WO2014199440A1 - Ion exchange membrane electrolytic cell - Google Patents

Ion exchange membrane electrolytic cell Download PDF

Info

Publication number
WO2014199440A1
WO2014199440A1 PCT/JP2013/066052 JP2013066052W WO2014199440A1 WO 2014199440 A1 WO2014199440 A1 WO 2014199440A1 JP 2013066052 W JP2013066052 W JP 2013066052W WO 2014199440 A1 WO2014199440 A1 WO 2014199440A1
Authority
WO
WIPO (PCT)
Prior art keywords
ion exchange
exchange membrane
cathode
electrolytic cell
metal
Prior art date
Application number
PCT/JP2013/066052
Other languages
French (fr)
Japanese (ja)
Inventor
清人 浅海
Original Assignee
クロリンエンジニアズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by クロリンエンジニアズ株式会社 filed Critical クロリンエンジニアズ株式会社
Priority to PCT/JP2013/066052 priority Critical patent/WO2014199440A1/en
Priority to CN201380047716.0A priority patent/CN104718317A/en
Publication of WO2014199440A1 publication Critical patent/WO2014199440A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • 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

Definitions

  • the present invention relates to an ion exchange membrane electrolytic cell (hereinafter, also simply referred to as “electrolytic cell”), and more particularly, to an ion exchange membrane electrolytic cell capable of achieving both protection of the ion exchange membrane and electrolytic performance of the electrolytic cell.
  • electrolytic cell an ion exchange membrane electrolytic cell
  • an anode, an ion exchange membrane, and a hydrogen generation cathode are arranged in close contact with each other in order to lower the electrolysis voltage.
  • anode and cathode of the rigid member are accommodated in the electrode chamber, the electrodes are kept in close contact with the ion exchange membrane and the electrode spacing is kept at a predetermined value. Was difficult.
  • an electrolytic cell using an elastic material as a material As a means for reducing the distance between the electrodes or the distance between the electrode and the electrode current collector or maintaining it at a substantially constant value, an electrolytic cell using an elastic material as a material is known.
  • an electrolytic cell in order to prevent the ion exchange membrane from being damaged by bringing the electrode into close contact with the ion exchange membrane and to keep the distance between the positive and negative electrodes to a minimum, the direction of the distance between the electrodes of at least one of the electrodes The electrode is pressed by an elastic member to adjust the holding pressure.
  • this elastic material non-rigid materials such as metal fine wire woven fabric, non-woven fabric and net, and rigid materials such as leaf springs are known.
  • Patent Document 1 a metal coil body is mounted between a cathode and a cathode end plate instead of a conventionally used leaf spring or metal mesh body, and the cathode is uniformly pressed in the direction of the diaphragm so that the respective members are brought into close contact with each other.
  • An electrolytic cell has been proposed.
  • patent document 2 as an improvement technique of patent document 1, a metal coil body is wound around a corrosion-resistant frame to produce an elastic cushion material, and this elastic cushion material is placed between a hydrogen generating cathode and a cathode current collector plate.
  • an ion exchange membrane electrolytic cell that is mounted and the hydrogen generating cathode is uniformly pressed against the ion exchange membrane.
  • the electrolytic cell in which the metal coil body and the elastic cushion material proposed in Patent Documents 1 and 2 are arranged has a feature of having resistance to the reverse pressure when the reverse pressure is applied from the counter electrode. Have.
  • the reaction force is large, the pressing pressure against the ion exchange membrane becomes strong, and there is a concern that blisters are likely to be generated in the ion exchange membrane. Therefore, it is preferable that the reaction force of the metal coil body or the elastic cushion material is small in consideration of the influence on the ion exchange membrane.
  • an object of the present invention is to provide an ion exchange membrane electrolytic cell capable of achieving both high protection of the ion exchange membrane and electrolytic performance of the electrolytic cell.
  • the ion exchange membrane electrolytic cell of the present invention is partitioned into an anode chamber for accommodating an anode and a cathode chamber for accommodating a cathode by an ion exchange membrane, and at least one of the anode chamber and the cathode chamber is made of a metal elastic body.
  • the metal elastic body is composed of at least two types of metal elastic bodies.
  • the metal elastic body is arranged between at least one of the cathode and the cathode current collector and between the anode and the anode current collector, and the reaction force of the metal elastic body
  • the electrode and the ion exchange membrane may be in close contact with each other, and the metal elastic body is disposed between at least one of the cathode and the cathode partition wall and between the anode and the anode partition wall.
  • the electrode and the ion exchange membrane may be in close contact with each other by force.
  • it is preferable that the said metal elastic body is an elastic cushion material wound around a corrosion-resistant flame
  • the said metal elastic body is a metal coil body. Furthermore, in the ion exchange membrane electrolytic cell of the present invention, it is preferable that an electrode catalyst is supported on at least one metal elastic body among the at least two metal elastic bodies.
  • the protection of the ion exchange membrane and the electrolytic performance of the electrolytic cell can be made highly compatible.
  • FIG. 1 is a schematic plan view showing an example in which a cathode and a cathode current collector in a cathode unit of a monopolar ion exchange membrane electrolytic cell according to a preferred embodiment of the present invention are electrically connected via a metal elastic body.
  • (A)-(f) is a schematic plan view which shows the example of arrangement
  • FIG. 6 is a cross-sectional view taken along line AA in FIG. It is a schematic plan view which shows the example which connected the cathode and cathode partition of the bipolar ion exchange membrane electrolytic cell unit which concerns on other suitable embodiment of this invention via the metal elastic body.
  • the ion exchange membrane electrolytic cell of the present invention is partitioned into an anode chamber containing an anode and a cathode chamber containing a cathode by an ion exchange membrane, and a metal elastic body is provided in at least one of the anode chamber and the cathode chamber. It is arranged.
  • a metal elastic body is disposed between at least one of a cathode and a cathode current collector and between an anode and an anode current collector, or a bipolar ion exchange membrane electrolysis
  • the tank include a metal elastic body disposed between at least one of the cathode and the cathode partition and between the anode and the anode partition.
  • FIG. 1 shows an example in which a cathode and a cathode current collector in a cathode unit of a monopolar ion exchange membrane electrolytic cell according to a preferred embodiment of the present invention are electrically connected via a metal elastic body. It is a schematic plan view shown.
  • a metal elastic body 15 is disposed between the hydrogen generating cathode 14 and the cathode current collector 13. Further, in the illustrated example, a pair of conductive rods 11 facing vertically are provided in the cathode unit 10, and a catholyte circulation energization member 12 is installed around the conductive rod 11.
  • the metal elastic body 15 is composed of at least two types of metal elastic bodies (metal coil bodies 15a and 15b in the illustrated example). In the illustrated example, a metal coil body 15a having a large winding diameter and a metal coil body 15b having a small winding diameter are used as the two types of metal elastic bodies.
  • FIG. 1 is a diagram showing an arrangement example of the metal coil body 15a having a large winding diameter and the metal coil body 15b having a small winding diameter.
  • FIG. 2 is a diagram showing an arrangement example of the metal coil body 15a having a large winding diameter and the metal coil body 15b having a small winding diameter.
  • FIG. 2A shows that a metal coil body 15a having a large winding diameter is disposed so as to contact both the cathode current collector 13 and the hydrogen generating cathode 14, and a metal coil body 15b having a small winding diameter is a cathode current collector.
  • B shows that a metal coil body 15a having a large winding diameter is disposed so as to be in contact with both the cathode current collector 13 and the hydrogen generating cathode 14, and is made of a metal having a small winding diameter.
  • the coil body 15b is disposed so as to be in contact with the hydrogen generating cathode 14, and (c) is disposed such that the metal coil body 15a having a large winding diameter is in contact with the cathode current collector 13, and is made of a metal having a small winding diameter.
  • the coil body 15b is arranged so as to be in contact with the hydrogen generating cathode 14, and both coils are in contact with each other without overlapping. Further, (d) is opposite to the case of (c) in the positional relationship between the metal coil body 15a having a large winding diameter and the metal coil body 15b having a small winding diameter.
  • the metal coil body 15a having a large winding diameter and the metal coil body 15b having a small winding diameter are arranged so as to be in partial contact with each other, and (f) is a metal coil having a large winding diameter in the case of (a). It arrange
  • the metal elastic body is resistant to the reverse pressure, but has a problem that the pressing pressure against the ion exchange membrane is increased.
  • at least two types of metal coil bodies 15a and 15b are used to achieve both reduction of the pressing pressure against the ion exchange membrane and resistance to reverse pressure.
  • FIG. 3 is a diagram showing a deformation process of the metal coil bodies 15a and 15b when a reverse pressure is applied to the metal coil bodies 15a and 15b of the type shown in FIG.
  • FIG. 3A shows a state in which no reverse pressure is applied to the cathode, and the metal coil body 15a having a large winding diameter presses the hydrogen generating cathode 14 uniformly.
  • FIG. 3B shows a state in which a reverse pressure is applied to the cathode, and the metal coil body 15a having a large winding diameter is gradually compressed.
  • FIG. 3C shows a state in which an excessive back pressure is applied to the cathode.
  • the metal coil body 15a having a large winding diameter is compressed, but the metal coil body 15b having a small winding diameter is in contact with the hydrogen generating cathode 14, thereby exhibiting resistance to the reverse pressure. .
  • the metal coil body 15b having a small winding diameter starts elastic deformation before the metal coil body 15a having a large winding diameter starts plastic deformation, and both metal coils It is preferable that the deformation due to the back pressure of the bodies 15a and 15b converge at the stage of elastic deformation.
  • the thickness of metal coil bodies 15a and 15b suitably in the range which can acquire the said effect.
  • metal coil bodies 15a and 15b having different thicknesses are exemplified as the metal elastic body 15.
  • the metal elastic body is made of a conductive material. There is no particular limitation as long as it has elastic properties and can supply power by pressing a flexible electrode against the ion exchange membrane.
  • a metal elastic body other than a metal coil body whether it is corrugated on a thin metal wire, a metal non-woven fabric, a knitted fabric made of metal wires, a woven fabric and a laminate thereof, or is it knitted three-dimensionally?
  • a shape obtained by knitting three-dimensionally and then applying swell processing or the like may be used.
  • the two types of metal elastic bodies 15 having different reaction forces may be used. That's fine.
  • a metal coil body having a different elastic modulus or a metal nonwoven fabric may be used as the metal elastic body 15 having a different reaction force.
  • the reaction force can be adjusted by adjusting the volume density of the metallic nonwoven fabric. That is, a metal nonwoven fabric having a small volume density functions as a metal elastic body having a relatively small reaction force, and a metal elastic body having a large volume density functions as a metal elastic body having a relatively large reaction force.
  • the reaction force of the metal elastic body 15 may be appropriately designed within a range in which the above effect can be obtained. For example, the ratio of reaction forces of two types of metal elastic bodies is about 0.5 to 0.9. And it is sufficient.
  • the metal elastic body 15 is made of, for example, nickel, nickel alloy, stainless steel, or copper having good corrosion resistance, such as nickel having good corrosion resistance, which is coated with plating or the like.
  • the manufactured wire etc. can be used.
  • the wire material processed into a spiral coil by roll processing can be used.
  • the cross-sectional shape of the obtained wire is preferably a circle, an ellipse, a rectangle with rounded corners, or the like from the viewpoint of preventing damage to the ion exchange membrane.
  • NiW2201 nickel wire having a diameter of 0.17 mm
  • a coil wire having a cross-sectional shape of about 0.05 mm ⁇ 0.5 mm with rounded corners and a winding diameter of about 6 mm is obtained. be able to.
  • FIG. 1 the metal coil bodies 15a and 15b are mounted as they are between the electrode in the electrolytic cell and its current collector. However, in the ion exchange membrane electrolytic cell of the present invention, the metal elastic body is attached to the corrosion-resistant frame. You may use the elastic cushion material comprised by winding.
  • FIG. 4 is a perspective view of an example of a corrosion-resistant frame in the elastic cushion material according to the present invention
  • FIG. 5 is a perspective view of an example of the elastic cushion material according to the present invention
  • the corrosion-resistant frame 103 according to the ion exchange membrane electrolytic cell of the present invention is a metal round bar and is composed of a reinforcing rod 102 spanned between a pair of round bars in the longitudinal direction of a rectangular frame 101. ing.
  • a metal round bar for example, a nickel round metal bar having a diameter of about 2 mm can be suitably used.
  • the elastic cushion material 104 according to the present invention winds a metal elastic body (in the illustrated example, metal coil bodies 15a and 15b) over substantially the entire length between a pair of round bars in the longitudinal direction of the corrosion-resistant frame 103. It can be obtained by turning (see FIG. 5).
  • the elastic cushion material 104 obtained in this way has the metal coil bodies 15a and 15b wound around the corrosion-resistant frame 103, so that the shape of the corrosion-resistant frame 103 is maintained, and the metal coil bodies 15a and 15b are There is almost no detachment from the corrosion-resistant frame 103, and the metal coil bodies 15 a and 15 b can be handled as being integrated with the corrosion-resistant frame 103.
  • the metal coil bodies 15a and 15b By winding the metal coil bodies 15a and 15b around the corrosion resistant frame 103, the following advantages can be obtained.
  • the metal coil bodies 15a and 15b have a high deformation rate, it is difficult to handle them, and it is often difficult to install the metal coil bodies 15a and 15b at predetermined locations in the electrolytic cell as intended by the operator. Furthermore, since it is easily deformed (the strength is insufficient), even if it is once installed at a predetermined location of the electrolytic cell, it is displaced by the electrolytic solution or generated gas in the electrolytic cell, and it becomes difficult to uniformly adhere each member.
  • the elastic cushion material 104 is made of, for example, a frame of four rectangular corrosion-resistant frames as shown in FIG. It is obtained by winding the metal coil bodies 15a and 15b between the two facing each other so as to obtain a substantially uniform density (see FIG.
  • this elastic cushion material 104 two layers of metal elastic bodies 15 (metal coil bodies 15a and 15b in the illustrated example) are usually laminated on the left and right sides of the corrosion-resistant frame (see FIG. 6), but the metal coil bodies themselves. Since the coil is easily deformed, adjacent coils are meshed with each other in a comb-like shape, and apparently has one layer.
  • the thus obtained elastic cushion material 104 has an appearance like a metal scrub for tableware washing.
  • the assembly of the elastic cushion material 104 using the metal elastic body 15 is an operation outside the electrolytic cell, it can be easily performed, and the obtained elastic cushion material 104 is stored in the electrolytic cell during the electrolytic cell assembly.
  • the target electrode and the mounted current collector may be mounted so as to be electrically connected.
  • the elastic cushion material 104 itself is not deformed so as to hinder assembly due to the strength of the corrosion-resistant frame even at the time of mounting, and can be easily installed at a predetermined location.
  • the metal elastic body 15 and the elastic cushion material 104 are not necessarily fixed to the cathode current collector 13 or the hydrogen generating cathode 14 by welding or the like, but may be fixed. Usually, electricity is flowed by a contact energization method.
  • the metal coil bodies 15a and 15b have been described as examples of the metal elastic body used for the elastic cushion material 104.
  • metal You may use the said metal elastic bodies, such as a nonwoven fabric made.
  • the diameter of the metal coil body (the apparent diameter of the coil) is mounted in the electrolytic cell. Accordingly, the elasticity is usually reduced to 10 to 70%, and this elasticity facilitates power supply to the electrode by elastically connecting the anode and the anode current collector or the cathode and the cathode current collector. If a metal coil body having a small wire diameter is used, the number of contact points between the electrode or current collector and the elastic cushion material inevitably increases, and uniform contact becomes possible.
  • the elastic cushion material 104 after being attached to the electrolytic cell is hardly subjected to plastic deformation because the shape is held by the corrosion-resistant frame 103, and can be reused in most cases even when the electrolytic cell is disassembled and reassembled. .
  • an elastic cushion material is provided between at least one electrode and the electrode current collector. If 104 or the like is positioned and then assembled as usual, an ion exchange membrane electrolytic cell in which an elastic cushion material or the like is held at a predetermined position can be obtained.
  • an electrode catalyst is supported on at least one metal elastic body of at least two types of metal elastic bodies (in the illustrated example, metal coil bodies 15a and 15b). Also good. That is, by causing the metal elastic body 15 itself to function as an electrode, it is not necessary to dispose the hydrogen generating cathode 14 in the illustrated example, and the merit that the number of parts can be reduced can be obtained.
  • a coating of an electrode catalyst material such as a platinum group metal-containing layer, a Raney nickel-containing layer, or an activated carbon-containing nickel layer may be formed on the surface of the metal elastic body.
  • Raney nickel catalyst may be subjected to dispersion plating with nickel on the surface of the elastic body, or a precious metal light metal such as hexachloroplatinum may be subjected to plating treatment such as brush plating, or may be baked.
  • FIG. 7 is a schematic plan view showing an example in which a cathode and a cathode partition of a bipolar ion exchange membrane electrolytic cell unit according to another preferred embodiment of the present invention are electrically connected via a metal elastic body.
  • FIG. 7 In the illustrated bipolar ion exchange membrane electrolytic cell unit 20, four anode holding members 23 (integrated in the illustrated example) are formed on the anode side of the anode partition 21 and the cathode partition 22 which are joined in the vertical direction. Are fixed by joining the belt-like joining portion 24 to the anode partition wall 21, and an anolyte circulation passage 25 is secured in each anode holding member 23.
  • a cathode holding member 26 corresponding to the anode holding member 23 is fixed to the cathode side of the joining partition wall by joining the strip-like joining portion 27 to the cathode partition wall 22, and each cathode holding member 26 has a catholyte circulation passage. 28 is secured.
  • a convex portion 29 is formed outside the center of the anode holding member 23, and power is supplied to the expanded metal anode 30 through the convex portion 29.
  • a metal elastic body 15 is disposed between the hydrogen generating cathode 31 and the cathode holding member 26.
  • the metal elastic body 15 includes at least two types of metal elastic bodies (in the illustrated example). Consists of metal coil bodies 15a, 15b). By setting it as this structure, the effect similar to the above-mentioned monopolar ion exchange membrane electrolytic cell can be acquired.
  • a mesh 32 is disposed to prevent the metal elastic body 15 from falling.
  • the details of the metal elastic body according to the present embodiment are the same as those of the metal elastic body 15 used in the above-described monopolar ion exchange membrane electrolytic cell, and the above-described elasticity is used instead of the metal elastic body 15.
  • a cushion material 104 may be used.
  • the cathode holding member 28 is disposed between the metal elastic body 15 and the cathode partition wall 22, but the present invention is not limited to such a form, and the gap between the electrode and the partition wall is not limited. It is only necessary that a metal elastic body is disposed on the metal and is electrically connected via the metal elastic body.
  • At least one metal elastic body in the illustrated example, a metal elastic body is used. It is preferable that an electrode catalyst is supported on the coil bodies 15a and 15b). That is, by making the metal elastic body itself function as an electrode, it is not necessary to arrange the electrode, the hydrogen generating cathode 31 in the illustrated example, and it is possible to obtain the merit that the number of parts can be reduced.
  • the ion exchange membrane electrolytic cell of the present invention has been described separately for the case where the ion exchange membrane electrolytic cell is a monopolar type and the case of a bipolar type, but the ion exchange membrane electrolytic cell of the present invention has the above-described configuration. It is only important to satisfy the above. For other structures, a conventionally used structure can be used as appropriate, and there is no particular limitation.
  • the shape of the cathode current collector may be a mesh shape or a plate shape, and the shape is not particularly limited.
  • the cathode is not particularly limited as long as it is pressed by the metal elastic body 15 or the elastic cushion material 104 and comes into contact with the ion exchange membrane, and any cathode can be used as long as it is usually used for electrolysis.
  • the catalyst film is thin, it is highly active, the surface of the film is smooth, and the ion-exchange membrane is not mechanically damaged.
  • Ru-La-Pt system, Ru-Ce Pyrolytic active cathodes selected from the group consisting of Pt, Pt—Ce, and Pt—Ni are preferred.
  • Example 1 A dimensional stability electrode manufactured by Permerek Electrode Co., Ltd. was adopted as the anode, and an active cathode of nickel micromesh substrate was adopted as the cathode.
  • the reaction surface sizes of the anode and the cathode were 110 mm in width and 1400 mm in height, respectively.
  • As the ion exchange membrane Flemion F-8020 manufactured by Asahi Glass Co., Ltd. was used.
  • a coil wire having a width of about 0.5 mm was produced by rolling a nickel wire (NW2201) having a wire diameter of 0.17 mm and a tensile strength of 620 to 680 N / m 2 .
  • NW2201 nickel wire
  • a metal coil body having a thickness of 5 mm was produced. The ratio of reaction forces of the obtained metal coil body was 0.7.
  • This metal coil body is wound around a nickel round bar frame (corrosion-resistant frame) with a diameter of 1.2 mm to adjust the shape to a rectangular parallelepiped shape, and an elastic cushion material having an approximate size of 10 mm thickness ⁇ 110 mm width ⁇ 350 mm length is formed. Produced. The coil linear density of this elastic cushion material was about 3 g / dm 2 . Nickel expanded metal was used as the cathode current collector.
  • the obtained elastic cushion material was inserted between the cathode current collector and the hydrogen generating cathode so that the elastic cushion material was elastic, and electrolysis was performed at a current density of 4 kA / m 2 for 30 days.
  • Example 2 Electrolysis was carried out under the same conditions as in Example 1, except that a metal coil body having a large winding diameter and a metal coil body having a small winding diameter were inserted between the cathode current collector and the hydrogen generating cathode without being wound around the corrosion-resistant frame. Went. In addition, the said metal coil body was made into the state shown to Fig.2 (a).
  • Example 3 Brush plating method (plating per current 0.5 A, 1 dm 2 ) using the elastic cushion material prepared in Example 1 as a cathode and a plastic brush containing a titanium rod impregnated with an aqueous hexachloroplatinic acid solution (20 g / liter) as an anode Platinum plating was performed on the ion exchange membrane side surface of each metal coil body constituting the elastic cushion material in 5 minutes.
  • the obtained platinum-plated elastic cushion material itself was used as a cathode, and electrolysis was performed under the same conditions as in Example 1 except that it was inserted between the cathode current collector and the ion exchange membrane.

