surface 17 a , that is, recessed from the first surface 17 a by a predetermined depth.
  • the second recess R 2 of the second pattern comprises a plurality of thick or coarse linear second recess portions 44 formed in the second surface 17 b of the matrix 17 and the second recess portions 44 are each opened to the second surface 17 b .
  • the first recess portions 42 and the second recess portions 44 are formed in the entire rectangular effective region excluding the peripheral portion of the matrix 17 .
  • a plurality of first recess portions 42 communicate with one second recess 44 and each of the communicating portions forms a through-hole 46 .
  • Each of the through-holes 46 opens to a part of the bottom surface 42 a of the first recess portion 42 and opens to the second surface 17 b of the matrix 17 .
  • the entire surface of the first electrode 14 is covered with an iridium oxide catalyst.
  • the iridium oxide catalyst produces a lower overvoltage in the gaseous chlorine production than in the competitive gaseous oxygen production, and if there are a certain number of chlorine ions around the anode, gaseous chlorine is selectively produced.
  • the first recess portions 42 are each formed into straight lines extending in the first direction X, for example, a horizontal direction.
  • the first recess portions 42 are arranged to be parallel to one another.
  • the first recess portions 42 are each formed to be longer than an opening width W 3 of the second recess portions 44 , which will be described later.
  • the first recess portions 42 each extend continuously from one end to the other end of the effective region of the first surface 17 a (central region of the rectangular shape, excluding the peripheral portion on the first surface).
  • An opening width W 1 of the first recess portions 42 is, for example, 0.4 mm, a pitch P 1 of the first recess portions 42 in the arranging direction Y is 0.5 mm, a depth D 1 of the first recesses 42 is less than a half of the thickness T of the matrix 17 , more specifically, for example, 0.1 to 0.2 mm.
  • the first recess portions 42 are each formed so as to widen from the bottom portion (bottom surface 42 a ) side toward the first surface 17 a , more specifically, to have substantially a trapezoidal shape in cross section.
  • the both side surfaces which define each first recess 42 extend while inclining with respect to the first surface 17 a .
  • some of the first recess portions 42 communicate with a plurality of second recess portions 44 by a through-width W 2 of 0.2 mm.
  • the second recess portions 44 on the second surface 17 b side are formed in a straight line extending in a direction crossing the first direction X, that is, for example, a second direction Y orthogonal to the direction X.
  • the second recess portions 44 are arranged to be parallel to each other.
  • the second recess portions 44 each extend from one end to the other end of the effective region (central region of the rectangular shape, excluding the peripheral portion on the second surface) of the second surface 17 b .
  • An opening width W 3 of the second recess portions 44 is sufficiently larger than the opening width W 1 of the first recess portions 42 , for example, 2.4 mm, a pitch P 2 of the second recess portions 44 in the arranging direction X is 3 mm, and a depth D 2 of the second recess portions 44 is greater than a half of the thickness T of the matrix 17 , more specifically, 0.6 to 0.7 mm.
  • the second recess portions 44 are each formed so as to widen from the bottom side toward the second surface 17 b , more specifically, to have substantially a trapezoidal shape in cross section.
  • the both side surfaces which define each second recess 44 42 extend while inclining with respect to the second surface 17 b .
  • the second recess portions 44 communicate with a plurality of first recess portions 42 by a through-width W 4 of 1.2 mm.
  • the first electrode 14 configured as above can be produced by the following procedure, for example. That is, the first surface 17 a and the second surface 17 b of the matrix 17 are etched to be partially cut out, thus forming the first recess R 1 of the first pattern and the second recess R 2 of the second pattern.
  • the cross-sections of the first recess portions 42 and the second recess portions 44 may be various shapes, more specifically, not only a trapezoidal but also rectangular, semicircular, elliptical, arc-like and the like. Further, the angle made by the first recess portions 42 and the second recess portions 44 crossing therewith is not limited to right-angles, but may be any other angles.
  • the first recess portions 42 and the second recess portions 44 of the first electrode 14 communicate respectively with each other at intersections to form a great number of through-holes 46 .
  • the first surface 17 a opposing the first diaphragm 16 includes the most, more specifically, 80% of the surface opened by the first recess portions 42 , and the area opened and made to communicate is set as low as 16% of the surface area of the electrode. Further, in consideration of the collection of bubbles from the through-holes 46 , the water flow is set in the width direction (the second direction Y) of the through-holes 46 .
  • the matrix 17 is etched from both sides, namely, the first and second surfaces 17 a and 17 b , and therefore it is possible to change the open aperture ratio in each surface.
