WO2010122785A1 - Ion-exchange membrane electrolyzer - Google Patents

Ion-exchange membrane electrolyzer Download PDF

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Publication number
WO2010122785A1
WO2010122785A1 PCT/JP2010/002854 JP2010002854W WO2010122785A1 WO 2010122785 A1 WO2010122785 A1 WO 2010122785A1 JP 2010002854 W JP2010002854 W JP 2010002854W WO 2010122785 A1 WO2010122785 A1 WO 2010122785A1
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Prior art keywords
electrode
exchange membrane
flat spring
electrolytic cell
ion exchange
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PCT/JP2010/002854
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French (fr)
Japanese (ja)
Inventor
隆 吉次
貞廣文夫
阿部祐紀
児玉義之
浅海清人
井口幸徳
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東ソー株式会社
クロリンエンジニアズ株式会社
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Publication of WO2010122785A1 publication Critical patent/WO2010122785A1/en

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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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type

Definitions

  • the present invention relates to an ion exchange membrane method electrolytic cell used for electrolysis of saline solution.
  • the power consumption required for electrolysis using an ion exchange membrane electrolytic cell depends on various factors, but the electrode spacing between the anode and the cathode greatly affects the cell voltage as well as the characteristics of the electrode and ion exchange membrane. Effect. In view of this, it has been practiced to reduce the energy consumption required for electrolysis by reducing the electrode interval and decreasing the electrolytic cell voltage.
  • a large electrolytic cell having an electrode area of several square meters is used. In such a large electrolytic cell, an anode, an ion exchange membrane, and a cathode are used.
  • both electrodes are brought into close contact with the ion exchange membrane to reduce the electrode interval. Therefore, it was difficult to maintain the predetermined value.
  • an electrolytic cell in which a spring member is used as at least one of the constituent members of the anode and the cathode and the electrode interval can be adjusted.
  • an ion exchange membrane electrolytic cell in which the distance between the electrodes is set to a predetermined size by holding the electrodes using a material having a spring property, even if a pressure abnormality occurs in the electrode chamber at the start of operation, etc.
  • an ion exchange membrane method electrolytic cell provided with energizing means in which a spring-like member holding an electrode does not lose its properties as a spring material due to plastic deformation (see, for example, Patent Document 1).
  • Patent Document 2 A zero-gap electrolytic cell in which a cathode is brought into contact with an ion exchange membrane by using a mat-like material overlaid with a metal wire fabric as an elastic body in place of the spring member has been proposed (for example, Patent Document 2). And Patent Document 3).
  • the present invention is an ion exchange membrane electrolytic cell in which an electrode is held by forming an electrical connection to one electrode by a spring-like member in order to reduce the electrode interval, and the electrode interval with the counter electrode is reduced,
  • An object of the present invention is to provide an ion exchange membrane electrolytic cell capable of stable operation at a lower electrolytic cell voltage.
  • an electrode having a small thickness or a small wire diameter is held by a spring-like holding body, and the electrode surface is also pressed by the spring-like member when pressed from the back side with the counter electrode. It is an object of the present invention to provide an ion-exchange membrane electrolytic cell capable of stable operation without causing unevenness in the surface.
  • a flat spring-like body formed integrally with a flat spring-like body holding member provided in the electrode chamber and in contact with the flat-plate spring-like body extending in the electrode direction and in contact with the electrode is energized.
  • a flat spring shape with a bent portion at a position extending on the same plane as the flat spring holding member from the base of the spring holding member, and a portion extending in the electrode direction contacting the tip side.
  • the electrode that contacts the body has a step width of 0.1 mm to 0.5 mm, a minor axis of 0.5 mm to 3.0 mm, a major axis of 1.0 mm to 6.0 mm, and a plate thickness of 0.1 mm to 0 mm.
  • An expanded metal electrode that is 5 mm or less is mounted, and the area represented by the product of the mesh length of the expanded metal electrode in the short direction and the length of the mesh in the long direction is defined as a flat spring-like body and an electrode.
  • the value divided by the number of contact parts with the contact part is 0 01cm 2 ⁇ 10cm 2, an ion exchange membrane method electrolysis bath the reaction force was 0.1 N ⁇ 4.0 N per electrode contact portion 1 point.
  • the area of one hole of the expanded metal electrode is approximated by (minor axis ⁇ major axis) / 2, and is defined as 0.5 to 18 mm 2 according to the minor axis and the major axis.
  • the area of one hole of the electrode is An area within the range of 1.0 to 10 mm 2 is preferred.
  • the aperture ratio of the electrode is preferably 45 to 60%.
  • the flat spring-like body contacts the electrode at a position extending on the same plane as the flat-plate spring-like body holding member provided at a distance from the coupling portion of the flat spring-like body holding member.
  • the said ion exchange membrane method electrolytic cell which has a part extended to the opposite side to the side, and also has a part extended in the said electrode direction which contacts the front end side.
  • the ion exchange membrane method electrolytic cell has a surface pressure of 10 Pa to 10 kPa on the ion exchange membrane of the electrode before the electrolytic solution is filled in the ion exchange membrane method electrolytic cell.
  • the flat spring-like body has the above-mentioned ion in which a concave portion in a direction perpendicular to the length direction of the flat spring-like body is formed between the base portion and the bent portion.
  • This is an exchange membrane method electrolytic cell.
  • the plate spring-like body holding member is the ion exchange membrane method electrolytic cell which is joined to the electrode chamber partition wall of the bipolar electrolytic cell to form a fixed and conductive connection.
  • the ion-exchange membrane electrolytic cell of the present invention is an expanded metal electrode that is held by a plurality of spring-like bodies from the side opposite to the side facing the counter electrode, and an electrical connection is formed by the spring-like bodies
  • the number of contact portions with the electrode by the spring-like body, and the pressure at each contact portion are of a specific size.
  • FIG. 1 is a view for explaining an embodiment of the ion exchange membrane electrolytic cell of the present invention.
  • FIG. 1A is a diagram for explaining a cross section cut along a plane perpendicular to an anode and a cathode of an ion exchange membrane method electrolytic cell in which a plurality of electrolytic cell units are stacked
  • FIG. 1B is a view from the cathode side of the electrolytic cell unit.
  • FIG. 1C is a cross-sectional view taken along line AA ′ in FIG. 1B.
  • FIG. 2 is a diagram for explaining an example of a flat spring-like body of the present invention.
  • FIG. 1A is a diagram for explaining a cross section cut along a plane perpendicular to an anode and a cathode of an ion exchange membrane method electrolytic cell in which a plurality of electrolytic cell units are stacked
  • FIG. 1B is a view from the cathode side of the electrolytic cell unit.
  • FIG. 2A is a perspective view of a flat spring-like body holding member to which a flat spring-like body is attached
  • FIG. 2B is a diagram illustrating a side surface of the flat spring-like body.
  • FIG. 3 is a diagram for explaining another example of the flat spring-like body of the present invention.
  • FIG. 3A is a perspective view of a flat spring-like body holding member to which a flat spring-like body is attached
  • FIG. 3B is a diagram illustrating a side surface of the flat spring-like body.
  • a flat plate spring-like body formed integrally with a flat spring-like body holding member provided in the electrode chamber and in contact with the flat plate spring-like body extending in the electrode direction is energized.
  • a portion extending on the same plane as the flat spring-shaped member holding member from the base of the flat-shaped member holding member has a portion extending to the opposite side of the electrode with which the flat spring-shaped member is in contact, and further on the tip side in the electrode direction
  • the electrode is in contact with the electrode and is in contact with the plate.
  • the electrode that contacts the flat spring-like body is highly stable and stable by an ion-exchange membrane electrolytic cell that uses an electrode with a specific shape and size. An ion exchange membrane electrolytic cell capable of being operated is provided.
  • ion exchange membrane electrolytic cells are required to have high rigidity, and therefore, each component member generally requires high rigidity.
  • the present invention dares to maintain an electrode interval stably even when an expanded metal electrode having a small thickness, step size, etc., and a small rigidity is used.
  • Ion-exchange membrane electrolysis that enables stable electrolysis at a low electrolysis voltage without being affected by the flatness around the contact area with the body or the influence of bubbles generated by electrolysis or the flow of electrolyte It has been found that the tank can be provided.
  • FIG. 1 is a diagram illustrating an embodiment of an ion exchange membrane electrolytic cell according to the present invention
  • FIG. 1A is a diagram illustrating a cross section of an ion exchange membrane electrolytic cell in which a plurality of electrolytic cell units are stacked.
  • FIG. 1B is a plan view seen from the cathode side of the electrolytic cell unit
  • FIG. 1C is a cross-sectional view taken along line AA ′ in FIG. 1B.
  • the ion exchange membrane method electrolytic cell 1 is assembled by laminating a predetermined number of bipolar electrolytic cell units 2 via an ion exchange membrane 3.
  • an anode 5 is disposed at a distance from the anode chamber partition wall 4, and an anode chamber 6 is formed.
  • a cathode 8 is disposed at a distance from the cathode chamber partition wall 7, and a cathode chamber 9 is formed between the cathode chamber partition wall 7 and the ion exchange membrane 3.
  • an anode chamber side gas / liquid separation means 40 and a cathode chamber side gas / liquid separation means 41 are provided above the anode chamber 6 and the cathode chamber 9, respectively.
  • an anolyte supply port 31 is attached to the anode chamber 6 of the electrolytic cell unit 2, and the anolyte and gas having a reduced concentration are discharged to the anode chamber side gas-liquid separation means 40 by overflow, that is, overflow.
  • An anolyte discharge port 32 is attached.
  • the cathode chamber 9 of the electrolytic cell unit 2 is provided with a catholyte supply port 33, and the cathode chamber-side gas-liquid separation means 41 discharges the catholyte and gas having a reduced concentration by overflow, that is, overflow.
  • a catholyte outlet 34 is attached.
  • the gas-liquid mixed fluid containing the gas generated at the anode undergoes gas-liquid separation at the upper portion of the anode chamber, and a part of the electrolytic solution flows out from the anolyte discharge port 32. Then, a part thereof descends in the anode chamber and is mixed with the anolyte supplied from the anolyte supply port 31 provided in the electrolytic cell and ejected into the anode chamber, and electrolysis is performed in the anode.