Abstract

Provided is an ion exchange membrane electrolytic cell, whereby it becomes possible to achieve both the protection of an ion exchange membrane and the development of the electrolytic performance of the electrolytic cell. An ion exchange membrane electrolytic cell partitioned with an ion exchange membrane into an anode chamber in which an anode is housed and a cathode chamber in which a hydrogen-generating cathode is housed, wherein a metallic elastic body (15) or an elastic cushioning material produced by winding a metallic elastic body around a corrosion-resistant frame is arranged between the hydrogen-generating cathode (14) and a cathode current collector (13) and/or between the anode and an anode current collector, and wherein at least two types of metallic elastic bodies are used as the metallic elastic body (15).

Description

イオン交換膜電解槽Ion exchange membrane electrolytic cell
　本発明は、イオン交換膜電解槽（以下、単に「電解槽」とも称する）に関し、詳しくは、イオン交換膜の保護と電解槽の電解性能とを両立させることができるイオン交換膜電解槽に関する。 The present invention relates to an ion exchange membrane electrolytic cell (hereinafter, also simply referred to as “electrolytic cell”), and more particularly, to an ion exchange membrane electrolytic cell capable of achieving both protection of the ion exchange membrane and electrolytic performance of the electrolytic cell.
　クロルアルカリ電解に使用するイオン交換膜電解槽では、通常、陽極、イオン交換膜および水素発生陰極の三者を密着状態で配置して電解電圧の低下を図っている。しかし、電解面積が数平方メートルにも達する大型の電解槽においては、剛性部材の陽極および陰極を電極室に収容した場合、両電極をイオン交換膜に密着させて電極間隔を所定値に保持することは困難であった。 In an ion exchange membrane electrolytic cell used for chloralkali electrolysis, usually, an anode, an ion exchange membrane, and a hydrogen generation cathode are arranged in close contact with each other in order to lower the electrolysis voltage. However, in a large electrolytic cell with an electrolysis area of several square meters, when the anode and cathode of the rigid member are accommodated in the electrode chamber, the electrodes are kept in close contact with the ion exchange membrane and the electrode spacing is kept at a predetermined value. Was difficult.
　電極間距離または電極と電極集電体間の距離を小さくするため、またはほぼ一定値に維持するための手段として、これらに材料として弾性材料を使用する電解槽が知られている。このような電解槽は、電極をイオン交換膜に均一に密着させてイオン交換膜の破損をさけるため、および陽－陰両電極間距離を最小に保つため、少なくとも一方の電極の極間距離方向への移動が自由な構造とし、電極を弾力性部材で押し狭持圧を調節している。この弾性材料としては、金属の細線の織布、不織布、網等の非剛性材料、および板バネ等の剛性材料が知られている。 As a means for reducing the distance between the electrodes or the distance between the electrode and the electrode current collector or maintaining it at a substantially constant value, an electrolytic cell using an elastic material as a material is known. In such an electrolytic cell, in order to prevent the ion exchange membrane from being damaged by bringing the electrode into close contact with the ion exchange membrane and to keep the distance between the positive and negative electrodes to a minimum, the direction of the distance between the electrodes of at least one of the electrodes The electrode is pressed by an elastic member to adjust the holding pressure. As this elastic material, non-rigid materials such as metal fine wire woven fabric, non-woven fabric and net, and rigid materials such as leaf springs are known.
　しかしながら、これまでの非剛性材料は、電解槽への装着後に、陽極側から過度に押圧された場合に、部分的に変形して電極間距離が不均一になったり、細線がイオン交換膜に突き刺さるといった欠点を有していた。また、板バネ等の剛性材料は、イオン交換膜を傷つけたり、塑性変形が生じて再使用が不可能になるといった欠点を有していた。さらに、食塩電解槽のようなイオン交換膜電解槽では、陽極や陰極をイオン交換膜に密着させて低電圧で運転を継続できることが望ましく、電極をイオン交換膜方向に押圧するための種々の方法が提案されている。 However, conventional non-rigid materials are partially deformed when the electrode is excessively pressed from the anode side after being attached to the electrolytic cell, resulting in non-uniform distance between the electrodes, or fine wires in the ion exchange membrane. It had the disadvantage of being pierced. In addition, rigid materials such as leaf springs have the drawback that the ion exchange membrane is damaged or plastic deformation occurs, making it impossible to reuse. Furthermore, in an ion exchange membrane electrolytic cell such as a salt electrolytic cell, it is desirable that the anode and the cathode be in close contact with the ion exchange membrane and the operation can be continued at a low voltage, and various methods for pressing the electrode toward the ion exchange membrane. Has been proposed.
　例えば、特許文献１では、従来用いられていた板バネや金属網状体に代わり、金属製コイル体を陰極と陰極端板の間に装着して陰極を隔膜方向に均一に押圧して各部材を密着させた電解槽が提案されている。また、特許文献２では、特許文献１の改良技術として、金属製コイル体を耐食性フレームに巻回して弾性クッション材を作製し、この弾性クッション材を水素発生陰極と陰極集電板との間に装着して水素発生陰極をイオン交換膜に均一に押圧させたイオン交換膜電解槽が提案されている。 For example, in Patent Document 1, a metal coil body is mounted between a cathode and a cathode end plate instead of a conventionally used leaf spring or metal mesh body, and the cathode is uniformly pressed in the direction of the diaphragm so that the respective members are brought into close contact with each other. An electrolytic cell has been proposed. Moreover, in patent document 2, as an improvement technique of patent document 1, a metal coil body is wound around a corrosion-resistant frame to produce an elastic cushion material, and this elastic cushion material is placed between a hydrogen generating cathode and a cathode current collector plate. There has been proposed an ion exchange membrane electrolytic cell that is mounted and the hydrogen generating cathode is uniformly pressed against the ion exchange membrane.
特公昭６３－５３２７２号公報Japanese Patent Publication No. 63-53272 特開２００４－３００５４３号公報JP 2004-300543 A
　特許文献１および２で提案されている、金属製コイル体や弾性クッション材が配置された電解槽は、対極から逆圧が加わった場合、逆圧に対して耐性を有しているという特長を有している。しかしながら、その反面、反力が大きいため、イオン交換膜への押し付け圧が強くなり、イオン交換膜にブリスターが発生しやすくなることが懸念される。したがって、イオン交換膜への影響を考慮して金属製コイル体または弾性クッション材の反力は小さい方が好ましい。しかしながら、反力を低下させると逆圧耐性が低くなり、金属製コイル体または弾性クッション材の接触抵抗も上昇してしまい、電解性能の低下を引き起こすことになり、イオン交換膜の保護と電解槽の性能向上を高度に両立させることは困難であった。 The electrolytic cell in which the metal coil body and the elastic cushion material proposed in Patent Documents 1 and 2 are arranged has a feature of having resistance to the reverse pressure when the reverse pressure is applied from the counter electrode. Have. However, on the other hand, since the reaction force is large, the pressing pressure against the ion exchange membrane becomes strong, and there is a concern that blisters are likely to be generated in the ion exchange membrane. Therefore, it is preferable that the reaction force of the metal coil body or the elastic cushion material is small in consideration of the influence on the ion exchange membrane. However, if the reaction force is lowered, the resistance to reverse pressure is lowered, the contact resistance of the metal coil body or the elastic cushion material is also raised, and the electrolytic performance is lowered, and the protection of the ion exchange membrane and the electrolytic cell It was difficult to achieve a high level of performance improvement.
　そこで、本発明の目的は、イオン交換膜の保護と電解槽の電解性能とを高度に両立させることができるイオン交換膜電解槽を提供することにある。 Therefore, an object of the present invention is to provide an ion exchange membrane electrolytic cell capable of achieving both high protection of the ion exchange membrane and electrolytic performance of the electrolytic cell.
　本発明者は、上記課題を解決するために鋭意検討した結果、下記構成とすることにより、上記課題を解消することができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that the above-described problems can be solved by adopting the following configuration, and has completed the present invention.
　すなわち、本発明のイオン交換膜電解槽は、イオン交換膜により陽極を収容する陽極室と陰極を収容する陰極室とに区画され、前記陽極室および前記陰極室のうち少なくとも一方に金属製弾性体が配置されてなるイオン交換膜電解槽において、
　前記金属製弾性体として、少なくとも２種の金属製弾性体からなることを特徴とするものである。 That is, the ion exchange membrane electrolytic cell of the present invention is partitioned into an anode chamber for accommodating an anode and a cathode chamber for accommodating a cathode by an ion exchange membrane, and at least one of the anode chamber and the cathode chamber is made of a metal elastic body. In an ion exchange membrane electrolytic cell in which
The metal elastic body is composed of at least two types of metal elastic bodies.
　本発明のイオン交換膜電解槽においては、前記金属製弾性体が、陰極と陰極集電体間および陽極と陽極集電体間の少なくとも一方に配置されてなり、前記金属製弾性体の反力により電極と前記イオン交換膜とが密着していてもよく、前記金属製弾性体が、陰極と陰極隔壁間および陽極と陽極隔壁間の少なくとも一方に配置されてなり、前記金属製弾性体の反力により電極と前記イオン交換膜とが密着していてもよい。また、本発明のイオン交換膜電解槽においては、前記金属製弾性体は耐食性フレームに巻回されてなる弾性クッション材であることが好ましい。さらに、本発明のイオン交換膜電解槽においては、前記金属製弾性体は、金属製コイル体であることが好ましい。さらにまた、本発明のイオン交換膜電解槽においては、前記少なくとも２種の金属製弾性体のうち少なくとも１種の金属製弾性体に、電極触媒が担持されていることが好ましい。 In the ion exchange membrane electrolytic cell of the present invention, the metal elastic body is arranged between at least one of the cathode and the cathode current collector and between the anode and the anode current collector, and the reaction force of the metal elastic body The electrode and the ion exchange membrane may be in close contact with each other, and the metal elastic body is disposed between at least one of the cathode and the cathode partition wall and between the anode and the anode partition wall. The electrode and the ion exchange membrane may be in close contact with each other by force. Moreover, in the ion exchange membrane electrolytic cell of this invention, it is preferable that the said metal elastic body is an elastic cushion material wound around a corrosion-resistant flame | frame. Furthermore, in the ion exchange membrane electrolytic cell of this invention, it is preferable that the said metal elastic body is a metal coil body. Furthermore, in the ion exchange membrane electrolytic cell of the present invention, it is preferable that an electrode catalyst is supported on at least one metal elastic body among the at least two metal elastic bodies.