  • this electrode can exhibit a function which cannot be attained with the conventional electrode having the same open aperture ratio in both surfaces, manufactured by, for example, a die cut process.
  • the open area ratio of the through-holes 46 formed by the first recess portions 42 and the second recess portions 44 communicating with each other with respect to the entire area of the first surface 17 a be no more than a half of the open area ratio of the first recess portions 42 to the entire area of the first surface.
  • the second electrode (cathode) 20 is similar in structure to the first electrode 14 .
  • the first electrode 14 is disposed in a direction where the extending direction Y of the second recess portions 44 and the extending direction of the circulation grooves (flow paths) 32 a of the anode cover 24 substantially coincide with each other.
  • the second surface 17 b of the first electrode 14 opposes the inner surface of the anode cover 24 and is in contact with the tip end surfaces of the ribs 33 .
  • water supplied to the anode chamber 15 b flows along the circulation grooves 32 a and the second recess portions 44 of the first electrode 14 , that is, in a direction crossing the first recess portions 42 of the first electrode 14 .
  • the first surface 17 a of the first electrode 14 opposes and is tightly attached to the first diaphragm 16 .
  • the first recess portions 42 are formed in about 80% of the effective region of the first surface 17 a , the bottom surfaces 42 a of the first recess portions 42 are apart from the first diaphragm 16 and the first surface of the first electrode 14 by a depth of the first recess portion 42 , which is 0.1 to 0.2 mm.
  • the main reaction occurs at the bottom surfaces (bottom portions) 42 a of the first recess portions 42 , slightly apart from the first diaphragm 16 , and hypochlorous acid, which is a produce, is collected from the tiny gaps made by the first recess portions 42 through the through-holes 46 into the anode chamber 15 b .
  • hypochlorous acid which is a produce
  • the electrolytic device 10 of the first embodiment which employs the first electrode 14 having the above-described structure, an outstanding advantageous effect can be obtained as compared to the case of employing a conventional electrode formed by stamping (punching process) or expanding after making nicks (expand/lath processing).
  • a great number of first recess portions 42 are formed in the first surface 17 a which opposes the first diaphragm 16 of the first electrode 14 and therefore the first electrode 14 and the first diaphragm 16 can be set apart from each other by a slight distance without providing a separate member such as a spacer.
  • an electrode is basically formed to include only through-holes made from the first to second surfaces 17 a and 17 b with the same open area. Therefore, if the first electrode 14 and the first diaphragm 16 are attached tightly to each other, the main reaction occurs on the first surface 17 a which opposes the first diaphragm 16 .
  • the first surface is tightly attached to the first diaphragm, a problem may arise, in which the diaphragm 16 is degraded by reaction products. Further, when the first surface and the first diaphragm are tightly attached, another problem may arise, in which products produced by the electrolytic reaction cannot be collected, thus degrading the efficiency.
  • the first recess portions 42 are formed in the first surface 17 a , which is the main reaction field, at an area ratio of high as 80%.
  • reaction products are quickly collected through a slight gap D 1 (first recess portion 42 ) and through-holes 46 into the circulation grooves 32 a , thereby making it possible to suppress degradation of the first diaphragm 16 .
  • the first recess portions 42 have an open area occupying ratio as high as possible, but in practice, the above-described effect can be sufficiently exhibited if they occupy 60% or more of the effective region of the first surface 17 a . Further, it is more effective if the pitch P 1 of arrangement of the first recess portions 42 is finer to collect the products from the portions thereof which are in contact with the first diaphragm 16 . In practice, the effect can be sufficiently exhibited if the pitch P 1 is 0.8 mm or less. It is ideal that the depth D 1 of the first recess portions 42 is less as possible, but in practice, the above-described effect can be sufficiently exhibited if it is 0.5 mm or less.
  • the minimum width of the region in the first surface 17 a of the first electrode 14 is set to 0.3 mm or less, that is, the value obtained by subtracting the opening width W 1 of the first recess portions 42 from the arrangement pitch P 1 of the first recesses 42 is 0.3 mm or less, it becomes easy to collect the substances produced by the electrolytic reaction from the first surface 17 a tightly attached to the diaphragm. Thus, the above-described effect can be exhibited.
  • One of the functions of the second recess portions 44 of the first electrode 14 is to form the through-holes 46 for collecting the products from the first recess portions 42 formed shallow at high precision to the anode chamber 15 b side.
  • Another function of the second recess portions 44 is to collect the current electrolyzed by the first recess portions 42 at lower resistance.
  • the second recess portions 44 are formed to be coarse linear dent portions which cross the first recess portions 42 .