  • the anolyte supply port and the anolyte discharge port are arranged on the same side, but the supply port and the discharge port may be arranged to face each other.
  • the liquid supply port and the catholyte supply port may be arranged on the same side.
  • the flat plate spring-like body holding member 11 is attached to the negative electrode chamber partition wall 7, and the flat plate spring-like body holding member 11 is attached to the flat plate spring-like body holding member 11. 12 are connected.
  • the base portions 13 of the flat spring-like body holding member 11 and the flat spring-like body 12 are formed with a line symmetry symmetrically with respect to a straight line in the height direction of the electrolytic cell, and extend from the pair of root portions 13a and 13b.
  • the flat spring-like body 12 extends in directions opposite to each other, and the flat spring-like body 12 has a bent portion 14 at a position spaced from the bases 13a, 13b of the flat spring-like body holding member 11, and The tip has an electrode contact portion 15 that contacts the electrode to form a conductive connection.
  • the bent portion 14 is a portion where the flat spring-like body is bent when a force in the flat spring-like body holding member surface direction is applied to the electrode contact portion 15 of the flat spring-like body 12.
  • the flat spring-like body shown in FIG. 1 when a force does not act on the flat spring-like body, it is formed in a portion extending in the horizontal direction from the coupling portion with the flat spring-like body holding member to form an electrode contact portion.
  • the tip portion extends from the rising portion 16 in the vertical direction.
  • the bent portion 14 is formed at a portion spaced from the root of the flat spring-like body holding member of the flat spring-like body 12, the flat spring-like body 12 is repeatedly pressed toward the flat spring-like body holding member 11 side. Even when pressed by an abnormal pressure that occurs rarely at the start of operation or the like, stress concentration on the root portion 13 to the flat spring-like body holding member of the flat spring-like body can be avoided. It is possible to prevent the joint from undergoing plastic deformation that is difficult to recover due to the concentration of stress on the surface.
  • the flat plate spring-like body 12 is formed with a concave portion 17 between the base portion 13 and the bent portion 14 and having a concave surface on the side in contact with the electrode surface, which is perpendicular to the length direction of the flat plate spring-like body. ing.
  • the concave part 17 is formed in the base part 13 of the flat spring-like body, a flat spring-like body having a great effect of preventing plastic deformation due to stress concentration on the base part 13 can be obtained.
  • the electrode contact portion 15 provided at the distal end portion of the flat spring-like body 12 is provided with an electrode contact portion 15 that is bent into an obtuse or curved shape and comes into contact with the electrode, and the electrode contact portion 15 serves as the cathode 8. Is energized in contact with.
  • the flat spring-like body 12 extends in a direction facing each other with an interval symmetrical to a straight line in the height direction of the electrolytic cell, and an electrode contact portion 15 provided at the tip thereof is in contact with the cathode 8.
  • the flat spring-like body 12 displaces the cathode 8 and the cathode surface in a direction perpendicular to the repulsive force and does not move the cathode 8 in parallel with the cathode surface, so that the ion exchange membrane surface is damaged. It is possible to adjust to a predetermined position without causing the above problem.
  • the flat spring-like body holding member 11 attached to the cathode chamber partition wall may be one member having the same size as the cathode surface, or a predetermined number of members may be arranged. Since the opening 25 is formed in the flat spring-shaped body holding member 11 when the flat plate spring-shaped body 11 is produced and cut and bent, the air bubbles rising along the electrode surface are removed.
  • the contained catholyte is subjected to electrolysis in the electrolytic cell together with the catholyte supplied through the catholyte supply port 33 through the opening 25 after the gas is separated at the upper part and descending the space on the cathode chamber partition wall 7 side. And discharged from the catholyte discharge port 34.
  • anode chamber partition 4 and the anode 5 are joined to the anode chamber partition 4 at the anode chamber partition junction 30. Both are joined by a continuous weld, a large number of spot-like welds, etc. to form a mechanical holding and conductive connection.
  • the anode chamber partition and the cathode chamber partition have a shape having irregularities such as a truss type, so that the rigidity of the electrode chamber made of a thin plate of titanium, nickel, etc. Can be increased.
  • the step contact width is 0.1 mm or more and 0.5 mm or less
  • the minor axis is 0.5 mm or more and 3.0 mm or less for the electrode in contact with the flat spring-like body.
  • An expanded metal electrode having a major axis of 1.0 mm to 6.0 mm and a plate thickness of 0.1 mm to 0.5 mm is mounted.
  • the minor axis is 0.5 mm or less
  • the major axis is 1.0 mm or less
  • the plate thickness is 0.1 mm or less
  • the rigidity of the electrode is reduced, and the flow of the electrolyte and the pressure of bubble generation This is not preferable because the retention of the affected shape deteriorates.
  • the step width is 0.5 mm
  • the minor axis is 3.0 mm
  • the major axis is 6.0 mm
  • the plate thickness exceeds 0.5 mm, it becomes difficult to precisely adjust the inter-electrode spacing by the spring-like holder.
  • the number of electrodes and the number of contact portions is increased to reduce the reaction force per flat spring-like body. It is preferable.
  • the reaction force is preferably 0.1 N or more and 4.0 N or less per location. When it is smaller than 0.1N, the conductive contact between the electrode and the flat spring-like body deteriorates, the electrolytic cell voltage increases, and stable operation becomes difficult. On the other hand, if it exceeds 4.0 N, the ion exchange membrane may be damaged when it comes into contact with the electrode and the ion exchange membrane.
  • the clamping pressure of the cathode, the ion exchange membrane and the anode is the electrode pressed by the flat spring-shaped body before filling the electrolytic solution into the ion exchange membrane method electrolytic cell.
  • the surface pressure on the ion exchange membrane is preferably 10 Pa to 1.5 kPa, more preferably 300 Pa to 1.5 kPa.
  • FIG. 2 is a diagram for explaining an example of a flat spring-like body of the present invention.
  • FIG. 2A is a perspective view of a flat spring-like body holding member to which a flat spring-like body is attached
  • FIG. 2B is a diagram illustrating a side surface of the flat spring-like body.
  • the plate spring-like body is in contact with the plate spring-like body at a position extending on the same plane as the plate spring-like body holding member provided at a distance from the coupling portion of the plate spring-like body holding member.
  • FIG. 3 is a diagram for explaining another example of the flat spring-like body of the present invention.
  • FIG. 3A is a perspective view of a flat spring-like body holding member to which a flat spring-like body is attached
  • FIG. 3B is a diagram illustrating a side surface of the flat spring-like body.
  • 3 is different from the ion exchange membrane electrolytic cell shown in FIG. 2 in that the length of the plate spring-like body in which the electrode surface side of the base portion 13 of the plate-spring-like body holding member 11 of the plate spring-like body 12 is electrically connected is depressed.
  • a concave portion 17 is formed in a direction perpendicular to the vertical direction. This is preferable because the compressed compression pressure can be absorbed more efficiently.
  • the number of electrode contact portions on the cathode is increased, and the reaction force per flat spring-like body is 0.1 N or more.
  • the reaction force is reduced when the compression pressure to the cathode suddenly increases, and the ion exchange membrane is damaged due to contact of the cathode with the ion exchange membrane, etc. The effect to prevent becomes remarkable.
  • the present invention will be described with reference to examples.
  • Example 1 A nickel expanded metal having a step width of 0.16 mm, a minor axis of 1.0 mm, a major axis of 2.0 mm and a plate thickness of 0.15 mm was cut into a length of 530 mm in the minor axis direction and a length of 400 mm in the major axis direction.
  • the short axis direction of the expanded metal was the vertical axis
  • the long axis direction was the horizontal axis.
  • the expanded metal was etched with 10% by mass hydrochloric acid at 50 ° C. for 15 minutes, washed with water and dried.
  • a platinum content of the dinitrodiammine platinum nitrate solution (manufactured by Tanaka Kikinzoku, platinum concentration: 4.5 mass%, solvent: 8 wt% nitric acid solution), nickel nitrate hexahydrate and water in a molar ratio of 0. 5.
  • a coating solution having a total concentration of platinum and nickel in the mixed solution of 5% by mass in terms of metal was prepared.
  • this coating solution was applied to the entire surface of the expanded metal using a brush, dried in a hot air dryer at 80 ° C. for 15 minutes, and then using a box-type electric furnace at 500 ° C. for 15 minutes under air circulation.
  • a thermal decomposition coating was formed by heat treatment. This series of operations was repeated 5 times, and the electrode coated with the platinum-nickel alloy was used as the cathode.
  • the area of one hole of this cathode is 1.0 mm 2 and the aperture ratio is about 51%.
  • An ion exchange membrane method electrolytic cell was assembled which was conductively connected to the cathode by a spring-like body. At this time, the electrolytic cell was tightened so that the surface pressure on the ion exchange membrane was 1.02 kPa.
  • the flat spring-like body has a total length of 100 mm, a width of 10 mm at the coupling portion 9, 5 mm at the bent portion 10, a length of 20 mm at the rising portion 11, and a length of 6 mm at the electrode contact portion, and is made of nickel.
  • the number of electrode contact portions was 316 points, and the cathode area per point was 6.7 cm 2 . At this time, the compressive stress was 0.67 N per point.
  • the pressure in the cathode chamber is set higher by 5 kPa than the pressure in the anode chamber, the ion exchange membrane is brought into close contact with the anode surface, the current density is 5 kA / m 2 , and the anode chamber outlet brine concentration:
  • the sodium chloride aqueous solution concentration was adjusted to 200 to 210 g / L and the cathode chamber outlet sodium hydroxide aqueous solution concentration range was 31 to 33% by mass.
  • the electrolytic cell voltage was measured and recorded at 1 second intervals over 5 minutes, and the voltage was stable at around 2.95V.
  • Comparative Example 1 As an expanded metal electrode, an expanded metal made of nickel having a step width of 1.5 mm, a short diameter: 6 mm, a long diameter: 15 mm, and a plate thickness: 1.5 mm is formed in the short diameter direction in the same manner as in Example 1. It was cut into a length of 530 mm and a length of 400 mm in the major axis direction. Also in this comparative example, the short diameter direction of the expanded metal was set to be vertical, and the long diameter direction was set to be horizontal. The area of one hole of this expanded metal electrode is 45 mm 2 and the aperture ratio is about 42%.
