WO2016043109A1 - 電解装置および電極 - Google Patents

電解装置および電極 Download PDF

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Publication number
WO2016043109A1
WO2016043109A1 PCT/JP2015/075626 JP2015075626W WO2016043109A1 WO 2016043109 A1 WO2016043109 A1 WO 2016043109A1 JP 2015075626 W JP2015075626 W JP 2015075626W WO 2016043109 A1 WO2016043109 A1 WO 2016043109A1
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WO
WIPO (PCT)
Prior art keywords
recess
electrode
recesses
electrolysis apparatus
diaphragm
Prior art date
Application number
PCT/JP2015/075626
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English (en)
French (fr)
Japanese (ja)
Inventor
横田　昌広
英男 太田
内藤　勝之
典裕 吉永
梅　武
富松　師浩
亮介 八木
Original Assignee
株式会社 東芝
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Application filed by 株式会社 東芝 filed Critical 株式会社 東芝
Priority to CN201580013302.5A priority Critical patent/CN106103805B/zh
Priority to JP2016512129A priority patent/JP6100438B2/ja
Priority to US15/062,619 priority patent/US20160186337A1/en
Publication of WO2016043109A1 publication Critical patent/WO2016043109A1/ja

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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
    • 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 of the present invention relate to an electrolysis apparatus and an electrode used in the electrolysis apparatus.
  • an electrolyzed water generator that generates alkali ion water, ozone water, hypochlorous acid water, or the like is known.
  • an apparatus having a three-chamber type electrolytic cell electrolytic cell
  • the interior of the three-chamber type electrolytic cell is divided into three chambers, an anode chamber, an intermediate chamber, and a cathode chamber, by a diaphragm.
  • chlorine gas generated in the anode chamber is obtained by flowing salt water in the intermediate chamber, flowing water in the left and right cathode chambers and the anode chamber, and electrolyzing the salt water in the intermediate chamber with the cathode and the anode. From this, hypochlorous acid water is generated and sodium hydroxide water is generated in the cathode chamber.
  • the produced hypochlorous acid water is used as sterilizing / disinfecting water, and sodium hydroxide water is used as washing water.
  • the problem to be solved by the present invention is to provide a long-life and high-efficiency electrolysis apparatus and an electrode used for the electrolysis apparatus, which suppress the deterioration of the diaphragm.
  • the electrolysis device includes a first electrode, a second electrode facing the first electrode, and at least one diaphragm disposed between the first electrode and the second electrode. It has an electrolytic cell.
  • the first electrode includes a first surface facing the diaphragm, a second surface located on the opposite side of the first surface, a first recess formed in a first pattern on the first surface, and a second surface and a first surface, respectively. And a plurality of through holes opened in one recess.
  • FIG. 1 is a block diagram schematically showing an electrolysis apparatus according to the first embodiment.
  • FIG. 2 is an exploded perspective view showing the electrolytic cell of the electrolysis apparatus according to the first embodiment.
  • FIG. 3 is a sectional view of the electrolytic cell.
  • FIG. 4 is an enlarged 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 an enlarged perspective view showing a part of the first electrode.
  • FIG. 8 is a plan view of the first electrode when the first electrode is viewed from the first surface side.
  • FIG. 9 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line AA in FIG.
  • FIG. 10 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line BB in FIG.
  • FIG. 11 is an enlarged perspective view showing a part of the first electrode of the electrolysis apparatus according to the first modification.
  • FIG. 12 is a plan view of the first electrode when the first electrode according to the first modification is viewed from the first surface side.
  • FIG. 15 is an enlarged perspective view showing a part of a first electrode of an electrolysis apparatus according to a second modification.
  • FIG. 16 is a plan view of the first electrode when the first electrode according to the second modification is viewed from the first surface side.
  • FIG. 17 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line EE of FIG. 18 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line FF in FIG.
  • FIG. 19 is an enlarged perspective view showing a part of a first electrode of an electrolysis apparatus according to a third modification.
  • FIG. 20 is a plan view of the first electrode when the first electrode according to the third modification is viewed from the first surface side.
  • FIG. 21 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line GG in FIG. 22 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line HH in FIG.
  • FIG. 23 is an enlarged perspective view showing a part of a first electrode of an electrolysis apparatus according to a fourth modification.