  • the intersections of the first recess portions 42 and the respective second recess portions 44 communicate with each other to extract hypochlorous acid or the like, produced in the first recess portions 42 from the through-holes 46 to the anode chamber 15 b side.
  • the area ratio of the through-holes 46 with respect to the area of the first electrode 14 is set as low as 16%. This is because the region of the first recess portions 42 , lost by the through-holes 46 should be made as small as possible. As the area of the through-holes 46 becomes larger, the number of chlorine ions lost by diffusion through the through-holes 46 increases. For this reason, the area of the through-holes 46 should desirably be set within 30% of the area of the electrode.
  • first recess portions 42 and the second recess portions 44 are formed into a linear shape, whose longitudinal directions cross each other orthogonally.
  • one first recess portion 42 communicate with a plurality of second recess portions 44 to form a through-hole 46 , thereby improving the drainage of the first recess portions 42 better than the case where the first recess portions 42 and the second recess portions 44 communicate with each other one to one. That is, a plurality of through-holes 46 are provided in one second recess 44 without making a dead end, thus forming such a structure for reaction products, especially, air bubbles to easily pass through.
  • the linear second recess portions 44 are arranged to intersect perpendicularly with the first recess portions 42 at a coarse pitch so as to set the ratio of the area of the through-holes to as low as 16% while keeping the ratio of the open area of the first recesses 42 as high as 80%.
  • the lowering of the concentration which is caused by the diffusion of the electrolyte from the through-holes 46 , can be prevented without the first diaphragm 16 being degraded by the reaction products.
  • the second recess portions 44 are arranged at a coarse pitch P 2 of several millimeters, for example, 3 mm, so that the volume of the matrix 17 remains at large and the current produced by electrolysis can be supplied at lower resistance. Further, the intensity of the electrode itself can be maintained.
  • the pitch P 2 is set to 1 mm or more to obtain a sufficient feed resistance.
  • the first embodiment it is possible to provide a long-life and efficient electrolytic device and an electrode, in which degradation of the diaphragm can be suppressed.
  • FIG. 11 is a partially expanded perspective view of the first electrode according to the first modification.
  • FIG. 12 is a plan view of the first electrode as viewed from the first surface side.
  • FIG. 13 is a sectional view of the first electrode and the anion-exchange membrane, taken along line C-C of FIG. 12 .
  • FIG. 14 is a sectional view of the first electrode and the anion-exchange membrane, taken along line D-D of FIG. 12 .
  • the basic specification of the first electrode 14 is the same as that of the first embodiment shown in FIGS. 4 to 10 except that the second recess portions 44 of the second recess portions R 2 are formed thin to have an arrangement pitch P 2 of 3 mm, as in the first embodiment, but an opening width W 3 of 1.6 mm and a through-width W 4 of 0.4 mm.
  • the area ratio of the through-holes 46 is decreased to low as about 5%, thereby making it possible to further suppress the chlorine ions having passed through the first diaphragm 16 to diffuse in the circulation grooves 32 a .
  • the chlorine ion concentration in the first surface 17 a of the first electrode 14 is increased to suppress the production of gaseous oxygen, thereby improving the production efficiency of acidic solution.
  • FIG. 15 is a partially expanded perspective view of the first electrode according to the second modification.
  • FIG. 16 is a plan view of the first electrode as viewed from the first surface side.
  • FIG. 17 is a sectional view of the first electrode and the anion-exchange membrane, taken along line E-E of FIG. 16 .
  • FIG. 18 is a sectional view of the first electrode and the anion-exchange membrane, taken along line F-F of FIG. 16 .
  • a plurality of second recess portions 44 which constitute the second recess R 2 formed in the second surface 17 b of the first electrode 14 each extend in the second direction Y which intersects the first direction X perpendicularly, but are divided into a plurality of sections without being continuous in the second direction.
  • the second recess portions 44 of each row contain a plurality of segments of second recess portions 44 arranged in the second direction Y at a predetermined gap.
  • the length of each segment of the second recess portions 44 in the second direction Y is equal to or greater than a total of widths of two or more of the first recess portions 42 .
  • first recess portions 42 is greater than the width W 3 of the second recess portions 44 .
  • the intersections of the first recess portions 42 and the second recess portions 44 communicate with each other to form a plurality of through-holes 46 .
  • a plurality of first recess portions 42 communicate with one segment of the second recess portions 44 .
  • the second recess portions 44 of each row is divided into a plurality of segments so that wide linear portions remain between adjacent pairs of the segments of each second recess.