  • This expanded metal substrate was etched with 10% by mass hydrochloric acid at a temperature of 50 ° C. for 15 minutes, washed with water and dried.
  • a platinum content of the dinitrodiammine platinum nitrate solution (manufactured by Tanaka Kikinzoku, platinum concentration: 4.5% by weight, solvent: 8% by weight nitric acid solution), nickel nitrate hexahydrate and water in a molar ratio of 0. 5.
  • a coating solution having a total concentration of platinum and nickel in the mixed solution of 5% by mass in terms of metal was prepared.
  • this coating solution is applied to the fine mesh electrode by using a brush, dried at 80 ° C. for 15 minutes in a hot air dryer, and then heat-treated at 500 ° C. for 15 minutes under air circulation using a box-type electric furnace. Then, a pyrolytic film was formed.
  • a comparative example ion exchange membrane electrolytic cell was assembled in the same manner as in Example 1. The tightening force at this time was 196 Pa in terms of the surface pressure of the cation exchange membrane.
  • the cathode has a total length of 100 mm, a bent portion at the center, a width of 20 mm at the portion in contact with the electrode and a width of 25 mm at the other portion, It was energized while being held by a nickel spring having a thickness of 0.9 mm.
  • the springs are arranged at intervals of 90 mm in the vertical direction and at intervals of 250 mm in the horizontal direction.
  • the number of locations where the tip and the electrode are in contact is 10 points, and the cathode area per contact point is 212 cm 2.
  • the reaction force at that time was 4.2 N per location.
  • the ion exchange membrane method electrolytic cell of the comparative example was set to 5 kPa higher than the pressure in the anode chamber, and the ion exchange membrane was brought into close contact with the anode surface in the same manner as in Example 1, and the current density was 6 kA / m 2.
  • the electrolytic cell voltage was measured and recorded at intervals of 1 second over 5 minutes, the voltage changed in the vicinity of 3.04 V, which was 0.09 V higher than the electrolytic cell of the example.
  • the ion exchange membrane method electrolytic cell of the present invention has a great effect of reducing the electrolysis voltage, and in the case of a salt water ion exchange membrane method electrolytic cell, the power intensity can be greatly reduced. This contributes to a decrease, and is extremely useful for an ion exchange membrane method electrolytic cell typified by a salt water ion exchange membrane method electrolytic cell.

Abstract

An ion-exchange membrane electrolyzer contacts, at an electrode contact portion, with a flat plate spring-like body extending in an electrode direction and integrally formed with a flat plate spring-like body holding member provided in an electrode chamber, and is electrically conducted to the flat plate spring-like body. The flat plate spring-like body has, at a position extending in the same plane as the flat plate spring-like body holding member at a distance from the joint thereof, a portion extending on the opposite side to an electrode with which the flat plate spring-like body contacts and also has a portion extending in the direction of an electrode contacting an end side. The electrode with which the flat plate spring-like body contacts is attached with an expanded metal electrode having a step size of 0.1 mm or more and 0.5 mm or less, a minor axis of 0.5 mm or more and 3.0 mm or less, a major axis of 1.0 mm or more and 6.0 mm or less, and a sheet thickness of 0.1 mm or more and 0.5 mm or less. A value obtained by dividing an area given by the product of lengths in short and long directions of a mesh of the expanded metal electrode by the number of contact portions between the flat plate spring-like body and the electrode contact portion is 0.01 to 10 cm2. A reaction force per electrode contact portion is 0.1 to 4.0 N.

Description

イオン交換膜法電解槽Ion exchange membrane electrolytic cell
　本発明は、食塩水の電気分解等に使用されるイオン交換膜法電解槽に関するものである。 The present invention relates to an ion exchange membrane method electrolytic cell used for electrolysis of saline solution.
　イオン交換膜法電解槽による電気分解に要する消費電力は、各種の要因によって左右されるが、電極、イオン交換膜等の特性とともに、陽極と陰極との間の電極間隔が電解槽電圧に大きく影響を及ぼす。そこで、電極間隔を小さくして、電解槽電圧を低下させて電気分解に要するエネルギー消費量を低下させることが行なわれている。
　食塩水の電気分解のイオン交換膜法電解槽では、電極面積が数平方メートルにも達する大型の電解槽が用いられているが、このような大型の電解槽では、陽極、イオン交換膜、陰極の三者を間隔を小さくして実質的に密着状態としようとすると、陽極、陰極を剛性の部材によって電極室に結合した場合には、両電極をイオン交換膜に密着させて電極間隔を小さくして所定の値に保持することは困難であった。 The power consumption required for electrolysis using an ion exchange membrane electrolytic cell depends on various factors, but the electrode spacing between the anode and the cathode greatly affects the cell voltage as well as the characteristics of the electrode and ion exchange membrane. Effect. In view of this, it has been practiced to reduce the energy consumption required for electrolysis by reducing the electrode interval and decreasing the electrolytic cell voltage.
In the electrolytic cell of the ion exchange membrane method for electrolysis of salt water, a large electrolytic cell having an electrode area of several square meters is used. In such a large electrolytic cell, an anode, an ion exchange membrane, and a cathode are used. In order to make the three members substantially in close contact with each other by reducing the interval, when the anode and the cathode are coupled to the electrode chamber by a rigid member, both electrodes are brought into close contact with the ion exchange membrane to reduce the electrode interval. Therefore, it was difficult to maintain the predetermined value.
　そこで、陽極または陰極の少なくともいずれか一方の構成部材にばね性の部材を使用して電極間隔を調整可能とした電解槽が提案されている。ばね性を有する材料を使用して電極を保持することによって電極間隔を所定の大きさとしたイオン交換膜法電解槽では、運転開始時等において電極室に圧力の異常が生じた場合であっても電極を保持するばね性の部材が塑性変形を生じてばね材としての特性を失うことがない通電手段を備えたイオン交換膜法電解槽が提案されている（例えば、特許文献１参照）。 Therefore, an electrolytic cell has been proposed in which a spring member is used as at least one of the constituent members of the anode and the cathode and the electrode interval can be adjusted. In an ion exchange membrane electrolytic cell in which the distance between the electrodes is set to a predetermined size by holding the electrodes using a material having a spring property, even if a pressure abnormality occurs in the electrode chamber at the start of operation, etc. There has been proposed an ion exchange membrane method electrolytic cell provided with energizing means in which a spring-like member holding an electrode does not lose its properties as a spring material due to plastic deformation (see, for example, Patent Document 1).
　上記のばね性部材の代わりに、金属ワイヤーの織物を重ねたマット状物を弾性体として使用して陰極をイオン交換膜に接触させるゼロ・ギャップ電解槽が提案されている（例えば、特許文献２及び特許文献３）。 A zero-gap electrolytic cell in which a cathode is brought into contact with an ion exchange membrane by using a mat-like material overlaid with a metal wire fabric as an elastic body in place of the spring member has been proposed (for example, Patent Document 2). And Patent Document 3).
特開２００７－３２１２２９号公報JP 2007-32229 A 特開２０００－１７８７８２号公報JP 2000-178782 A 特開２００１－０６４７９２号公報JP 2001-064792 A
　本発明は、電極間隔を小さくするために一方の電極にばね状の部材によって電気的接続を形成して電極を保持し、対極との電極間隔を小さくしたイオン交換膜法電解槽であって、より低い電解槽電圧で安定した運転が可能なイオン交換膜法電解槽を提供することを課題とするものである。
　また、薄い板厚、あるいは小さな線径の部材で構成された剛性が小さな電極をばね状保持体によって保持するとともに、ばね状の部材で対極との背面側から押圧した際にも押圧によって電極面に部分的に凹凸を生じることがなく、安定した運転が可能なイオン交換膜法電解槽を提供することを課題とするものである。 The present invention is an ion exchange membrane electrolytic cell in which an electrode is held by forming an electrical connection to one electrode by a spring-like member in order to reduce the electrode interval, and the electrode interval with the counter electrode is reduced, An object of the present invention is to provide an ion exchange membrane electrolytic cell capable of stable operation at a lower electrolytic cell voltage.
In addition, an electrode having a small thickness or a small wire diameter is held by a spring-like holding body, and the electrode surface is also pressed by the spring-like member when pressed from the back side with the counter electrode. It is an object of the present invention to provide an ion-exchange membrane electrolytic cell capable of stable operation without causing unevenness in the surface.
　本発明は、電極室内に設けた平板ばね状体保持部材と一体に形成されて電極方向に延びた平板ばね状体と電極接触部において接触して通電されており、平板ばね状体は、平板ばね状体保持部材の付け根部から平板ばね状体保持部材と同一平面上を延びた位置に、屈曲部を有し、更に先端側に接触する電極方向へ延びた部分を有し、平板ばね状体が接触する電極には、刻み幅が０．１ｍｍ以上０．５ｍｍ以下、短径が０．５ｍｍ以上３．０ｍｍ以下、長径が１．０ｍｍ以上６．０ｍｍ以下、板厚０．１ｍｍ以上０．５ｍｍ以下であるエキスパンデッドメタル電極を装着し、前記エキスパンデッドメタル電極のメッシュの短目方向長さとメッシュの長目方向長さとの積で表される面積を、平板ばね状体と電極接触部との接触部の数で除した値が０．０１ｃｍ2～１０ｃｍ2、電極接触部１点当たりの反力を０．１Ｎ～４．０Ｎとしたイオン交換膜法電解槽である。
　このエキスパンデッドメタル電極の一つの空孔の面積は、（短径×長径）÷２で近似され、上記の短径及び長径によれば、０．５～１８ｍｍ2と規定される。
　しかしながら、電極の一つの空孔の面積が小さすぎると電極から発生する気体の抜けが悪くなり好ましくなく、大きすぎると電極自体の強度が低下して好ましくなく、電極の一つの空孔の面積は１．０～１０ｍｍ2の範囲内の面積が好ましい。
　また、電極の開口率は、余り小さいと電極から発生する気体の抜けが悪くなり好ましくなく、大きすぎると電極自体の強度が低下して好ましくなく、電極の開口率は４５～６０％が好ましい。 In the present invention, a flat spring-like body formed integrally with a flat spring-like body holding member provided in the electrode chamber and in contact with the flat-plate spring-like body extending in the electrode direction and in contact with the electrode is energized. A flat spring shape with a bent portion at a position extending on the same plane as the flat spring holding member from the base of the spring holding member, and a portion extending in the electrode direction contacting the tip side. The electrode that contacts the body has a step width of 0.1 mm to 0.5 mm, a minor axis of 0.5 mm to 3.0 mm, a major axis of 1.0 mm to 6.0 mm, and a plate thickness of 0.1 mm to 0 mm. An expanded metal electrode that is 5 mm or less is mounted, and the area represented by the product of the mesh length of the expanded metal electrode in the short direction and the length of the mesh in the long direction is defined as a flat spring-like body and an electrode. The value divided by the number of contact parts with the contact part is 0 01cm 2 ~ 10cm 2, an ion exchange membrane method electrolysis bath the reaction force was 0.1 N ~ 4.0 N per electrode contact portion 1 point.