  • FIG. 24 is an enlarged perspective view showing a part of a first electrode of an electrolysis apparatus according to a fifth modification.
  • FIG. 25 is an enlarged perspective view showing a part of the first electrode of the electrolysis apparatus according to the sixth modification.
  • FIG. 26 is an enlarged perspective view showing a part of the first electrode of the electrolysis apparatus according to the seventh modification.
  • FIG. 27 is a plan view of the first electrode when the first electrode according to the seventh modification is viewed from the first surface side.
  • 28 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line II of FIG.
  • FIG. 29 is an enlarged perspective view showing a part of a first electrode of an electrolysis apparatus according to an eighth modification.
  • FIG. 30 is a plan view of the first electrode when the first electrode according to the eighth modification is viewed from the first surface side.
  • 31 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line JJ in FIG.
  • FIG. 1 is a diagram schematically showing an electrolysis apparatus according to the first embodiment.
  • the electrolyzer 10 is configured as an electrolyzed water generator.
  • the electrolyzer 10 includes a so-called three-chamber type electrolytic cell 11.
  • the electrolytic cell 11 is formed in a flat rectangular box shape, and the inside thereof includes an intermediate chamber 15a and an intermediate chamber 15a by an anion exchange membrane 16 as a first diaphragm and a cation exchange membrane 18 as a second diaphragm. It is partitioned into an anode chamber 15b and a cathode chamber 15c located on both sides.
  • a first electrode (anode) 14 is provided in the anode chamber 15 b and faces the anion exchange membrane 16.
  • a second electrode (cathode) 20 is provided in the cathode chamber 15 c and faces the cation exchange membrane 18.
  • the electrolyzer 10 includes an electrolytic solution supply unit 19 that supplies an electrolytic solution, for example, saturated saline, to the intermediate chamber 15a of the electrolytic cell 11, and water that supplies electrolyzed water, for example, water to the anode chamber 15b and the cathode chamber 15c.
  • a supply unit 21 and a power supply 23 for applying a positive voltage and a negative voltage to the first electrode 14 and the second electrode 20 are provided.
  • the electrolyte supply unit 19 includes a salt water tank 25 that generates saturated saline, a supply pipe 19a that guides the saturated saline from the salt water tank 25 to the lower portion of the intermediate chamber 15a, and a liquid feed pump 29 provided in the supply pipe 19a. And a drain pipe 19b for sending the electrolytic solution flowing in the intermediate chamber 15a from the upper portion of the intermediate chamber 15a to the salt water tank 25.
  • the water supply unit 21 includes a water supply source (not shown) that supplies water, a water supply pipe 21a that guides water from the water supply source to the lower portions of the anode chamber 15b and the cathode chamber 15c, and water that flows through the anode chamber 15b.
  • a first drain pipe 21b that discharges from the cathode chamber 15c
  • a second drain pipe 21c that drains water flowing through the cathode chamber 15c from the upper part of the cathode chamber 15c
  • a gas-liquid separator 27 provided in the second drain pipe 21c
  • the liquid feed pump 29 is operated to supply saturated saline to the intermediate chamber 15a of the electrolytic cell 11, and water is supplied to the anode chamber 15b and the cathode chamber 15c.
  • a positive voltage and a negative voltage are applied from the power source 23 to the first electrode 14 and the second electrode 20, respectively.
  • Sodium ions ionized in the brine flowing into the intermediate chamber 15a are attracted to the second electrode 20, pass through the cation exchange membrane 18, and flow into the cathode chamber 15c.
  • water is electrolyzed by the 2nd electrode 20, and hydrogen gas and sodium hydroxide aqueous solution are obtained.
  • the sodium hydroxide aqueous solution and hydrogen gas generated in this way flow out from the cathode chamber 15c to the second drain pipe 21c, and are separated into the sodium hydroxide aqueous solution and hydrogen gas by the gas-liquid separator 27.
  • the separated sodium hydroxide aqueous solution (alkaline water) is discharged through the second drain pipe 21c.
  • the chlorine ions ionized in the salt water in the intermediate chamber 15a are attracted to the first electrode 14, pass through the anion exchange membrane 16, and flow into the anode chamber 15b. Then, chlorine ions give electrons to the anode at the first electrode 14 to generate chlorine gas. Thereafter, the chlorine gas reacts with water in the anode chamber 15b to produce hypochlorous acid and hydrochloric acid.