本発明のイオン交換膜電解槽によれば、イオン交換膜の保護と電解槽の電解性能とを高度に両立させることができる。 According to the ion exchange membrane electrolytic cell of the present invention, the protection of the ion exchange membrane and the electrolytic performance of the electrolytic cell can be made highly compatible.
本発明の一好適な実施の形態に係る単極式イオン交換膜電解槽の陰極ユニット中の陰極と陰極集電体とを、金属製弾性体を介して電気的接続した例を示す概略平面図である。1 is a schematic plan view showing an example in which a cathode and a cathode current collector in a cathode unit of a monopolar ion exchange membrane electrolytic cell according to a preferred embodiment of the present invention are electrically connected via a metal elastic body. It is. （ａ）～（ｆ）は、それぞれ巻き径の大きい金属製コイル体と巻き径が小さい金属製コイル体との配置例を示す概略平面図である。(A)-(f) is a schematic plan view which shows the example of arrangement | positioning with a metal coil body with a large winding diameter, and a metal coil body with a small winding diameter, respectively. 金属製コイル体に順次逆圧が加わった場合における、金属製コイル体の変形過程を示す説明図である。It is explanatory drawing which shows the deformation | transformation process of a metal coil body in case back pressure is added to a metal coil body sequentially. 本発明に係る弾性クッション材に用いる耐食性フレームの一例の斜視図である。It is a perspective view of an example of the corrosion-resistant frame used for the elastic cushion material concerning the present invention. 本発明に係る弾性クッション材の一例の斜視図である。It is a perspective view of an example of the elastic cushion material concerning the present invention. 図５のＡ－Ａ線断面図である。FIG. 6 is a cross-sectional view taken along line AA in FIG. 本発明の他の好適な実施の形態に係る複極式イオン交換膜電解槽ユニットの陰極と陰極隔壁とを、金属製弾性体を介して電気的に接続した例を示す概略平面図である。It is a schematic plan view which shows the example which connected the cathode and cathode partition of the bipolar ion exchange membrane electrolytic cell unit which concerns on other suitable embodiment of this invention via the metal elastic body.
　以下、本発明の実施の形態について、図面を参照しつつ詳細に説明する。
　本発明のイオン交換膜電解槽は、イオン交換膜により陽極を収容する陽極室と陰極を収容する陰極室に区画されたものであり、陽極室および陰極室のうち少なくとも一方に金属製弾性体が配置されてなる。例えば、単極式イオン交換膜電解槽において、金属製弾性体が、陰極と陰極集電体間および陽極と陽極集電体間の少なくとも一方に配置されたものや、複極式イオン交換膜電解槽において、金属製弾性体が、陰極と陰極隔壁間および陽極と陽極隔壁間の少なくとも一方に配置されたものを挙げることができる。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
The ion exchange membrane electrolytic cell of the present invention is partitioned into an anode chamber containing an anode and a cathode chamber containing a cathode by an ion exchange membrane, and a metal elastic body is provided in at least one of the anode chamber and the cathode chamber. It is arranged. For example, in a monopolar ion exchange membrane electrolytic cell, a metal elastic body is disposed between at least one of a cathode and a cathode current collector and between an anode and an anode current collector, or a bipolar ion exchange membrane electrolysis Examples of the tank include a metal elastic body disposed between at least one of the cathode and the cathode partition and between the anode and the anode partition.
　図１は、本発明の一好適な実施の形態に係る単極式イオン交換膜電解槽の陰極ユニット中の陰極と陰極集電体とを、金属製弾性体を介して電気的接続した例を示す概略平面図である。図示する単極式イオン交換膜電解槽の陰極ユニット１０においては、水素発生陰極１４と陰極集電体１３との間に金属製弾性体１５が配置されている。また、図示例においては、陰極ユニット１０内には、上下方向を向く１対の導電棒１１が立設され、この導電棒１１の周囲に陰極液循環通電部材１２が設置され、この通電部材１２の面に沿って陰極集電体１３が電気的に接続されている。本発明のイオン交換膜電解槽においては、この金属製弾性体１５は、少なくとも２種の金属製弾性体（図示例においては金属製コイル体１５ａ、１５ｂ）からなる。図示例においては、２種の金属製弾性体として、巻き径が大きい金属製コイル体１５ａと、巻き径が小さい金属製コイル体１５ｂが用いられている。 FIG. 1 shows an example in which a cathode and a cathode current collector in a cathode unit of a monopolar ion exchange membrane electrolytic cell according to a preferred embodiment of the present invention are electrically connected via a metal elastic body. It is a schematic plan view shown. In the cathode unit 10 of the illustrated monopolar ion exchange membrane electrolytic cell, a metal elastic body 15 is disposed between the hydrogen generating cathode 14 and the cathode current collector 13. Further, in the illustrated example, a pair of conductive rods 11 facing vertically are provided in the cathode unit 10, and a catholyte circulation energization member 12 is installed around the conductive rod 11. The cathode current collector 13 is electrically connected along the surface. In the ion exchange membrane electrolytic cell of the present invention, the metal elastic body 15 is composed of at least two types of metal elastic bodies ( metal coil bodies 15a and 15b in the illustrated example). In the illustrated example, a metal coil body 15a having a large winding diameter and a metal coil body 15b having a small winding diameter are used as the two types of metal elastic bodies.
　図１においては、巻き径の大きい金属製コイル体１５ａが陰極集電体１３および水素発生陰極１４の両方に接するように配置され、巻き径の小さい金属製コイル体１５ｂは水素発生陰極１４に接するように配置されているが、本発明においては、かかる形態に制限されるものではない。図２は巻き径の大きい金属製コイル体１５ａおよび巻き径が小さい金属製コイル体１５ｂの配置例を示す図である。図２（ａ）は、巻き径の大きい金属製コイル体１５ａが陰極集電体１３および水素発生陰極１４の両方に接するように配置され、巻き径が小さい金属製コイル体１５ｂが陰極集電体１３に接するように配置されており、（ｂ）は、巻き径の大きい金属製コイル体１５ａが陰極集電体１３および水素発生陰極１４の両方に接するように配置され、巻き径の小さい金属製コイル体１５ｂが水素発生陰極１４に接するように配置されており、（ｃ）は、巻き径の大きい金属製コイル体１５ａが陰極集電体１３に接するように配置され、巻き径の小さい金属製コイル体１５ｂが水素発生陰極１４に接するように配され、かつ、両コイルが重なり合わずに接している。また、（ｄ）は、巻き径の大きい金属製コイル体１５ａと巻き径が小さい金属製コイル体１５ｂとの位置関係が（ｃ）の場合と逆であり、（ｅ）は、（ｂ）の場合において巻き径の大きい金属製コイル体１５ａと巻き径が小さい金属製コイル体１５ｂとが部分的に接するように配置され、（ｆ）は、（ａ）の場合において巻き径の大きい金属製コイル体１５ａと巻き径が小さい金属製コイル体１５ｂとが部分的に接するように配置されている。 In FIG. 1, the metal coil body 15 a having a large winding diameter is disposed so as to contact both the cathode current collector 13 and the hydrogen generating cathode 14, and the metal coil body 15 b having a small winding diameter is in contact with the hydrogen generating cathode 14. However, the present invention is not limited to such a configuration. FIG. 2 is a diagram showing an arrangement example of the metal coil body 15a having a large winding diameter and the metal coil body 15b having a small winding diameter. FIG. 2A shows that a metal coil body 15a having a large winding diameter is disposed so as to contact both the cathode current collector 13 and the hydrogen generating cathode 14, and a metal coil body 15b having a small winding diameter is a cathode current collector. (B) shows that a metal coil body 15a having a large winding diameter is disposed so as to be in contact with both the cathode current collector 13 and the hydrogen generating cathode 14, and is made of a metal having a small winding diameter. The coil body 15b is disposed so as to be in contact with the hydrogen generating cathode 14, and (c) is disposed such that the metal coil body 15a having a large winding diameter is in contact with the cathode current collector 13, and is made of a metal having a small winding diameter. The coil body 15b is arranged so as to be in contact with the hydrogen generating cathode 14, and both coils are in contact with each other without overlapping. Further, (d) is opposite to the case of (c) in the positional relationship between the metal coil body 15a having a large winding diameter and the metal coil body 15b having a small winding diameter. In the case, the metal coil body 15a having a large winding diameter and the metal coil body 15b having a small winding diameter are arranged so as to be in partial contact with each other, and (f) is a metal coil having a large winding diameter in the case of (a). It arrange | positions so that the body 15a and the metal coil body 15b with a small winding diameter may touch partially.
　上述の通り、金属製弾性体は逆圧に対して耐性がある反面、イオン交換膜に対する押し付け圧が強くなってしまうという不具合を有している。本発明においては、少なくとも２種の金属製コイル体１５ａ、１５ｂを用いて、イオン交換膜に対する押し付け圧の低減と逆圧に対する耐性とを両立させている。 As described above, the metal elastic body is resistant to the reverse pressure, but has a problem that the pressing pressure against the ion exchange membrane is increased. In the present invention, at least two types of metal coil bodies 15a and 15b are used to achieve both reduction of the pressing pressure against the ion exchange membrane and resistance to reverse pressure.