The area of one hole of the expanded metal electrode is approximated by (minor axis × major axis) / 2, and is defined as 0.5 to 18 mm 2 according to the minor axis and the major axis.
However, if the area of one hole of the electrode is too small, the escape of gas generated from the electrode is deteriorated, and if it is too large, the strength of the electrode itself is lowered, which is not preferable. The area of one hole of the electrode is An area within the range of 1.0 to 10 mm 2 is preferred.
On the other hand, if the aperture ratio of the electrode is too small, the escape of gas generated from the electrode is worsened, and if it is too large, the strength of the electrode itself is lowered, which is undesirable. The aperture ratio of the electrode is preferably 45 to 60%.
　また、前記平板ばね状体は、前記平板ばね状体保持部材の結合部から距離を設けた前記平板ばね状体保持部材と同一平面上を延びた位置に前記平板ばね状体が接触する前記電極側とは反対側へ延びる部分を有し、更に先端側に接触する前記電極方向へ延びる部分を有した前記のイオン交換膜法電解槽である。
　また、イオン交換膜法電解槽への電解液の充填前の前記電極のイオン交換膜への面圧を１０Ｐａ～１０ｋＰａとしたイオン交換膜法電解槽である。
　また、平板ばね状体は、付け根部と屈曲部との間に、平板ばね状体が接触する電極面側が窪んだ平板ばね状体の長さ方向に垂直な方向の凹部を形成した前記のイオン交換膜法電解槽である。
　前記の平板ばね状体保持部材は、複極型電解槽の電極室隔壁と接合されて固定および導電接続を形成したものである前記のイオン交換膜法電解槽である。 Further, the flat spring-like body contacts the electrode at a position extending on the same plane as the flat-plate spring-like body holding member provided at a distance from the coupling portion of the flat spring-like body holding member. It is the said ion exchange membrane method electrolytic cell which has a part extended to the opposite side to the side, and also has a part extended in the said electrode direction which contacts the front end side.
Further, the ion exchange membrane method electrolytic cell has a surface pressure of 10 Pa to 10 kPa on the ion exchange membrane of the electrode before the electrolytic solution is filled in the ion exchange membrane method electrolytic cell.
Further, the flat spring-like body has the above-mentioned ion in which a concave portion in a direction perpendicular to the length direction of the flat spring-like body is formed between the base portion and the bent portion. This is an exchange membrane method electrolytic cell.
The plate spring-like body holding member is the ion exchange membrane method electrolytic cell which is joined to the electrode chamber partition wall of the bipolar electrolytic cell to form a fixed and conductive connection.
　本発明のイオン交換膜法電解槽は、電極の対極に面する側とは反対側から複数個のばね状体で保持され、前記ばね状体によって電気的接続が形成されるエキスパンデッドメタル電極として、板厚、刻み幅、短径、長径が小さく、十分な剛性がない部材を使用した場合に、前記ばね状体による電極との接触部の数、および各接触部における圧力を特定の大きさとすることによって、電気分解で発生する気泡や電解液の流動による悪影響を受けることなく電力原単位が小さな電解槽を提供することができるという効果を奏する。 The ion-exchange membrane electrolytic cell of the present invention is an expanded metal electrode that is held by a plurality of spring-like bodies from the side opposite to the side facing the counter electrode, and an electrical connection is formed by the spring-like bodies When using a member with a small plate thickness, step width, short diameter, long diameter, and insufficient rigidity, the number of contact portions with the electrode by the spring-like body, and the pressure at each contact portion are of a specific size. By doing so, there is an effect that it is possible to provide an electrolytic cell with a small electric power unit without being adversely affected by bubbles generated by electrolysis or the flow of the electrolytic solution.
図１は、本発明のイオン交換膜法電解槽の一実施例を説明する図である。図１Ａは、複数個の電解槽ユニットを積層したイオン交換膜法電解槽の陽極および陰極に垂直な面で切断した断面を説明する図であり、図１Ｂは、電解槽ユニットの陰極側から見た平面図であり、図１Ｃは、図１Ｂにおいて、Ａ－Ａ’線で切断した断面図である。FIG. 1 is a view for explaining an embodiment of the ion exchange membrane electrolytic cell of the present invention. FIG. 1A is a diagram for explaining a cross section cut along a plane perpendicular to an anode and a cathode of an ion exchange membrane method electrolytic cell in which a plurality of electrolytic cell units are stacked, and FIG. 1B is a view from the cathode side of the electrolytic cell unit. FIG. 1C is a cross-sectional view taken along line AA ′ in FIG. 1B. 図２は、本発明の平板状ばね状体の一例を説明する図である。図２Ａは、平板ばね状体を取り付けた平板ばね状体保持部材の斜視図であり、図２Ｂは、その平板ばね状体の側面を説明する図である。FIG. 2 is a diagram for explaining an example of a flat spring-like body of the present invention. FIG. 2A is a perspective view of a flat spring-like body holding member to which a flat spring-like body is attached, and FIG. 2B is a diagram illustrating a side surface of the flat spring-like body. 図３は、本発明の平板状ばね状体の他の例を説明する図である。図３Ａは、平板ばね状体を取り付けた平板ばね状体保持部材の斜視図であり、図３Ｂは、その平板ばね状体の側面を説明する図である。FIG. 3 is a diagram for explaining another example of the flat spring-like body of the present invention. FIG. 3A is a perspective view of a flat spring-like body holding member to which a flat spring-like body is attached, and FIG. 3B is a diagram illustrating a side surface of the flat spring-like body.
　以下、本発明の実施の形態について詳細に説明する。
　本発明は、電極室内に設けた平板ばね状体保持部材と一体に形成されて電極方向に延びる平板ばね状体と電極接触部において接触して通電されており、平板ばね状体は、平板ばね状体保持部材の付け根部から平板ばね状体保持部材と同一平面上を延びた位置に、平板ばね状体が接触する電極とは反対側へ延びた部分を有し、更に先端側に電極方向へ延びて電極との間で通電接触を行うものであって、平板ばね状体が接触する電極には、特定の形状および寸法を有する電極を用いたイオン交換膜法電解槽によって剛性が大きく安定した運転が可能なイオン交換膜法電解槽を提供するものである。 Hereinafter, embodiments of the present invention will be described in detail.
In the present invention, a flat plate spring-like body formed integrally with a flat spring-like body holding member provided in the electrode chamber and in contact with the flat plate spring-like body extending in the electrode direction is energized. A portion extending on the same plane as the flat spring-shaped member holding member from the base of the flat-shaped member holding member has a portion extending to the opposite side of the electrode with which the flat spring-shaped member is in contact, and further on the tip side in the electrode direction The electrode is in contact with the electrode and is in contact with the plate. The electrode that contacts the flat spring-like body is highly stable and stable by an ion-exchange membrane electrolytic cell that uses an electrode with a specific shape and size. An ion exchange membrane electrolytic cell capable of being operated is provided.
　大型のイオン交換膜法電解槽にあっては、大きな剛性が求められるために、一般に各構成部材には剛性が大きなものが必要とされている。
　これに対して、本発明は、敢えて、厚み、刻み幅等が小さく、剛性が小さなエキスパンデッドメタル製電極を用いた場合にも、電極間隔を安定に保持し、更には電極と平板ばね状体との接触部の周囲において平面性が悪化したり、電気分解で発生する気泡や電解液の流れによる影響を受けることなく、低い電気分解電圧で安定した電気分解が可能なイオン交換膜法電解槽が提供可能であることを見いだしたものである。 Large ion exchange membrane electrolytic cells are required to have high rigidity, and therefore, each component member generally requires high rigidity.
On the other hand, the present invention dares to maintain an electrode interval stably even when an expanded metal electrode having a small thickness, step size, etc., and a small rigidity is used. Ion-exchange membrane electrolysis that enables stable electrolysis at a low electrolysis voltage without being affected by the flatness around the contact area with the body or the influence of bubbles generated by electrolysis or the flow of electrolyte It has been found that the tank can be provided.
　図１は、本発明のイオン交換膜法電解槽の一実施例を説明する図であり、図１Ａは、複数個の電解槽ユニットを積層したイオン交換膜法電解槽の断面を説明する図であり、図１Ｂは、電解槽ユニットの陰極側から見た平面図であり、図１Ｃは、図１Ｂにおいて、Ａ－Ａ’線で切断した断面図である。
　図１Ａに示すように、イオン交換膜法電解槽１は複極式の電解槽ユニット２の所定の個数をイオン交換膜３を介して積層して組み立てられている。
　電解槽ユニット２には、陽極室隔壁４から間隔を設けて陽極５が配置され、陽極室６が形成されている。また、陰極室隔壁７から間隔を設けて陰極８が配置されており、陰極室隔壁７とイオン交換膜３の間に陰極室９が形成されている。
　また、陽極室６、陰極室９の上部には、それぞれ陽極室側気液分離手段４０、陰極室側気液分離手段４１が設けられている。 FIG. 1 is a diagram illustrating an embodiment of an ion exchange membrane electrolytic cell according to the present invention, and FIG. 1A is a diagram illustrating a cross section of an ion exchange membrane electrolytic cell in which a plurality of electrolytic cell units are stacked. FIG. 1B is a plan view seen from the cathode side of the electrolytic cell unit, and FIG. 1C is a cross-sectional view taken along line AA ′ in FIG. 1B.