  • the acidic water hypochlorous acid water and hydrochloric acid
  • FIG. 2 is an exploded perspective view of the electrolytic cell
  • FIG. 3 is a cross-sectional view of the electrolytic cell.
  • the electrolytic cell 11 has a rectangular frame-shaped intermediate frame 22 that functions as a partition, and a rectangular plate shape that has an outer diameter dimension substantially equal to that of the intermediate frame 22 and covers one side surface of the intermediate frame.
  • An anode cover (first cover member) 24 and a rectangular plate-like cathode cover (second cover member) 26 having an outer diameter dimension substantially equal to that of the intermediate frame 22 and covering the other side surface of the intermediate frame.
  • An anion exchange membrane 16 is disposed between the intermediate frame 22 and the anode cover 24 as a first diaphragm that separates the intermediate chamber 15a and the anode chamber 15b.
  • the anode chamber 15b is adjacent to the anion exchange membrane 16 in a first manner.
  • An electrode (anode) 14 is disposed.
  • a cation exchange membrane 18 is disposed as a second diaphragm separating the intermediate chamber 15a and the cathode chamber 15c, and the cathode chamber 15c is adjacent to the cation exchange membrane 18 in the second region.
  • An electrode (cathode) 20 is disposed.
  • a first inlet 34 communicating with the intermediate chamber 15a is formed at the lower end of the intermediate frame 22, and a first outlet 36 communicating with the intermediate chamber 15a is provided at the upper end.
  • a supply pipe 19a and a drain pipe 19b are connected to the first inlet 34 and the first outlet 36, respectively.
  • a plurality of linear ribs 33 project from the inner surface of the anode cover 24 and extend, for example, in the vertical direction (second direction Y). These ribs 33 are provided in parallel to each other and at a predetermined interval. Between these ribs 33, flow grooves 32 a extending in the vertical direction are formed. In addition, a pair of upper and lower horizontal grooves that communicate the ends of the flow grooves 32 a are formed on the inner surface of the anode cover 24.
  • An anode chamber 15 b is defined by the flow grooves 32 a and the lateral grooves and the anion exchange membrane 16. Further, the flow groove 32a and the lateral groove form a flow path for flowing water.
  • a second inflow port 37 communicating with the lower end of the flow groove 32a is formed in the lower part of the anode cover 24, and a second outflow port 38 communicating with the upper end of the flow groove 32a is provided in the upper part of the anode cover 24.
  • a water supply pipe 21a and a first drain pipe 21b are connected to the second inlet 37 and the second outlet 38, respectively.
  • a cathode chamber 15 c is defined by the flow grooves 32 b and the lateral grooves and the cation exchange membrane 18. Further, the flow groove 32b and the lateral groove form a flow path for flowing water.
  • a third inflow port 39 communicating with the lower end of the flow groove 32b is formed in the lower part of the cathode cover 26, and a third outflow port 41 communicating with the upper end of the flow groove 32b is provided in the upper part.
  • a water supply pipe 21a and a second drain pipe 21c are connected to the third inlet 39 and the third outlet 41, respectively.
  • a plurality of fixing bolts 50 are inserted through the peripheral edge of each constituent member, for example, inserted from the anode cover 24 side, and the tip portion protrudes from the cathode cover 26.
  • a nut 52 is screwed into the tip of each fixing bolt 50.
  • the peripheral portions of the constituent members are fastened to each other by the fixing bolt 50 and the nut 52 as fastening members, and the water tightness of the intermediate chamber 15a, the anode chamber 15b, and the cathode chamber 15c is maintained.
  • the anion exchange membrane 16 and the cation exchange membrane 18 each have an outer diameter substantially equal to that of the intermediate frame 22, and are formed in a thin rectangular plate shape having a thickness of about 100 to 200 ⁇ m. Is formed.
  • the anion exchange membrane 16 and the cation exchange membrane 18 have a characteristic of allowing only specific ions to pass therethrough.
  • 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 face one side of the intermediate frame 22, and the peripheral edge thereof is in close contact with the intermediate frame 22 via the sealing material 40.
  • the cation exchange membrane 18 is disposed to face the other surface side of the intermediate frame 22, and the peripheral edge thereof is in close contact with the intermediate frame 22 via the sealing material 40.