　図３は、図２（ａ）に示すタイプの金属製コイル体１５ａ、１５ｂに逆圧が加わった場合における、金属製コイル体１５ａ、１５ｂの変形過程を示す図である。図３（ａ）は、陰極に逆圧が加わっていない状態を示しており、巻き径が大きい金属製コイル体１５ａが水素発生陰極１４を均一に押圧している。図３（ｂ）は、陰極に逆圧が加わった状態を示しており、巻き径の大きい金属製コイル体１５ａが徐々に圧縮されていく。図３（ｃ）は陰極に対して過度の逆圧が加わった状態を示している。過度の逆圧が加わると、巻き径の大きい金属製コイル体１５ａは圧縮されてしまうが、巻き径の小さい金属製コイル体１５ｂが水素発生陰極１４と接し、これにより逆圧に対する耐性を発揮する。上記効果を良好に得るためには、巻き径の大きい金属製コイル体１５ａが塑性変形を開始する前に、巻き径の小さい金属製コイル体１５ｂが弾性変形を開始し、かつ、両金属製コイル体１５ａ、１５ｂの逆圧による変形が弾性変形の段階で収束していることが好ましい。なお、金属製コイル体１５ａ、１５ｂの厚みは上記効果を得ることができる範囲で適宜設計すればよい。 FIG. 3 is a diagram showing a deformation process of the metal coil bodies 15a and 15b when a reverse pressure is applied to the metal coil bodies 15a and 15b of the type shown in FIG. FIG. 3A shows a state in which no reverse pressure is applied to the cathode, and the metal coil body 15a having a large winding diameter presses the hydrogen generating cathode 14 uniformly. FIG. 3B shows a state in which a reverse pressure is applied to the cathode, and the metal coil body 15a having a large winding diameter is gradually compressed. FIG. 3C shows a state in which an excessive back pressure is applied to the cathode. When excessive back pressure is applied, the metal coil body 15a having a large winding diameter is compressed, but the metal coil body 15b having a small winding diameter is in contact with the hydrogen generating cathode 14, thereby exhibiting resistance to the reverse pressure. . In order to obtain the above effect satisfactorily, the metal coil body 15b having a small winding diameter starts elastic deformation before the metal coil body 15a having a large winding diameter starts plastic deformation, and both metal coils It is preferable that the deformation due to the back pressure of the bodies 15a and 15b converge at the stage of elastic deformation. In addition, what is necessary is just to design the thickness of metal coil bodies 15a and 15b suitably in the range which can acquire the said effect.
　図１においては、金属製弾性体１５として、厚みの異なる金属製コイル体１５ａ、１５ｂを例に挙げているが、本発明のイオン交換膜電解槽においては、金属製弾性体は導電性材料からなり、かつ、弾性的性質を有するものであって、柔軟な電極をイオン交換膜に押し付けて給電することができるものであれば、特に制限はない。例えば、金属製コイル体以外の金属製弾性体として、金属細線に波形型付けしたものや、金属製の不織布、金属ワイヤーからなる編物、織物およびこれらの積層体、または三次元的に編んであるか、三次元的に編んだ後これにうねり加工等を施した形状のものを用いてもよい。 In FIG. 1, metal coil bodies 15a and 15b having different thicknesses are exemplified as the metal elastic body 15. However, in the ion exchange membrane electrolytic cell of the present invention, the metal elastic body is made of a conductive material. There is no particular limitation as long as it has elastic properties and can supply power by pressing a flexible electrode against the ion exchange membrane. For example, as a metal elastic body other than a metal coil body, whether it is corrugated on a thin metal wire, a metal non-woven fabric, a knitted fabric made of metal wires, a woven fabric and a laminate thereof, or is it knitted three-dimensionally? Alternatively, a shape obtained by knitting three-dimensionally and then applying swell processing or the like may be used.
　なお、図１～３では２種類の金属製コイル体１５ａ、１５ｂの厚みを変えた場合を例に挙げているが、厚み以外にも、反力の異なる２種の金属製弾性体１５であればよい。例えば、反力の異なる金属製弾性体１５として、弾性率の異なる金属製コイル体や、金属製不織布を用いてもよい。この場合、金属製不織布の体積密度を調整することにより、反力を調整することができる。すなわち、体積密度が小さい金属不織布が、相対的に反力が小さい金属製弾性体として機能し、体積密度が大きい金属製弾性体が、相対的に反力が大きい金属製弾性体として機能する。なお、金属製弾性体１５の反力は、上記効果を得ることができる範囲で適宜設計すればよく、例えば、２種の金属製弾性体の反力の比率を０．５～０．９程度とすればよい。 1 to 3 exemplify the case where the thicknesses of the two types of metal coil bodies 15a and 15b are changed. In addition to the thickness, the two types of metal elastic bodies 15 having different reaction forces may be used. That's fine. For example, as the metal elastic body 15 having a different reaction force, a metal coil body having a different elastic modulus or a metal nonwoven fabric may be used. In this case, the reaction force can be adjusted by adjusting the volume density of the metallic nonwoven fabric. That is, a metal nonwoven fabric having a small volume density functions as a metal elastic body having a relatively small reaction force, and a metal elastic body having a large volume density functions as a metal elastic body having a relatively large reaction force. The reaction force of the metal elastic body 15 may be appropriately designed within a range in which the above effect can be obtained. For example, the ratio of reaction forces of two types of metal elastic bodies is about 0.5 to 0.9. And it is sufficient.
　かかる金属製弾性体１５の材質としては、例えば、良好な耐食性を示すニッケル、ニッケル合金、ステンレス鋼、または銅等の固有抵抗の小さい金属に良好な耐食性を示すニッケル等をめっき等で被覆して製造した線材等を用いることができる。金属製弾性体１５として金属製コイル体１５ａ、１５ｂを用いる場合は、上記線材をロール加工により螺旋コイルに加工したものを用いることができる。得られた線材の断面形状は、イオン交換膜の損傷を防止するという観点から、円、楕円、角部が丸い矩形等であることが好ましい。具体的には、直径０．１７ｍｍのニッケル線（ＮＷ２２０１）をロール加工すると、断面形状が約０．０５ｍｍ×０．５ｍｍの角部が丸い矩形となり、巻き径が約６ｍｍであるコイル線を得ることができる。 The metal elastic body 15 is made of, for example, nickel, nickel alloy, stainless steel, or copper having good corrosion resistance, such as nickel having good corrosion resistance, which is coated with plating or the like. The manufactured wire etc. can be used. When the metal coil bodies 15a and 15b are used as the metal elastic body 15, the wire material processed into a spiral coil by roll processing can be used. The cross-sectional shape of the obtained wire is preferably a circle, an ellipse, a rectangle with rounded corners, or the like from the viewpoint of preventing damage to the ion exchange membrane. Specifically, when a nickel wire (NW2201) having a diameter of 0.17 mm is rolled, a coil wire having a cross-sectional shape of about 0.05 mm × 0.5 mm with rounded corners and a winding diameter of about 6 mm is obtained. be able to.
　図１においては、金属製コイル体１５ａ、１５ｂはそのまま電解槽内の電極とその集電体間に装着されているが、本発明のイオン交換膜電解槽においては、耐食性フレームに金属製弾性体を巻回して構成した弾性クッション材を用いてもよい。図４は、本発明に係る弾性クッション材中の耐食性フレームの一例の斜視図であり、図５は、本発明に係る弾性クッション材の一例の斜視図であり、図６は、図５のＡ－Ａ線縦断面図である。 In FIG. 1, the metal coil bodies 15a and 15b are mounted as they are between the electrode in the electrolytic cell and its current collector. However, in the ion exchange membrane electrolytic cell of the present invention, the metal elastic body is attached to the corrosion-resistant frame. You may use the elastic cushion material comprised by winding. FIG. 4 is a perspective view of an example of a corrosion-resistant frame in the elastic cushion material according to the present invention, FIG. 5 is a perspective view of an example of the elastic cushion material according to the present invention, and FIG. FIG.
　図４に例示すように、本発明のイオン交換膜電解槽に係る耐食性フレーム１０３は金属丸棒で長方形の枠１０１の長手方向の１対の丸棒間に掛け渡された補強杆１０２から成っている。この金属丸棒としては、例えば、直径約２ｍｍのニッケル製金属丸棒を好適に用いることができる。本発明に係る弾性クッション材１０４は、耐食性フレーム１０３の長手方向の１対の丸棒間のほぼ全長に渡って、金属製弾性体（図示例においては、金属製コイル体１５ａ、１５ｂ）を巻回することにより、得ることができる（図５参照）。このようにして得られた弾性クッション材１０４は、金属製コイル体１５ａ、１５ｂが耐食性フレーム１０３に巻回されているため、耐食性フレーム１０３の形状のまま保持され、金属製コイル体１５ａ、１５ｂが耐食性フレーム１０３から離脱することはほとんどなく、金属製コイル体１５ａ、１５ｂを耐食性フレーム１０３と一体化したものとして取り扱うことができる。金属製コイル体１５ａ、１５ｂを耐食性フレーム１０３に巻回することにより、以下の利点を得ることができる。 As shown in FIG. 4, the corrosion-resistant frame 103 according to the ion exchange membrane electrolytic cell of the present invention is a metal round bar and is composed of a reinforcing rod 102 spanned between a pair of round bars in the longitudinal direction of a rectangular frame 101. ing. As this metal round bar, for example, a nickel round metal bar having a diameter of about 2 mm can be suitably used. The elastic cushion material 104 according to the present invention winds a metal elastic body (in the illustrated example, metal coil bodies 15a and 15b) over substantially the entire length between a pair of round bars in the longitudinal direction of the corrosion-resistant frame 103. It can be obtained by turning (see FIG. 5). The elastic cushion material 104 obtained in this way has the metal coil bodies 15a and 15b wound around the corrosion-resistant frame 103, so that the shape of the corrosion-resistant frame 103 is maintained, and the metal coil bodies 15a and 15b are There is almost no detachment from the corrosion-resistant frame 103, and the metal coil bodies 15 a and 15 b can be handled as being integrated with the corrosion-resistant frame 103. By winding the metal coil bodies 15a and 15b around the corrosion resistant frame 103, the following advantages can be obtained.
　すなわち、金属製コイル体１５ａ、１５ｂは変形率が高いため、取扱い難く、作業員の意図通りに電解槽の所定箇所に設置することが困難になることが多い。さらに容易に変形する（強度が不十分である）ため、一旦電解槽の所定箇所に設置しても電解槽内の電解液や生成ガスにより偏位して各部材の均一密着が困難になることがある。これに対して弾性クッション材１０４は、例えば、図４に示すように、長方形状の耐食性フレーム４本の枠杆からなる。このうち対向する２本の間に、ほぼ均一密度になるように金属製コイル体１５ａ、１５ｂを巻回すことにより得られる（図５参照）。この弾性クッション材１０４では、耐食性フレームの左右に通常２層の金属製弾性体１５（図示例においては金属製コイル体１５ａ、１５ｂ）が積層されるが（図６参照）、金属製コイル体自体が変形し易いため、隣接するコイル同士が櫛歯状に噛み合わされて、見掛け上、１層になっている。このようにして得られた弾性クッション材１０４は、食器洗浄用の金属タワシのような外観を有している。 That is, since the metal coil bodies 15a and 15b have a high deformation rate, it is difficult to handle them, and it is often difficult to install the metal coil bodies 15a and 15b at predetermined locations in the electrolytic cell as intended by the operator. Furthermore, since it is easily deformed (the strength is insufficient), even if it is once installed at a predetermined location of the electrolytic cell, it is displaced by the electrolytic solution or generated gas in the electrolytic cell, and it becomes difficult to uniformly adhere each member. There is. On the other hand, the elastic cushion material 104 is made of, for example, a frame of four rectangular corrosion-resistant frames as shown in FIG. It is obtained by winding the metal coil bodies 15a and 15b between the two facing each other so as to obtain a substantially uniform density (see FIG. 5). In this elastic cushion material 104, two layers of metal elastic bodies 15 ( metal coil bodies 15a and 15b in the illustrated example) are usually laminated on the left and right sides of the corrosion-resistant frame (see FIG. 6), but the metal coil bodies themselves. Since the coil is easily deformed, adjacent coils are meshed with each other in a comb-like shape, and apparently has one layer. The thus obtained elastic cushion material 104 has an appearance like a metal scrub for tableware washing.