As shown in FIG. 1A, the ion exchange membrane method electrolytic cell 1 is assembled by laminating a predetermined number of bipolar electrolytic cell units 2 via an ion exchange membrane 3.
In the electrolytic cell unit 2, an anode 5 is disposed at a distance from the anode chamber partition wall 4, and an anode chamber 6 is formed. Further, a cathode 8 is disposed at a distance from the cathode chamber partition wall 7, and a cathode chamber 9 is formed between the cathode chamber partition wall 7 and the ion exchange membrane 3.
In addition, an anode chamber side gas / liquid separation means 40 and a cathode chamber side gas / liquid separation means 41 are provided above the anode chamber 6 and the cathode chamber 9, respectively.
　また、電解槽ユニット２の陽極室６には、陽極液供給口３１が取り付けられ、陽極室側気液分離手段４０には、濃度が低下した陽極液と気体を溢流、すなわちオーバーフローによって排出する陽極液排出口３２が取り付けられている。
　また、電解槽ユニット２の陰極室９には、陰極液供給口３３が取り付けられ、陰極室側気液分離手段４１には、濃度が低下した陰極液と気体を溢流、すなわちオーバーフローによって排出する陰極液排出口３４が取り付けられている。 Further, an anolyte supply port 31 is attached to the anode chamber 6 of the electrolytic cell unit 2, and the anolyte and gas having a reduced concentration are discharged to the anode chamber side gas-liquid separation means 40 by overflow, that is, overflow. An anolyte discharge port 32 is attached.
The cathode chamber 9 of the electrolytic cell unit 2 is provided with a catholyte supply port 33, and the cathode chamber-side gas-liquid separation means 41 discharges the catholyte and gas having a reduced concentration by overflow, that is, overflow. A catholyte outlet 34 is attached.
　陽極で発生した気体を含んだ気液混合流体が陽極室の上部で気液分離し、電解液の一部は陽極液排出口３２から流出する。そして一部は陽極室内を下降し、電解槽に設けた陽極液供給口３１から供給されて陽極室内へ噴出する陽極液とともに混合されて陽極において電気分解が行われる。
　なお、陽極液供給口、陽極液排出口は、図に示すように、それぞれを同一の側に配置する例を示したが、供給口と排出口を対向して配置しても良く、また陽極液供給口と陰極液供給口を同一の側に配置しても良い。 The gas-liquid mixed fluid containing the gas generated at the anode undergoes gas-liquid separation at the upper portion of the anode chamber, and a part of the electrolytic solution flows out from the anolyte discharge port 32. Then, a part thereof descends in the anode chamber and is mixed with the anolyte supplied from the anolyte supply port 31 provided in the electrolytic cell and ejected into the anode chamber, and electrolysis is performed in the anode.
As shown in the figure, the anolyte supply port and the anolyte discharge port are arranged on the same side, but the supply port and the discharge port may be arranged to face each other. The liquid supply port and the catholyte supply port may be arranged on the same side.
　図１Ｂおよび図１Ｃに示すように、陰極室隔壁７には、平板ばね状体保持部材１１が陰極室隔壁接合部２０に取り付けられており、平板ばね状体保持部材１１には平板ばね状体１２が結合されている。
　平板ばね状体保持部材１１と平板ばね状体１２のつけ根部１３は、電解槽の高さ方向の直線に線対称に間隔を設けて形成されており、一対のつけ根部１３ａ、１３ｂから延びた平板ばね状体１２は互いに反対方向へ伸びており、平板ばね状体１２は平板ばね状体保持部材１１のつけ根１３ａ、１３ｂから間隔を設けた位置に屈曲部１４を有し、屈曲部１４の先端部には電極と接触して導電接続を形成する電極接触部１５を有している。 As shown in FIG. 1B and FIG. 1C, the flat plate spring-like body holding member 11 is attached to the negative electrode chamber partition wall 7, and the flat plate spring-like body holding member 11 is attached to the flat plate spring-like body holding member 11. 12 are connected.
The base portions 13 of the flat spring-like body holding member 11 and the flat spring-like body 12 are formed with a line symmetry symmetrically with respect to a straight line in the height direction of the electrolytic cell, and extend from the pair of root portions 13a and 13b. The flat spring-like body 12 extends in directions opposite to each other, and the flat spring-like body 12 has a bent portion 14 at a position spaced from the bases 13a, 13b of the flat spring-like body holding member 11, and The tip has an electrode contact portion 15 that contacts the electrode to form a conductive connection.
　屈曲部１４は、平板ばね状体１２の電極接触部１５に平板ばね状体保持部材面方向への力が加わった際に平板ばね状体が折れ曲がる部分である。図１に示す平板ばね状体では、平板ばね状体に力が作用しない場合に平板ばね状体保持部材との結合部から水平方向に延びた部分に形成されており、電極接触部を形成した先端部分が立ち上がり部１６から垂直方向へと延びている。 The bent portion 14 is a portion where the flat spring-like body is bent when a force in the flat spring-like body holding member surface direction is applied to the electrode contact portion 15 of the flat spring-like body 12. In the flat spring-like body shown in FIG. 1, when a force does not act on the flat spring-like body, it is formed in a portion extending in the horizontal direction from the coupling portion with the flat spring-like body holding member to form an electrode contact portion. The tip portion extends from the rising portion 16 in the vertical direction.
　屈曲部１４は、平板ばね状体１２の平板ばね状体保持部材のつけ根部から間隔を設けた部分に形成されるので、平板ばね状体１２が平板ばね状体保持部材１１側へ繰り返し押圧された場合、あるいは運転開始時等にまれに生じる異常な圧力で押圧された場合でも、平板ばね状体の平板ばね状体保持部材へのつけ根部１３に対する応力の集中が避けられるので、つけ根部１３への応力の集中によって結合部が回復しがたい塑性変形を受けることを防止することができる。 Since the bent portion 14 is formed at a portion spaced from the root of the flat spring-like body holding member of the flat spring-like body 12, the flat spring-like body 12 is repeatedly pressed toward the flat spring-like body holding member 11 side. Even when pressed by an abnormal pressure that occurs rarely at the start of operation or the like, stress concentration on the root portion 13 to the flat spring-like body holding member of the flat spring-like body can be avoided. It is possible to prevent the joint from undergoing plastic deformation that is difficult to recover due to the concentration of stress on the surface.
　また、平板ばね状体１２には、つけ根部１３と屈曲部１４との間に、電極面と接触する側の面が窪んだ、平板ばね状体の長さ方向に垂直な凹部１７が形成されている。このように、平板ばね状体のつけ根部１３に凹部１７を形成した場合には、つけ根部１３への応力集中による塑性変形を防止する効果が大きな平板ばね状体を得ることができる。 Further, the flat plate spring-like body 12 is formed with a concave portion 17 between the base portion 13 and the bent portion 14 and having a concave surface on the side in contact with the electrode surface, which is perpendicular to the length direction of the flat plate spring-like body. ing. Thus, when the concave part 17 is formed in the base part 13 of the flat spring-like body, a flat spring-like body having a great effect of preventing plastic deformation due to stress concentration on the base part 13 can be obtained.
　また、平板ばね状体１２の先端部に設けられる電極接触部１５には、鈍角状あるいは曲面状に曲げられて電極と接触する電極接触部１５が設けられており、電極接触部１５が陰極８と接触して通電される。
　平板ばね状体１２は、電解槽の高さ方向の直線に線対称に間隔を設けて互いに向き合う方向へ伸びており、その先端部に設けた電極接触部１５が陰極８と接触している。このため、電極接触部１５に接触した陰極８には、陰極８を陰極面に平行な方向へ移動させようとする力は殆ど作用せず、陰極面に直角方向の力のみが作用する。 Further, the electrode contact portion 15 provided at the distal end portion of the flat spring-like body 12 is provided with an electrode contact portion 15 that is bent into an obtuse or curved shape and comes into contact with the electrode, and the electrode contact portion 15 serves as the cathode 8. Is energized in contact with.
The flat spring-like body 12 extends in a direction facing each other with an interval symmetrical to a straight line in the height direction of the electrolytic cell, and an electrode contact portion 15 provided at the tip thereof is in contact with the cathode 8. For this reason, almost no force that moves the cathode 8 in a direction parallel to the cathode surface acts on the cathode 8 in contact with the electrode contact portion 15, and only a force in a direction perpendicular to the cathode surface acts.
　また、平板ばね状体１２は、その反発力によって陰極８と陰極面とを直角の方向へと変位させ、陰極８を陰極面と平行に移動させることはないので、イオン交換膜面を傷つける等の問題を生じることなく所定の位置に調整することが可能となる。
　陰極室隔壁に装着する平板ばね状体保持部材１１は、陰極面と同等の大きさの１個の部材であっても、あるいは複数個の部材を所定の個数配置したものであっても良い。
　平板ばね状体保持部材１１には、平板ばね状体１１を作製する際に、板材を切断して折り曲げ加工した際に開口部２５が形成されているので、電極面に沿って上昇した気泡を含んだ陰極液は、上部において気体を分離した後に開口部２５を通じて、陰極室隔壁７側の空間を下降して、陰極液供給口３３を通じて供給された陰極液とともに電解槽内で電気分解を受け、陰極液排出口３４から排出される。 Further, the flat spring-like body 12 displaces the cathode 8 and the cathode surface in a direction perpendicular to the repulsive force and does not move the cathode 8 in parallel with the cathode surface, so that the ion exchange membrane surface is damaged. It is possible to adjust to a predetermined position without causing the above problem.
The flat spring-like body holding member 11 attached to the cathode chamber partition wall may be one member having the same size as the cathode surface, or a predetermined number of members may be arranged.
Since the opening 25 is formed in the flat spring-shaped body holding member 11 when the flat plate spring-shaped body 11 is produced and cut and bent, the air bubbles rising along the electrode surface are removed. The contained catholyte is subjected to electrolysis in the electrolytic cell together with the catholyte supplied through the catholyte supply port 33 through the opening 25 after the gas is separated at the upper part and descending the space on the cathode chamber partition wall 7 side. And discharged from the catholyte discharge port 34.