  • the first diaphragm and the second diaphragm are not limited to ion exchange membranes, and may be porous membranes having water permeability.
  • the first electrode 14 and the second electrode 20 are formed of a metal flat plate having a thickness of about 1 mm, and are formed in a rectangular shape having an outer diameter substantially the same as the outer diameter of the intermediate frame 22.
  • a fine through hole for allowing liquid to pass through is formed in the central portion (effective region) of the first electrode 14 and the second electrode 20, and a plurality of through holes for inserting the fixing bolt 50 are formed in the peripheral portion.
  • the 1st electrode 14 has the connecting terminal 14b which protrudes from the one side edge.
  • the 2nd electrode 20 has the connecting terminal 20b which protrudes from the one side edge.
  • the first electrode 14 is disposed to face the anion exchange membrane 16 and is in close contact with the anion exchange membrane 16.
  • the second electrode 20 is disposed opposite the cation exchange membrane 18 and is in close contact with the cation exchange membrane 18.
  • FIG. 4 is an enlarged perspective view showing the first electrode and the anode cover
  • FIG. 5 is a perspective view showing the first surface side of the first electrode
  • FIG. 6 is a perspective view showing the second surface side of the first electrode.
  • 7 is an enlarged perspective view of a part of the first electrode
  • FIG. 8 is a plan view of the first electrode when the first electrode is viewed from the first surface side
  • FIG. 9 is a line of FIG.
  • FIG. 10 is a cross-sectional view of the first electrode and the anion exchange membrane along the line AA
  • FIG. 10 is a cross-sectional view of the first electrode and the anion exchange membrane along the line BB in FIG.
  • the first electrode 14 has, for example, a porous structure and a mesh structure in which a large number of recesses and through holes are formed in a base material 17 made of a rectangular metal plate.
  • the base material 17 has the 1st surface 17a and the 2nd surface 17b which opposes substantially parallel to the 1st surface 17a.
  • the distance between the first surface 17a and the second surface 17b, that is, the plate thickness T is, for example, 0.8 mm.
  • the first surface 17 a faces the first diaphragm 16, and the second surface 17 b faces the anode cover 24.
  • a metal such as titanium can be used as the base material 17.
  • the first surface 17a of the base material 17 is formed with a first recess R1 having the first pattern over the entire surface, and the second surface 17b of the base material 17 has a second pattern different from the first pattern.
  • a second recess R2 is formed over the entire surface.
  • the first pattern first recess R1 includes a plurality of thin linear first recesses 42 formed on the first surface 17a of the base material 17, and each of these first recesses 42 is a first recess. Opened to the surface 17a.
  • the second recess R2 of the second pattern has a plurality of thick or rough linear second recesses 44 formed on the second surface 17b of the base material 17, and each of these second recesses 44 is a second surface 17b. Is open.
  • the first recess 42 and the second recess 44 are formed in the entire rectangular effective region except for the peripheral edge of the base material 17.
  • a plurality of first recesses 42 communicate with one second recess 44, and each form a through hole 46.
  • the entire surface of the first electrode 14 is coated with an iridium oxide catalyst.
  • the iridium oxide catalyst has a lower overvoltage for chlorine gas generation than competing oxygen gas generation, and selectively generates chlorine gas if there is a certain amount of chlorine ions around the anode.
  • the plurality of first recesses 42 are formed in an elongated linear shape and extend in the first direction X, for example, the horizontal direction.
  • the plurality of first recesses 42 are provided in parallel with each other.
  • Each first recess 42 is formed longer than an opening width W3 of a second recess 44 described later.
  • the first recess 42 continuously extends from one end to the other end of the effective area of the first surface 17a (rectangular central area excluding the peripheral edge of the first surface).
  • each first recess 42 is, for example, 0.4 mm
  • the pitch P1 in the arrangement direction Y of the first recesses 42 is 0.5 mm
  • the depth D1 of the first recesses 42 is half the plate thickness T of the substrate 17. It is formed shallower, for example, 0.1 to 0.2 mm.
  • each first recess 42 is formed so as to increase in width from the bottom side toward the first surface 17a, that is, has a substantially trapezoidal cross-sectional shape. Both side surfaces defining the first recess 42 extend with an inclination with respect to the first surface 17a. Thereby, some 1st recessed parts 42 are connected to the several 2nd recessed part 44 with the penetration width W2 of 0.2 mm.