　金属製弾性体１５を使用する弾性クッション材１０４の組立は、電解槽外の作業であるため、容易に行うことができ、得られた弾性クッション材１０４は、電解槽組立時に、電解槽内の対象電極と装着の集電体を電気的に接続するように装着するようにすればよい。この装着時にも弾性クッション材１０４自体は耐食性フレームの強度により組立に支障が出る程には変形しないため、容易に所定箇所に設置できる。本発明においては、これらの金属製弾性体１５や弾性クッション材１０４等は、必ずしも陰極集電体１３や水素発生陰極１４に溶接等で固定する必要はないが、固定しても構わない。通常、電気は接触通電方式で流すことにする。なお、ここまで、弾性クッション材１０４に用いる金属製弾性体として金属製コイル体１５ａ、１５ｂを例に用いて説明してきたが、本発明においては、金属製コイル体１５ａ、１５ｂ以外にも、金属製不織布等の上記金属製弾性体を用いてもよい。 Since the assembly of the elastic cushion material 104 using the metal elastic body 15 is an operation outside the electrolytic cell, it can be easily performed, and the obtained elastic cushion material 104 is stored in the electrolytic cell during the electrolytic cell assembly. The target electrode and the mounted current collector may be mounted so as to be electrically connected. The elastic cushion material 104 itself is not deformed so as to hinder assembly due to the strength of the corrosion-resistant frame even at the time of mounting, and can be easily installed at a predetermined location. In the present invention, the metal elastic body 15 and the elastic cushion material 104 are not necessarily fixed to the cathode current collector 13 or the hydrogen generating cathode 14 by welding or the like, but may be fixed. Usually, electricity is flowed by a contact energization method. Heretofore, the metal coil bodies 15a and 15b have been described as examples of the metal elastic body used for the elastic cushion material 104. However, in the present invention, in addition to the metal coil bodies 15a and 15b, metal You may use the said metal elastic bodies, such as a nonwoven fabric made.
　金属製コイル体１５ａ、１５ｂや金属製コイル体１５ａ、１５ｂを巻回して得られた弾性クッション材１０４においては、金属製コイル体の径（コイルの見掛け上の直径）は電解槽内に装着されることにより通常１０～７０％まで縮んで弾性が生じ、この弾性により陽極と陽極集電体、または陰極と陰極集電体を弾性的に接続して電極への給電が容易になる。線径の小さい金属製コイル体を使用すれば必然的に電極や集電体と弾性クッション材との接触点の数が多くなり、均一接触が可能になる。電解槽に装着された後の弾性クッション材１０４は、その耐食性フレーム１０３により形状が保持されるため、塑性変形を受けることがほとんどなく、電解槽の解体－再組立時にもほとんどの場合再使用できる。 In the elastic cushion material 104 obtained by winding the metal coil bodies 15a and 15b and the metal coil bodies 15a and 15b, the diameter of the metal coil body (the apparent diameter of the coil) is mounted in the electrolytic cell. Accordingly, the elasticity is usually reduced to 10 to 70%, and this elasticity facilitates power supply to the electrode by elastically connecting the anode and the anode current collector or the cathode and the cathode current collector. If a metal coil body having a small wire diameter is used, the number of contact points between the electrode or current collector and the elastic cushion material inevitably increases, and uniform contact becomes possible. The elastic cushion material 104 after being attached to the electrolytic cell is hardly subjected to plastic deformation because the shape is held by the corrosion-resistant frame 103, and can be reused in most cases even when the electrolytic cell is disassembled and reassembled. .
　本発明のイオン交換膜電解槽においては、金属製弾性体１５や、弾性クッション材１０４を含むイオン交換膜電解槽を組み立てる際には、少なくとも一方の電極とその電極集電体間に弾性クッション材１０４等を位置させ、その後は通常通りに組立てれば所定の位置に弾性クッション材等が保持されたイオン交換膜電解槽が得られる。 In the ion exchange membrane electrolytic cell of the present invention, when assembling the metal elastic body 15 and the ion exchange membrane electrolytic cell including the elastic cushion material 104, an elastic cushion material is provided between at least one electrode and the electrode current collector. If 104 or the like is positioned and then assembled as usual, an ion exchange membrane electrolytic cell in which an elastic cushion material or the like is held at a predetermined position can be obtained.
　本発明のイオン交換膜電解槽においては、少なくとも２種の金属製弾性体（図示例においては金属製コイル体１５ａ、１５ｂ）のうち少なくとも１種の金属製弾性体に、電極触媒を担持させてもよい。すなわち、金属製弾性体１５自身を電極として機能させることにより、図示例における水素発生陰極１４を配置する必要がなくなり、部品点数を減らすことができるというメリットを得ることができる。金属製弾性体に電極触媒を担持させるには、金属製弾性体の表面に白金族金属含有層、ラネーニッケル含有層、活性炭含有ニッケル層等の電極触媒物質の被覆を形成すればよく、例えば、金属製弾性体の表面にラネーニッケル触媒をニッケルにより分散メッキを施したり、ヘキサクロロ白金等の貴金属軽金属を筆めっき等のめっき処理を施したり、焼き付けを施すことが挙げられる。 In the ion exchange membrane electrolytic cell of the present invention, an electrode catalyst is supported on at least one metal elastic body of at least two types of metal elastic bodies (in the illustrated example, metal coil bodies 15a and 15b). Also good. That is, by causing the metal elastic body 15 itself to function as an electrode, it is not necessary to dispose the hydrogen generating cathode 14 in the illustrated example, and the merit that the number of parts can be reduced can be obtained. In order to support the electrode catalyst on the metal elastic body, a coating of an electrode catalyst material such as a platinum group metal-containing layer, a Raney nickel-containing layer, or an activated carbon-containing nickel layer may be formed on the surface of the metal elastic body. For example, Raney nickel catalyst may be subjected to dispersion plating with nickel on the surface of the elastic body, or a precious metal light metal such as hexachloroplatinum may be subjected to plating treatment such as brush plating, or may be baked.
　次に、本発明の他の好適な実施の形態に係る複極式のイオン交換膜電解槽について説明する。図７は、本発明の他の好適な実施の形態に係る複極式イオン交換膜電解槽ユニットの陰極と陰極隔壁とを、金属製弾性体を介して電気的に接続した例を示す概略平面図である。図示する複極式イオン交換膜電解槽ユニット２０内には、接合された陽極隔壁２１と陰極隔壁２２の陽極側には上下方向を向く４個の陽極保持部材２３（図示例においては一体化されている）が帯状接合部２４を陽極隔壁２１に接合することにより固定され、各陽極保持部材２３の中には陽極液循環通路２５が確保されている。また、接合隔壁の陰極側には陽極保持部材２３に対応する陰極保持部材２６が帯状接合部２７を陰極隔壁２２に接合することにより固定され、各陰極保持部材２６の中には陰極液循環通路２８が確保されている。陽極保持部材２３の中央外側には凸状部２９が形成され、この凸状部２９を通してエキスパンデッドメタル状の陽極３０へ給電を行う。 Next, a bipolar ion exchange membrane electrolytic cell according to another preferred embodiment of the present invention will be described. FIG. 7 is a schematic plan view showing an example in which a cathode and a cathode partition of a bipolar ion exchange membrane electrolytic cell unit according to another preferred embodiment of the present invention are electrically connected via a metal elastic body. FIG. In the illustrated bipolar ion exchange membrane electrolytic cell unit 20, four anode holding members 23 (integrated in the illustrated example) are formed on the anode side of the anode partition 21 and the cathode partition 22 which are joined in the vertical direction. Are fixed by joining the belt-like joining portion 24 to the anode partition wall 21, and an anolyte circulation passage 25 is secured in each anode holding member 23. Further, a cathode holding member 26 corresponding to the anode holding member 23 is fixed to the cathode side of the joining partition wall by joining the strip-like joining portion 27 to the cathode partition wall 22, and each cathode holding member 26 has a catholyte circulation passage. 28 is secured. A convex portion 29 is formed outside the center of the anode holding member 23, and power is supplied to the expanded metal anode 30 through the convex portion 29.
　本発明の他の好適な実施の形態に係る複極式イオン交換膜電解槽においては、陰極（水素発生陰極３１）と陰極隔壁２２との間および陽極３０と陽極隔壁２１と間の少なくとも一方に、図示例においては、水素発生陰極３１と陰極保持部材２６との間に金属製弾性体１５が配置されてなり、この金属製弾性体１５は、少なくとも２種の金属製弾性体（図示例においては金属製コイル体１５ａ、１５ｂ）からなる。かかる構成とすることにより、上述の単極式イオン交換膜電解槽と同様の効果を得ることができる。なお、図示例においては、金属製弾性体１５が落ち込むのを防止するために、メッシュ３２が配置されている。 In the bipolar ion exchange membrane electrolytic cell according to another preferred embodiment of the present invention, at least one between the cathode (hydrogen generating cathode 31) and the cathode partition wall 22 and between the anode 30 and the anode partition wall 21. In the illustrated example, a metal elastic body 15 is disposed between the hydrogen generating cathode 31 and the cathode holding member 26. The metal elastic body 15 includes at least two types of metal elastic bodies (in the illustrated example). Consists of metal coil bodies 15a, 15b). By setting it as this structure, the effect similar to the above-mentioned monopolar ion exchange membrane electrolytic cell can be acquired. In the illustrated example, a mesh 32 is disposed to prevent the metal elastic body 15 from falling.
　本実施の形態に係る金属製弾性体の詳細については、上述の単極式イオン交換膜電解槽に用いる金属製弾性体１５と同様であり、また、金属製弾性体１５に代えて上述の弾性クッション材１０４を用いてもよい。なお、図示例においては、金属製弾性体１５と陰極隔壁２２の間に、陰極保持部材２８が配置されているが、本発明はかかる形態に制限されるものではなく、電極と隔壁との間に金属製弾性体が配置され、この金属製弾性体を介して電気的に接続されていればよい。 The details of the metal elastic body according to the present embodiment are the same as those of the metal elastic body 15 used in the above-described monopolar ion exchange membrane electrolytic cell, and the above-described elasticity is used instead of the metal elastic body 15. A cushion material 104 may be used. In the illustrated example, the cathode holding member 28 is disposed between the metal elastic body 15 and the cathode partition wall 22, but the present invention is not limited to such a form, and the gap between the electrode and the partition wall is not limited. It is only necessary that a metal elastic body is disposed on the metal and is electrically connected via the metal elastic body.