　一方、陽極室隔壁４には、陽極室隔壁接合部３０において陽極室隔壁４と陽極５が接合されている。両者は、連続的な溶接部、多数の点状の溶接部等によって接合されて機械的な保持と導電接続が形成されている。 On the other hand, the anode chamber partition 4 and the anode 5 are joined to the anode chamber partition 4 at the anode chamber partition junction 30. Both are joined by a continuous weld, a large number of spot-like welds, etc. to form a mechanical holding and conductive connection.
　また、本発明のイオン交換膜法電解槽においては、陽極室隔壁と陰極室隔壁がトラス型等の凹凸を有する形状を有しているので、チタン、ニッケル等の薄板で作製した電極室の剛性を高めることができる。 Further, in the ion exchange membrane method electrolytic cell of the present invention, the anode chamber partition and the cathode chamber partition have a shape having irregularities such as a truss type, so that the rigidity of the electrode chamber made of a thin plate of titanium, nickel, etc. Can be increased.
　更に、本発明のイオン交換膜法電解槽にあっては、平板ばね状体が接触する電極には、刻み幅が０．１ｍｍ以上０．５ｍｍ以下、短径が０．５ｍｍ以上３．０ｍｍ以下、長径が１．０ｍｍ以上６．０ｍｍ以下、板厚０．１ｍｍ以上０．５ｍｍ以下であるエキスパンデッドメタル電極を装着したことを特徴としている。
　刻み幅が０．１ｍｍ以下、短径が０．５ｍｍ以下、長径が１．０ｍｍ以下、板厚０．１ｍｍ以下では、電極の剛性が小さくなって、電解液の流動、気泡の発生の圧力によって影響を受ける形状の保持性が悪化するので好ましくない。
　また、刻み幅が０．５ｍｍ、短径が３．０ｍｍ、長径が６．０ｍｍ、板厚０．５ｍｍを超えるとばね状保持体によって電極間間隔を精密に調整することが困難となる。 Furthermore, in the ion exchange membrane method electrolytic cell of the present invention, the step contact width is 0.1 mm or more and 0.5 mm or less, and the minor axis is 0.5 mm or more and 3.0 mm or less for the electrode in contact with the flat spring-like body. An expanded metal electrode having a major axis of 1.0 mm to 6.0 mm and a plate thickness of 0.1 mm to 0.5 mm is mounted.
When the step size is 0.1 mm or less, the minor axis is 0.5 mm or less, the major axis is 1.0 mm or less, and the plate thickness is 0.1 mm or less, the rigidity of the electrode is reduced, and the flow of the electrolyte and the pressure of bubble generation This is not preferable because the retention of the affected shape deteriorates.
If the step width is 0.5 mm, the minor axis is 3.0 mm, the major axis is 6.0 mm, and the plate thickness exceeds 0.5 mm, it becomes difficult to precisely adjust the inter-electrode spacing by the spring-like holder.
　従来、このような刻み幅、厚み等が小さなエキスパンデッドメタル電極を装着して平板ばね状体を接触させて電極の保持と通電を行った場合には、平板ばね状体がエキスパンデッドメタルと接触する電極接触部における圧縮応力による電極の歪みが大きくなり、イオン交換膜と電極との距離が大きくなり、所望の性能を得ることができないものと考えられていた。
　しかしながら、本発明者らは、このようなエキスパンデッドメタル電極を使用した場合にも、ばね状体の電極接触部における圧縮応力およびイオン交換膜への面圧を所定の範囲内に保持することによって電極の歪みを小さくした電気分解性能が良好なイオン交換膜法電解槽を提供することを見出したものである。 Conventionally, when an expanded metal electrode having a small step size, thickness, etc. is mounted and the flat spring-like body is brought into contact with the electrode and the electrode is held and energized, the flat spring-like body is expanded metal. It has been considered that the strain of the electrode due to the compressive stress at the electrode contact portion in contact with the electrode increases, the distance between the ion exchange membrane and the electrode increases, and the desired performance cannot be obtained.
However, the present inventors maintain the compressive stress and the surface pressure on the ion exchange membrane in the electrode contact portion of the spring-like body within a predetermined range even when such an expanded metal electrode is used. The present inventors have found that an ion-exchange membrane electrolytic cell having good electrolysis performance with reduced electrode distortion is provided.
　本発明のイオン交換膜法電解槽においては、エキスパンデッドメタル電極に対する圧縮応力を低下させるために、電極と接触部の数を多くして、平板ばね状体一箇所当りの反力を低下させることが好ましい。
　反力は、一個所当たり、０．１Ｎ以上、４．０Ｎ以下とすることが好ましい。０．１Ｎよりも小さい場合には、電極と平板ばね状体との導電接触が悪化して電解槽電圧が上昇するとともに安定した運転が困難となる。また、４．０Ｎよりも大きくなると、電極とイオン交換膜へ接触した際にイオン交換膜の損傷等が生じる可能性がある。
　特に、この圧縮応力を低下させる為に、陰極５上での電極接触部１５の数を多くして、平板ばね状体１点当りの反力を所定の範囲とすることが好ましい。
　これによって、陰極５への圧縮圧力が急激に上昇する際に陰極の歪みを小さくして、陰極５がイオン交換膜６へ接触すること等によるイオン交換膜６の破損を防止する効果が顕著となる。 In the ion exchange membrane electrolytic cell of the present invention, in order to reduce the compressive stress on the expanded metal electrode, the number of electrodes and the number of contact portions is increased to reduce the reaction force per flat spring-like body. It is preferable.
The reaction force is preferably 0.1 N or more and 4.0 N or less per location. When it is smaller than 0.1N, the conductive contact between the electrode and the flat spring-like body deteriorates, the electrolytic cell voltage increases, and stable operation becomes difficult. On the other hand, if it exceeds 4.0 N, the ion exchange membrane may be damaged when it comes into contact with the electrode and the ion exchange membrane.
In particular, in order to reduce this compressive stress, it is preferable to increase the number of electrode contact portions 15 on the cathode 5 so that the reaction force per point of the flat spring-like body is within a predetermined range.
As a result, the effect of reducing the distortion of the cathode when the compression pressure to the cathode 5 suddenly increases and preventing the ion exchange membrane 6 from being damaged due to the cathode 5 coming into contact with the ion exchange membrane 6 is remarkable. Become.
　また、イオン交換膜法電解槽を組み立てる際には、陰極、イオン交換膜および陽極の締め付け圧力は、イオン交換膜法電解槽への電解液の充填前において、平板ばね状体によって押圧される電極のイオン交換膜への面圧を１０Ｐａ～１．５ｋＰａとすることが好ましく、３００Ｐａ～１．５ｋＰａとすることが更に好ましい。
　このように１０Ｐａ以上の面圧となるように締め付けることにより、イオン交換膜と陰極および陽極との間隔が大きくなることを防止し、電解槽電圧の低下が可能となる。
　また、１．５ｋＰａを超えると、イオン交換膜にかかる圧力が大きくなり過ぎて、イオン交換膜が破損する危険性が生じるので、本願発明では、上限値を１．５ｋＰａ以下とすることが好ましい。 Further, when assembling the ion exchange membrane method electrolytic cell, the clamping pressure of the cathode, the ion exchange membrane and the anode is the electrode pressed by the flat spring-shaped body before filling the electrolytic solution into the ion exchange membrane method electrolytic cell. The surface pressure on the ion exchange membrane is preferably 10 Pa to 1.5 kPa, more preferably 300 Pa to 1.5 kPa.
By tightening so that the surface pressure becomes 10 Pa or more in this way, it is possible to prevent the interval between the ion exchange membrane, the cathode and the anode from becoming large, and to reduce the electrolytic cell voltage.
Moreover, since the pressure concerning an ion exchange membrane will become large too much when it exceeds 1.5 kPa and an ion exchange membrane will be damaged, it is preferable in this invention that an upper limit shall be 1.5 kPa or less.
　図２は、本発明の平板状ばね状体の一例を説明する図である。図２Ａは、平板ばね状体を取り付けた平板ばね状体保持部材の斜視図であり、図２Ｂは、その平板ばね状体の側面を説明する図である。
　この平板ばね状体１２の平板ばね状体保持部材１１のつけ根部１３から距離を設けた位置に、電極接触部１５が平板ばね状体保持部材１１側へ押圧された際に曲がる屈曲部１４とともに、前記平板ばね状体は、前記平板ばね状体保持部材の結合部から距離を設けた前記平板ばね状体保持部材と同一平面上を延びた位置に、前記平板ばね状体が接触する前記電極側とは反対側へ延びる部分１９を有している。
　その結果、ばね状部材が大きく押圧された場合にも、屈曲部１４および電極側とは反対側へ延びる部分１９によって応力を吸収することができるので、つけ根部１３に回復不可能な塑性変形を生じることがないイオン交換膜法電解槽を提供することができる。 FIG. 2 is a diagram for explaining an example of a flat spring-like body of the present invention. FIG. 2A is a perspective view of a flat spring-like body holding member to which a flat spring-like body is attached, and FIG. 2B is a diagram illustrating a side surface of the flat spring-like body.
Along with the bent portion 14 that bends when the electrode contact portion 15 is pressed toward the flat spring-shaped body holding member 11 at a position away from the base portion 13 of the flat spring-shaped body holding member 11 of the flat spring-shaped body 12. The plate spring-like body is in contact with the plate spring-like body at a position extending on the same plane as the plate spring-like body holding member provided at a distance from the coupling portion of the plate spring-like body holding member. It has a portion 19 extending to the side opposite to the side.
As a result, even when the spring-like member is largely pressed, the stress can be absorbed by the bent portion 14 and the portion 19 extending to the side opposite to the electrode side. An ion exchange membrane electrolytic cell that does not occur can be provided.