  • the second recess portions 44 are formed concurrently with the circulation grooves 32 a , but the first electrode 14 may be placed in the direction in which the second recess portions 44 intersect perpendicularly with the circulation grooves 32 a.
  • FIG. 19 is a partially expanded perspective view of the first electrode according to the third modification.
  • FIG. 20 is a plan view of the first electrode as viewed from the first surface side.
  • FIG. 21 is a sectional view of the first electrode and the anion-exchange membrane, taken along line G-G of FIG. 20 .
  • FIG. 22 is a sectional view of the first electrode and the anion-exchange membrane, taken along line H-H of FIG. 20 .
  • the first electrode 14 comprises a large number of first recess portions 42 formed in the first surface 17 a , which constitute the first recess R 1 .
  • the second recesses formed in the second surface 17 b of the first electrode 14 are formed from the through-holes 47 . That is, the through-holes 47 are opened in the first surface 17 a and the second surface 17 b of the matrix 17 .
  • the through-holes 47 each have, for example, a circular shape whose diameter is larger than the width W 1 of the first recess portions 42 . In other words, the opening length of the through-holes 47 in the second direction Y is grater than the width W 1 of the first recess portions 42 .
  • a plurality of first recess portions 42 communicate with one through-hole 47 .
  • the first recess portions 42 of the first electrode 14 are formed by etching or photolithography, but the through-holes 47 as the second recesses are not so highly precise and may be formed by the conventional punch process.
  • FIG. 23 is a partially expanded perspective view of the first electrode according to the fourth modification.
  • a plurality of first recess portions 42 which constitute the first recess R 1 formed in the first surface 17 a of the first electrode 14 each extend in the first direction X, but are divided into a plurality of sections without being continuous in this direction.
  • the first recess portions 42 of each row contain a plurality of segments of first recess portions 42 arranged in the first direction X at a predetermined gap.
  • the length of each segment of the first recess portions 42 is greater than the width W 3 of the second recess portions 44 .
  • intersections of the first recess portions 42 and the second recess portions 44 communicate with each other to form a plurality of through-holes 46 .
  • a plurality of segments of first recess portions 42 communicate with a respective second recess portion 44 .
  • the first recess portions 42 of each row is divided into a plurality of segments so that linear portions remain between adjacent pairs of the segments of each first recess.
  • FIG. 24 is a partially expanded perspective view of the first electrode according to the fifth modification.
  • the shape of the first recess portions 42 formed in the first surface 17 a of the first electrode 14 is not limited to linear, but may be in some other shape.
  • the first recess portions 42 formed in the first surface 17 a of the first electrode 14 are not linear, but extend along the direction X while being bent at two or more locations.
  • FIG. 25 is a partially expanded perspective view of the first electrode according to the fifth modification.
  • the first recess portions 42 which formed in the first surface 17 a of the first electrode 14 and constitute the first recess R 1 extending along the first direction X to be curved or waved at two or more locations.
  • FIG. 26 is a partially expanded perspective view showing the first electrode according to the seventh modification.
  • FIG. 27 is a plan view of the first electrode as viewed from the first surface side.
  • FIG. 28 is a sectional view of the first electrode and the anion-exchange membrane, taken along line I-I of FIG. 27 .
  • the first recess R 1 formed in the first surface 17 a of the first electrode 14 include a plurality of third recess portions 45 in addition to the first recess portions 42 .
  • the third recess portions 45 are formed by forming a notch in at least one part of a wall portion which separates adjacent pairs of first recesses 42 from each other.
  • the third recess portions 45 are each opened in regions other than the through-holes 46 in the first surface 17 a , so as to make adjacent pairs of first recess portions 42 communicate with each other.
  • the third recess portions 45 each extend over the most of the region between two through-holes 46 adjacent in the first direction X.
  • the area on the first surface 17 a which is brought into in contact with the diaphragm can be further reduced by providing the third recess portions.
  • the main reaction region of the electrode is the lower surfaces of the first recesses R 1 and the area of the reaction region can be expanded by the third recess portions.
  • FIG. 29 is a partially expanded perspective view showing the first electrode according to the eighth modification.
  • FIG. 30 is a plan view of the first electrode as viewed from the first surface side.
  • FIG. 31 is a sectional view of the first electrode and the anion-exchange membrane, taken along line J-J of FIG. 30 .
  • the basic structure of the first electrode 14 is the same as that of the seventh modification described above except that the third recess portions 45 are intermittently formed at two or more locations in the first direction X in the region between two through-holes 46 adjacent in the first direction X. That is, the third recess portions 45 are formed so that the wall portion which separates the adjacent first recess portions 42 from each other remain partially.