　また、本発明の他の好適な実施の形態に係る複極式イオン交換膜電解槽においても、少なくとも２種の金属製弾性体のうち少なくとも１種の金属製弾性体（図示例においては金属製コイル体１５ａ、１５ｂ）に、電極触媒が担持されていることが好ましい。すなわち、金属製弾性体自身を電極として機能させることにより、電極、図示例における水素発生陰極３１を配置する必要がなくなり、部品点数を減らすことができるというメリットを得ることができる。 Also, in the bipolar ion exchange membrane electrolytic cell according to another preferred embodiment of the present invention, at least one metal elastic body (in the illustrated example, a metal elastic body) is used. It is preferable that an electrode catalyst is supported on the coil bodies 15a and 15b). That is, by making the metal elastic body itself function as an electrode, it is not necessary to arrange the electrode, the hydrogen generating cathode 31 in the illustrated example, and it is possible to obtain the merit that the number of parts can be reduced.
　以上、本発明のイオン交換膜電解槽について、イオン交換膜電解槽が単極式の場合と複極式の場合とに分けて説明してきたが、本発明のイオン交換膜電解槽は、上記構成を満足することのみが重要であり、それ以外の構造については、従来から用いられている構造を適宜用いることができ、特に制限はない。 As described above, the ion exchange membrane electrolytic cell of the present invention has been described separately for the case where the ion exchange membrane electrolytic cell is a monopolar type and the case of a bipolar type, but the ion exchange membrane electrolytic cell of the present invention has the above-described configuration. It is only important to satisfy the above. For other structures, a conventionally used structure can be used as appropriate, and there is no particular limitation.
　例えば、陰極集電体の形状は、メッシュ状であっても板状であってもよく、その形状については特に限定されるものではない。また、陰極については、金属製弾性体１５または弾性クッション材１０４により押圧されてイオン交換膜に接触するものであるのであれば特に制限はなく、通常、電解用に用いられるものであれば、いかなるものをも用いることができるが、触媒皮膜が薄くとも高活性であって、かつ、皮膜表面が平滑で、イオン交換膜を機械的に傷つけることのない、Ｒｕ－Ｌａ－Ｐｔ系、Ｒｕ－Ｃｅ系、Ｐｔ－Ｃｅ系、および、Ｐｔ－Ｎｉ系からなる群から選択される熱分解型活性陰極が好適である。 For example, the shape of the cathode current collector may be a mesh shape or a plate shape, and the shape is not particularly limited. Further, the cathode is not particularly limited as long as it is pressed by the metal elastic body 15 or the elastic cushion material 104 and comes into contact with the ion exchange membrane, and any cathode can be used as long as it is usually used for electrolysis. Although the catalyst film is thin, it is highly active, the surface of the film is smooth, and the ion-exchange membrane is not mechanically damaged. Ru-La-Pt system, Ru-Ce Pyrolytic active cathodes selected from the group consisting of Pt, Pt—Ce, and Pt—Ni are preferred.
　本発明のイオン交換膜電解槽を使用して食塩電解を行うには、陽極室に食塩水溶液等の電解液を、陰極室に希釈苛性ソーダ水溶液を供給しながら、両極間に通電する。弾性クッション材等が電極として機能する電解槽では、弾性クッション材等の高強度及び強靭性によりこの状態が長期間維持されるため、イオン交換膜等が機械的に損傷したりすることなく、また過度に変形して給電が不十分になることがなく、苛性ソーダ等を高効率で製造できる。 In order to perform salt electrolysis using the ion exchange membrane electrolytic cell of the present invention, current is supplied between both electrodes while supplying an electrolyte such as a saline solution to the anode chamber and a dilute caustic soda solution to the cathode chamber. In an electrolytic cell in which an elastic cushion material or the like functions as an electrode, this state is maintained for a long time due to the high strength and toughness of the elastic cushion material or the like, so that the ion exchange membrane or the like is not mechanically damaged. Caustic soda or the like can be manufactured with high efficiency without excessive deformation and insufficient power supply.
　以下、実施例を用いて本発明をより詳細に説明する。
＜実施例１＞
　陽極としてペルメレック電極株式会社製の寸法安定性電極を採用し、陰極としてニッケル製マイクロメッシュ基材の活性陰極を採用した。陽極および陰極の反応面サイズはそれぞれ幅１１０ｍｍ、高さ１４００ｍｍとした。イオン交換膜は旭硝子株式会社製のＦｌｅｍｉｏｎＦ－８０２０を用いた。 Hereinafter, the present invention will be described in more detail with reference to examples.
<Example 1>
A dimensional stability electrode manufactured by Permerek Electrode Co., Ltd. was adopted as the anode, and an active cathode of nickel micromesh substrate was adopted as the cathode. The reaction surface sizes of the anode and the cathode were 110 mm in width and 1400 mm in height, respectively. As the ion exchange membrane, Flemion F-8020 manufactured by Asahi Glass Co., Ltd. was used.
　また、線径が０．１７ｍｍで、引張強度６２０～６８０Ｎ／ｍ２のニッケル線（ＮＷ２２０１）をロール加工により約０．５ｍｍ幅のコイル線を作製した。得られたコイル線を用いて、反力の小さい金属製コイル体としてコイルの巻き径が６．５ｍｍにした金属製コイル、および相対的に反力の大きい金属製コイル体としてコイルの巻き径４．５ｍｍにした金属製コイル体を作製した。得られた金属製コイル体の反力の比は０．７であった。この金属製コイル体を、直径１．２ｍｍのニッケル丸棒製枠（耐食性フレーム）に巻回して直方体状に形状を整え、概略サイズが厚さ１０ｍｍ×幅１１０ｍｍ×長さ３５０ｍｍの弾性クッション材を作製した。この弾性クッション材のコイル線密度は約３ｇ／ｄｍ２であった。陰極集電体としてニッケル製エキスパンデッドメタルを用いた。 Further, a coil wire having a width of about 0.5 mm was produced by rolling a nickel wire (NW2201) having a wire diameter of 0.17 mm and a tensile strength of 620 to 680 N / m 2 . Using the obtained coil wire, a metal coil having a coil winding diameter of 6.5 mm as a metal coil body having a small reaction force, and a coil winding diameter 4 as a metal coil body having a relatively large reaction force. A metal coil body having a thickness of 5 mm was produced. The ratio of reaction forces of the obtained metal coil body was 0.7. This metal coil body is wound around a nickel round bar frame (corrosion-resistant frame) with a diameter of 1.2 mm to adjust the shape to a rectangular parallelepiped shape, and an elastic cushion material having an approximate size of 10 mm thickness × 110 mm width × 350 mm length is formed. Produced. The coil linear density of this elastic cushion material was about 3 g / dm 2 . Nickel expanded metal was used as the cathode current collector.
　得られた弾性クッション材を、陰極集電体と水素発生陰極間に弾性クッション材に弾性が生じるように挿入し、電流密度４ｋＡ／ｍ２で３０日間電解を行った。 The obtained elastic cushion material was inserted between the cathode current collector and the hydrogen generating cathode so that the elastic cushion material was elastic, and electrolysis was performed at a current density of 4 kA / m 2 for 30 days.
＜実施例２＞
　巻き径が大きい金属製コイル体と、巻き径が小さい金属製コイル体とを耐食性フレームに巻き付けずに陰極集電体と水素発生陰極間に挿入したこと以外は実施例１と同様の条件で電解を行った。なお、上記金属製コイル体は図２（ａ）に示す状態とした。 <Example 2>
Electrolysis was carried out under the same conditions as in Example 1, except that a metal coil body having a large winding diameter and a metal coil body having a small winding diameter were inserted between the cathode current collector and the hydrogen generating cathode without being wound around the corrosion-resistant frame. Went. In addition, the said metal coil body was made into the state shown to Fig.2 (a).
＜実施例３＞
　実施例１で作製した弾性クッション材を陰極とし、ヘキサクロロ白金酸水溶液（２０ｇ／リットル）を含浸したチタン棒が入ったプラスチックブラシを陽極とした筆めっき法（電流０．５Ａ、１ｄｍ２当たりのめっき時間５分）により弾性クッション材を構成する各金属製コイル体のイオン交換膜側表面に白金めっきを行った。得られた白金めっき付き弾性クッション材自体を陰極として、陰極集電体とイオン交換膜の間に挿入した以外は実施例１と同様の条件で電解を行った。 <Example 3>
Brush plating method (plating per current 0.5 A, 1 dm 2 ) using the elastic cushion material prepared in Example 1 as a cathode and a plastic brush containing a titanium rod impregnated with an aqueous hexachloroplatinic acid solution (20 g / liter) as an anode Platinum plating was performed on the ion exchange membrane side surface of each metal coil body constituting the elastic cushion material in 5 minutes. The obtained platinum-plated elastic cushion material itself was used as a cathode, and electrolysis was performed under the same conditions as in Example 1 except that it was inserted between the cathode current collector and the ion exchange membrane.
＜比較例１＞
　巻き径の小さい金属製コイル体のみを耐食性フレームに巻き付けて弾性クッション材を作製し、この弾性クッション材を陰極集電体と水素発生陰極との間に設置したこと以外は実施例１と同様の条件で電解を行った。 <Comparative Example 1>
An elastic cushion material is produced by winding only a metal coil body having a small winding diameter around a corrosion-resistant frame, and this elastic cushion material is installed between the cathode current collector and the hydrogen generating cathode. Electrolysis was performed under conditions.
＜結果＞
　実施例１～３のイオン交換膜電解槽は、運転期間中、電解条件が安定し、高濃度の苛性ソーダが得られた。また、イオン交換膜にはブリスターの発生は見られなかった。一方、比較例１のイオン交換膜電解槽では、運転期間中に電解性能の低下がみられた。 <Result>
In the ion exchange membrane electrolytic cells of Examples 1 to 3, the electrolysis conditions were stable during the operation period, and high-concentration caustic soda was obtained. In addition, no blisters were observed in the ion exchange membrane. On the other hand, in the ion exchange membrane electrolytic cell of Comparative Example 1, a decrease in electrolytic performance was observed during the operation period.
１０　単極式イオン交換膜電解槽の陰極ユニット
１１　導電棒
１２　通電部材
１３　陰極集電体
１４　水素発生陰極
１５　金属製弾性体
１５ａ、１５ｂ　金属製コイル体
２０　複極式イオン交換膜電解槽ユニット
２１　陽極隔壁
２２　陰極隔壁
２３　陽極保持部材
２４　帯状接合体
２５　陽極液循環通路
２６　陰極保持部材
２７　帯状接合部
２８　陰極液循環通路
２９　凸状部
３０　陽極
３１　水素発生陰極
３２　メッシュ
１０１　長方形枠
１０２　補強杆
１０３　耐食性フレーム
１０４　弾性クッション材
  DESCRIPTION OF SYMBOLS 10 Cathode unit 11 of a unipolar ion exchange membrane electrolytic cell 11 Conductive rod 12 Current supply member 13 Cathode current collector 14 Hydrogen generating cathode 15 Metal elastic body 15a, 15b Metal coil body 20 Bipolar ion exchange membrane electrolytic cell unit 21 Anode partition wall 22 Cathode partition wall 23 Anode holding member 24 Band-shaped joined body 25 Anode solution circulation passage 26 Cathode holding member 27 Band-shaped joint portion 28 Catholyte circulation passage 29 Convex portion 30 Anode 31 Hydrogen generating cathode 32 Mesh 101 Rectangular frame 102 Reinforcement rod 103 Corrosion resistant frame 104 Elastic cushion material