　図３は、本発明の平板状ばね状体の他の例を説明する図である。図３Ａは、平板ばね状体を取り付けた平板ばね状体保持部材の斜視図であり、図３Ｂは、その平板ばね状体の側面を説明する図である。
　図３は、図２に示したイオン交換膜電解槽とは、平板ばね状体１２の平板ばね状体保持部材１１のつけ根部１３の導電接続する電極面側が窪んだ、平板ばね状体の長さ方向に垂直な方向の凹部１７を形成したものである。
　これによって、押圧される圧縮圧力を更に効率良く吸収できるので好ましい。 FIG. 3 is a diagram for explaining another example of the flat spring-like body of the present invention. FIG. 3A is a perspective view of a flat spring-like body holding member to which a flat spring-like body is attached, and FIG. 3B is a diagram illustrating a side surface of the flat spring-like body.
3 is different from the ion exchange membrane electrolytic cell shown in FIG. 2 in that the length of the plate spring-like body in which the electrode surface side of the base portion 13 of the plate-spring-like body holding member 11 of the plate spring-like body 12 is electrically connected is depressed. A concave portion 17 is formed in a direction perpendicular to the vertical direction.
This is preferable because the compressed compression pressure can be absorbed more efficiently.
　本発明のイオン交換膜法電解槽においては、この圧縮応力を低下させる為に、陰極上での電極接触部の数を多くして、平板ばね状体１点当りの反力を０．１Ｎ以上、４．０Ｎ以下として反力を低下させることによって陰極への圧縮圧力が急激に上昇する際に陰極の歪みを小さくして、陰極がイオン交換膜へ接触すること等によるイオン交換膜の破損を防止する効果が顕著となる。
　以下、実施例を示して本発明を説明する。 In the ion exchange membrane electrolytic cell of the present invention, in order to reduce this compressive stress, the number of electrode contact portions on the cathode is increased, and the reaction force per flat spring-like body is 0.1 N or more. By reducing the reaction force to 4.0 N or less, the distortion of the cathode is reduced when the compression pressure to the cathode suddenly increases, and the ion exchange membrane is damaged due to contact of the cathode with the ion exchange membrane, etc. The effect to prevent becomes remarkable.
Hereinafter, the present invention will be described with reference to examples.
　実施例１
　刻み幅０．１６ｍｍ、短径１．０ｍｍ、長径２．０ｍｍ、板厚０．１５ｍｍのニッケル製のエキスパンデッドメタルを、短径方向の長さ５３０ｍｍ、長径方向の長さ４００ｍｍに切断した。本実施例では、エキスパンドメタルの短径方向を縦、長径方向を横とした。このエキスパンデッドメタルを１０質量％の塩酸を用いて温度５０℃で１５分間エッチングした後、水洗、乾燥した。
　次いで、ジニトロジアンミン白金硝酸溶液（田中貴金属製、白金濃度：４．５質量％、溶媒：８重量％硝酸溶液）と硝酸ニッケル６水和物と水を用いて白金含有量がモル比で０．５、混合液中の白金とニッケルの合計濃度が金属換算で５質量％の塗布液を調製した。 Example 1
A nickel expanded metal having a step width of 0.16 mm, a minor axis of 1.0 mm, a major axis of 2.0 mm and a plate thickness of 0.15 mm was cut into a length of 530 mm in the minor axis direction and a length of 400 mm in the major axis direction. In this example, the short axis direction of the expanded metal was the vertical axis, and the long axis direction was the horizontal axis. The expanded metal was etched with 10% by mass hydrochloric acid at 50 ° C. for 15 minutes, washed with water and dried.
Subsequently, a platinum content of the dinitrodiammine platinum nitrate solution (manufactured by Tanaka Kikinzoku, platinum concentration: 4.5 mass%, solvent: 8 wt% nitric acid solution), nickel nitrate hexahydrate and water in a molar ratio of 0. 5. A coating solution having a total concentration of platinum and nickel in the mixed solution of 5% by mass in terms of metal was prepared.
　次いで、この塗布液を前記エキスパンデッドメタルに刷毛を用い全面に塗布し、熱風式乾燥機内で８０℃１５分間乾燥後、箱型電気炉を用いて空気流通下のもと５００℃で１５分間熱処理して熱分解被膜の形成を行った。この一連の操作を５回繰り返して、白金－ニッケル合金を被覆した電極を陰極とした。
　この陰極の一つの空孔の面積は、１．０ｍｍ2であり、開口率は約５１％である。
　次いで、得られた陰極と、チタンのエキスパンデッドメタル基体に電極触媒被覆を形成した陽極（ペルメレック電極製ＤＳＥ）、陽イオン交換膜（旭化成ケミカルズ製アシプレックス）を用いて、陰極側には平板ばね状体によって陰極への導電接続をしたイオン交換膜法電解槽を組み立てた。
　このとき、電解槽の締付は、イオン交換膜への面圧が１．０２ｋＰａとなるように行った。 Next, this coating solution was applied to the entire surface of the expanded metal using a brush, dried in a hot air dryer at 80 ° C. for 15 minutes, and then using a box-type electric furnace at 500 ° C. for 15 minutes under air circulation. A thermal decomposition coating was formed by heat treatment. This series of operations was repeated 5 times, and the electrode coated with the platinum-nickel alloy was used as the cathode.
The area of one hole of this cathode is 1.0 mm 2 and the aperture ratio is about 51%.
Next, using the obtained cathode, an anode having an electrode catalyst coating on a titanium expanded metal substrate (DSE manufactured by Permelec Electrode), and a cation exchange membrane (Aciplex manufactured by Asahi Kasei Chemicals), a flat plate is formed on the cathode side. An ion exchange membrane method electrolytic cell was assembled which was conductively connected to the cathode by a spring-like body.
At this time, the electrolytic cell was tightened so that the surface pressure on the ion exchange membrane was 1.02 kPa.
　また、平板ばね状体として図２で示したものと同様の形状のものを使用した。
　平板ばね状体の全長１００ｍｍ、幅は結合部９で１０ｍｍ、屈曲部１０で５ｍｍ、立ち上がり部１１の長さ２０ｍｍ、電極接触部の長さ６ｍｍでニッケル製である。
　電極接触部の数は、３１６点とし、１点当りの陰極面積を６．７ｃｍ2とした。この時、圧縮応力は一点当たり０．６７Ｎとなった。 Moreover, the thing of the same shape as what was shown in FIG. 2 was used as a flat spring-like body.
The flat spring-like body has a total length of 100 mm, a width of 10 mm at the coupling portion 9, 5 mm at the bent portion 10, a length of 20 mm at the rising portion 11, and a length of 6 mm at the electrode contact portion, and is made of nickel.
The number of electrode contact portions was 316 points, and the cathode area per point was 6.7 cm 2 . At this time, the compressive stress was 0.67 N per point.
　前記のイオン交換膜法電解槽を用い、陽極室の圧力に対し、陰極室の圧力を５ｋＰａ高く設定しイオン交換膜を陽極表面に密着させ、電流密度５ｋＡ／ｍ2、陽極室出口塩水濃度：２００～２１０ｇ／Ｌ、陰極室出口水酸化ナトリウム水溶液濃度：３１ないし３３質量％の範囲に調整して、温度：９０℃にて食塩水の電気分解試験を行い、電解槽電圧を測定した。電解槽電圧は、５分間にわたり、１秒間隔で測定・記録したところ、電圧は２．９５Ｖ付近で安定していた。 Using the above-mentioned ion exchange membrane method electrolytic cell, the pressure in the cathode chamber is set higher by 5 kPa than the pressure in the anode chamber, the ion exchange membrane is brought into close contact with the anode surface, the current density is 5 kA / m 2 , and the anode chamber outlet brine concentration: The sodium chloride aqueous solution concentration was adjusted to 200 to 210 g / L and the cathode chamber outlet sodium hydroxide aqueous solution concentration range was 31 to 33% by mass. The electrolytic cell voltage was measured and recorded at 1 second intervals over 5 minutes, and the voltage was stable at around 2.95V.
　比較例１
　エキスパンデッドメタル電極として、刻み幅：１．５ｍｍ、短径：６ｍｍ、長径：１５ｍｍ、板厚：１．５ｍｍのニッケル製のエキスパンデッドメタルを、実施例１と同様にして短径方向の長さ５３０ｍｍ、長径方向の長さ４００ｍｍに切断した。本比較例においても、エキスパンドメタルの短径方向を縦、長径方向を横とした。
　このエキスパンデッドメタル電極の一つの空孔の面積は、４５ｍｍ2であり、開口率は約４２％である。
　このエキスパンデッドメタル製の基体を１０質量％の塩酸を用いて温度５０℃で１５分間エッチングした後、水洗、乾燥した。 Comparative Example 1
As an expanded metal electrode, an expanded metal made of nickel having a step width of 1.5 mm, a short diameter: 6 mm, a long diameter: 15 mm, and a plate thickness: 1.5 mm is formed in the short diameter direction in the same manner as in Example 1. It was cut into a length of 530 mm and a length of 400 mm in the major axis direction. Also in this comparative example, the short diameter direction of the expanded metal was set to be vertical, and the long diameter direction was set to be horizontal.
The area of one hole of this expanded metal electrode is 45 mm 2 and the aperture ratio is about 42%.
This expanded metal substrate was etched with 10% by mass hydrochloric acid at a temperature of 50 ° C. for 15 minutes, washed with water and dried.
　次いで、ジニトロジアンミン白金硝酸溶液（田中貴金属製、白金濃度：４．５重量％、溶媒：８重量％硝酸溶液）と硝酸ニッケル６水和物と水を用いて白金含有量がモル比で０．５、混合液中の白金とニッケルの合計濃度が金属換算で５質量％の塗布液を調製した。
　次いで、この塗布液を前記ファインメッシュ電極に刷毛を用い全面に塗布し、熱風式乾燥機内で８０℃１５分間乾燥後、箱型電気炉を用いて空気流通下のもと５００℃で１５分間熱処理して熱分解被膜の形成を行った。この一連の操作を５回繰り返して、白金－ニッケル合金を被覆した電極を陰極とした。
　実施例１と同様にして比較例のイオン交換膜法電解槽を組み立てた。
　このときの締付力を、陽イオン交換膜の面圧で１９６Ｐａとした。 Subsequently, a platinum content of the dinitrodiammine platinum nitrate solution (manufactured by Tanaka Kikinzoku, platinum concentration: 4.5% by weight, solvent: 8% by weight nitric acid solution), nickel nitrate hexahydrate and water in a molar ratio of 0. 5. A coating solution having a total concentration of platinum and nickel in the mixed solution of 5% by mass in terms of metal was prepared.