  • the third recess portions 45 are formed in the region between two through-holes 46 adjacent in the first direction X. Further, the third recess portions 45 are formed in one row along the second direction Y.
  • the third recess portions are provided intermittently, i.e., the length or width of each third recess portion is reduced, and thus the amount of deformation of the diaphragm which may warp along the first recesses R 1 can be reduced. Therefore, it is possible to set the positions of the diaphragm and the electrode more precisely.
  • the first electrode 14 comprises a catalytic layer 54 formed on the first recess R 1 except for the first surface 17 a .
  • the catalyst is formed on the entire first electrode 14 but the first surface 17 a , which is a region brought into contact with the diaphragm.
  • the eighth modification is described for the case where the third recess portions are arranged in line along the second direction Y, but the arrangement is not limited to this.
  • the third recess portions may as well be arranged to be shifted from each other in the first direction, or, for example, in a staggered manner.
  • the present invention is not limited to the embodiments and modifications described above but the constituent elements of the invention can be modified in various manners without departing from the spirit and scope of the invention.
  • Various aspects of the invention can also be extracted from any appropriate combination of a plurality of constituent elements disclosed in the embodiments and modifications. Some constituent elements may be deleted in all of the constituent elements disclosed in the embodiments. The constituent elements described in different embodiments may be combined arbitrarily.
  • the first electrode and the second electrode are not limited to rectangular shapes, but various other forms may be selected.
  • the material of each structural component is not limited to that employed in the embodiments or modifications discussed, but various other materials may be selected as needed.
  • the electrode structure discussed above may be applied not only to the first electrode but also to the second electrode (cathode).
  • the electrolytic cell of the electrode device is not limited to a three-chamber type, but it may as well be applied to a two-chamber- or single-chamber type or any electrolytic cells with electrodes in general.
  • the electrolytes and product are not limited to salt or hypochlorous acid, but may be developed into various electrolytes and products.

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Publication number Priority date Publication date Assignee Title
US20180134540A1 (en) * 2016-11-17 2018-05-17 Vicente P. Garcia Portable water dispenser having a pressure booster faucet for pushing water through an ionizing device
CN108588747A (zh) * 2018-06-29 2018-09-28 山东新日电气设备有限公司 一种等梯度间距电极电解装置
US20210119229A1 (en) * 2019-05-22 2021-04-22 Sumitomo Electric Industries, Ltd. Metal porous sheet, fuel cell, and water electrolysis device
WO2021110590A1 (en) * 2019-12-05 2021-06-10 Weco, Sas Waste water treatment system and method of treating waste water

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WO2017158832A1 (ja) * 2016-03-18 2017-09-21 株式会社 東芝 電解用電極、電極ユニット、及び電解水生成装置
JP7169021B1 (ja) * 2021-12-28 2022-11-10 株式会社アクト 生成装置

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JPS5127877A (ja) * 1974-08-26 1976-03-09 Hodogaya Chemical Co Ltd Denkyokukozotai
US4293394A (en) * 1980-03-31 1981-10-06 Ppg Industries, Inc. Electrolytically producing chlorine using a solid polymer electrolyte-cathode unit
DE3277447D1 (en) * 1981-11-24 1987-11-12 Ici Plc Electrolytic cell of the filter press type
JP3772055B2 (ja) * 1999-08-30 2006-05-10 株式会社トクヤマ 電解槽
JP2006176835A (ja) * 2004-12-22 2006-07-06 Nissan Motor Co Ltd 水電解装置の製造方法
US20120171596A1 (en) * 2009-08-04 2012-07-05 Donald Bennett Hilliard Solid oxide electrolytic device
JP6038604B2 (ja) * 2012-11-20 2016-12-07 株式会社東芝 電気化学セル、及びこのセルを用いた減酸素装置、並びにこの減酸素装置を用いた冷蔵庫

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180134540A1 (en) * 2016-11-17 2018-05-17 Vicente P. Garcia Portable water dispenser having a pressure booster faucet for pushing water through an ionizing device
CN108588747A (zh) * 2018-06-29 2018-09-28 山东新日电气设备有限公司 一种等梯度间距电极电解装置
US20210119229A1 (en) * 2019-05-22 2021-04-22 Sumitomo Electric Industries, Ltd. Metal porous sheet, fuel cell, and water electrolysis device
WO2021110590A1 (en) * 2019-12-05 2021-06-10 Weco, Sas Waste water treatment system and method of treating waste water

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CN106103805B (zh) 2018-03-09

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