  • the plurality of second recesses 44 formed on the second surface 17b side is formed in an elongated linear shape, and intersects the first direction X, for example, the second direction orthogonal to the first direction X. It extends to Y.
  • the plurality of second recesses 44 are provided in parallel with each other. Each second recess 44 extends continuously from one end to the other end of the effective area of the second surface 17b (a rectangular central area excluding the peripheral edge of the second surface).
  • each second recess 44 is sufficiently larger than the opening width W1 of the first recess 42, for example, 2.4 mm, the pitch P2 in the arrangement direction X of the second recess 44 is 3 mm, and the depth of the second recess 44
  • the depth D2 is deeper than half of the plate thickness T of the substrate 17, and is formed to be 0.6 to 0.7 mm, for example.
  • each second recess 44 is formed so as to increase in width from the bottom side toward the second surface 17b and has a substantially trapezoidal cross-sectional shape. Both side surfaces defining the second recess 44 extend inclining with respect to the second surface 17b. Thereby, the 2nd recessed part 44 is connected to the some 1st recessed part 42 by 1.2 mm of penetration width W4.
  • the first electrode 14 configured as described above, for example, etches the first surface 17a and the second surface 17b of the base material 17 to partially scrape the first recess R1 and the second pattern having the first pattern. It can produce by forming 2nd dent R2 which has.
  • the cross-sectional shapes of the first recess 42 and the second recess 44 are not limited to a trapezoidal shape, and may be various shapes such as a rectangular shape, a semicircular shape, an elliptical shape, and an arc shape. Further, the angle at which the first recess 42 and the second recess 44 intersect is not limited to a right angle, and may be any other angle.
  • the first recess 42 and the second recess 44 of the first electrode 14 communicate with each other at the intersections, thereby forming a large number of through holes 46.
  • an opening is formed in a majority of 80% of the surface by the first recess 42, and the area of the communication opening is 16% of the area of the electrode surface. Keep it low.
  • the flow of water is in the width direction of the through hole 46 (second direction Y).
  • the function which cannot be achieved by the conventional electrode of can be exhibited.
  • the ratio of the opening area to the entire area of the first surface 17a of the first surface 17a of the through hole 46 formed by communicating the first recess 42 and the second recess 44 is the ratio of the opening area ratio to the entire area of the first surface 17a of the first recess 42. It is desirable to be less than half.
  • the second electrode (cathode) 20 is configured in the same manner as the first electrode 14.
  • the first electrode 14 is arranged in a direction in which the extending direction Y of the second recess 44 and the extending direction of the flow groove (flow path) 32 a of the anode cover 24 are substantially coincident. ing.
  • the second surface 17 b of the first electrode 14 faces the inner surface of the anode cover 24 and is in contact with the tip surface of the rib 33. Thereby, the water supplied to the anode chamber 15 b flows along the flow groove 32 a and the second recess 44 of the first electrode 14, that is, in a direction intersecting with the first recess 42 of the first electrode 14.
  • the first surface 17 a of the first electrode 14 faces the first diaphragm 16 and is in close contact with the first diaphragm 16. Since the first recesses 42 are formed in about 80% of the effective area of the first surface 17a, these first recesses 42 are formed in the first diaphragm 16 by a depth of 0.1 to 0.2 mm. It is away from. As shown in FIG. 10, the main reaction occurs in the bottom region of the first recess 42 slightly away from the first diaphragm 16, and the product hypochlorous acid is generated from a slight gap formed by the first recess 42. It is collected in the anode chamber through the through hole 46. Thereby, it is possible to achieve both high generation efficiency and prevention of diaphragm deterioration.
  • the electrolysis apparatus 10 by using the first electrode 14 having the above-described configuration, it is formed by a conventional punching (punching process) or cutting and extending (expanding / lass process) manufacturing method. Compared with the case where the made electrode is used, the outstanding effect can be acquired.
  • the first electrode 14 and the first diaphragm 16 can be formed without providing a separate member such as a spacer by forming a large number of first recesses 42 in the first surface 17a of the first electrode 14 facing the first diaphragm 16. A small distance can be separated from each other, and as a result, both production efficiency and diaphragm deterioration can be improved.
  • the conventional electrodes for die cutting can basically only form through holes that penetrate the first and second surfaces 17a and 17b in the same area, the main reaction is caused when the first electrode 14 and the first diaphragm 16 are brought into close contact with each other. It occurs on the first surface 17a facing the first diaphragm 16. Since the first surface is in close contact with the first diaphragm, there is a problem that the diaphragm 16 is deteriorated by the reaction product. In addition, when the first surface and the first diaphragm are in close contact with each other, there is a problem in that the product produced by the electrolytic reaction here cannot be recovered and efficiency is deteriorated.
  • the reaction product since the first recess 42 (first recess R1) having an area ratio of 80% is formed on the first surface 17a, which is the main reaction site, the reaction product has a slight gap D1 and through-holes. 46 is promptly collected in the flow groove 32a, and deterioration of the first diaphragm 16 can be suppressed.
  • the first recess 42 has a large opening area occupancy, but in practice, the above-described effects can be sufficiently obtained if 60% or more of the effective area of the first surface 17a. Further, the finer the arrangement pitch P1 of the first recesses 42 is, the more advantageous is the product recovery from the portion in contact with the first diaphragm 16, but practically the effect is sufficiently exhibited if the pitch P1 is 0.8 mm or less. can do.
  • the depth D1 of the first recess 42 is ideally shallow, but in practice, the effect can be exhibited if it is 0.5 mm or less.
  • the minimum width of the region forming the first surface 17a of the first electrode 14 is 0.3 mm or less, that is, the value obtained by subtracting the opening width W1 of the first recess 42 from the arrangement pitch P1 of the first recess 42 is 0. If it is 3 mm or less, the substance produced
  • One of the roles of the second recess 44 of the first electrode 14 is to form a through hole 46 for collecting the product from the first recess 42 formed shallow with high definition to the anode chamber 15b side.
  • Another role of the second recess 44 is to collect the current electrolyzed in the first recess 42 with a low resistance.
  • the second recess 44 is a rough linear recess that intersects the first recess 42.
  • the area ratio of the through-hole 46 with respect to the area of the 1st electrode 14 is made low with 16%. This is to make the first recess 42 region lost by the through hole 46 as small as possible. As the area of the through hole 46 increases, more chlorine ions are diffused through the through hole 46. Therefore, the area of the through hole 46 is desirably within 30% of the electrode area.
  • the first recess 42 and the second recess 44 are linear, and the longitudinal directions thereof are orthogonal to each other. For this reason, one first recess 42 communicates with a plurality of second recesses 44 to form a through hole 46, compared with a case where the first recess 42 and the second recess 44 penetrate one-to-one. Thus, drainage of the first recess 42 is improved. That is, a plurality of through-holes 46 are provided in one second recess 44 without becoming a narrow path, so that a reaction product, in particular, bubbles are easily removed.
  • the area ratio of the through holes 46 is set to 16 while keeping the opening area ratio of the first recesses 42 as high as 80%. It is as small as%. This prevents the reaction product from deteriorating the first diaphragm 16 and the electrolyte from diffusing from the through hole 46 to lower the concentration.
  • the second recess 44 has a rough pitch P2 of several mm, for example, 3 mm, leaving a large volume of the base material 17 so that the electric current generated by electrolysis can be supplied with low resistance, and the strength of the electrode itself. Is maintained. In practice, a sufficient feed resistance can be obtained by setting the pitch P2 to 1 mm or more. From the above, according to the first embodiment, it is possible to provide a long-life and high-efficiency electrolysis device and electrode that suppress the deterioration of the diaphragm.
  • FIG. 11 is an enlarged perspective view showing a part of the first electrode according to the first modification
  • FIG. 12 is a plan view of the first electrode when the first electrode is viewed from the first surface side
  • FIG. FIG. 14 is a cross-sectional view of the first electrode and the anion exchange membrane along line CC in FIG. 12, and
  • FIG. 14 is a cross-sectional view of the first electrode and the anion exchange membrane along line DD in FIG.
  • the basic specification of the first electrode 14 is the same as that of the first electrode 14 of the first embodiment shown in FIGS. 4 to 10.
  • the second recesses 44 of the second recesses R2 are formed in narrow recesses having an opening width W3 of 1.6 mm and a through width W4 of 0.4 mm while the arrangement pitch P2 remains 3 mm.
  • the area ratio of the through-holes 46 can be lowered to about 5%, and the chlorine ions that have passed through the first diaphragm 16 can be further suppressed from diffusing into the flow grooves 32a.
  • the chlorine ion concentration on the first surface 17a of the first electrode 14 is increased to suppress the generation of oxygen gas, and the generation efficiency of acidic water is improved.
  • FIG. 15 is an enlarged perspective view showing a part of the first electrode according to the second modification
  • FIG. 16 is a plan view of the first electrode when the first electrode is viewed from the first surface side
  • FIG. FIG. 18 is a cross-sectional view of the first electrode and the anion exchange membrane along line EE in FIG. 16
  • FIG. 18 is a cross-sectional view of the first electrode and the anion exchange membrane along line FF in FIG.
  • the plurality of second recesses 44 constituting the second recess R ⁇ b> 2 formed on the second surface 17 b of the first electrode 14 are arranged in the first direction X.
  • the second recesses 44 in each row include a plurality of second recesses 44 that are arranged at a predetermined interval in the second direction Y.
  • the length along the second direction Y of each second recess 44 is formed to be equal to or greater than the width of the first recess 42.
  • first recess 42 is longer than the width W3 of the second recess 44.
  • the intersections of the first recess 42 and the second recess 44 communicate with each other to form a plurality of through holes 46.
  • a plurality of first recesses 42 communicate with one second recess 44.
  • the second recesses 44 in each row are divided into a plurality of portions, and a wide linear portion is left between the second recesses.
  • the second recess 44 is configured in parallel with the flow groove 32a.
  • the first electrode 14 may be installed in a direction in which the second recess 44 is orthogonal to the flow groove 32a. Good.
  • FIG. 19 is an enlarged perspective view showing a part of the first electrode according to the second modification
  • FIG. 20 is a plan view of the first electrode when the first electrode is viewed from the first surface side
  • FIG. 20 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line GG in FIG. 20
  • FIG. 22 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line HH in FIG.
  • the first electrode 14 has a large number of first recesses 42 formed on the first surface 17a and constituting the first recess R1.
  • the second recess formed in the second surface 17 b of the first electrode 14 is formed by the through hole 47. That is, a plurality of through holes 47 are opened in the first surface 17 a and the second surface 17 b of the base material 17.
  • the through hole 47 is formed, for example, in a circular shape having a larger diameter than the width W1 of the first recess 42, that is, the through hole 47 has an opening length in the second direction Y longer than the width W1 of the first recess 42. Is formed.
  • a plurality of first recesses 42 communicate with one through hole 47.
  • the first recess 42 of the first electrode 14 is formed by etching or photolithography because high definition is required, but the through hole 47 as the second recess is low-definition and may be formed by existing punching.
  • FIG. 23 is an enlarged perspective view showing a part of the first electrode according to the fourth modification.
  • the plurality of first recesses 42 formed on the first surface 17a of the first electrode 14 and constituting the first recess R1 are not continuous in the first direction X but are divided into a plurality of parts.
  • the first recesses 42 in each row include a plurality of first recesses 42 arranged in the first direction X at a predetermined interval.
  • the length of each first recess 42 is longer than the width W ⁇ b> 3 of the second recess 44.
  • the intersections of the first recess 42 and the second recess 44 communicate with each other to form a plurality of through holes 46.
  • a plurality of first recesses 42 communicate with one second recess 44.
  • the first recesses 42 in each row are divided into a plurality of portions, and linear portions are left between these first recesses.
  • FIG. 24 is an enlarged perspective view showing a part of the first electrode according to the fifth modification.
  • the 1st recessed part 42 formed in the 1st surface 17a of the 1st electrode 14 is not restricted to linear form, It is good also as another shape.
  • the plurality of first recesses 42 formed on the first surface 17a of the first electrode 14 are not linear but extend along the first direction X and are bent at a plurality of locations. It is formed in a shape.
  • FIG. 25 is an enlarged perspective view showing a part of the first electrode according to the fifth modification.
  • the plurality of first recesses 42 formed on the first surface 17 a of the first electrode 14 and constituting the first recess R ⁇ b> 1 extend along the first direction X and are curved at a plurality of locations. It is formed in a linear or wavy shape.
  • FIG. 26 is an enlarged perspective view showing a part of the first electrode according to the seventh modification
  • FIG. 27 is a plan view of the first electrode when the first electrode is viewed from the first surface side
  • FIG. FIG. 27 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line II in FIG. 26.