Next, this coating solution is applied to the fine mesh electrode by using a brush, dried at 80 ° C. for 15 minutes in a hot air dryer, and then heat-treated at 500 ° C. for 15 minutes under air circulation using a box-type electric furnace. Then, a pyrolytic film was formed. This series of operations was repeated 5 times, and the electrode coated with the platinum-nickel alloy was used as the cathode.
A comparative example ion exchange membrane electrolytic cell was assembled in the same manner as in Example 1.
The tightening force at this time was 196 Pa in terms of the surface pressure of the cation exchange membrane.
　また、前記陰極には、図３Ｂに断面図を示すように、全長１００ｍｍで、中央に屈曲部を有し、電極と接触する電極接触する部分の幅２０ｍｍ、その他の部分の幅２５ｍｍで、板厚０．９ｍｍのニッケル製のばねによって保持するとともに通電した。
　このばねは、縦方向に９０ｍｍ間隔、横方向は２５０ｍｍ間隔を設けて配置して、先端部と電極が接触する個所の数は、１０点とし、接触する個所１点当りの陰極面積を２１２ｃｍ2とし、その時の反力は１個所当たり４．２Ｎとなった。 Further, as shown in the cross-sectional view of FIG. 3B, the cathode has a total length of 100 mm, a bent portion at the center, a width of 20 mm at the portion in contact with the electrode and a width of 25 mm at the other portion, It was energized while being held by a nickel spring having a thickness of 0.9 mm.
The springs are arranged at intervals of 90 mm in the vertical direction and at intervals of 250 mm in the horizontal direction. The number of locations where the tip and the electrode are in contact is 10 points, and the cathode area per contact point is 212 cm 2. The reaction force at that time was 4.2 N per location.
　比較例のイオン交換膜法電解槽を実施例１と同様にして、陽極室の圧力に対し、陰極室の圧力を５ｋＰａ高く設定しイオン交換膜を陽極表面に密着させ、電流密度６ｋＡ／ｍ2、陽極室出口塩水濃度：２００～２１０ｇ／Ｌ、陰極室出口水酸化ナトリウム水溶液濃度：３１～３３質量％に維持しながら、温度：９０℃で食塩水の電気分解試験を行い、電解槽電圧を測定した。電解槽電圧は、５分間にわたり、１秒間隔で測定して記録したところ、電圧は３．０４Ｖ付近で推移し、実施例の電解槽に比較しても０．０９Ｖ高い電圧となった。 The ion exchange membrane method electrolytic cell of the comparative example was set to 5 kPa higher than the pressure in the anode chamber, and the ion exchange membrane was brought into close contact with the anode surface in the same manner as in Example 1, and the current density was 6 kA / m 2. The anode chamber outlet brine concentration: 200 to 210 g / L, the cathode chamber outlet sodium hydroxide aqueous solution concentration: 31 to 33% by mass, and the saline electrolysis test was performed at a temperature of 90 ° C. It was measured. When the electrolytic cell voltage was measured and recorded at intervals of 1 second over 5 minutes, the voltage changed in the vicinity of 3.04 V, which was 0.09 V higher than the electrolytic cell of the example.
　本発明のイオン交換膜法電解槽は、電解電圧の低減効果が大きく、食塩水のイオン交換膜法電解槽の場合には、電力原単位を大幅に減少することができるので、膨大な電力の減少に寄与するものとなり、食塩水のイオン交換膜法電解槽に代表されるイオン交換膜法電解槽に極めて有用なものである。 The ion exchange membrane method electrolytic cell of the present invention has a great effect of reducing the electrolysis voltage, and in the case of a salt water ion exchange membrane method electrolytic cell, the power intensity can be greatly reduced. This contributes to a decrease, and is extremely useful for an ion exchange membrane method electrolytic cell typified by a salt water ion exchange membrane method electrolytic cell.
１…イオン交換膜法電解槽、２…電解槽ユニット、３…イオン交換膜、４…陽極室隔壁、５…陽極、６…陽極室、７…陰極室隔壁、８…陰極、９…陰極室、１１…平板ばね状体保持部材、１２…平板ばね状体、１３，１３ａ，１３ｂ…つけ根部、１４…屈曲部、１５…電極接触部、１６…立ち上がり部、１７…凹部、１９…電極側とは反対側へ延びる部分、２０…陰極室隔壁接合部、２５…開口部、３０…陽極室隔壁接合部、３１…陽極液供給口、３２…陽極液排出口、３４…陰極液排出口、４０…陽極室側気液分離手段、４１…陰極室側気液分離手段 DESCRIPTION OF SYMBOLS 1 ... Ion exchange membrane method electrolytic cell, 2 ... Electrolytic cell unit, 3 ... Ion exchange membrane, 4 ... Anode chamber partition, 5 ... Anode, 6 ... Anode chamber, 7 ... Cathode chamber partition, 8 ... Cathode, 9 ... Cathode chamber , 11: flat spring-like body holding member, 12: flat spring-like body, 13, 13a, 13b ... root portion, 14 ... bent portion, 15 ... electrode contact portion, 16 ... rising portion, 17 ... concave portion, 19 ... electrode side 20 ... cathode chamber partition wall junction, 25 ... opening, 30 ... anode chamber partition junction, 31 ... anolyte supply port, 32 ... anolyte discharge port, 34 ... catholyte discharge port, 40: anode chamber side gas-liquid separation means, 41: cathode chamber side gas-liquid separation means

Claims (5)

  1. 　イオン交換膜法電解槽において、電極室内に設けた平板ばね状体保持部材と一体に形成されて電極方向に延びた平板ばね状体と電極接触部において接触して通電する平板ばね状体が、平板ばね状体保持部材の付け根部から距離を設けた平板ばね状体保持部材と同一平面上を延びた位置に、平板ばね状体が接触する電極とは反対側へ延びた部分を有し、更に先端側に接触する電極方向へ延びた部分を有し、平板ばね状体が接触する電極は、刻み幅が０．１ｍｍ以上０．５ｍｍ以下、短径が０．５ｍｍ以上３．０ｍｍ以下、長径が１．０ｍｍ以上６．０ｍｍ以下、板厚０．１ｍｍ以上０．５ｍｍ以下であるエキスパンデッドメタル電極を装着し、前記エキスパンデッドメタル電極のメッシュの短目方向長さとメッシュの長目方向長さとの積で表される面積を、平板ばね状体と電極接触部との接触部の数で除した値が０．０１ｃｍ2～１０ｃｍ2、電極接触部１点当たりの反力を０．１Ｎ～４．０Ｎとしたことを特徴とするイオン交換膜法電解槽。 In the ion exchange membrane method electrolytic cell, a flat spring body that is formed integrally with a flat spring holding member provided in the electrode chamber and that extends in the electrode direction and contacts the electrode contact portion and energizes, The plate spring-like body holding member has a portion extending on the opposite side of the electrode in contact with the plate spring-like body at a position extending on the same plane as the flat spring-like body holding member provided at a distance from the base of the flat spring-like body holding member, Furthermore, the electrode which has a portion extending in the electrode direction in contact with the tip side, and the flat spring-like body contacts, has a step width of 0.1 mm to 0.5 mm, a minor axis of 0.5 mm to 3.0 mm, An expanded metal electrode having a major axis of 1.0 mm or more and 6.0 mm or less and a plate thickness of 0.1 mm or more and 0.5 mm or less is mounted, and the length of the expanded metal electrode in the short direction and the length of the mesh Expressed by the product of the direction length The area that the value obtained by dividing the number of contact portions between the plate spring and the electrode contact portion 0.01 cm 2 ~ 10 cm 2, and the reaction force per electrode contact portion 1 point and 0.1 N ~ 4.0 N An ion exchange membrane electrolytic cell characterized by the above.
  2. 　前記平板ばね状体は、前記平板ばね状体保持部材の結合部から距離を設けた前記平板ばね状体保持部材と同一平面上を延びた位置に前記平板ばね状体が接触する前記電極側とは反対側へ延びる部分を有し、更に先端側に接触する前記電極方向へ延びる部分を有したことを特徴とする請求項１記載のイオン交換膜電解槽。 The flat spring-like body is disposed on the electrode side where the flat spring-like body contacts a position extending on the same plane as the flat spring-like body holding member provided at a distance from a coupling portion of the flat spring-like body holding member. 2. The ion exchange membrane electrolytic cell according to claim 1, further comprising a portion extending in the opposite direction and further having a portion extending in the electrode direction in contact with the tip side.
  3. 　イオン交換膜法電解槽への電解液の充填前の前記電極のイオン交換膜への面圧を１０Ｐａ～１．５ｋＰａとしたことを特徴とする請求項１または２のいずれか１項記載のイオン交換膜電解槽。 The ion according to any one of claims 1 and 2, wherein a surface pressure of the electrode on the ion exchange membrane before filling the electrolytic solution in the ion exchange membrane method electrolytic cell is set to 10 Pa to 1.5 kPa. Exchange membrane electrolytic cell.
  4. 　前記平板ばね状体は、付け根部と屈曲部との間に、平板ばね状体が接触する電極面側が窪んだ平板ばね状体の長さ方向に垂直な方向の凹部を形成したことを特徴とする請求項１から３のいずれか１項記載のイオン交換膜電解槽。 The flat spring-like body is characterized in that a recess in a direction perpendicular to the length direction of the flat spring-like body is formed between the base portion and the bent portion. The ion exchange membrane electrolytic cell according to any one of claims 1 to 3.
  5. 　前記の平板ばね状体保持部材は、複極型電解槽の電極室隔壁と接合されて固定および導電接続を形成したことを特徴とする請求項１から４のいずれか１項記載のイオン交換膜電解槽。 5. The ion exchange membrane according to claim 1, wherein the flat spring-shaped body holding member is bonded to an electrode chamber partition wall of a bipolar electrolytic cell to form a fixed and conductive connection. 6. Electrolytic tank.
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