Claims (6)

  1. 　イオン交換膜により陽極を収容する陽極室と陰極を収容する陰極室とに区画され、前記陽極室および前記陰極室のうち少なくとも一方に金属製弾性体が配置されてなるイオン交換膜電解槽において、
    　前記金属製弾性体として、少なくとも２種の金属製弾性体からなることを特徴とするイオン交換膜電解槽。     In an ion exchange membrane electrolytic cell that is partitioned into an anode chamber containing an anode by an ion exchange membrane and a cathode chamber containing a cathode, and a metal elastic body is disposed in at least one of the anode chamber and the cathode chamber,
    An ion exchange membrane electrolytic cell comprising at least two kinds of metal elastic bodies as the metal elastic bodies.
  2. 　前記金属製弾性体が、陰極と陰極集電体間および陽極と陽極集電体間の少なくとも一方に配置されてなり、前記金属製弾性体の反力により電極と前記イオン交換膜とが密着している請求項１記載のイオン交換膜電解槽。 The metal elastic body is disposed between at least one of the cathode and the cathode current collector and between the anode and the anode current collector, and the electrode and the ion exchange membrane are brought into close contact by the reaction force of the metal elastic body. The ion exchange membrane electrolytic cell according to claim 1.
  3. 　前記金属製弾性体が、陰極と陰極隔壁間および陽極と陽極隔壁間の少なくとも一方に配置されてなり、前記金属製弾性体の反力により電極と前記イオン交換膜とが密着している請求項１記載のイオン交換膜電解槽。 The metal elastic body is disposed between at least one of a cathode and a cathode partition and between an anode and an anode partition, and the electrode and the ion exchange membrane are in close contact with each other by a reaction force of the metal elastic body. 2. The ion exchange membrane electrolytic cell according to 1.
  4. 　前記金属製弾性体が耐食性フレームに巻回されてなる弾性クッション材である請求項１記載のイオン交換膜電解槽。 The ion exchange membrane electrolytic cell according to claim 1, wherein the metal elastic body is an elastic cushion material formed by winding the metal elastic body around a corrosion-resistant frame.
  5. 　前記金属製弾性体が、金属製コイル体である請求項１記載のイオン交換膜電解槽。 The ion exchange membrane electrolytic cell according to claim 1, wherein the metal elastic body is a metal coil body.
  6. 　前記少なくとも２種の金属製弾性体のうち少なくとも１種の金属製弾性体に、電極触媒が担持されている請求項１記載のイオン交換膜電解槽。
          The ion exchange membrane electrolytic cell according to claim 1, wherein an electrode catalyst is supported on at least one metal elastic body among the at least two metal elastic bodies.
PCT/JP2013/066052 2013-06-11 2013-06-11 Ion exchange membrane electrolytic cell WO2014199440A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2013/066052 WO2014199440A1 (en) 2013-06-11 2013-06-11 Ion exchange membrane electrolytic cell
CN201380047716.0A CN104718317A (en) 2013-06-11 2013-06-11 Ion exchange membrane electrolytic cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2013/066052 WO2014199440A1 (en) 2013-06-11 2013-06-11 Ion exchange membrane electrolytic cell