  • the first recess R1 formed on the first surface 17a of the first electrode 14 includes a plurality of third recesses in addition to the plurality of first recesses 42.
  • a recess 45 is provided.
  • the third recess 45 is formed by providing a notch in at least a part of the wall that separates the adjacent first recesses 42.
  • the plurality of third recesses 45 open to the first surface 17a in regions other than the through-holes 46, and the adjacent first recesses 42 communicate with each other.
  • each third recess 45 extends over most of the region between two through holes 46 adjacent in the first direction X.
  • the area of the first surface 17a contacting the diaphragm can be further reduced by providing the plurality of third recesses.
  • the main reaction region of the electrode is the bottom surface of the first recess R1, and the area of the reaction region can be increased by providing the third recess.
  • FIG. 29 is an enlarged perspective view showing a part of the first electrode according to the eighth modification
  • FIG. 30 is a plan view of the first electrode when the first electrode is viewed from the first surface side
  • FIG. 31 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line JJ in FIG. 30.
  • the basic configuration of the first electrode 14 is the same as that of the seventh modification described above, but the plurality of third recesses 45 are formed in the first direction X.
  • the plurality of third recesses 45 are formed so as to partially leave wall portions separating the adjacent first recesses 42.
  • four third recesses 45 are provided in a region between two through holes 46 adjacent to each other in the first direction X.
  • the plurality of third recesses 45 are provided in a line along the second direction Y.
  • the diaphragm that bends along the first recess R1 by intermittently providing a plurality of third recesses, that is, by reducing the length or width of each third recess.
  • the amount of deformation can be reduced, and the diaphragm, electrode, and position can be defined more accurately.
  • the first electrode 14 includes the catalyst layer 54 formed on the first recess R1 except for the first surface 17a. That is, in the first electrode 14, no catalyst is formed only on the first surface 17a, which is a region in contact with the diaphragm. As a result, the first surface in contact with the diaphragm does not undergo an electrolytic reaction, and the life of the diaphragm can be extended.
  • the plurality of third recesses are arranged in a straight line in the second direction Y.
  • the present invention is not limited to this, and the plurality of third recesses are arranged in the first direction. They may be arranged so as to be shifted from each other. For example, they may be arranged in a staggered manner.
  • the present invention is not limited to the above-described embodiments and modifications as they are, and can be embodied by modifying the components without departing from the scope of the invention in the implementation stage.
  • various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiment and the modified examples. For example, some components may be deleted from all the components shown in the embodiment.
  • constituent elements over different embodiments and modifications may be appropriately combined.
  • the first electrode and the second electrode are not limited to a rectangular shape, and other various shapes can be selected.
  • the material of each constituent member is not limited to the above-described embodiments and modifications, and other materials can be appropriately selected.
  • the electrode structure described above may be applied not only to the first electrode but also to the second electrode (cathode).
  • the electrolyzer of the electrolyzer is not limited to a three-chamber type electrolyzer, and can be applied to a two-chamber or one-chamber electrolyzer and other electrolyzers using electrodes.
  • Electrolytes and products are not limited to salts and hypochlorous acid, and may be applied to various electrolytes and products.

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  • Metallurgy (AREA)
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PCT/JP2015/075626 2014-09-19 2015-09-09 電解装置および電極 WO2016043109A1 (ja)

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Cited By (2)

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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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GB201619493D0 (en) * 2016-11-17 2017-01-04 Garcia Vicente 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
WO2020235237A1 (ja) * 2019-05-22 2020-11-26 住友電気工業株式会社 金属多孔体シート、燃料電池及び水電解装置
EP4069647A1 (en) * 2019-12-05 2022-10-12 WeCo, SAS Waste water treatment system and method of treating waste water

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JPS56152983A (en) * 1980-03-31 1981-11-26 Ppg Industries Inc Solid polymer electrolyte cathod unit
JPS5893881A (ja) * 1981-11-24 1983-06-03 インペリアル・ケミカル・インダストリ−ズ・ピ−エルシ− 電極構造体およびそれを備えた電解槽
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TWI841088B (zh) * 2021-12-28 2024-05-01 日商亞淨透股份有限公司 生成裝置

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CN106103805B (zh) 2018-03-09

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