Publications (1)

Publication Number Publication Date
WO2014199440A1 true WO2014199440A1 (en) 2014-12-18

Family

ID=52021776

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/066052 WO2014199440A1 (en) 2013-06-11 2013-06-11 Ion exchange membrane electrolytic cell

Country Status (2)

Country Link
CN (1) CN104718317A (en)
WO (1) WO2014199440A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3641037A1 (en) * 2018-10-18 2020-04-22 Panasonic Intellectual Property Management Co., Ltd. Electrochemical hydrogen pump
CN111910205A (en) * 2020-09-23 2020-11-10 江阴市宏泽氯碱设备制造有限公司 Novel elastic structure membrane polar distance ion membrane electrolytic cell

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004300543A (en) * 2003-03-31 2004-10-28 Chlorine Eng Corp Ltd Electrode for electrolysis and ion-exchange membrane electrolytic cell using it
JP2004300547A (en) * 2003-03-31 2004-10-28 Chlorine Eng Corp Ltd Ion-exchange membrane electrolytic cell using hydrogen-generating cathode
JP2006322018A (en) * 2005-05-17 2006-11-30 Chlorine Eng Corp Ltd Ion exchange membrane type electrolytic cell
JP2009120882A (en) * 2007-11-13 2009-06-04 Tosoh Corp Electrolytic cell structural member and electrolytic cell using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004300543A (en) * 2003-03-31 2004-10-28 Chlorine Eng Corp Ltd Electrode for electrolysis and ion-exchange membrane electrolytic cell using it
JP2004300547A (en) * 2003-03-31 2004-10-28 Chlorine Eng Corp Ltd Ion-exchange membrane electrolytic cell using hydrogen-generating cathode
JP2006322018A (en) * 2005-05-17 2006-11-30 Chlorine Eng Corp Ltd Ion exchange membrane type electrolytic cell
JP2009120882A (en) * 2007-11-13 2009-06-04 Tosoh Corp Electrolytic cell structural member and electrolytic cell using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3641037A1 (en) * 2018-10-18 2020-04-22 Panasonic Intellectual Property Management Co., Ltd. Electrochemical hydrogen pump
CN111910205A (en) * 2020-09-23 2020-11-10 江阴市宏泽氯碱设备制造有限公司 Novel elastic structure membrane polar distance ion membrane electrolytic cell

Also Published As

Publication number Publication date
CN104718317A (en) 2015-06-17

Similar Documents

Publication Publication Date Title
JP4846869B1 (en) Cathode structure for electrolysis and electrolytic cell using the same
CN1537973B (en) Electrode for electrolysis and ion exchange membrane electrolytic cell
JP5945154B2 (en) Ion exchange membrane electrolytic cell
JP5970250B2 (en) Elastic cushion material for ion exchange membrane electrolytic cell
JP3860132B2 (en) Ion exchange membrane electrolyzer using hydrogen generating cathode
JP4246530B2 (en) Electrode for electrolysis and ion exchange membrane electrolytic cell using the same
WO2014199440A1 (en) Ion exchange membrane electrolytic cell
JP5493787B2 (en) Ion exchange membrane electrolytic cell
JP2013216922A (en) Ion exchange membrane electrolytic cell
JP2014221930A (en) Ion exchange membrane electrolytic cell
JP3869383B2 (en) Ion-exchange membrane electrolytic cell using liquid-permeable gas diffusion cathode
TW202124779A (en) Elastic mat for alkaline water electrolysis vessel
JP5653209B2 (en) Ion exchange membrane electrolytic cell
JP6318678B2 (en) Ion exchange membrane electrolytic cell
WO2016067389A1 (en) Ion-exchange membrane electrolytic cell
JP2014214350A (en) Ion exchange membrane electrolytic bath

Legal Events

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

Ref document number: 13886875

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13886875

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP